CN114768792B - Purifying agent for sewage treatment and preparation method thereof - Google Patents
Purifying agent for sewage treatment and preparation method thereof Download PDFInfo
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- CN114768792B CN114768792B CN202210558874.3A CN202210558874A CN114768792B CN 114768792 B CN114768792 B CN 114768792B CN 202210558874 A CN202210558874 A CN 202210558874A CN 114768792 B CN114768792 B CN 114768792B
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- bismuth
- salt
- solution
- tungstate
- purifying agent
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- 239000012629 purifying agent Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010865 sewage Substances 0.000 title claims description 30
- 239000000243 solution Substances 0.000 claims abstract description 96
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 77
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 74
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000003756 stirring Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 33
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 33
- 238000001291 vacuum drying Methods 0.000 claims abstract description 29
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 19
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 150000001621 bismuth Chemical class 0.000 claims abstract description 10
- 150000000922 Holmium Chemical class 0.000 claims abstract description 8
- 150000001206 Neodymium Chemical class 0.000 claims abstract description 8
- 150000001216 Samarium Chemical class 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 27
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 12
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 9
- 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 8
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 claims description 8
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 8
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 8
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 4
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- BONORRGKLJBGRV-UHFFFAOYSA-N methapyrilene hydrochloride Chemical compound Cl.C=1C=CC=NC=1N(CCN(C)C)CC1=CC=CS1 BONORRGKLJBGRV-UHFFFAOYSA-N 0.000 claims description 3
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 3
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 claims description 3
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 3
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 15
- 239000003242 anti bacterial agent Substances 0.000 abstract description 14
- 229940088710 antibiotic agent Drugs 0.000 abstract description 14
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- SYZKBMPNHSQNHG-UHFFFAOYSA-N [Na].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN Chemical compound [Na].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN SYZKBMPNHSQNHG-UHFFFAOYSA-N 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229960003405 ciprofloxacin Drugs 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical group [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 4
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- NVFXKYPPSRPHEL-UHFFFAOYSA-J dicopper;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O NVFXKYPPSRPHEL-UHFFFAOYSA-J 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- -1 nitrogen ions Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The application belongs to the technical field of wastewater treatment, and particularly relates to a purifying agent for wastewater treatment and a preparation method thereof. The preparation method comprises the following steps: stirring and dissolving a bismuth source in nitric acid, stirring and dissolving tungstate in deionized water, slowly dripping a tungstate solution into the bismuth source solution, and uniformly stirring to obtain a mixed solution; then samarium salt and holmium salt are added into the solution to obtain a precursor solution, and the precursor solution is placed into a reaction kettle for high-temperature reaction; cooling to room temperature, taking out a reaction product, washing, and vacuum drying to obtain Sm and Ho co-doped bismuth tungstate; dissolving bismuth salt in nitric acid solution, dropwise adding vanadate aqueous solution, stirring uniformly, adding surfactant, copper salt and neodymium salt, and preparing Sm and Ho co-doped bismuth tungstate, regulating pH, performing hydrothermal reaction, filtering, washing, and vacuum drying to obtain the purifying agent. The purifying agent disclosed by the application has excellent purifying capability for treating antibiotics in wastewater.
Description
Technical Field
The application belongs to the technical field of wastewater treatment. More particularly, to a purifying agent for sewage treatment and a preparation method thereof.
Background
Antibiotics (Antibiotics) are a secondary metabolite that can interfere with the development of living cells and inhibit microorganisms by targeting the bacteria to the target specificity. However, the unreasonable use and lack of strict supervision for a long time make antibiotics change from the great application of wearing a light ring in the medical community into environmental pollutants, and the environmental pollution problem caused by the antibiotics is increasingly serious, so that the antibiotics not only threaten human health, but also seriously affect the ecological environment.
