CN110102314A - A kind of S-Cu1-XCoXFe2O4Class fenton catalyst, catalyst system and its preparation method and application - Google Patents
A kind of S-Cu1-XCoXFe2O4Class fenton catalyst, catalyst system and its preparation method and application Download PDFInfo
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- CN110102314A CN110102314A CN201910305121.XA CN201910305121A CN110102314A CN 110102314 A CN110102314 A CN 110102314A CN 201910305121 A CN201910305121 A CN 201910305121A CN 110102314 A CN110102314 A CN 110102314A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 104
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000000843 powder Substances 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000003814 drug Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- 229940079593 drug Drugs 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N Aminoantipyrine Natural products CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 abstract description 17
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 abstract description 17
- 229960005222 phenazone Drugs 0.000 abstract description 17
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 abstract description 12
- 150000002894 organic compounds Chemical class 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229960000935 dehydrated alcohol Drugs 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910016514 CuFeO2 Inorganic materials 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- -1 antibiotic Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002260 anti-inflammatory agent Substances 0.000 description 2
- 229940124599 anti-inflammatory drug Drugs 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- UZUFPBIDKMEQEQ-UHFFFAOYSA-N perfluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UZUFPBIDKMEQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000932 sedative agent Substances 0.000 description 2
- 230000001624 sedative effect Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940034610 toothpaste Drugs 0.000 description 2
- 239000000606 toothpaste Substances 0.000 description 2
- JNURPZYKCOQGOX-UHFFFAOYSA-N C(CCCCCCC)(=O)O.[F] Chemical compound C(CCCCCCC)(=O)O.[F] JNURPZYKCOQGOX-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920006926 PFC Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
-
- 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
- C02F2101/345—Phenols
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of S-Cu1‑XCoXFe2O4Class fenton catalyst, catalyst system and its preparation method and application.The preparation method includes the following steps: S1: solvent will be added after copper source, cobalt source and ferric iron source mixed dissolution, carry out hydro-thermal reaction and obtain Cu1‑ XCoXFe2O4Powder；S2: by Cu1‑XCoXFe2O4Powder is added in sulfuric acid solution, is stirred to react to obtain powder；S3: powder is calcined up to the S-Cu1‑XCoXFe2O4Class fenton catalyst.Preparation method simple process provided by the invention, material source are wide, at low cost, environmental-friendly；S-Cu is prepared1‑XCoXFe2O4Class fenton catalyst, catalytic activity is high, and applied widely, reaction rate is fast, Yi Huishou, with HCO3 ‑/H2O2In conjunction with can quickly remove the refractory organic compounds such as a variety of refractory organic compounds, especially antipyrine, Acid Orange II.
Description
Technical field
The invention belongs to water process catalysis material fields, and in particular to a kind of S-Cu1-XCoXFe2O4Class fenton catalyst is urged
Change system and its preparation method and application.
Background technique
As pollution problem increasingly sharpens, water environment pollution object abundance, complicated component.Especially some novel micros are dirty
Contaminate object, such as drug (such as anti-inflammatory drug, antibiotic, sedative) and personal care articles (PPCPs, such as cosmetics, toothpaste, hair care
Agent etc.), incretion interferent (EDCs, such as bisphenol-A, Polychlorinated biphenyls), perfluorinated compound (PFCs, such as perfluor tetradecylic acid, complete
Fluorine octanoic acid, perfluoro-pelargonic acid etc.) etc. environmental pollution and potential impact problem have become the focus of scholars and public attention.People
Solve pollution problem and face new challenges and higher requirement.Class fenton catalyst technology is one in high-level oxidation technology
Kind, it overcomes the shortcomings that homogeneous Fenton generates iron cement and stringent pH condition, while recyclable, avoids secondary
Pollution.Thus people are received as a kind of promising technology of green widely to pay close attention to.The ferrite of spinel structure is because of material
Expect from a wealth of sources, be more common class fenton catalyst, but itself there is need to consume a large amount of H2O2Equal self characters
Limitation.
Therefore, it is high to develop a kind of catalytic activity, refractory organic compounds capable of being fast degraded and H2O2Small novel of consumption
Class fenton catalyst has important research significance.
