CN108772101A - A kind of efficient metal complex molecule catalyst and its preparation and application - Google Patents
A kind of efficient metal complex molecule catalyst and its preparation and application Download PDFInfo
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- CN108772101A CN108772101A CN201810935921.5A CN201810935921A CN108772101A CN 108772101 A CN108772101 A CN 108772101A CN 201810935921 A CN201810935921 A CN 201810935921A CN 108772101 A CN108772101 A CN 108772101A
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- catalyst
- metal complex
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- ofloxacin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 36
- 229960001699 ofloxacin Drugs 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 35
- 238000001914 filtration Methods 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 19
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002738 chelating agent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims 2
- 238000007146 photocatalysis Methods 0.000 claims 2
- AYIRNRDRBQJXIF-NXEZZACHSA-N (-)-Florfenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)C=C1 AYIRNRDRBQJXIF-NXEZZACHSA-N 0.000 claims 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229960003760 florfenicol Drugs 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 125000005909 ethyl alcohol group Chemical group 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 8
- 150000001805 chlorine compounds Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 5
- -1 hydroxyl radical free radical Chemical class 0.000 description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 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
- 229940097267 cobaltous chloride Drugs 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- QFSKIUZTIHBWFR-UHFFFAOYSA-N chromium;hydrate Chemical compound O.[Cr] QFSKIUZTIHBWFR-UHFFFAOYSA-N 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical class C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WEEZYXRBIUDTAN-UHFFFAOYSA-N CCCN[N]1(N)NCCN1 Chemical compound CCCN[N]1(N)NCCN1 WEEZYXRBIUDTAN-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
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- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
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- Hydrology & Water Resources (AREA)
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Abstract
The present invention relates to environmental catalysis Material Fields, provide a kind of preparation method and applications of efficient metal complex molecule catalyst.The present invention is to be carried out complexation reaction using Nitrogen element organic matter as ligand with the villaumite of one of Fe, Cu, Co, Ni, finally synthesized a kind of metal complex molecule, which can be used for ultraviolet light Fenton systems, be catalyzed H under visible light2O2Oxidative degradation organic matter.Catalyst prepared by the present invention has many advantages, such as to prepare simple, stable structure and catalytic activity is high, has potential application prospect.
Description
Technical field
The invention belongs to environmental catalysis Material Fields, are related to a kind of preparation method of efficient metal complex molecule catalyst
And its application, the organic pollution suitable for ultraviolet catalytic oxidation degradation industrial wastewater.
Background technology
With the quickening of China's process of industrialization, the discharge capacity of all types of industries waste water increases year by year, results in water pollution and asks
Topic increasingly aggravates.High concentrated organic wastewater is contained in industrial wastewater, such water is mainly the works such as leather, food, medicine, chemical industry
Caused by industry production process, wherein containing a large amount of toxicity height, complicated component, organic matter difficult to degrade, it is strong to affect human body
Health, the sustainable development for destroying environment, therefore, the harmless treatment for organic wastewater are always focus of people's attention.
With the continuous improvement of environmental standard, traditional method for processing organic wastewater such as biochemical process, absorption method, extraction is
Through that cannot reach requirement instantly, therefore, there is an urgent need for a kind of concise in technology, the method for processing organic wastewater of high treating effect.It is advanced
Oxidation technology is to handle one of organic wastewater with difficult degradation thereby most efficient method instantly, and wherein Fenton methods are as high-level oxidation technology
In one kind, with Fe2+As catalyst, with H2O2Effect generates a large amount of hydroxyl radical free radical, by the oxidation operation in waste water
For nontoxic small-molecule substance, the hardly degraded organic substance that traditional technology can not remove can be removed in this way, however Fenton oxygen
Change method is limited (pH=2-4) by pH, and when actual treatment needs to consume a large amount of soda acid to adjust pH, Fe3+It is converted into Fe2+Speed
Degree is slower, reduces whole treatment effeciency, and Fe2+Easily it is oxidized to Fe3+, a large amount of reluctant iron cements are generated, it is above to lack
Point limits the practical application of Fenton oxidation method.