The components of the antibiotic wastewater are complex, on one hand, the Chemical Oxygen Demand (COD) and the solid suspended matter concentration (SS) are high, and meanwhile, the pH fluctuation range is large; on the other hand, the wastewater has a certain biotoxicity. Based on these characteristics, antibiotic wastewater is rendered difficult to treat. At present, the treatment technology of antibiotic wastewater mainly focuses on the following three fields: biological treatment techniques, physical treatment techniques, advanced oxidation treatment techniques.
For the treatment of antibiotic wastewater, the most obvious advantage is considered to be advanced oxidation technology (APOs). In a very short action time, the technology can destroy and mineralize organic pollutants in the wastewater, and realizes the conversion from high toxicity to low toxicity and even non-toxic. Among AOPs, electrochemical oxidation, fenton, photocatalytic oxidation, and the like are often applied to the treatment of antibiotic wastewater.
The photocatalytic oxidation technique mainly refers to the technique of irradiating electrons (e) - ) This movement creates photogenerated electron-hole pairs, by transition to the conduction band. Cavities (h) left on the valence band + ) Has oxidability and can be used for preparing OH - And oxidation of H2O to hydroxyl radicals (. OH); and e - (reducibility) can then be combined with O 2 Reaction to generate superoxide radical (O) 2 - )。·O 2 - On the one hand, the catalyst can be used as an oxidant to directly oxidize pollutants, and on the other hand, the catalyst can be used for degrading the pollutants after generating OH through protonation. h is a + 、·OH、·O 2 - The organic matters are degraded into CO by various active free radicals 2 And H 2 O. The photocatalytic oxidation technology uses renewable resources, namely solar energy, as a light source, is green and clean, has no secondary pollution, and is a hot spot for researches of researchers in the field of photocatalysis.
BiVO 4 Exhibits n-type semiconductor properties, has a perovskite-like structure, and has a forbidden bandwidth (E g ) Narrower 2.3-2.4 eV, has strong light response in the visible light region with the wavelength of 520nm, andhas strong oxidation-reduction capability.
Dong Duo and the like prepare monoclinic B-Er-BiVO by a citric acid complexation method 4 After B and Er are doped, the visible light absorption wavelength range is prolonged to 540nm, eg=2.03 eV, and the visible light absorption wavelength range is purer BiVO 4 Is small. B-Er-BiVO 4 0.015g of catalyst, 50mL of RhB with C=10mg/L, pH =3 is degraded, and a 250W halogen tungsten lamp is irradiated for 50min, so that the degradation rate is more than 90%. In the reaction process e - And h + As reactive groups to participate in the reaction.
CN111054401a discloses a preparation method of bismuth vanadate/bismuth oxyiodide/bismuth tungstate double-Z photocatalytic material, the sunlight light response range and light absorption capacity of the composite material can be regulated and controlled mainly by regulating the addition of bismuth vanadate and bismuth tungstate, the target bismuth vanadate/bismuth oxyiodide/bismuth tungstate double-Z photocatalytic material is obtained, the light absorption capacity and light response capacity of the bismuth vanadate/bismuth oxyiodide/bismuth tungstate double-Z photocatalytic material prepared by a hydrothermal method are effectively enhanced, the mobility of a photo-generated carrier of the Z photocatalytic material is effectively improved, and the Z photocatalytic material has good degradation effect on aniline and can be used for photocatalytic degradation of toxic and harmful pollutants in the environment.
CN104475139B discloses a co-doped bismuth phosphate-based composite photocatalytic material, which consists of fluorine and nitrogen co-doped bismuth phosphate, bismuth tungstate and bismuth vanadate, wherein the molar ratio of fluorine and nitrogen co-doped bismuth phosphate, bismuth tungstate and bismuth vanadate is 1:0.1 to 0.3:0.1 to 0.3. The application also discloses a preparation method of the composite material, which comprises the following steps: and carrying out microwave hydrothermal reaction on bismuth nitrate pentahydrate, phosphate, ammonium tungstate and ammonium metavanadate to obtain mixed powder, adding ammonium chloride, carrying out microwave hydrothermal reaction again, centrifuging and drying to obtain the product. According to the co-doped bismuth phosphate-based composite photocatalytic material, the electron capturing capability of three semiconductor interfaces of bismuth phosphate, bismuth tungstate and bismuth vanadate is effectively improved through the co-doping of nonmetallic fluorine and nitrogen ions, and the migration efficiency of electron holes is enhanced; the three semiconductors of bismuth phosphate, bismuth tungstate and bismuth vanadate are compounded at the interface to form a heterostructure, so that the separation of photogenerated carriers is effectively promoted, and the photocatalytic activity of a compound system is further improved.