Summary of the invention
It is an object of the invention to overcome in the prior art class fenton catalyst catalytic activity it is low, degrade hardly degraded organic substance
Matter is slow, needs to consume a large amount of H2O2Defect and deficiency, a kind of S-Cu is provided1-XCoXFe2O4The preparation method of class fenton catalyst.
Preparation method simple process provided by the invention, material source are wide, at low cost, environmental-friendly；The S-Cu being prepared1- XCoXFe2O4Class fenton catalyst catalytic activity is high, and applied widely, reaction rate is fast, Yi Huishou, with HCO3 -/H2O2In conjunction with can
Quickly remove the refractory organic compounds such as a variety of refractory organic compounds, especially antipyrine, Acid Orange II, H2O2Consumption
It is small.
Another object of the present invention is to provide a kind of S-Cu1-XCoXFe2O4Class fenton catalyst.
Another object of the present invention is to provide above-mentioned S-Cu1-XCoXFe2O4Class fenton catalyst is in sewage treatment field
Application.
Another object of the present invention is to provide a kind of catalyst systems.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of S-Cu1-XCoXFe2O4The preparation method of class fenton catalyst, includes the following steps:
S1: will be added surfactant after copper source, cobalt source and ferric iron source mixed dissolution, stirring, adjust pH be 8.0~
It stirs after 9.0, for 24 hours in 180~200 DEG C of hydro-thermal reactions, washs, it is dry after Magnetic Isolation, grind to obtain Cu1-XCoXFe2O4Powder；
S2: by Cu1-XCoXFe2O4Powder is added in sulfuric acid solution, is stirred to react, and filters, and washing, drying and grinding is at powder；
S3: powder is placed at 500~600 DEG C and calcines 2~4h to get the S-Cu1-XCoXFe2O4Class fenton catalyst；
Wherein, 0.25≤X≤0.75.
The present invention prepares Cu using hydro-thermal method1-XCoXFe2O4Then powder modifies Cu using S1-XCoXFe2O4, to improve
The performance of catalyst improves the catalyst activity of catalyst, and preparation process is simple, and material source is wide, at low cost, environmental-friendly；
S-Cu is prepared1-XCoXFe2O4Class fenton catalyst, catalytic activity is high, and applied widely, reaction rate is fast, Yi Huishou, with
HCO3 -/H2O2It is difficult to degrade organic in conjunction with can quickly remove a variety of refractory organic compounds, especially antipyrine, Acid Orange II etc.
Substance.
The copper source of this field routine, cobalt source, ferric iron source are used equally in the present invention.
Preferably, copper source described in S1 is one or more of copper nitrate, copper sulphate or copper chloride.
Preferably, cobalt source described in S1 is one or more of cobalt nitrate, cobaltous sulfate or cobalt chloride.
Preferably, ferric iron source described in S1 is one or more of ferric nitrate or iron chloride.
Preferably, solvent described in S1 is one or more of ethylene glycol or polyethylene glycol.
Preferably, X=0.75 described in S1.
Preferably, it is 8 that pH is adjusted in S1.
Preferably, pH is adjusted using ammonium hydroxide in S1.
Preferably, the temperature of the hydro-thermal reaction is 180 DEG C, and the time is for 24 hours.
Preferably, the process of the washing is successively to wash through deionized water and dehydrated alcohol.
Preferably, the concentration of sulfuric acid solution is 0.5~1.0mol/L in S2.
Preferably, Cu in S21-XCoXFe2O4The quality molar ratio of powder and sulfuric acid is 80~160:1g/mol.
Preferably, the temperature calcined in S3 is 500 DEG C, time 2h.
A kind of S-Cu1-XCoXFe2O4Class fenton catalyst is prepared by above-mentioned preparation method.
Preferably, the S-Cu1-XCoXFe2O4The partial size of class fenton catalyst is 30~40nm.
Preferably, the S-Cu1-XCoXFe2O4The mass fraction of S is 2.0~4.0% in class fenton catalyst.
Above-mentioned S-Cu1-XCoXFe2O4Application of the class fenton catalyst in sewage treatment field is also in protection model of the invention
In enclosing.
Preferably, the S-Cu1-XCoXFe2O4Class fenton catalyst is in processing drug containing or the sewage of personal-care supplies
In application.
