CN106423103A - Preparation and application of composite hydrogel capable of adsorbing and catalytically degrading antibiotics - Google Patents
Preparation and application of composite hydrogel capable of adsorbing and catalytically degrading antibiotics Download PDFInfo
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- CN106423103A CN106423103A CN201611061164.0A CN201611061164A CN106423103A CN 106423103 A CN106423103 A CN 106423103A CN 201611061164 A CN201611061164 A CN 201611061164A CN 106423103 A CN106423103 A CN 106423103A
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- preparation
- copper sulfide
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- hydrogel
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000000017 hydrogel Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003242 anti bacterial agent Substances 0.000 title claims description 4
- 229940088710 antibiotic agent Drugs 0.000 title claims description 4
- 230000000593 degrading effect Effects 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 claims abstract description 26
- 230000005855 radiation Effects 0.000 claims abstract description 23
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 claims abstract description 17
- 125000003368 amide group Chemical group 0.000 claims abstract description 15
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 71
- 230000003115 biocidal effect Effects 0.000 claims description 30
- 229940018557 citraconic acid Drugs 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- 229910052724 xenon Inorganic materials 0.000 claims description 16
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000009388 chemical precipitation Methods 0.000 claims description 2
- 229940124307 fluoroquinolone Drugs 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 150000002835 noble gases Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- 239000002351 wastewater Substances 0.000 abstract description 9
- DFQUBYCHLQAFOW-NSCUHMNNSA-N (e)-4-(methylamino)-4-oxobut-2-enoic acid Chemical compound CNC(=O)\C=C\C(O)=O DFQUBYCHLQAFOW-NSCUHMNNSA-N 0.000 abstract 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 abstract 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000001782 photodegradation Methods 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 40
- 230000015556 catabolic process Effects 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 29
- 229910021641 deionized water Inorganic materials 0.000 description 29
- 239000000499 gel Substances 0.000 description 20
- 238000001179 sorption measurement Methods 0.000 description 19
- 238000004140 cleaning Methods 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 239000010453 quartz Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 230000010355 oscillation Effects 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 229910052927 chalcanthite Inorganic materials 0.000 description 9
- 230000001376 precipitating effect Effects 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 229960001180 norfloxacin Drugs 0.000 description 8
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000012984 antibiotic solution Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229960005404 sulfamethoxazole Drugs 0.000 description 4
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical group [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- TZJKHERXIDPDTK-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C12.[F] Chemical compound N1=CC=CC2=CC=CC=C12.[F] TZJKHERXIDPDTK-UHFFFAOYSA-N 0.000 description 1
- 241000233803 Nypa Species 0.000 description 1
- 235000005305 Nypa fruticans Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method and an application of composite hydrogel containing carboxyl groups and amide groups and supporting a nanometer photocatalyst copper sulfide. The preparation method comprises the step that 2-hydroxyethyl acrylate, N-methylmaleamic acid and distilled water are uniformly mixed and subjected to irradiation polymerization, polymer hydrogel is obtained and taken as a supporter to support the nanometer photocatalyst nanometer copper sulfide with an in-situ precipitation method by aid of a precipitant, wherein the mole ratio of 2-hydroxyethyl acrylate to N-methylmaleamic acid monomers is 1-9 to 9-1, high-energy rays for irradiation polymerization are <60>Co-gamma rays or <137>Cs-gamma rays, the radiation dose is 1*10<4>-1*10<8> Gy, and the polymerization temperature ranges from subzero 95 DEG C to subzero 63 DEG C; an aqueous solution of 2-hydroxyethyl acrylate and N-methylmaleamic acid is subjected to irradiation polymerization under shield gas; the nanometer photocatalyst copper sulfide is supported with a chemical in-situ precipitation method. The composite hydrogel has a remarkable effect when applied to photo-degradation of organic pollutants in wastewater, has higher mechanical property and thermal stability and is high in reuse efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of composite aquogel with absorption-catalytic degradation antibiotic function and
Application in water process.
Background technology
Antibiotic is a kind of chemical substance that can suppress with humble concentration or affect it to plant biological function.Its discovery with
Application, has played huge effect in terms of human health care and the animals and plants prevention and control of plant diseases, pest control.But, produce in a large number with it and answer
With pollution problem also becomes increasingly severe.Antibiotic complex structure, has stronger bacteria growing inhibiting and kills antibacterial
Effect, belongs to recalcitrant substance.So, once causing antibiotic to pollute it is easy to be enriched with the environment, inducible resistance bacterium
Strain produces, and after antibiotic enters water body, not only can induce generation resistant gene, also can be combined to aquatile with other pollutant
Produce complicated composite toxicity effect with the mankind.Therefore, the Impacts on ecology and environment of antibiotic is increasingly subject to vast environmental area
The concern of person.
Treatment technology containing antibiotic water body mainly includes (1) Physical, and the antibiotic in water body is not occurring chemical shape
It is adsorbed in the case of state change, concentrate, separate, including physical absorption, extraction and membrance separation etc.；(2) bioanalysises, using micro- life
The effect such as the absorption of thing or plant, accumulation, enrichment, flocculation removes the antibiotic in water body, including activated sludge process, anoxia/good
Oxygen method, flocculation sediment etc.；(3) chemical method, the antibiotic in water body is reacted with chemical substance and is removed, or at other
Under initiation conditions, chemical form is occurred to change and the removal that is degraded, including advanced oxidation processes, photocatalytic method, electrochemical oxidation process
Deng.Because Physical can only realize the concentration of antibiotic and transfer it is impossible to realize the basic removal of antibiotic；And bioanalysises remove
The effect on driving birds is not good of antibiotic in water body；The antibiotic that chemical method can effectively be degraded in removal water body, also faces cost mistake simultaneously
The difficult problem reclaiming of high, chemical reagent.And adopt physisorphtion be enriched with, then chemical catalysis degraded antibiotic possess certain
Feasibility and application prospect.Therefore, research and development preparation has the material of absorption-catalytic degradation function, reduces its cost, improves it and follow
Ring utilization ratio, for antibiotic in water body, the technological innovation removing and engineer applied are significant.