CN103212404B discloses a kind ofMethod for preparing bismuth vanadate-bismuth tungstate heterojunction photocatalyst by ultrasonic method, which comprises preparing Bi by ultrasonic method 2 WO 6 Then preparing BiVO by adopting a microwave method 4 Finally, adopting an ultrasonic method to convert Bi 2 WO 6 And BiVO 4 And combining to prepare the bismuth vanadate-bismuth tungstate heterojunction. The method has the advantages of simple operation, environmental protection and low cost, and is suitable for mass production. The prepared flaky bismuth vanadate-bismuth tungstate heterojunction has higher photocatalytic activity, and the product is used as a photocatalyst for photocatalytic degradation of ciprofloxacin, so that a novel photocatalyst is provided for treatment of ciprofloxacin medical wastewater.
Although the photocatalyst has a certain effect in the prior art for treating antibiotics in wastewater, the treatment period is long and the degradation efficiency is low, so that development of a novel purifying agent for treating wastewater containing antibiotics is urgently needed, and the antibiotics can be rapidly treated in a short time.
Disclosure of Invention
The application aims to overcome the defects and the shortcomings in the prior art and provide a purifying agent for sewage treatment and a preparation method thereof. The preparation method comprises the following steps: stirring and dissolving a bismuth source in nitric acid, stirring and dissolving tungstate in deionized water, slowly dripping a tungstate solution into the bismuth source solution, and uniformly stirring to obtain a mixed solution; then samarium salt and holmium salt are added into the solution to obtain a precursor solution, and the precursor solution is placed into a reaction kettle for high-temperature reaction; cooling to room temperature, taking out a reaction product, washing, and vacuum drying to obtain Sm and Ho co-doped bismuth tungstate; dissolving bismuth salt in nitric acid solution, dropwise adding vanadate aqueous solution, stirring uniformly, adding surfactant, copper salt and neodymium salt, and preparing Sm and Ho co-doped bismuth tungstate, regulating pH, performing hydrothermal reaction, filtering, washing, and vacuum drying to obtain the purifying agent. The purifying agent disclosed by the application has excellent purifying capability for treating antibiotics in wastewater.
The application aims to provide a preparation method of a purifying agent for sewage treatment.
It is another object of the present application to provide a purifying agent for sewage treatment.
The above object of the present application is achieved by the following technical scheme:
a method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
(1) Preparation of Sm and Ho co-doped bismuth tungstate
Stirring and dissolving a bismuth source in nitric acid, stirring and dissolving tungstate in deionized water, slowly dripping a tungstate solution into the bismuth source solution, and uniformly stirring to obtain a mixed solution; adding a certain amount of samarium salt and holmium salt into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for a certain time at a high temperature in a constant-temperature oven; naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, washing, and vacuum drying to obtain Sm and Ho co-doped bismuth tungstate;
(2) Preparation of the purifying agent
Dissolving bismuth salt in nitric acid solution, dropwise adding vanadate aqueous solution, stirring uniformly, adding surfactant, copper salt and neodymium salt, adding Sm and Ho co-doped bismuth tungstate obtained in the step (1), adding alkaline solution to adjust pH to 8-10, performing hydrothermal reaction in a water bath reaction kettle, filtering, washing, and vacuum drying to obtain the purifying agent.