Preferably, the drug is one or more of anti-inflammatory drug, antibiotic or sedative；The personal-care supplies
For one or more of cosmetics, toothpaste or conditioner；The incretion interferent is one of bisphenol-A or Polychlorinated biphenyls
Or it is several；The perfluorinated compound is one or more of perfluor tetradecylic acid, perfluoro caprylic acid or perfluoro-pelargonic acid.
It is further preferable that the S-Cu1-XCoXFe2O4Class fenton catalyst is in processing PPCPs, incretion interferent or dye
Expect the application in waste water class sewage.
A kind of catalyst system, including above-mentioned S-Cu is also claimed in the present invention1-XCoXFe2O4Class fenton catalyst and
HCO3 -/H2O2。
Bicarbonate radical (HCO3 -) it is common anion, it is widely present in natural water.Bicarbonate activates peroxidating
Hydrogen (HCO3 -/H2O2) in conjunction with metal ion or catalyst and the Fenton-like that forms is as a kind of emerging Wastewater Treatment Technology
Art has been shown to the waste water such as a variety of dyestuffs of degrading.
The present invention is by S-Cu1-XCoXFe2O4Class fenton catalyst and HCO3 -/H2O2It is degradable a variety of to constitute catalyst system
The refractory organic compounds such as refractory organic compounds, especially antipyrine, Acid Orange II.
S-Cu1-XCoXFe2O4Class fenton catalyst, HCO3 -And H2O2The proportion relation of three can refer to existing condition.
Preferably, S-Cu in the catalyst system1-XCoXFe2O4Class fenton catalyst, HCO3 -And H2O2Molar ratio be
3~10:1:6.8~20.4.
It is further preferable that S-Cu in the catalyst system1-XCoXFe2O4Class fenton catalyst, HCO3 -And H2O2Mole
Than for 3:1:17.
Compared with prior art, the invention has the following beneficial effects:
Preparation method simple process provided by the invention, material source is wide, at low cost and no pollution to the environment；It is prepared into
The S-Cu arrived1-XCoXFe2O4Class fenton catalyst not only remains the catalytic performance of unit metal catalyst, while having metal
Between synergistic function, catalytic activity is high, and applied widely, reaction condition is mild and simple and easy, medicine capable of being fast degraded
The refractory organic compounds such as object, PPCPs.
Detailed description of the invention
Fig. 1 is the S-Cu that the embodiment of the present invention 1 provides0.25Co0.75Fe2O4The scanning electron microscope (SEM) photograph of class fenton catalyst；
Fig. 2 is the S-Cu that the embodiment of the present invention 1 provides0.25Co0.75Fe2O4The XPS map of class fenton catalyst；
Fig. 3 is the S-Cu that the embodiment of the present invention 1 provides0.25Co0.75Fe2O4Class fenton catalyst and Cu1-XCoXFe2O4Class is fragrant
The removal effect of catalyst to antipyrine；
Fig. 4 is the S-Cu that the embodiment of the present invention 1 provides0.25Co0.75Fe2O4Class fenton catalyst is in different catalysts dosage
Under to the removal effect of antipyrine；
Fig. 5 is the S-Cu that the embodiment of the present invention 1 provides0.25Co0.75Fe2O4Class fenton catalyst is in different catalysts dosage
Under to the removal effect of Acid Orange II；
Fig. 6 is the S-Cu that the embodiment of the present invention 1 provides0.25Co0.75Fe2O4Class fenton catalyst and CuFeO2And CoFeO2It is right
The removal effect of antipyrine.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed
The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And replacement belongs to scope of the present invention.
Embodiment 1
The present embodiment provides a kind of S-Cu1-XCoXFe2O4Class fenton catalyst, specifically includes S-Cu0.25Co0.75Fe2O4Class
Fenton catalyst, S-Cu0.5Co0.5Fe2O4Class fenton catalyst, S-Cu0.75Co0.25Fe2O4Class fenton catalyst.
It is prepared via a method which to obtain.