Now there are some researches show, the compound of the group such as amide-containing, carboxyl due to introduce the higher nitrogen of cloud density,
Oxygen atom, easily with metal ion generation ligand complex, therefore have amide groups, carboxyl aquogel polymer monomer to metal from
Son has good absorption property, technology can be provided to prop up for aquogel polymer carrier adsorption load nano-copper sulfide photocatalyst
Support.Number of patent application discloses a kind of calcium alginate-Graphene-nano-Au composite hydrogel for CN201610116387.6 and urges
The preparation method of agent, it is simultaneously introduced the crosslinked synthesis of calcium chloride solution by Graphene, calcium alginate and nanometer gold.Patent Shen
Number please disclose a kind of temperature-sensitive hydrogel supported tungsten oxide catalysts and preparation method thereof for CN201310188394.3, it adopts temperature
Quick type monomer, cationic monomer and function monomer, add a certain amount of initiator and cross-linking agent to be prepared from.Number of patent application is
CN201110403006.X discloses a kind of method of supermolecule intelligent gel rubber material load palladium catalysis Heck reaction, and it utilizes cup
Supermolecule intelligent gel P [NIPA-co-Calix], the P of preparation are prepared in arene derivatives and NIPA copolymerization
[NIPA-co-Calix] hydrogel loaded palladium catalyst is it is adaptable to catalysis Heck reacts.CN201210226921.0 discloses one
Plant the preparation method with the difunctional hydrogel of adsoption catalysis, it adopts acrylic acid is that monomer prepares hydrogel, then loads your gold
Belong to and obtain support type hydrogel, the organic dyestuff that can effectively degrade in water body, including anion and the dye of positive ion, have preferably
Recycling effect.
In addition, dawn extensive region etc. of recording (national macromolecule science free paper session thesis summary set theme L macromolecule in 2015
Compound system, 2015, sodium alginate/nanometer silver hybridized hydrogel:A kind of recyclable photocatalytic degradation material) report
With sodium alginate as solution, Calcium Carbonate-GDL is cross-linking system, directly adds nano-silver hydrosol, be prepared in cross-linking process
The sodium alginate of different silver carrying amounts/nanometer silver hybridized hydrogel, has investigated its photocatalytic degradation effect to methylene blue.
Sahiner,N.(Soft and flexible hydrogel templates of different sizes and
various functionalities for metal nanoparticle preparation and their use in
Catalysis.Progress in Polymer Science.2013) report the preparation side of in situ CdS-loaded hydrogel
Method, has inquired into it further and has been applied to adsorb and degrade remove the feasibility of Organic substance in water body.Dong, Shuoxun etc.
(Characterization and adsorption properties of a lanthanum-loaded magnetic
Cationic hydrogel composite for fluoride removal.Water Research.2016) report one
The synthetic method of the magnetic cation hydrogel (MCH-La) of kind of novel load lanthanum, probed in its Adsorption drinking water fluorine from
The effect of son.
At present, for macromolecule hydrogel preparation, the macromolecule hydrogel of existing synthetic due to have one kind or
Multiple special functional groups, have certain effect to the Adsorption of the organic pollution in water body, but its building-up process needs
Cross-linking agent to be added, initiator, the polyalcohol hydrogel purity obtaining is not high, and high-energy ray irradiation polymerization need not add other
Material, method more cleans.In addition, adopting noble metal catalyst existing supported catalyst dosage form hydrogel, relatively costly more, and
The in-situ precipitate preparation method of copper sulfide photocatalyst is simple, cheap and easily-available.Modification technology is combined using irradiation method, both can make
Standby pure polyalcohol hydrogel, can be modified again after the production, and loaded optic catalyst can go eliminating water with green high-efficient
Organic pollution in body
Content of the invention
The present invention seeks to, a kind of tool carboxyl and amide groups are provided and load the compound water congealing of nano-photocatalyst copper sulfide
The preparation method of glue and its application to antibiotic absorption-catalytic degradation.
The technical scheme is that：Have carboxyl and amide groups and be loaded with the composite aquogel of nano-photocatalyst copper sulfide
Preparation method, obtains polymer through irradiation polymerization after uniformly being mixed by 2- 2-(Acryloyloxy)ethanol, N- citraconic acid and distilled water
Hydrogel, then with this hydrogel as carrier, by situ Precipitation precipitant loaded optic catalyst nano-copper sulfide；
2- 2-(Acryloyloxy)ethanol, the mol ratio of N- citraconic acid monomer are 1～9：9～1, especially 4～6：6～4；Institute
The high-energy ray stating irradiation polymerization is60Co- gamma-rays or137Cs- gamma-rays, radiation dose is 1 × 104～1 × 108Gy, polymerization
Temperature is -95 DEG C～-63 DEG C；
Described irradiation polymerization is that the aqueous solution of 2- 2-(Acryloyloxy)ethanol and N- citraconic acid is carried out under a shielding gas；Negative
The method carrying nano-photocatalyst copper sulfide is the chemical in situ sedimentation method.
Polyalcohol hydrogel adopts chemical precipitation method to load nano-copper sulfide in situ, and composite aquogel vulcanizes for nanometer
Copper.