Preferably, in the step (1), the molar concentration of the nitric acid is 2mol/L, and the molar ratio of the bismuth source to the tungstate is 2:1; the bismuth source is at least one of bismuth nitrate, bismuth chloride and bismuth acetate; the tungstate is at least one of sodium tungstate and potassium tungstate.
Preferably, in the step (1), the molar ratio of the samarium salt, the holmium salt and the bismuth source is: 0.01-0.05:0.01-0.05:1; the samarium salt is at least one of samarium nitrate, samarium chloride and samarium acetate; the holmium salt is at least one of holmium nitrate, holmium chloride and holmium acetate.
Preferably, in the step (1), the reaction temperature is 160-200 ℃ and the reaction time is 10-14 h; the washing is to sequentially wash with ethanol and deionized water for 3 times; the vacuum drying is carried out for 8-12 h at 60-80 ℃.
Preferably, in the step (2), the bismuth salt is at least one of bismuth nitrate, bismuth chloride and bismuth acetate; the vanadium salt is at least one of sodium tungstate and potassium tungstate; the molar ratio of the bismuth salt to the vanadate is 1:1.
Preferably, in the step (2), the washing is sequentially performed with ethanol and deionized water for 3 times; the copper salt is at least one of copper nitrate, copper acetate and copper chloride; the neodymium salt is at least one of neodymium nitrate, neodymium acetate and neodymium chloride; the surfactant is sodium ethylenediamine tetraacetate.
Preferably, in the step (2), the molar ratio of bismuth salt, EDTA, copper salt and neodymium salt is 1:0.5-1.5:0.02-0.04:0.02-0.04.
Preferably, in the step (2), the alkali is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
Preferably, in the step (2), the vacuum drying is performed at 60-80 ℃ for 8-12 hours, and the hydrothermal reaction condition is performed at 150-180 ℃ for 8-14 hours.
A purifying agent for sewage treatment prepared based on the above-described method for preparing a purifying agent for sewage treatment.
The application has the following beneficial effects:
(1) The purifying agent for sewage treatment prepared by two-step hydrothermal method has excellent photocatalytic performance and has excellent purifying capacity on antibiotics in the wastewater.
(2) The Sm and Ho co-doped bismuth tungstate is prepared by a hydrothermal method, and the effective separation of photogenerated electrons and holes is promoted by utilizing the synergistic effect of Sm and Ho, so that more oxidizing groups are generated to oxidize antibiotics.
(3) Copper and neodymium are co-doped into bismuth vanadate through a hydrothermal method, the effective separation of photo-generated electrons and holes is promoted by utilizing the synergistic effect of Sm and Ho, the photocatalytic capacity of bismuth vanadate is effectively improved, and the heterojunction is formed between bismuth vanadate and bismuth tungstate, so that the photocatalytic capacity is further improved, and the purifying capacity of a purifying agent is improved.
Detailed Description
The present application is further illustrated below with reference to specific examples, which are not intended to limit the application in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present application are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
(1) Preparation of Sm and Ho co-doped bismuth tungstate
5mmol of bismuth nitrate is stirred and dissolved in 10mL of 2M nitric acid, 2.5mmol of sodium tungstate is stirred and dissolved in 9mL of deionized water, then sodium tungstate solution is slowly dripped into bismuth nitrate solution, and the mixture solution is obtained after uniform stirring; then adding 0.15mmol of samarium nitrate and 0.15mmol of holmium nitrate into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for 12 hours at 180 ℃ in a constant-temperature oven; naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10 hours to obtain Sm and Ho co-doped bismuth tungstate;
(2) Preparing a purifying agent;
dissolving 2mmol of bismuth nitrate in 10mL of 2M nitric acid solution, dropwise adding 10mL of 0.2mol/L sodium vanadate aqueous solution, uniformly stirring, then adding 2mmol of ethylenediamine tetraacetic acid sodium, 0.06mmol of copper nitrate and 0.06mol of neodymium nitrate, and Sm and Ho co-doped bismuth tungstate obtained in the step (1), adding sodium hydroxide solution to adjust pH to 9, performing hydrothermal reaction in a water bath reaction kettle for 12h at 170 ℃, filtering, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10h to obtain the purifying agent.
