CN105295059B - A kind of method of the chloromethylated polystyrene polymer and adsorption recovery Phenols In Industrial Liquid Waste class of immobilized cationization beta-cyclodextrin - Google Patents
A kind of method of the chloromethylated polystyrene polymer and adsorption recovery Phenols In Industrial Liquid Waste class of immobilized cationization beta-cyclodextrin Download PDFInfo
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- CN105295059B CN105295059B CN201510853037.3A CN201510853037A CN105295059B CN 105295059 B CN105295059 B CN 105295059B CN 201510853037 A CN201510853037 A CN 201510853037A CN 105295059 B CN105295059 B CN 105295059B
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- cyclodextrin
- immobilized
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- cationization
- chloromethylated polystyrene
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- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 56
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 50
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 50
- 229920000642 polymer Polymers 0.000 title claims abstract description 46
- 239000001116 FEMA 4028 Substances 0.000 title claims abstract description 39
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 39
- 235000011175 beta-cyclodextrine Nutrition 0.000 title claims abstract description 39
- 229960004853 betadex Drugs 0.000 title claims abstract description 39
- 150000002989 phenols Chemical class 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 13
- 239000010808 liquid waste Substances 0.000 title claims abstract description 7
- 238000011084 recovery Methods 0.000 title abstract description 8
- 239000003463 adsorbent Substances 0.000 claims abstract description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229940097362 cyclodextrins Drugs 0.000 claims abstract description 7
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- 239000002351 wastewater Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- -1 methyl Hydroxypropyl Chemical group 0.000 claims description 6
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 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 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000007265 chloromethylation reaction Methods 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical compound CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 5
- 229960004889 salicylic acid Drugs 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 abstract 1
- 239000004952 Polyamide Substances 0.000 abstract 1
- 150000001896 cresols Chemical class 0.000 abstract 1
- 238000003795 desorption Methods 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229940090668 parachlorophenol Drugs 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 229940068984 polyvinyl alcohol Drugs 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- RLMOTNBFJWWVFS-UHFFFAOYSA-N chloroethane;n-ethylethanamine Chemical compound CCCl.CCNCC RLMOTNBFJWWVFS-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- URCAYJXJXYLGTI-UHFFFAOYSA-N ethene fluorobenzene Chemical compound C=C.FC1=CC=CC=C1 URCAYJXJXYLGTI-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000250 methylamino group Chemical class [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 230000000926 neurological effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of methods of the chloromethylated polystyrene polymer and adsorption recovery Phenols In Industrial Liquid Waste class of immobilized cationization beta-cyclodextrin.This method is adsorbent using the polymer that the immobilized cationized cyclodextrins of chloromethylated polystyrene are formed, phenolic substances in industrial wastewater is selectively adsorbed in polymer, and the regeneration and reuse of adsorbent material then can be realized by the processing of simply desorption.There is the Phenol Industrial Wastewater of phenolic hydroxyl group to adsorb to containing cresols, phenol, chlorophenol and salicylic acid etc. using the adsorbent, maximal absorptive capacity can achieve 96,140,250,170mg/g respectively, and just reach balance in 2 hours.The result shows that its adsorbance is apparently higher than the maximal absorptive capacity that adsorbent material has been commercialized to phenols in polyamide, DM301 and S-8 etc..Preparation process of the invention is simple and reusable, low in cost, easy to operate, adsorption efficiency is high, energy conservation and environmental protection and the advantages that can recycle phenols.
Description
Technical field
The invention belongs to waste water post-processing technology fields, specifically, being related to the immobilized cationization beta-cyclodextrin of one kind
The method of chloromethylated polystyrene polymer and adsorption recovery Phenols In Industrial Liquid Waste class.