It is any one in copper sulfate, copper chloride and copper nitrate for the cupric salt that in-situ precipitate is reacted, used is heavy
Shallow lake agent is Na2S solution.
Load nano-copper sulfide in-situ precipitate reaction temperature be 25 ± 5 DEG C, pH be 6～8, speed of agitator be 100～
Carry out under conditions of 150r/min.
Described irradiation polymerization is the aqueous solution of 2- 2-(Acryloyloxy)ethanol and N- citraconic acid under protective gas atmosphere
Carry out, the uniform mixing of 2- 2-(Acryloyloxy)ethanol and N- citraconic acid and the volume ratio of water are 1:1～5.
Described uniform mixing refers to mix and use supersound process 2- 2-(Acryloyloxy)ethanol and N- citraconic acid with water
30min fully dissolve after gained solution.
Described protective gas is the gas on polyreaction no impact, and to exclude in the air oxygen, protective gas selects
The noble gases such as nitrogen, helium, argon, optimum selection is nitrogen.
Tool carboxyl and the compound water congealing of amide groups and load nano-photocatalyst copper sulfide that described preparation method obtains
Glue is applied in water process, removes at least one of containing fluoroquinolones or sulfa antibiotics antibiotic for adsorbing-degrading
Application.
The composite aquogel of described tool carboxyl and amide groups and load nano-photocatalyst copper sulfide is applied to antibiotic
Absorption-degraded remove it is characterised in that using 100W～500W xenon lamp simulated visible light as light source, wave-length coverage
390nm～780nm, reaction is 25 ± 5 DEG C in temperature, and pH is 2～10, and speed of agitator enters under conditions of 100～150r/min
OK.
The invention has the beneficial effects as follows：The tool hydroxyl that the present invention provides and the hydrogel carrier of amide groups have preferable hole
Structure, can effectively can be resisted with the functional group of carried metal semiconductor catalyst containing multiple in loaded optic catalyst and absorption
Raw element；The composite aquogel of load nano-photocatalyst copper sulfide is because the loading of nano-copper sulfide is so that the machinery of hydrogel
Intensity enhancing, improves to the adsorption and enrichment ability of antibiotic, and under the radiation of visible light of xenon lamp simulation, antibiotic can be compound
Hydrogel surface catalytic degradation reaches most of mineralising.The present invention prepares hydrogel using high energy low-temp radiating technology, using the longevity
Life length, initiator need not be added it is ensured that polyalcohol hydrogel relatively pure, and preparation method simple it is easy to operation, produce
Advantage of lower cost.Can directly reuse after composite aquogel absorption-catalytic degradation antibiotic.
Brief description
Fig. 1 is the scanning electricity having hydroxyl and amide groups and the composite aquogel of load nano-copper sulfide that embodiment 1 is given
Mirror (upper figure)-electronic energy spectrum (figure below)；
Fig. 2 be embodiment 3 be given tool hydroxyl and amide groups and load nano-copper sulfide composite aquogel to antibiotic
The recycling effect that absorption-degraded removes.
Specific embodiment
The present invention is described further with specific embodiment below in conjunction with the accompanying drawings.
Specifically, polyalcohol hydrogel carrier loads nano-photocatalyst copper sulfide in situ, main inclusion is following
Step：
(1) weigh appropriate carrier hydrogel to be placed in Cu (II) solution of 30～50mL, at 25 ± 5 DEG C, pH is 6～8, turns
Speed is for, under conditions of 100～150r/min, stirring 24h；
(2) leach the hydrogel in above-mentioned solution, clean, dry, be subsequently placed in Na2In S solution, at 25 ± 5 DEG C, pH is
6～8, under conditions of rotating speed is 100～150r/min, stirring 12h fully reacts；
(3) reacted for in-situ precipitate composite aquogel is filtered, deionized water cleans up, and puts in baking oven with 40
± 5 DEG C of drying, you can obtain composite aquogel.
What the present invention obtained has hydroxyl and amide groups and loads the composite aquogel of nano-photocatalyst copper sulfide to antibiosis
Absorption-the catalytic degradation of element, concrete operations are as follows：
(1) weigh the composite aquogel of the tool hydroxyl being dried to constant weight and amide groups and load nano-copper sulfide, put respectively
In conical flask and quartz test tube；
(2) add certain density containing antibiotic solution in conical flask, conical flask is placed in constant temperature oscillator, 25 ±
5 DEG C, pH is 2～8, and rotating speed carries out the unglazed adsorption and enrichment of constant temperature 12 hours under conditions of 100～150r/min；Add necessarily dense
Degree containing antibiotic solution in quartz test tube, be placed in constant temperature photo catalysis reactor, magnetic stirrer, at 25 ± 5 DEG C, pH
It is 2～10 for pH, under conditions of rotating speed is 100～150r/min, the xenon lamp simulated visible light light source using 100W～500W shines
Penetrate, wave-length coverage 390nm～780nm.Solution after fully dark absorption and after photocatalytic degradation, by high-performance liquid chromatogram determination
Concentration before and after calculating, measures the salinity of antibiotic catalytic degradation by TOC instrument.
Polyalcohol hydrogel loads nano-copper sulfide in situ, mainly includes the following steps that：
(1) weigh appropriate carrier hydrogel to be placed in Cu (II) solution of 30～50mL, at 25 ± 5 DEG C, pH is 6～8, turns
Cu (II), for, under conditions of 100～150r/min, stirring 24h, is inhaled to the adsorption of copper ion by speed by carrier hydrogel
Invest on carrier hydrogel；
(2) leach the hydrogel in above-mentioned solution, clean, dry, be subsequently placed in Na2In S solution, at 25 ± 5 DEG C, pH is
6～8, under conditions of rotating speed is 100～150r/min, fully reaction stirring 12h.Na2S as in-situ precipitate agent be adsorbed in load
Cu (II) on body hydrogel generates nano-copper sulfide and is carried on hydrogel, and the color of solution is changed into blackish green, shows that CuS is micro-
Grain generates；
(3) reacted for in-situ precipitate composite aquogel is filtered, deionized water is cleaned, and puts in baking oven with 40 ± 5
DEG C dry, you can obtain composite aquogel.