Example 2
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
(1) Preparation of Sm and Ho co-doped bismuth tungstate
Stirring and dissolving 6mmol of bismuth chloride in 12mL of 2M nitric acid, stirring and dissolving 3mmol of potassium tungstate in 10mL of deionized water, slowly dripping sodium tungstate solution into bismuth nitrate solution, and uniformly stirring to obtain a mixed solution; then adding a certain amount of 0.3mmol of samarium chloride and 0.06mmol of holmium acetate into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for 10 hours at a high temperature of 200 ℃ in a constant-temperature oven; naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 80 ℃ for 8 hours to obtain Sm and Ho co-doped bismuth tungstate;
(2) Preparing a purifying agent;
dissolving 3mmol of bismuth chloride in 12mL of 2M nitric acid solution, dropwise adding 10mL of 0.3mol/L potassium vanadate aqueous solution, stirring uniformly, adding 4.5mmol of ethylenediamine tetraacetic acid sodium salt, 0.06mmol of copper chloride, 0.12mmol of neodymium acetate and Sm and Ho co-doped bismuth tungstate obtained in the step (1), adding alkali to adjust pH to 10, performing hydrothermal reaction in a water bath reaction kettle for 8h at 180 ℃, filtering, sequentially washing with ethanol and deionized water for 3 times, and performing vacuum drying at 80 ℃ for 8h to obtain the purifying agent.
Example 3
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
(1) Preparation of Sm and Ho co-doped bismuth tungstate
3mmol of bismuth acetate is stirred and dissolved in 8mL of 2M nitric acid, 1.5mmol of sodium tungstate is stirred and dissolved in 8mL of deionized water, then sodium tungstate solution is slowly dripped into bismuth nitrate solution, and the mixture solution is obtained after uniform stirring; adding 0.03mmol of samarium acetate and 0.15mmol of holmium chloride into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, reacting at 160 ℃ in a constant-temperature oven for 14h, naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, sequentially cleaning with ethanol and deionized water for 3 times, and vacuum drying at 60 ℃ for 12h to obtain Sm and Ho co-doped bismuth tungstate;
(2) Preparing a purifying agent;
1.5mmol of bismuth acetate is dissolved in 8mL of 2M nitric acid solution, 10mL of 0.15mol/L sodium vanadate aqueous solution is added dropwise, after uniform stirring, 0.75mmol of ethylenediamine tetraacetic acid sodium, 0.06mmol of copper acetate and 0.03mmol of neodymium chloride as well as Sm and Ho co-doped bismuth tungstate obtained in the step (1) are added, alkali is added to adjust the pH value to 8, the mixture is subjected to hydrothermal reaction in a water bath reaction kettle at 150 ℃ for 14h, filtering, washing with ethanol and deionized water for 3 times in sequence, and vacuum drying at 60 ℃ for 12h, thus obtaining the purifying agent.
Comparative example 1
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
(1) Preparation of Sm-doped bismuth tungstate
5mmol of bismuth nitrate is stirred and dissolved in 10mL of 2M nitric acid, 2.5mmol of sodium tungstate is stirred and dissolved in 9mL of deionized water, then sodium tungstate solution is slowly dripped into bismuth nitrate solution, and the mixture solution is obtained after uniform stirring; then adding 0.3mmol of samarium nitrate into the solution, stirring fully to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for 12 hours at 180 ℃ in a constant-temperature oven; naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, sequentially cleaning the reaction product with ethanol and deionized water for 3 times, and vacuum drying the reaction product at 70 ℃ for 10 hours to obtain Sm doped bismuth tungstate;
(2) Preparing a purifying agent;
dissolving 2mmol of bismuth nitrate in 10mL of 2M nitric acid solution, dropwise adding 10mL of 0.2mol/L sodium vanadate aqueous solution, uniformly stirring, then adding 2mmol of ethylenediamine tetraacetic acid sodium, 0.06mmol of copper nitrate and 0.06mol of neodymium nitrate, and Sm-doped bismuth tungstate obtained in the step (1), adding sodium hydroxide solution to adjust pH to 9, performing hydrothermal reaction in a water bath reaction kettle at 170 ℃ for 12h, filtering, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10h to obtain the purifying agent.