Lightwave CATV oxidation technology is advanced oxidation technology developed in recent years, and the system is without being aided with high temperature
High pressure, it is easy to operate, and the shortcomings that overcome traditional Fenton methods, avoid causing secondary pollution to environment.The irradiation of ultraviolet light
Energy is provided for reaction, reaction can be promoted to generate more hydroxyl radical free radicals, improves H2O2Practical efficiency, carry simultaneously
The activation energy of catalyst has been risen, the reaction time is shortened.However Photo-Fenton, now still in laboratory stage, input industry is answered
Few, this has that utilization rate of ultraviolet light is low, operating cost is high mainly due to common photo Fenton, research
Person is still constantly improving technology, currently, for the Main way of Photo-Fenton processing hardly degraded organic substance research,
First, other substances or iron ion is immobilized are introduced in system, second is that preparing other efficient catalyst to improve oxidation effect
Rate.
Transition-metal catalyst is the metal complexes using transition metal as activated centre, with higher catalysis
It activity and selectivity and prepares simple, is a novel single site catalysts, in the system, ligand structure is to catalyst
Catalytic activity have tremendous influence, the actual performance of subtle variation can be largely change catalyst.It grinds
Study carefully and show that the transient metal complex of nitrogen atom bidentate ligand coordination has higher catalytic activity, and can increase
The dispersion degree of heart metallic atom, therefore, the present invention is quasi- to use itrogenous organic substance as ligand, prepares a kind of efficient metal combination
Object molecular catalyst is applied to ultraviolet light Fenton systems.
Invention content
The present invention provide it is a kind of for photo Fenton processing industrial wastewater in hardly degraded organic substance it is efficient, stablize
The preparation method of metal complex molecular catalyst, it is intended to solve existing lightwave CATV catalyst hydrogen peroxide utilization rate at present
The low, defects such as catalytic activity is low.
To achieve the goals above, the present invention by adjusting organic ligand and central metal atom type, to prepare
Several lightwave CATV catalyst with different structure.
In the present invention, we demonstrate that the metal complex molecular catalyst is in ultraviolet light and H2O2In the presence of, it can be with
Ofloxacin in effective catalytic degradation waste water, has potential scale application foreground.
Gained catalyst structure formula of the invention be in A, B, C, D one of which or two more than：
Wherein M is Fe, Cu, Co, one kind in Ni.
Specific preparation process is as follows：
(1) metal salt is thrown in ethyl alcohol, methanol or ether, is slowly dropped into chelating agent and stirred, obtain mixed solution.
(2) mixed solution in (1) is placed in oil bath pan, 50-90 DEG C of (most suitable is 60-80 DEG C) high temperature reflux 2-8h is (most suitable
For 2-4h), after washed filtering, washed filtering vacuumizes, and obtains the metal complex.
Wherein, step (1) described chelating agent be o-phenylenediamine, ethylenediamine, 1,10- Phens and 2,2'- bipyridyls its
One of, metal salt is one of copper chloride, iron chloride, cobalt chloride, nickel chloride, and the molar ratio of metal salt and chelating agent is 1：
(most suitable is 1 to 1-3：2)
The catalyst is used for ultraviolet catalytic wet type H2O2Oxidation processes organic wastewater intermittent reaction condition is：
Normal pressure, initial pH on wastewater：3-7 (preferably pH：5-7), 10-80 DEG C of reaction temperature (preferably 30-60 DEG C), it is ultraviolet
Luminous intensity is 50-5000W (preferably 500-1000W), and catalyst amounts are 0.01-1.0g/L (preferably 0.1-0.5g/
L)。
The present invention is to be coordinated using Nitrogen element organic matter as ligand with the villaumite of one of Fe, Cu, Co, Ni
Reaction, finally synthesizes a kind of metal complex molecule, which can be used for lightwave CATV system, be catalyzed H under visible light2O2
Oxidative degradation organic matter.Catalyst prepared by the present invention has many advantages, such as to prepare simple, stable structure and catalytic activity is high, has
Potential application prospect.