Absorption-catalytic degradation to antibiotic for the composite aquogel of tool hydroxyl and amide groups and load nano-copper sulfide, tool
Gymnastics is made as follows：
(1) weigh the composite aquogel of the tool hydroxyl being dried to constant weight and amide groups and load nano-copper sulfide, put respectively
In conical flask and quartz test tube；
(2) add certain density containing antibiotic solution in conical flask, conical flask is placed in constant temperature oscillator, 25 ±
5 DEG C, pH is 2～8, and rotating speed carries out the unglazed adsorption and enrichment of constant temperature 12 hours under conditions of 100～150r/min；Add necessarily dense
Degree containing antibiotic solution in quartz test tube, be placed in constant temperature photo catalysis reactor, magnetic stirrer, at 25 ± 5 DEG C, pH
It is 2～10 for pH, under conditions of rotating speed is 100～150r/min, the xenon lamp simulated visible light light source using 100W～500W shines
Penetrate, wave-length coverage 390nm～780nm.Solution after fully dark absorption and after photocatalytic degradation, by high-performance liquid chromatogram determination
Concentration before and after calculating, measures the salinity of antibiotic catalytic degradation by TOC instrument.
The present invention is further described by embodiment, but the invention is not limited in following examples.
Embodiment 1
(1) prepare solution：The N- citraconic acid monomer weighing certain mass is dissolved in deionized water, as component A, so
Add a certain amount of 2- 2-(Acryloyloxy)ethanol backward in above-mentioned solution as component B, distilled water as component C, according to (A+B)：C
For 1:3 (V/V) dissolving mixing, wherein A：B is 1：9(mol/mol)；Ultrasonic 30min makes solution be sufficiently mixed uniformly, mixes the most backward
Close in liquid and be filled with protective gas N2, sealing is it is ensured that anaerobic state.
(2) radiation polymerization technique：At a temperature of -78 DEG C, adopt60Co- gamma-rays be irradiation bomb, radiation dose be 1 ×
104Gy.
(3) load nano-copper sulfide in situ：Hydrogel carrier after irradiation polymerization, deionized water cleaning is repeatedly clean
Afterwards, dry and obtain xerogel.The xerogel weighing 0.5g is put in the conical flask of 100ml, adds the 0.020mol of 50ml
CuSO4·5H2O solution, 150r/min constant temperature oscillation 24h under the conditions of 25 DEG C, leach hydrogel, cleaning under room temperature is dried, then
It is placed in the Na of the 0.02mol/l of 50ml2In S solution, vibration 12h is complete to precipitating under the same conditions.Compound Water after load
It is standby that gel deionized water cleans up post-drying.The knot being obtained using the copper nitrate of same molar ratio, copper chloride solution
Fruit indifference (similarly hereinafter).
(4) absorption-degradation effect：Select the Sulfamethoxazole (being designated as SMZ, similarly hereinafter) in sulfa antibiotics and fluorine quinoline promise
Norfloxacin (being designated as NOR, similarly hereinafter) in ketone antibiotic is representative.Take 0.1g composite aquogel, the 50mg/L of 50ml respectively
Each 2 parts of SMZ and NOR solution；Portion puts into 100ml conical flask, and in 150r/min agitator under the conditions of being placed in 25 DEG C, lucifuge is inhaled
Attached 12h；Portion is put in 50ml quartz test tube, is placed in constant temperature photo catalysis reactor, magnetic stirrer, using 100W xenon
Lamp simulated visible light irradiates 24h.Fully dark adsorb after and photocatalytic degradation after solution, after measured and calculate, composite aquogel
20.81mg/g and 19.90mg/g is respectively to the dark adsorption capacity of SMZ and NOR；The light degradation to SMZ and NOR for the composite aquogel
Efficiency is respectively 93.85% and 86.42%；The salinity of the catalytic degradation to SMZ and NOR for the composite aquogel is respectively
45.34% and 74.95%.
Figure one is the scanning electron microscope-electronic energy spectrum of the composite aquogel after loading copper sulfide, as shown in the figure nanometer sulfuration
Copper has successfully loaded on hydrogel.
Embodiment 2
(1) prepare solution：The N- citraconic acid monomer weighing certain mass is dissolved in deionized water, as component A, so
Add a certain amount of 2- 2-(Acryloyloxy)ethanol backward in above-mentioned solution as component B, distilled water as component C, according to (A+B)：C
For 1:4 (V/V) dissolving mixing, wherein A：B is 1：9(mol/mol)；Ultrasonic 30min makes solution be sufficiently mixed uniformly, mixes the most backward
Close in liquid and be filled with protective gas N2, sealing is it is ensured that anaerobic state.
(2) radiation polymerization technique：At a temperature of -95 DEG C, adopt60Co- gamma-rays be irradiation bomb, radiation dose be 1 ×
108Gy.
(3) load nano-copper sulfide in situ：Hydrogel carrier after irradiation polymerization, deionized water cleaning is repeatedly clean
Afterwards, dry and obtain xerogel.The xerogel weighing 0.5g is put in the conical flask of 100ml, adds the 0.040mol/l's of 50ml
CuSO4·5H2O solution, 120r/min constant temperature oscillation 24h under the conditions of 25 DEG C, leach hydrogel, cleaning under room temperature is dried, then
It is placed in the Na of the 0.04mol/l of 50ml2In S solution, vibration 12h is complete to precipitating under the same conditions.Compound Water after load
It is standby that gel deionized water cleans up post-drying.