Comparative example 2
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
(1) Preparation of Ho doped bismuth tungstate
5mmol of bismuth nitrate is stirred and dissolved in 10mL of 2M nitric acid, 2.5mmol of sodium tungstate is stirred and dissolved in 9mL of deionized water, then sodium tungstate solution is slowly dripped into bismuth nitrate solution, and the mixture solution is obtained after uniform stirring; then adding 0.3mmol of holmium nitrate into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for 12 hours at 180 ℃ in a constant-temperature oven; naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, sequentially cleaning the reaction product with ethanol and deionized water for 3 times, and vacuum drying the reaction product at 70 ℃ for 10 hours to obtain Ho doped bismuth tungstate;
(2) Preparing a purifying agent;
dissolving 2mmol of bismuth nitrate in 10mL of 2M nitric acid solution, dropwise adding 10mL of 0.2mol/L sodium vanadate aqueous solution, uniformly stirring, then adding 2mmol of ethylenediamine tetraacetic acid sodium, 0.06mmol of copper nitrate and 0.06mol of neodymium nitrate, and Ho-doped bismuth tungstate obtained in the step (1), adding sodium hydroxide solution to adjust pH to 9, performing hydrothermal reaction in a water bath reaction kettle at 170 ℃ for 12h, filtering, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10h to obtain the purifying agent.
Comparative example 3
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
(1) Preparation of Sm and Ho co-doped bismuth tungstate
5mmol of bismuth nitrate is stirred and dissolved in 10mL of 2M nitric acid, 2.5mmol of sodium tungstate is stirred and dissolved in 9mL of deionized water, then sodium tungstate solution is slowly dripped into bismuth nitrate solution, and the mixture solution is obtained after uniform stirring; then adding 0.15mmol of samarium nitrate and 0.15mmol of holmium nitrate into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for 12 hours at 180 ℃ in a constant-temperature oven; naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10 hours to obtain Sm and Ho co-doped bismuth tungstate;
(2) Preparing a purifying agent;
dissolving 2mmol of bismuth nitrate in 10mL of 2M nitric acid solution, dropwise adding 10mL of 0.2mol/L sodium vanadate aqueous solution, uniformly stirring, then adding 2mmol of ethylenediamine tetraacetic acid sodium salt, 0.12mmol of copper nitrate and Sm and Ho co-doped bismuth tungstate obtained in the step (1), adding sodium hydroxide solution to adjust the pH value to 9, performing hydrothermal reaction in a water bath reaction kettle at 170 ℃ for 12h, filtering, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10h to obtain the purifying agent.
Comparative example 4
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
(1) Preparation of Sm and Ho co-doped bismuth tungstate
5mmol of bismuth nitrate is stirred and dissolved in 10mL of 2M nitric acid, 2.5mmol of sodium tungstate is stirred and dissolved in 9mL of deionized water, then sodium tungstate solution is slowly dripped into bismuth nitrate solution, and the mixture solution is obtained after uniform stirring; then adding 0.15mmol of samarium nitrate and 0.15mmol of holmium nitrate into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for 12 hours at 180 ℃ in a constant-temperature oven; naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10 hours to obtain Sm and Ho co-doped bismuth tungstate;
(2) Preparing a purifying agent;
dissolving 2mmol of bismuth nitrate in 10mL of 2M nitric acid solution, dropwise adding 10mL of 0.2mol/L sodium vanadate aqueous solution, uniformly stirring, then adding 2mmol of ethylenediamine tetraacetic acid sodium and 0.12mol of neodymium nitrate, and Sm and Ho co-doped bismuth tungstate obtained in the step (1), adding sodium hydroxide solution to adjust the pH value to 9, performing hydrothermal reaction in a water bath reaction kettle at 170 ℃ for 12h, filtering, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10h to obtain the purifying agent.