Background technique
Currently, China's environmental pollution is extremely serious, organic pollution is still a more scabrous problem, traditional environmentally friendly work
Skill and environment-friendly materials cannot efficiently solve increasingly increased various complicated pollution problems, therefore develop new environment-friendly materials,
Water-purifying material cheap, without secondary pollution is developed, cost of water treatment is reduced, purification efficiency is improved and has become environmental protection neck
Domain urgent problem to be solved.And the waste water of phenolic substances is to the very harmful of human body and other biological in organic pollution, if long
Phase, which drinks the water containing phenol, can cause dizzy, anaemia and neurological conditions；Phenols wastewater, which enters rivers,lakes and seas, will affect aquatic life
The growth and breeding of object；If carrying out the underproduction irrigated will also result in crops with the excessive water quality containing phenol and withering.Meanwhile phenol
It is also generally acknowledged carcinogen, it has been included in the pollutant blacklist of 129 kinds of priority acccess controls by American National Environmental Protection Agency at present.I
State's phenol wastewater is mainly derived from coke-oven plant, petrochemical plant, resin processing plant, chemical plant, plastic molding and processing plant etc., is wherein with phenol in chemical plant
The phenolic substancess such as a large amount of phenol and salicylic acid can be unavoidably generated during raw material production salicylic acid, and if these substances can return
Receive the unification for re-using the social benefit, economic benefit and environmental benefit that will realize factory and enterprise.
Based on the above reasons, to the recycling of this kind of phenolic compound at the hot spot of current research.Chinese patent (publication number
101417834 A 2009 of CN) it discloses and a kind of keeps phenols wastewater serial by KL-13X first with heterogeneous catalytic oxidation technology
Oxidizing tower catalysis oxidation occurs on a catalyst, so that phenols wastewater be made to degrade, method processing quickly, no solid waste, but this method
Phenols can not be recycled to reach the economic unification with environmental protection, and cannot be reused, it is possible to create exhaust emission.Chinese patent
(publication No. CN 103304005A 2013) reports a kind of phenol using in hollow-fibre membrane removing phenol wastewater, with phosphoric acid
Extractant and strippant are mixed and made into treatment fluid using kerosene or benzene as diluent as extraction agent carrier by tributyl, will be located
The tube side of liquid injection film device is managed, waste water injects shell side, reaches separating effect, although processing capacity is big, device is expensive,
And there are secondary pollution, treatment process trouble to environment using substances such as benzene.Recently, Chinese patent (publication No. CN
104724783A 2015) disclose it is a kind of phenols wastewater is extracted using dephenolize extractant methyl n-butyl ketone, obtain
Extraction phase and raffinate phase, this method can be effectively removed high concentration phenols wastewater, but this method needs specific extractant, cost compared with
It is high and the disadvantages of cannot reuse.
Although absorption method using wide, is targetedly adsorbed specific organic pollutant in field of waste water treatment
The research of material is rarely reported, using the collaboration of weak interaction and interaction force between Subjective and Objective to improve to object
The research of absorption is concerned in recent years, and this kind of material there is apparent adsorption effect therefore to open specific organic substance
Issue specifically for phenolic compound in water adsorption recovery method and adsorbent material prepare it is very necessary.
Summary of the invention
The purpose of the present invention is to overcome the deficiency in the prior art, provides a kind of chloromethyl of immobilized cationization beta-cyclodextrin
Change the method for poly styrene polymer and adsorption recovery Phenols In Industrial Liquid Waste class.
To achieve the goals above, the present invention adopts the following technical scheme:
The present invention is immobilized to have hydrophobic sky on the basis of chloromethylated polystyrene polymer backbone contains benzene radicals
The cationized cyclodextrins of chamber, water-wetted surface and quaternary ammonium group, in conjunction with phenolic substances phenolic hydroxyl group is hydrophilic and phenyl ring hydrophobic property, close
At poly- to high molecular polymer, that is, immobilized cationization beta-cyclodextrin chloromethylation of the selective absorption of phenolic compound
Styrene polymer.
A kind of chloromethylated polystyrene polymer of immobilized cationization beta-cyclodextrin, is prepared by following steps:
(1) in mass ratio by the etherifying agent of cyclodextrin and 2,3- epoxypropyltrimethylchloride chloride or other active groups
For 1:1~10:1 mixing, 10mL water is added, and make its pH=13 with sodium hydrate regulator solution, finally at 40~90 DEG C
React 1~4.5h, the cyclodextrin being cationized；
(2) by styrene or other contain the olefines and p-chloromethyl styrene 1:1~4:1 ratio in mass ratio of phenyl ring
Mixed monomer dissolves the dispersant into water as polymerized monomer, at room temperature, crosslinking agent, polymerized monomer, initiation is added
Agent is reacted at 40~80 DEG C；After completion of the reaction i.e. obtain polymer, through hot water washing for several times after, by obtained product into
Row drying, obtains high molecular polymer；The weight fraction ratio of each substance are as follows: 10~40 parts of polymerized monomer, crosslinking agent: 1~3 part,
Dispersing agent: 0.1~2 part, initiator: 0.1~4 part, water: 100~400 parts；
(3) cationized cyclodextrins and water obtained step (1) are mixed in 1:10~1:70 ratio, make the ring that is cationized
Dextrin dissolution, and pyridine is added, 1h is stirred at room temperature, then at a temperature of 40~90 DEG C, chloromethyl made from step (2) is added
Change polystyrene reactant for 24 hours；The chloromethylated polystyrene and cationized cyclodextrins ratio of addition are 1:1~3:1；It has reacted
Required polymer is obtained after finishing, after hot water washing for several times, obtained product is dried, immobilized cationization β-is obtained
The chloromethylated polystyrene polymer of cyclodextrin.