(4) absorption-degradation effect：Selection SMZ and NOR is representative.Take 0.1g composite aquogel, the 50mg/L of 50ml respectively
Each 2 parts of SMZ and NOR solution；Portion puts into 100ml conical flask, and in 120r/min agitator under the conditions of being placed in 25 DEG C, lucifuge is inhaled
Attached 12h；Portion is put in 50ml quartz test tube, is placed in constant temperature photo catalysis reactor, magnetic stirrer, using 200W xenon
Lamp simulated visible light irradiates 24h.After measured and calculate, composite aquogel is respectively to the dark adsorption capacity of SMZ and NOR
23.98mg/g and 22.69mg/g；Composite aquogel is respectively 95.91% and 87.59% to the degradation efficiency of SMZ and NOR；Multiple
The salinity of the catalytic degradation to SMZ and NOR for the Heshui gel is respectively 47.41% and 77.17%.
Embodiment 3
(1) prepare solution：The N- citraconic acid monomer weighing certain mass is dissolved in deionized water, as component A, so
Add a certain amount of 2- 2-(Acryloyloxy)ethanol backward in above-mentioned solution as component B, distilled water as component C, according to (A+B)：C
For 1:3 (V/V) dissolving mixing, wherein A：B is 1：4(mol/mol)；Ultrasonic 30min makes solution be sufficiently mixed uniformly, mixes the most backward
Close in liquid and be filled with protective gas N2, sealing is it is ensured that anaerobic state.
(2) radiation polymerization technique：At a temperature of -63 DEG C, adopt137Cs- gamma-rays be irradiation bomb, radiation dose be 1 ×
104Gy.
(3) load nano-copper sulfide in situ：Hydrogel carrier after irradiation polymerization, deionized water cleaning is repeatedly clean
Afterwards, dry and obtain xerogel.The xerogel weighing 0.5g is put in the conical flask of 100ml, adds the 0.040mol/l's of 50ml
CuSO4·5H2O solution, 130r/min constant temperature oscillation 24h under the conditions of 25 DEG C, leach hydrogel, cleaning under room temperature is dried, then
It is placed in the Na of the 0.02mol/l of 50ml2In S solution, vibration 12h is complete to precipitating under the same conditions.Compound Water after load
It is standby that gel deionized water cleans up post-drying.
(4) absorption-degradation effect：Selection SMZ and NOR is representative.Take 0.1g composite aquogel, the 50mg/L of 50ml respectively
Each 2 parts of SMZ and NOR solution；Portion puts into 100ml conical flask, and in 130r/min agitator under the conditions of being placed in 25 DEG C, lucifuge is inhaled
Attached 12h；Portion is put in 50ml quartz test tube, is placed in constant temperature photo catalysis reactor, magnetic stirrer, using 300W xenon
Lamp simulated visible light irradiates 24h.After measured and calculate, composite aquogel is respectively to the dark adsorption capacity of SMZ and NOR
25.73mg/g and 23.69mg/g；Composite aquogel is respectively 84.86% and 86.54% to the degradation efficiency of SMZ and NOR；Multiple
The salinity of the catalytic degradation to SMZ and NOR for the Heshui gel is respectively 55.28% and 81.32%.
Fig. 2 is that the composite aquogel after load copper sulfide in embodiment 3 adsorbs-degrade the recycling effect removing SMZ.
Embodiment 4
(1) prepare solution：The N- citraconic acid monomer weighing certain mass is dissolved in deionized water, as component A, so
Add a certain amount of 2- 2-(Acryloyloxy)ethanol backward in above-mentioned solution as component B, distilled water as component C, according to (A+B)：C
For 1:4 (V/V) dissolving mixing, wherein A：B is 1：4(mol/mol)；Ultrasonic 30min makes solution be sufficiently mixed uniformly, mixes the most backward
Close in liquid and be filled with protective gas N2, sealing is it is ensured that anaerobic state.
(2) radiation polymerization technique：At a temperature of -78 DEG C, adopt137Cs- gamma-rays be irradiation bomb, radiation dose be 1 ×
108Gy.
(3) load nano-copper sulfide in situ：Hydrogel carrier after irradiation polymerization, deionized water cleaning is repeatedly clean
Afterwards, dry and obtain xerogel.The xerogel weighing 0.5g is put in the conical flask of 100ml, adds the 0.040mol/l's of 50ml
CuSO4·5H2O solution, 150r/min constant temperature oscillation 24h under the conditions of 25 DEG C, leach hydrogel, cleaning under room temperature is dried, then
It is placed in the Na of the 0.06mol/l of 50ml2In S solution, vibration 12h is complete to precipitating under the same conditions.Compound Water after load
It is standby that gel deionized water cleans up post-drying.
(4) absorption-degradation effect：Selection SMZ and NOR is representative.Take 0.1g composite aquogel, the 30mg/L of 30ml respectively
Each 2 parts of SMZ and NOR solution；Portion puts into 100ml conical flask, and in 150r/min agitator under the conditions of being placed in 25 DEG C, lucifuge is inhaled
Attached 12h；Portion is put in 50ml quartz test tube, is placed in constant temperature photo catalysis reactor, magnetic stirrer, using 400W xenon
Lamp simulated visible light irradiates 24h.After measured and calculate, composite aquogel is respectively to the dark adsorption capacity of SMZ and NOR
18.08mg/g and 19.90mg/g；Composite aquogel is respectively 96.60% and 86.21% to the degradation efficiency of SMZ and NOR；Multiple
The salinity of the catalytic degradation to SMZ and NOR for the Heshui gel is respectively 45.83% and 78.56%.