Comparative example 5
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
preparation of Sm and Ho co-doped bismuth tungstate
5mmol of bismuth nitrate is stirred and dissolved in 10mL of 2M nitric acid, 2.5mmol of sodium tungstate is stirred and dissolved in 9mL of deionized water, then sodium tungstate solution is slowly dripped into bismuth nitrate solution, and the mixture solution is obtained after uniform stirring; then adding 0.15mmol of samarium nitrate and 0.15mmol of holmium nitrate into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for 12 hours at 180 ℃ in a constant-temperature oven; and naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, sequentially cleaning the reaction product with ethanol and deionized water for 3 times, and vacuum drying the reaction product at 70 ℃ for 10 hours to obtain the Sm and Ho co-doped bismuth tungstate purifying agent.
Comparative example 6
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
2mmol bismuth nitrate is dissolved in 10mL 2M nitric acid solution, 10mL 0.2mol/L sodium vanadate aqueous solution is added dropwise, after uniform stirring, 2mmol ethylenediamine tetraacetic acid sodium salt, 0.06mmol copper nitrate and 0.06mol neodymium nitrate are added, then sodium hydroxide solution is added to adjust pH to 9, the mixture is reacted in a water bath reaction kettle in a hydrothermal way at 170 ℃ for 12h, filtered, washed with ethanol and deionized water for 3 times in sequence, and dried in vacuum at 70 ℃ for 10h, thus obtaining the purifying agent.
Comparative example 7
A method for preparing a purifying agent for sewage treatment, the method comprising the steps of:
(1) Preparation of Sm and Ho co-doped bismuth tungstate
5mmol of bismuth nitrate is stirred and dissolved in 10mL of 2M nitric acid, 2.5mmol of sodium tungstate is stirred and dissolved in 9mL of deionized water, then sodium tungstate solution is slowly dripped into bismuth nitrate solution, and the mixture solution is obtained after uniform stirring; then adding 0.15mmol of samarium nitrate and 0.15mmol of holmium nitrate into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for 12 hours at 180 ℃ in a constant-temperature oven; naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10 hours to obtain Sm and Ho co-doped bismuth tungstate;
(2) Preparing a purifying agent;
dissolving 2mmol of bismuth nitrate in 10mL of 2M nitric acid solution, dropwise adding 10mL of 0.2mol/L sodium vanadate aqueous solution, uniformly stirring, then adding 0.06mmol of copper nitrate and 0.06mol of neodymium nitrate, and Sm and Ho co-doped bismuth tungstate obtained in the step (1), adding sodium hydroxide solution to adjust pH to 9, performing hydrothermal reaction in a water bath reaction kettle at 170 ℃ for 12h, filtering, sequentially washing with ethanol and deionized water for 3 times, and vacuum drying at 70 ℃ for 10h to obtain the purifying agent.
The catalysts (0.1 g/L) of examples 1-3 and comparative examples 1-7 were respectively ultrasonically dispersed in ciprofloxacin solution (10 mg/L), and after a dark reaction for 30 minutes under magnetic stirring, they were stirred under irradiation of a xenon lamp (350W) to perform a photocatalytic reaction. The absorption spectrum of the solution was measured by an ultraviolet-visible spectrophotometer, and the degradation rate of ciprofloxacin was calculated by the change of the absorption peak intensity, and the specific test results are shown in table 1.
As can be seen from Table 1, the purifying agents for wastewater treatment prepared by the present application have excellent removing ability for antibiotics in wastewater, and can purify the antibiotics in wastewater well by utilizing the synergistic effect between the components, as can be seen from the comparative examples of examples 1 to 3 and comparative examples 1 to 7.