In the chloromethylated polystyrene polymer of above-mentioned immobilized cationization beta-cyclodextrin, the cyclodextrin is α-
Cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin or hydroxypropyl-β-cyclodextrin.
In the chloromethylated polystyrene polymer of above-mentioned immobilized cationization beta-cyclodextrin, the active group
Etherifying agent is 2,3- epoxypropyltrimethylchloride chloride, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, N- (2,3- glycidyl) three
Methylamine salt or diethylamide ethyl chloride.
In the chloromethylated polystyrene polymer of above-mentioned immobilized cationization beta-cyclodextrin, the alkene containing phenyl ring
Hydro carbons is styrene, methyl styrene, p-methylstyrene, chlorostyrene, bromstyrol, fluorobenzene ethene or to chloromethylbenzene second
Alkene.
In the chloromethylated polystyrene polymer of above-mentioned immobilized cationization beta-cyclodextrin, the dispersing agent is poly-
Vinyl alcohol, polyethylene glycol, hydroxyethyl cellulose, hydroxypropyl cellulose or methylcellulose.
In the chloromethylated polystyrene polymer of above-mentioned immobilized cationization beta-cyclodextrin, the initiator was
Aoxidize the mixture of one or both of dibenzoyl, cumyl peroxide and azodiisobutyronitrile.
In the chloromethylated polystyrene polymer of above-mentioned immobilized cationization beta-cyclodextrin, the crosslinking agent is two
Vinyl benzene, diisocyanate, acrylic acid, methacrylic acid, hydroxypropyl acrylate or hydroxy propyl methacrylate.
Industrial wastewater is recycled using the chloromethylated polystyrene Polymer adsorption of above-mentioned immobilized cationization beta-cyclodextrin
The method of middle phenols, includes the following steps:
(1) chloromethylated polystyrene polymer is added in the industrial wastewater containing phenolic compound, is shaken at room temperature
It swings or stirs, be separated by filtration, Phenol for Waste Water class compound is attracted in chloromethylated polystyrene polymer；
(2) the chloromethylated polystyrene polymer of absorbing phenolic compound is added in desorbing agent, is shaken at room temperature
It swings or stirs, filter, phenolic compound is desorbed, recycling obtains phenolic compound and chloromethylated polystyrene polymer；
(3) the chloromethylated polystyrene polymer of recycling is placed in 60~70 DEG C of drying in oven, dry 5~6h, storage
It deposits in case next time uses.
The mass volume ratio of the adsorbent material chloromethylated polystyrene polymer and industrial wastewater is 1:10~10:1
(g/L)。
The desorbing agent is the mixture of ethyl alcohol or ethyl alcohol and sodium hydroxide.
In above-mentioned adsorption recovery phenolic compound, phenolic compound and eluant, eluent in obtained eluent can lead to
Peracid, recrystallization recycling.Phenols In Industrial Liquid Waste substance content after adsorption recovery is extremely low, classification recovering effect compared with
It is good.Adsorbent material can be recycled and be reused, this has rush using expanding to the commercialization of this adsorbent and in the industry
Into effect.
Compared with prior art, the method have the advantages that:
1. chloromethylated polystyrene polymer synthesized by the present invention, synthesis step is simple, environmentally protective, without secondary dirt
Dye；And this adsorbent material, acid, alkali, organic solvent are not dissolved in, there is good mechanical strength, can be repeated several times use, is produced
It is at low cost, it is saved under normal temperature and pressure.