Embodiment 5
(1) prepare solution：The N- citraconic acid monomer weighing certain mass is dissolved in deionized water, as component A, so
Add a certain amount of 2- 2-(Acryloyloxy)ethanol backward in above-mentioned solution as component B, distilled water as component C, according to (A+B)：C
For 1:4 (V/V) dissolving mixing, wherein A：B is 1：3(mol/mol)；Ultrasonic 30min makes solution be sufficiently mixed uniformly, mixes the most backward
Close in liquid and be filled with protective gas N2, sealing is it is ensured that anaerobic state.
(2) radiation polymerization technique：At a temperature of -95 DEG C, adopt60Co- gamma-rays be irradiation bomb, radiation dose be 1 ×
106Gy.
(3) load nano-copper sulfide in situ：Hydrogel carrier after irradiation polymerization, deionized water cleaning is repeatedly clean
Afterwards, dry and obtain xerogel.The xerogel weighing 0.5g is put in the conical flask of 100ml, adds the 0.040mol/l's of 50ml
CuSO4·5H2O solution, 100r/min constant temperature oscillation 24h under the conditions of 20 DEG C, leach hydrogel, cleaning under room temperature is dried, then
It is placed in the Na of the 0.04mol/l of 50ml2In S solution, vibration 12h is complete to precipitating under the same conditions.Compound Water after load
It is standby that gel deionized water cleans up post-drying.
(4) absorption-degradation effect：Selection SMZ and NOR is representative.Take 0.1g composite aquogel, the 50mg/L of 50ml respectively
Each 2 parts of SMZ and NOR solution；Portion puts into 100ml conical flask, and in 100r/min agitator under the conditions of being placed in 20 DEG C, lucifuge is inhaled
Attached 12h；Portion is put in 50ml quartz test tube, is placed in constant temperature photo catalysis reactor, magnetic stirrer, using 500W xenon
Lamp simulated visible light irradiates 12h.After measured and calculate, composite aquogel is respectively to the dark adsorption capacity of SMZ and NOR
21.85mg/g and 22.29mg/g；Composite aquogel is respectively 89.54% and 86.75% to the degradation efficiency of SMZ and NOR；Multiple
The salinity of the catalytic degradation to SMZ and NOR for the Heshui gel is respectively 41.32% and 75.90%.
Embodiment 6
(1) prepare solution：The N- citraconic acid monomer weighing certain mass is dissolved in deionized water, as component A, so
Add a certain amount of 2- 2-(Acryloyloxy)ethanol backward in above-mentioned solution as component B, distilled water as component C, according to (A+B)：C
For 1:4 (V/V) dissolving mixing, wherein A：B is 1：4(mol/mol)；Ultrasonic 30min makes solution be sufficiently mixed uniformly, mixes the most backward
Close in liquid and be filled with protective gas N2, sealing is it is ensured that anaerobic state.
(2) radiation polymerization technique：At a temperature of -63 DEG C, adopt60Co- gamma-rays be irradiation bomb, radiation dose be 1 ×
106Gy.
(3) load nano-copper sulfide in situ：Hydrogel carrier after irradiation polymerization, deionized water cleaning is repeatedly clean
Afterwards, dry and obtain xerogel.The xerogel weighing 0.5g is put in the conical flask of 100ml, adds the 0.040mol/l's of 50ml
CuSO4·5H2O solution, 120r/min constant temperature oscillation 24h under the conditions of 30 DEG C, leach hydrogel, cleaning under room temperature is dried, then
It is placed in the Na of the 0.04mol/l of 50ml2In S solution, vibration 12h is complete to precipitating under the same conditions.Compound Water after load
It is standby that gel deionized water cleans up post-drying.
(4) absorption-degradation effect：Selection SMZ and NOR is representative.Take 0.1g composite aquogel, the 50mg/L of 40ml respectively
Each 2 parts of SMZ and NOR solution；Portion puts into 100ml conical flask, and in 120r/min agitator under the conditions of being placed in 30 DEG C, lucifuge is inhaled
Attached 12h；Portion is put in 50ml quartz test tube, is placed in constant temperature photo catalysis reactor, magnetic stirrer, using 500W xenon
Lamp simulated visible light irradiates 12h.After measured and calculate, composite aquogel is respectively to the dark adsorption capacity of SMZ and NOR
23.12mg/g and 25.28mg/g；Composite aquogel is respectively 95.73% and 88.12% to the degradation efficiency of SMZ and NOR；Multiple
The salinity of the catalytic degradation to SMZ and NOR for the Heshui gel is respectively 43.18% and 77.05%.
Embodiment 7
(1) prepare solution：The N- citraconic acid monomer weighing certain mass is dissolved in deionized water, as component A, so
Add a certain amount of 2- 2-(Acryloyloxy)ethanol backward in above-mentioned solution as component B, distilled water as component C, according to (A+B)：C
For 2:3 (V/V) dissolving mixing, wherein A：B is 1：3(mol/mol)；Ultrasonic 30min makes solution be sufficiently mixed uniformly, mixes the most backward
Close in liquid and be filled with protective gas N2, sealing is it is ensured that anaerobic state.
(2) radiation polymerization technique：At a temperature of -78 DEG C, adopt137Cs- gamma-rays be irradiation bomb, radiation dose be 1 ×
104Gy.