Description of the drawings
Fig. 1 are removal rate and time chart of the catalyst to Ofloxacin of the preparation of embodiment 1.
Specific implementation mode
Below in conjunction with embodiment to invention be further described, but protection scope of the present invention be not limited to it is following
Embodiment
Embodiment 1；
(1) 1.0g anhydrous ferric chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into ethylenediamine and stirred, mixed
Solution, wherein anhydrous ferric chloride and ethylenediamine molar ratio are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 1 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, handling result such as Fig. 1 (to be not added with catalyst as contrast groups, other conditions are with addition catalyst group).
Table 1
Embodiment 2；
(1) 1.0g anhydrous cupric chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into ethylenediamine and stirred, mixed
Solution, wherein anhydrous cupric chloride and ethylenediamine molar ratio are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 2 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 78%.
Embodiment 3；
(1) 1.0g waterless cobaltous chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into ethylenediamine and stirred, mixed
Solution, wherein waterless cobaltous chloride and ethylenediamine molar ratio are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 3 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 85%.
Embodiment 4；
(1) 1.0g anhydrous ferric chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into o-phenylenediamine and stirred, mixed
Close solution, wherein anhydrous ferric chloride and o-phenylenediamine molar ratio are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 4 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 91%.
Embodiment 5；
(1) 1.0g Dehydrated nickel chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into 2,2'- bipyridyls and stirred, obtained
To mixed solution, wherein Dehydrated nickel chloride and 2,2'- bipyridyl molar ratios are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 5 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 78%.
Embodiment 6；
(1) 1.0g waterless cobaltous chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into 1,10- Phens and stirred,
Obtain mixed solution, wherein waterless cobaltous chloride and 1,10- Phen molar ratios are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 6 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 84%.
Embodiment 7；
(1) 1.0g anhydrous cupric chlorides are thrown in 30mL absolute methanols, are slowly dropped into 1,10- Phens and stirred,
Obtain mixed solution, wherein anhydrous cupric chloride and 1,10- Phen molar ratios are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 7 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 82%.
Embodiment 8；
(1) 1.0g waterless cobaltous chlorides are thrown in 30mL absolute methanols, are slowly dropped into 2,2'- bipyridyls and stirred, obtained
To mixed solution, wherein waterless cobaltous chloride and 1,10- Phen molar ratios are 1：3；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 8 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 77%.
Embodiment 9；
(1) 1.0g Dehydrated nickel chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into 1,10- Phens and stirred,
Obtain mixed solution, wherein Dehydrated nickel chloride and 1,10- Phen molar ratios are 1：3；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 5h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 9 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 87%.
Embodiment 10；
(1) 1.0g Dehydrated nickel chlorides are thrown in 30mL anhydrous ethers, are slowly dropped into o-phenylenediamine and stirred, mixed
Close solution, wherein Dehydrated nickel chloride and o-phenylenediamine molar ratio are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 2h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 10 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 91%.
Embodiment 11；
(1) 1.0g Dehydrated nickel chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into ethylenediamine and stirred, mixed
Solution, wherein Dehydrated nickel chloride and ethylenediamine molar ratio are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 60 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.Final catalyst is confirmed by nuclear magnetic resoance spectrum.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by the present embodiment 11 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 81%.
Comparative example 1；
(1) 1.0g anhydrous Manganese chloride is thrown in 30mL absolute ethyl alcohols, is slowly dropped into ethylenediamine and stirred, mixed
Solution, wherein anhydrous Manganese chloride and ethylenediamine molar ratio are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by this comparative example 1 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 43%.
Comparative example 2；
(1) 1.0g anhydrous cupric chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into 5,10,15,20. tetraphenylporphyrins
And stir, obtain mixed solution, wherein anhydrous cupric chloride and 5,10,15,20. tetraphenylporphyrin molar ratios are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by this comparative example 2 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate 39%.