2. adsorption separating method of the present invention directly puts into adsorbent chloromethylated polystyrene polymer containing phenols
In the industrial wastewater of compound, highly selective adsorption separation process can be completed at normal temperature.
3. the present invention is desorbed using alkali and alcohol mixture matter, the regeneration technology of adsorbent is simple, and cost recovery is low.
4. the obtained adsorbent material of the present invention carries out static and dynamic to phenolic compound aqueous solution at normal temperature and inhales
It is attached, there is good selective absorption effect, and after desorptive activation, reuse, adsorbance is held essentially constant.
Specific embodiment
The present invention will be further explained with reference to the examples below, but scope of protection of the present invention is not limited thereto.
Formulas I~III is the synthetic method of immobilization cyclo-dextrin-modified resin
Embodiment 1:
The preparation (1) of adsorbent material:
1g beta-cyclodextrin is dissolved in 10mL pure water, stirring 10min makes it dissolve, and 7g2,3- epoxy is added
Ammonium chloride (ETMAC), and with sodium hydrate regulator solution pH make its 13,4.5h is stirred at 70 DEG C, filter, evaporation obtain it is brown
Color dope i.e. cationization beta-cyclodextrin；0.12g polyvinyl alcohol is dissolved in the pure water of 50mL, 2.6g sodium chloride is added,
10g styrene, 1g divinylbenzene, 3.6g p-chloromethyl styrene and 0.16g mistake are slowly added into the solution at room temperature
The mixed solution of Benzoyl Oxide reacts 30min, then heats at 60 DEG C, reacts 2h, is continuously heating to 80 DEG C, reaction
10h, obtained product is cooling, filtering, dry in 70 DEG C of air dry oven after being washed for several times with 60~80 DEG C of warm water
6h obtains light yellow final products Chloromethyl polystyrene；1g cationization beta-cyclodextrin is dissolved in 70mL water, 10mL pyrrole is added
1h is stirred in pyridine at room temperature, and 2g chloromethylated polystyrene is then added, and the product cooling obtained for 24 hours, mistake are reacted at 73 DEG C
Filter, after being washed for several times with 60~80 DEG C of warm water, dry 6h, obtains yellow and surface is smooth in 70 DEG C of air dry oven
Final products, that is, immobilized chloromethylated polystyrene the adsorbent of cationization beta-cyclodextrin.
The synthetic method of formula (I) cation cyclodextrin
The synthetic method of formula (II) chloromethylated polystyrene
The solid support method of formula (III) cation cyclodextrin
Embodiment 2:
The preparation (2) of adsorbent material:
1g beta-cyclodextrin is dissolved in 10mL pure water, stirring 10min makes it dissolve, and 1g2,3- epoxy is added
Ammonium chloride (ETMAC), and with sodium hydrate regulator solution pH make its 13,4.5h is stirred at 70 DEG C, filter, evaporation obtain depth
Brown viscous object i.e. cationization beta-cyclodextrin；0.48g polyvinyl alcohol is dissolved in the pure water of 200mL, 6.4g chlorination is added
Sodium is slowly added to 30g styrene, 4g divinylbenzene, 10g p-chloromethyl styrene and 0.64g into the solution at room temperature
The mixed solution of benzoyl peroxide reacts 30min, then heats at 60 DEG C, reacts 2h, is continuously heating to 80 DEG C, reaction
10h, obtained product is cooling, filtering, dry in 70 DEG C of air dry oven after being washed for several times with 60~80 DEG C of warm water
6h obtains yellow final products chloromethylated polystyrene；1g cationization beta-cyclodextrin is dissolved in 20mL water, 2mL pyrrole is added
1h is stirred in pyridine at room temperature, and 5g chloromethylated polystyrene is then added, and the product cooling obtained for 24 hours, mistake are reacted at 90 DEG C
Filter, after being washed for several times with 60~80 DEG C of warm water, dry 6h, obtains dark brown and rough surface in 70 DEG C of air dry oven
Final products, that is, immobilized cationization beta-cyclodextrin chloromethylated polystyrene adsorbent.