(1) 8.08g ferric nitrate (Fe (NO is weighed3)3·9H2O), 2.18g cobalt nitrate (Co (NO3)3·6H2) and 0.60g nitre O
Sour copper (S-Cu (NO3)3·6H2O) put into beaker, be added 30mL deionized water and stir be completely dissolved after, be added 50mL second two
Alcohol surfactant after magnetic stirs 30min, is added dropwise ammonium hydroxide and continues magnetic to pH value of solution=8 and stir 1h, then transfer them to
In the hydrothermal reaction kettle of polytetrafluoroethylsubstrate substrate, reacted for 24 hours under the conditions of 180 DEG C, after cooled to room temperature, sediment is spent
Ionized water and dehydrated alcohol respectively wash 3 times, are dried in vacuo 12h in 60 DEG C of baking ovens after Magnetic Isolation, and finally grinding obtains
Cu0.25Co0.75Fe2O4Powder.
Cobalt nitrate (Co (NO in set-up procedure (1)3)2·6H2O) dosage is 1.45g and copper nitrate (Cu (NO3)2·
6H2O dosage) is 1.21g, and Cu is prepared0.5Co0.5Fe2O4Powder.
Cobalt nitrate (Co (NO in set-up procedure (1)3)2·6H2O) dosage is 0.73g and copper nitrate (Cu (NO3)2·
6H2O dosage) is 1.81g, and Cu is prepared0.75Co0.25Fe2O4Powder.
(2) by 4g Cu0.25Co0.75Fe2O4Powder, 4g Cu0.5Co0.5Fe2O4Powder, 4g Cu0.75Co0.25Fe2O4Powder
0.5mol/L H is put into respectively2SO4In the beaker of 50mL solution, at 40 DEG C of holding after strong magnetic agitation 1h, is filtered, obtained
Sediment deionized water and dehydrated alcohol wash after in 60 DEG C of vacuum drying 6h, grind into powder.
(3) dried powder is placed in Muffle furnace again and calcines 2h at 500 DEG C, respectively obtain S-Cu0.25Co0.75Fe2O4Class
Fenton catalyst, S-Cu0.5Co0.5Fe2O4Class fenton catalyst, S-Cu0.75Co0.25Fe2O4Class fenton catalyst.
It is S-Cu such as Fig. 10.25Co0.75Fe2O4Class fenton catalyst scanning electron microscope (SEM) photograph, partial size are about 40nm；S-
Cu0.5Co0.5Fe2O4Class fenton catalyst, S-Cu0.75Co0.25Fe2O4The partial size of class fenton catalyst is also about 40nm.
Fig. 2 is S-Cu0.25Co0.75Fe2O4The XPS map of class fenton catalyst, from figure it is found that the XPS spectrum peak of Fe2p exists
Fe is shown at 710.90eV and 724.00eV3+In the presence of.Co2p shows Co in 780.40eV, 783.00eV and 796.30eV2+
In the presence of.The XPS spectrum peak of Cu2p corresponds to Cu2p3/2 in 934.00eV and shows Cu2+In the presence of.There is a S2p in left and right at 168.40eV
Broad peak, mainly with S6+In the presence of.The result shows that after S modification, Fe3+、Co2+、Cu2+And S6+It is present in the surface of catalyst, and
2.0~4.0% are accounted for containing S element.
Embodiment 2
The present embodiment provides a kind of S-Cu0.25Co0.75Fe2O4Class fenton catalyst is prepared via a method which to obtain.
(1) 8.08g ferric nitrate (Fe (NO is weighed3)3·9H2O), 2.11g cobaltous sulfate (CoSO4·7H2) and 0.62g sulfuric acid O
Copper (CuSO4·5H2O) put into beaker, be added 30mL deionized water and stir be completely dissolved after, be added 50mL polyethylene glycol table
Face activating agent after magnetic stirs 30min, is added dropwise ammonium hydroxide and continues magnetic to pH value of solution=10 and stir 1h, then transfer them to poly- four
In the hydrothermal reaction kettle of vinyl fluoride substrate, reacted for 24 hours under the conditions of 180 DEG C, after cooled to room temperature, sediment deionization
Water and dehydrated alcohol respectively wash 3 times, are dried in vacuo 12h in 60 DEG C of baking ovens after Magnetic Isolation, and finally grinding obtains
Cu0.25Co0.75Fe2O4Catalyst fines.Partial size is about 16nm.
(2) by 2.0g Cu0.25Co0.75Fe2O4Powder puts into 0.5mol/L H2SO4In the beaker of 50mL solution, 40 are kept
At DEG C after strong magnetic agitation 1h, filtered, obtained sediment deionized water and dehydrated alcohol wash after in 60 DEG C of vacuum
Dry 6h, grind into powder.