(3) load nano-copper sulfide in situ：Hydrogel carrier after irradiation polymerization, deionized water cleaning is repeatedly clean
Afterwards, dry and obtain xerogel.The xerogel weighing 0.5g is put in the conical flask of 100ml, adds the 0.040mol/l's of 50ml
CuSO4·5H2O solution, 150r/min constant temperature oscillation 24h under the conditions of 25 DEG C, leach hydrogel, cleaning under room temperature is dried, then
It is placed in the Na of the 0.04mol/l of 50ml2In S solution, vibration 12h is complete to precipitating under the same conditions.Compound Water after load
It is standby that gel deionized water cleans up post-drying.
(4) absorption-degradation effect：Selection SMZ and NOR is representative.Take 0.1g composite aquogel, the 100mg/ of 30ml respectively
Each 2 parts of the SMZ and NOR solution of L；Portion puts into 100ml conical flask, and in 150r/min agitator under the conditions of being placed in 25 DEG C, lucifuge is inhaled
Attached 12h；Portion is put in 50ml quartz test tube, is placed in constant temperature photo catalysis reactor, magnetic stirrer, using 100W xenon
Lamp simulated visible light irradiates 24h.After measured and calculate, composite aquogel is respectively to the dark adsorption capacity of SMZ and NOR
38.96mg/g and 42.15mg/g；Composite aquogel is respectively 81.94% and 80.16% to the degradation efficiency of SMZ and NOR；Multiple
The salinity of the catalytic degradation to SMZ and NOR for the Heshui gel is respectively 35.05% and 66.73%.
Embodiment 8
(1) prepare solution：The N- citraconic acid monomer weighing certain mass is dissolved in deionized water, as component A, so
Add a certain amount of 2- 2-(Acryloyloxy)ethanol backward in above-mentioned solution as component B, distilled water as component C, according to (A+B)：C
For 2:3 (V/V) dissolving mixing, wherein A：B is 1：4(mol/mol)；Ultrasonic 30min makes solution be sufficiently mixed uniformly, mixes the most backward
Close in liquid and be filled with protective gas N2, sealing is it is ensured that anaerobic state.
(2) radiation polymerization technique：At a temperature of -95 DEG C, adopt60Co- gamma-rays be irradiation bomb, radiation dose be 1 ×
106Gy.
(3) load nano-copper sulfide in situ：Hydrogel carrier after irradiation polymerization, deionized water cleaning is repeatedly clean
Afterwards, dry and obtain xerogel.The xerogel weighing 0.5g is put in the conical flask of 100ml, adds the 0.060mol/l's of 50ml
CuSO4·5H2O solution, 150r/min constant temperature oscillation 24h under the conditions of 25 DEG C, leach hydrogel, cleaning under room temperature is dried, then
It is placed in the Na of the 0.04mol/l of 50ml2In S solution, vibration 12h is complete to precipitating under the same conditions.Compound Water after load
It is standby that gel deionized water cleans up post-drying.
(4) absorption-degradation effect：Selection SMZ and NOR is representative.Take 0.2g composite aquogel, the 200mg/ of 50ml respectively
Each 2 parts of the SMZ and NOR solution of L；Portion puts into 100ml conical flask, and in 150r/min agitator under the conditions of being placed in 25 DEG C, lucifuge is inhaled
Attached 12h；Portion is put in 50ml quartz test tube, is placed in constant temperature photo catalysis reactor, magnetic stirrer, using 500W xenon
Lamp simulated visible light irradiates 12h.After measured and calculate, composite aquogel is respectively to the dark adsorption capacity of SMZ and NOR
40.58mg/g and 48.95mg/g；Composite aquogel is respectively 81.05% and 80.26% to the degradation efficiency of SMZ and NOR；Multiple
The salinity of the catalytic degradation to SMZ and NOR for the Heshui gel is respectively 39.95% and 65.86%.
Embodiment 9
(1) prepare solution：The N- citraconic acid monomer weighing certain mass is dissolved in deionized water, as component A, so
Add a certain amount of 2- 2-(Acryloyloxy)ethanol backward in above-mentioned solution as component B, distilled water as component C, according to (A+B)：C
For 2:3 (V/V) dissolving mixing, wherein A：B is 1：4(mol/mol)；Ultrasonic 30min makes solution be sufficiently mixed uniformly, mixes the most backward
Close in liquid and be filled with protective gas N2, sealing is it is ensured that anaerobic state.
(2) radiation polymerization technique：At a temperature of -78 DEG C, adopt60Co- gamma-rays be irradiation bomb, radiation dose be 1 ×
104Gy.
(3) load nano-copper sulfide in situ：Hydrogel carrier after irradiation polymerization, deionized water cleaning is repeatedly clean
Afterwards, dry and obtain xerogel.The xerogel weighing 0.5g is put in the conical flask of 100ml, adds the 0.040mol/l's of 50ml
CuSO4·5H2O solution, 140r/min constant temperature oscillation 24h under the conditions of 25 DEG C, leach hydrogel, cleaning under room temperature is dried, then
It is placed in the Na of the 0.04mol/l of 50ml2In S solution, vibration 12h is complete to precipitating under the same conditions.Compound Water after load
It is standby that gel deionized water cleans up post-drying.
(4) absorption-degradation effect：Selection SMZ and NOR is representative.Take 0.1g composite aquogel, the 50mg/L of 30ml respectively
Each 2 parts of SMZ and NOR solution；Portion puts into 100ml conical flask, and in 140r/min agitator under the conditions of being placed in 25 DEG C, lucifuge is inhaled
Attached 12h；Portion is put in 50ml quartz test tube, is placed in constant temperature photo catalysis reactor, magnetic stirrer, using 100W xenon
Lamp simulated visible light irradiates 24h.After measured and calculate, composite aquogel is respectively to the dark adsorption capacity of SMZ and NOR
20.08mg/g and 21.45mg/g；Composite aquogel is respectively 87.92% and 90.70% to the degradation efficiency of SMZ and NOR；Multiple
The salinity of the catalytic degradation to SMZ and NOR for the Heshui gel is respectively 45.25% and 75.88%.