Embodiment 3:
The preparation (3) of adsorbent material:
1g beta-cyclodextrin is dissolved in 20mL pure water, stirring 10min makes it dissolve, and 10g2,3- glycidyl front three is added
Ammonium chloride (ETMAC), and with sodium hydrate regulator solution pH make its 13,4.5h is stirred at 70 DEG C, is filtered, evaporation obtains
Dark brown dope i.e. cationization beta-cyclodextrin；0.24g polyvinyl alcohol is dissolved in the pure water of 100mL, 3.2g chlorine is added
Change sodium, be slowly added at room temperature into the solution 15g styrene, 2g divinylbenzene, 15g p-chloromethyl styrene and
The mixed solution of 0.32g benzoyl peroxide reacts 30min, then heats at 60 DEG C, reacts 2h, is continuously heating to 80 DEG C,
10h is reacted, obtained product is cooling, filtering, after being washed for several times with 60~80 DEG C of warm water, does in 70 DEG C of air dry oven
Dry 6h obtains yellow final products Chloromethyl polystyrene；1g cationization beta-cyclodextrin is dissolved in 10mL water, 1mL pyrrole is added
1h is stirred in pyridine at room temperature, and 2.5g chloromethylated polystyrene is then added, and the product cooling obtained for 24 hours is reacted at 30 DEG C,
Filtering, after being washed for several times with 60~80 DEG C of warm water, dry 6h, is obtained faint yellow and powder in 70 DEG C of air dry oven
Final products, that is, immobilized chloromethylated polystyrene the adsorbent of beta-cyclodextrin.
Embodiment 4:
The processing of wastewater containing phenol solution:
By the adsorbent material 0.15g of embodiment 1, puts into the phenolic waste water solution of 100mL 500mg/L and is placed at 25 DEG C,
2h is vibrated with the full temperature culture shaking table of the speed oscillation of 200rpm, after oscillation, supernatant is taken to use UV-Vis spectrophotometry
Luminosity measures the content of Phenol in Aqueous Solution, is learnt by result, and the adsorbance of adsorbent Pyrogentisinic Acid is 140mg/g；Then with 0.4%
+ 50% ethyl alcohol of sodium hydroxide is eluted, and the content of Phenol in Aqueous Solution sodium is surveyed using ultraviolet-visible spectrophotometer, by tying
Eluting rate known to fruit is 95%.
Embodiment 5:
The processing of the waste water solution containing salicylic acid:
By the adsorbent material 0.15g of embodiment 1, puts into the salicylic acid waste water solution of 100mL 400mg/L and be placed in 25 DEG C
Under, 2h is vibrated with the full temperature culture shaking table of the speed oscillation of 200rpm, after oscillation, supernatant is taken to use ultraviolet-visible light
Spectrophotometric measures salicylic content in solution, is learnt by result, and the adsorbance of adsorbent Pyrogentisinic Acid is 170mg/g；Then
It is eluted with+50% ethyl alcohol of 0.02% sodium hydroxide, surveys sodium salicylate in solution using ultraviolet-visible spectrophotometer
Content, eluting rate is 80% as can be seen from the results.
Embodiment 6:
The processing of the waste water solution containing parachlorophenol:
By the adsorbent material 0.15g of embodiment 1, puts into the parachlorophenol waste water solution of 100mL 500mg/L and be placed in 25
At DEG C, 2h is vibrated with the full temperature culture shaking table of the speed oscillation of 200rpm, after oscillation, supernatant is taken to use ultraviolet-visible
Light spectrophotometric measures the content of Phenol in Aqueous Solution, is learnt by result, and adsorbent is 250mg/g to the adsorbance of parachlorophenol；
Then it is eluted with+50% ethyl alcohol of 0.4% sodium hydroxide, surveys parachlorphenol in solution using ultraviolet-visible spectrophotometer
The content of sodium, eluting rate is 90% as can be seen from the results.
Embodiment 7:
The processing of the waste water solution containing p-cresol:
By the adsorbent material 0.15g of embodiment 1, puts into the parachlorophenol waste water solution of 100mL 200mg/L and be placed in 25
At DEG C, 2h is vibrated with the full temperature culture shaking table of the speed oscillation of 200rpm, after oscillation, supernatant is taken to use ultraviolet-visible
Light spectrophotometric measures the content of Phenol in Aqueous Solution, is learnt by result, and adsorbent is 96mg/g to the adsorbance of parachlorophenol；So
It is eluted afterwards with+50% ethyl alcohol of 0.4% sodium hydroxide, surveys p-cresol in solution using ultraviolet-visible spectrophotometer
The content of sodium, eluting rate is 85% as can be seen from the results.