(3) dried powder is placed in Muffle furnace again and calcines 4h at 500 DEG C, obtain S-Cu0.25Co0.75Fe2O4Class Fenton
Catalyst.Its partial size is about 40nm.
Embodiment 3
The present embodiment provides a kind of S-Cu1-XCoXFe2O4Class fenton catalyst is prepared via a method which to obtain.
(1) 5.41g iron chloride (FeCl is weighed3·6H2O), 1.78g cobalt chloride (CoCl2·6H2) and 0.43g copper chloride O
(CuCl2·6H2O) put into beaker, be added 30mL deionized water and stir be completely dissolved after, be added 50mL ethylene glycol solvent, magnetic
After stirring 30min, ammonium hydroxide is added dropwise and continues magnetic to pH value of solution=9 and stirs 1h, then transfers them to polytetrafluoroethylsubstrate substrate
In hydrothermal reaction kettle, 20h is reacted under the conditions of 200 DEG C, after cooled to room temperature, sediment deionized water and dehydrated alcohol
Each washing 3 times, dries 12h after Magnetic Isolation in 60 DEG C of baking ovens, and finally grinding obtains Cu0.25Co0.75Fe2O4Catalyst powder
End.
(2) by 3.0g Cu0.25Co0.75Fe2O4Powder puts into 0.5mol/L H2SO4In the beaker of 50mL solution, 40 are kept
At DEG C after strong magnetic agitation 1h, filtered, obtained sediment deionized water and dehydrated alcohol wash after in 60 DEG C of vacuum
Dry 6h, grind into powder.
(3) dried powder is placed in Muffle furnace again and calcines 4h at 500 DEG C, obtain S-Cu0.25Co0.75Fe2O4Class Fenton
Catalyst.Its partial size is about 40nm.
The S-Cu being prepared with embodiment 11-XCoXFe2O4Class fenton catalyst and refractory organic compounds antipyrine
With the performance for measuring its catalytic degradation refractory organic compounds for Acid Orange II.
(1) S-Cu that embodiment 1 provides0.25Co0.75Fe2O4Class fenton catalyst and Cu1-XCoXFe2O4Class fenton catalyst
To the removal effect of antipyrine
In the antipyrine solution that 50mL concentration is 50mg/L, 0.5g/L implementation is separately added into the waste water that pH is 8.35
The S-Cu that example 1 provides0.25Co0.75Fe2O4Class fenton catalyst and 50mmol H2O2(A), 40min is reacted at room temperature, and
With only addition 0.5g/L S-Cu1-XCoXFe2O450mmolH is only added in class fenton catalyst (B)2O2(C)、0.5g/L
Cu0.25Co0.75Fe2O4With 50mmol H2O2(D)、0.5g/LCu0.5Co0.5Fe2O4With 50mmol H2O2(E)、0.5g/
LCu0.75Co0.25Fe2O4With 50mmol H2O2(F) effect degraded compares.Degradation rate such as Fig. 3.As can be seen from Figure 3, S-
Cu1-XCoXFe2O4Class fenton catalyst (B) is to antipyrine substantially without suction-operated；H2O2(C) to its oxidation less than
10%.Multi-metallic catalyst can be catalyzed H2O2Fast degradation is carried out to antipyrine.Wherein, Cu0.25Co0.75Fe2O4
(94.38%) it is higher than Cu0.5Co0.5Fe2O4(89.17%) and Cu0.75Co0.25Fe2O4(69.87%).And pass through sulphur (S) modification pair
After catalyst modification, S-Cu0.25Co0.75Fe2O4Degradation rate has reached 97.80%.Therefore, S modification, which further improves, urges
The catalytic performance of agent.