The above examples are preferred embodiments of the present application, but the embodiments of the present application are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present application should be made in the equivalent manner, and the embodiments are included in the protection scope of the present application.
Claims (9)
1. A preparation method of a purifying agent for sewage treatment is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Preparation of Sm and Ho co-doped bismuth tungstate
Stirring and dissolving a bismuth source in nitric acid, stirring and dissolving tungstate in deionized water, slowly dripping a tungstate solution into the bismuth source solution, and uniformly stirring to obtain a mixed solution; adding a certain amount of samarium salt and holmium salt into the solution, stirring thoroughly to obtain a precursor solution, placing the precursor solution into a reaction kettle, and reacting for a certain time at a high temperature in a constant-temperature oven; naturally cooling the reaction kettle to room temperature, taking out a reaction product in the kettle, washing, and vacuum drying to obtain Sm and Ho co-doped bismuth tungstate; in step (1), the molar ratio of the bismuth source to the tungstate is 2:1; the molar ratio of the samarium salt, the holmium salt and the bismuth source is as follows: 0.01-0.05:0.01-0.05:1;
(2) Preparation of the purifying agent
Dissolving bismuth salt in a nitric acid solution, dropwise adding an aqueous solution of vanadate, uniformly stirring, then adding a surfactant, copper salt and neodymium salt, and Sm and Ho co-doped bismuth tungstate obtained in the step (1), adding an alkali solution to adjust the pH value, performing hydrothermal reaction in a water bath reaction kettle, filtering, washing and vacuum drying to obtain a purifying agent;
in step (2), the molar ratio of bismuth salt to vanadate is 1:1; the molar ratio of bismuth salt to EDTA to copper salt to neodymium salt is 1:0.5-1.5:0.02-0.04:0.02-0.04.
2. The method for preparing a purifying agent for sewage treatment according to claim 1, wherein: in the step (1), the molar concentration of the nitric acid is 2mol/L, and the bismuth source is at least one of bismuth nitrate, bismuth chloride and bismuth acetate; the tungstate is at least one of sodium tungstate and potassium tungstate.
3. The method for preparing a purifying agent for sewage treatment according to claim 1, wherein: in the step (1), the samarium salt is at least one of samarium nitrate, samarium chloride and samarium acetate; the holmium salt is at least one of holmium nitrate, holmium chloride and holmium acetate.
4. The method for preparing a purifying agent for sewage treatment according to claim 1, wherein: in the step (1), the reaction temperature is 160-200 ℃ and the reaction time is 10-14 h; the washing is to sequentially wash with ethanol and deionized water for 3 times; the vacuum drying is carried out for 8-12 h at 60-80 ℃.
5. The method for preparing a purifying agent for sewage treatment according to claim 1, wherein: in the step (2), the bismuth salt is at least one of bismuth nitrate, bismuth chloride and bismuth acetate; the vanadate is at least one of sodium vanadate and potassium vanadate.
6. The method for preparing a purifying agent for sewage treatment according to claim 1, wherein: in the step (2), the washing is carried out by sequentially washing 3 times with ethanol and deionized water; the copper salt is at least one of copper nitrate, copper acetate and copper chloride; the neodymium salt is at least one of neodymium nitrate, neodymium acetate and neodymium chloride; the surfactant is sodium ethylenediamine tetraacetate.
7. The method for preparing a purifying agent for sewage treatment according to claim 1, wherein: in the step (2), the alkali is at least one of sodium hydroxide, potassium hydroxide and ammonia water; the pH is 8-10.
8. The method for preparing a purifying agent for sewage treatment according to claim 1, wherein: in the step (2), the vacuum drying is carried out for 8-12 hours at 60-80 ℃, and the hydrothermal reaction condition is that the reaction is carried out for 8-14 hours at 150-180 ℃.
9. A purifying agent for sewage treatment prepared by the method for preparing a purifying agent for sewage treatment according to any one of claims 1 to 8.
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