Application examples 1
Collection Nanjing pig farm waste water, the mensure content of wherein norfloxacin is about 100ng/L.To this Wastewater Pretreatment
Afterwards, the dry composite hydrogel of embodiment 1 gained is made 0.5cm cubed pieces, add 2g in the waste water of 1L, in 25 DEG C of bars
Under part, after 150r/min oscillation treatment 12h, in waste water, the unglazed adsorption rate of norfloxacin is 74%；Increase dry composite water-setting
When glue is to 3g/L, the clearance of norfloxacin can reach more than 95%.Under the same terms, using 100W xenon lamp simulated visible light
After irradiating 12h, composite aquogel is 100% to the degradation efficiency of norfloxacin, and composite aquogel drops to the catalysis of norfloxacin
The salinity of solution is 88.69%.
Application examples 2
Gather certain fish farm waste water, the mensure content of wherein Sulfamethoxazole is about 350ng/L.Pre- place is carried out to this waste water
After reason, the dry composite hydrogel of embodiment 3 gained is made the cubed pieces of 0.5cm, add 3g in the waste water of 1L, 25
Under the conditions of DEG C, after 150r/min oscillation treatment 12h, in waste water, the unglazed adsorption rate of Sulfamethoxazole is 65%；Increase and be dried again
When Heshui gel is to 5g/L, the clearance of norfloxacin can reach more than 90%.Under the same terms, using the simulation of 500W xenon lamp
After radiation of visible light 12h, composite aquogel is 98.5% to the degradation efficiency of Sulfamethoxazole, and composite aquogel is to norfloxacin
Catalytic degradation salinity be 79.96%.
Although the present invention is disclosed above with preferred embodiment, so it is not limited to the present invention.By changing structure
Cycle and physical dimension, we can realize the same beam splitting effect in different-waveband.Have in the technical field of the invention
Usually intellectual, without departing from the spirit and scope of the present invention, when can be used for a variety of modifications and variations.Therefore, the present invention
Protection domain when being defined depending on those as defined in claim.
Claims (9)
1. a kind of composite aquogel preparation method having carboxyl and amide groups and being loaded with nano-photocatalyst copper sulfide, its feature
It is, after uniformly being mixed by 2- 2-(Acryloyloxy)ethanol, N- citraconic acid and distilled water, obtain polymer water-setting through irradiation polymerization
Glue, then with this hydrogel as carrier, nano-photocatalyst nano-copper sulfide is loaded by situ Precipitation precipitant；
2- 2-(Acryloyloxy)ethanol, the mol ratio of N- citraconic acid monomer are 1～9：9～1, the high-energy ray of described irradiation polymerization
For60Co- gamma-rays or137Cs- gamma-rays, radiation dose is 1 × 104～1 × 108Gy, polymerization temperature is -95 DEG C～-63 DEG C；
Described irradiation polymerization is that the aqueous solution of 2- 2-(Acryloyloxy)ethanol and N- citraconic acid is carried out under a shielding gas；Load is received
The method of rice photocatalyst copper sulfide is the chemical in situ sedimentation method.
2. preparation method as claimed in claim 1 is it is characterised in that polyalcohol hydrogel adopts chemical precipitation method to load in situ
Nano-copper sulfide, composite aquogel is nano-copper sulfide.
3. preparation method as claimed in claim 2 is it is characterised in that the cupric salt for in-situ precipitate reaction is sulphuric acid
Any one in copper, copper chloride and copper nitrate, precipitant used is Na2S solution.
4. preparation method as claimed in claim 2 or claim 3 is it is characterised in that the in-situ precipitate of load nano-copper sulfide is reacted in temperature
Spend for 25 ± 5 DEG C, pH is 6～8, and speed of agitator is carried out under conditions of 100～150r/min.
5. preparation method described as claimed in claim 1 is it is characterised in that irradiation polymerization is 2- 2-(Acryloyloxy)ethanol and N-
The aqueous solution of citraconic acid is carried out under protective gas atmosphere, the uniform mixing of 2- 2-(Acryloyloxy)ethanol and N- citraconic acid
Volume ratio with water is 1:1～5.
6. preparation method described as claimed in claim 1 is it is characterised in that uniform mixing refers to 2- 2-(Acryloyloxy)ethanol
The solution of gained after mixing with water and use supersound process 30min fully to dissolve with N- citraconic acid.
7. preparation method described as claimed in claim 1 is it is characterised in that protective gas is on polyreaction no impact
Gas, to exclude in the air oxygen, protective gas selects the noble gases such as nitrogen, helium, argon, and optimum selection is nitrogen.
8. the preparation method any one of claim 1-7 obtains tool carboxyl and amide groups and load nano-photocatalyst
The composite aquogel of copper sulfide is applied in water process, removes containing fluoroquinolones or sulfa antibiotics for adsorbing-degrading
At least one of antibiotic application.
9. application as described in claim 8 is it is characterised in that adopt the xenon lamp simulated visible light of 100W～500W as light
Source, wave-length coverage 390nm～780nm, reaction is 25 ± 5 DEG C in temperature, and pH is 2～10, and speed of agitator is 100～150r/min
Under conditions of carry out.
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| CN113087244A (en) * | 2021-04-14 | 2021-07-09 | 广州普德生物科技有限公司 | System for purifying antibiotics in drinking water of water plant |
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