Claims (8)
1. a kind of chloromethylated polystyrene polymer of immobilized cationization beta-cyclodextrin, it is characterised in that by following steps system
It is standby to form:
(1) by cyclodextrin and 2,3- epoxypropyltrimethylchloride chloride is 1:1~10:1 mixing in mass ratio, adds 10mL
Water, and make its pH=13 with sodium hydrate regulator solution, 1~4.5h is finally reacted at 40~90 DEG C, is cationized
Cyclodextrin；
(2) styrene or other olefines for containing phenyl ring and p-chloromethyl styrene 1:1~4:1 ratio in mass ratio are mixed
Monomer as polymerized monomer, dissolve the dispersant into water, at room temperature, be added crosslinking agent, polymerized monomer, initiator,
40~80 DEG C are reacted；Polymer is obtained after completion of the reaction, after hot water washing for several times, obtained product is done
It is dry, obtain high molecular polymer；The weight fraction ratio of each substance are as follows: 10~40 parts of polymerized monomer, crosslinking agent: 1~3 part, dispersion
Agent: 0.1~2 part, initiator: 0.1~4 part, water: 100~400 parts；
(3) cationized cyclodextrins and water obtained step (1) are mixed in 1:10~1:70 ratio, make cationized cyclodextrins
Dissolution, and pyridine is added, 1h is stirred at room temperature, then at a temperature of 40~90 DEG C, it is poly- that chloromethylation made from step (2) is added
Styrene reacts for 24 hours；The chloromethylated polystyrene and cationized cyclodextrins ratio of addition are 1:1~3:1；After completion of the reaction
Required polymer is obtained, after hot water washing for several times, obtained product is dried, obtains immobilized cationization β-ring paste
The chloromethylated polystyrene polymer of essence.
2. the chloromethylated polystyrene polymer of immobilized cationization beta-cyclodextrin according to claim 1, feature
It is, the cyclodextrin is beta-cyclodextrin or hydroxypropyl-β-cyclodextrin.
3. the chloromethylated polystyrene polymer of immobilized cationization beta-cyclodextrin according to claim 1, feature
It is, the dispersing agent is polyvinyl alcohol, polyethylene glycol, hydroxyethyl cellulose, hydroxypropyl cellulose or methylcellulose.
4. the chloromethylated polystyrene polymer of immobilized cationization beta-cyclodextrin according to claim 1, feature
It is, the initiator is one or both of dibenzoyl peroxide, cumyl peroxide and azodiisobutyronitrile
Mixture.
5. the chloromethylated polystyrene polymer of immobilized cationization beta-cyclodextrin according to claim 1, feature
It is, the crosslinking agent is divinylbenzene, diisocyanate, acrylic acid, methacrylic acid, hydroxypropyl acrylate or methyl
Hydroxypropyl acrylate.
6. the chloromethylated polystyrene Polymer adsorption using immobilized cationization beta-cyclodextrin described in claim 1 recycles
The method of Phenols In Industrial Liquid Waste class, it is characterised in that include the following steps:
(1) the chloromethylated polystyrene polymer of immobilized cationization beta-cyclodextrin is added to the work containing phenolic compound
It in industry waste water, vibrates or stirs at room temperature, be separated by filtration, Phenol for Waste Water class compound is attracted to immobilized cationization β-ring paste
In the chloromethylated polystyrene polymer of essence；
(2) the chloromethylated polystyrene polymer of the immobilized cationization beta-cyclodextrin of absorbing phenolic compound is added to
In desorbing agent, at room temperature vibrate or stir, filtering, phenolic compound is desorbed, recycling obtain phenolic compound and it is immobilized sun from
The chloromethylated polystyrene polymer of sonization beta-cyclodextrin；
(3) the chloromethylated polystyrene polymer of the immobilized cationization beta-cyclodextrin of recycling is placed in 60~70 DEG C of baking ovens
Drying, dry 5~6h, storage is in case use next time.
7. according to the method described in claim 6, it is characterized in that, the chloromethyl of the immobilized cationization beta-cyclodextrin of adsorbent material
The mass volume ratio for changing poly styrene polymer and industrial wastewater is 1:10~10:1g/L.
8. according to the method described in claim 6, it is characterized in that, desorbing agent is the mixing of ethyl alcohol or ethyl alcohol and sodium hydroxide
Object.
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