Comparative example 3；
(1) 1.0g nitric hydrate chromium is thrown in 30mL anhydrous propanones, is slowly dropped into 2,2'- bipyridyls and stirred, obtained
To mixed solution, wherein nitric hydrate chromium and 2,2'- bipyridyl molar ratios are 1：2；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 1h, washed filtering vacuumizes,
Obtain final catalyst.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by this comparative example 3 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 37%.
Comparative example 4；
(1) 1.0g anhydrous ferric chlorides are thrown in 30mL anhydrous propanones, are slowly dropped into 1,10- Phens and stirred,
Obtain mixed solution, wherein anhydrous ferric chloride and 1,10- Phen molar ratios are 1：4；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by this comparative example 4 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 44%.
Comparative example 5；
(1) 1.0g Dehydrated nickel chlorides are thrown to 30mL, in 0.05mol/L citric acid solutions, are slowly dropped into ethylenediamine simultaneously
Stirring, obtains mixed solution, wherein Dehydrated nickel chloride and ethylenediamine molar ratio are 1：4；
(2) mixed solution in step (1) being placed in oil bath pan, after 80 DEG C of high temperature reflux 4h, washed filtering vacuumizes,
Obtain final catalyst.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by this comparative example 5 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 42%.
Comparative example 6；
(1) 1.0g anhydrous ferric chlorides are thrown in 30mL absolute ethyl alcohols, are slowly dropped into o-phenylenediamine and stirred, mixed
Close solution, wherein Dehydrated nickel chloride and o-phenylenediamine molar ratio are 1：2；
(2) by step (1) mixed solution be placed in oil bath pan, 40 DEG C reflux 1h after, washed filtering is vacuumized, is obtained
Final catalyst.
Finally gained catalyst is kept in dark place under 40 DEG C or less, drying condition.
The catalyst obtained by this comparative example 6 is taken to handle Ofloxacin under ultraviolet light Fenton systems, the place taken
Manage bar part such as table 1, after reacting 70min, Ofloxacin removal rate is 31%.
Claims (8)
1. a kind of high dispersion metal complex molecule catalyst, which is characterized in that structural formula A, B, C, D are one such or two
Kind or more：
Wherein M is Fe, Cu, Co, one kind in Ni.
2. a kind of preparation method of metal complex molecule as described in claim 1, its step are as follows：
(1) one or two or more kinds of soluble metallic salts in Fe, Cu, Co, Ni are thrown in ethyl alcohol, methanol or ether
In one or two or more kinds of solvents, instills chelating agent and stir, obtain mixed solution；
(2) mixed solution in step (1) is placed in 50-90 DEG C of (most suitable is 60-80 DEG C) high temperature reflux 2-8h (most suitable is 2-4h),
It after washed filtering, vacuumizes, obtains the metal complex.
3. preparation method according to claim 2, which is characterized in that the chelating agent be o-phenylenediamine, ethylenediamine, 1,
One of 10- Phens and 2,2'- bipyridyls or two kinds or more.
4. preparation method according to claim 2, which is characterized in that the metal salt is copper chloride, iron chloride, chlorination
One of cobalt, nickel chloride or two kinds or more.
5. according to the preparation method described in claim 2,3 or 4, which is characterized in that the molar ratio of metal salt and chelating agent is 1：
(most suitable is 1 to 1-3：2).
6. a kind of metal complex molecular catalyst as described in claim 1 is in photocatalysis wet type H2O2Oxidation processes organic wastewater
In application.
7. application as claimed in claim 6, which is characterized in that the catalyst is used for photocatalysis wet type H2O2Oxidation processes have
Machine waste water interval reaction condition is：
Normal pressure, initial pH on wastewater：3-7 (preferably pH：5-7), 10-80 DEG C of reaction temperature (preferably 30-60 DEG C), luminous intensity is
50-5000W (preferably 500-1000W), catalyst amounts are 0.01-1.0g/L (preferably 0.1-0.5g/L).
8. application as claimed in claim 6, which is characterized in that the organic wastewater is that o-chlorphenol, Ofloxacin, soil are mould
One or two or more kinds in element, Florfenicol.
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