(2) S-Cu that embodiment 1 provides0.25Co0.75Fe2O4Class fenton catalyst replaces peace under different catalysts dosage
Than the removal effect of woods
In the antipyrine solution that 50mL concentration is 50mg/L, be separately added into 0 in the waste water that pH is 8.35,0.1,0.3,
0.5, the S-Cu that 0.7 and 1.0g/L embodiment 1 provides1-XCoXFe2O4Class fenton catalyst and 50mmol H2O2, in room temperature condition
Lower reaction 40min, degradation rate such as Fig. 4.As can be seen from Figure 4, when catalyst amounts are 0g/L, i.e., existing for no catalyst
In the case of, HCO3 -/H2O2System is to the removal rate of ANT less than 10%.With being increasing for catalyst amounts, antipyrine
Removal rate also constantly increase.When catalyst amounts are 0.3g/L, 40min ANT is substantially completely removed；Continue to increase and urge
The removal rate of the amount of agent, ANT is essentially identical, or even is declined.Excessive catalyst is largely catalyzed consumption H2O2, while can
Reacting between ANT and the-OH of generation free radical can be hindered, thus unfavorable and ANT removal.Therefore, catalyst is taken most preferably to throw
Dosage is 0.3g/L.
(3) S-Cu that embodiment 1 provides0.25Co0.75Fe2O4Removal effect of the class fenton catalyst to Acid Orange II
The S- that 0.3g/L embodiment 1 provides is added in the Acid Orange II solution that 50mL concentration is 100mg/L
Cu0.25Co0.75Fe2O4Class fenton catalyst, 0.1g/L NaHCO3With 30mmol/L H2O2, at room temperature, reaction
10min, the percent of decolourization for the catalyst that embodiment 1 provides is up to 100%, such as Fig. 5.
(4) S-Cu that embodiment 1 provides0.25Co0.75Fe2O4Class fenton catalyst is under different catalysts dosage to acidity
The removal effect of orange II
0,0.1,0.3,0.5 and 1.0g/L is separately added into the Acid Orange II solution that 50mL concentration is 100mg/L to implement
The S-Cu that example 1 provides0.25Co0.75Fe2O4Class fenton catalyst, 0.1g/L NaHCO3With 30mmol/L H2O2, in room temperature condition
Under, react 10min.
Such as Fig. 5.It is similar with degradation antipyrine, with being increasing for catalyst amounts, the percent of decolourization of Acid Orange II
Also it is continuously improved.When catalyst amounts are 0.3g/L, 10min Acid Orange II percent of decolourization is reacted up to 100%.
(5) S-Cu that embodiment 1 provides0.25Co0.75Fe2O4Class fenton catalyst and CuFeO2And CoFeO2To antipyrine
Removal effect see Fig. 6,10min unanimously, when the dosage of each catalyst is 0.3g/L, is reacted in processing step and (4).
It can be seen that S-Cu0.25Co0.75Fe2O4Class fenton catalyst is to the removal rate of antipyrine in 40min
97.80%, respectively higher than CuFeO2Catalyst (34.85%) and CoFeO2Catalyst (31.02%).Illustrate the S- of S modification
Cu0.25Co0.75Fe2O4Class fenton catalyst shows preferable catalytic performance.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of S-Cu1-XCoXFe2O4The preparation method of class fenton catalyst, which comprises the steps of:
S1: will be added surfactant after copper source, cobalt source and ferric iron source mixed dissolution, stirring, after adjusting pH is 8.0~9.0
Stirring for 24 hours in 180~200 DEG C of hydro-thermal reactions is washed, dry after Magnetic Isolation, grinds to obtain Cu1-XCoXFe2O4Powder；
S2: by Cu1-XCoXFe2O4Powder is added in sulfuric acid solution, is stirred to react, and filters, and washing, drying and grinding is at powder；
S3: powder is placed at 500~600 DEG C and calcines 2~4h to get the S-Cu1-XCoXFe2O4Class fenton catalyst；
Wherein, 0.25≤X≤0.75.
2. preparation method according to claim 1, which is characterized in that copper source described in S1 is copper nitrate, copper sulphate or chlorination
One or more of copper；The cobalt source is one or more of cobalt nitrate, cobaltous sulfate or cobalt chloride；The ferric iron source is
One or more of ferric nitrate or iron chloride；The surfactant is one or more of ethylene glycol or polyethylene glycol.
3. preparation method according to claim 1, which is characterized in that X=0.75 described in S1.
4. preparation method according to claim 1, which is characterized in that the concentration of sulfuric acid solution is 0.5~1.0mol/L in S2.
5. preparation method according to claim 1, which is characterized in that Cu in S21-XCoXFe2O4The quality of powder and sulfuric acid is rubbed
You are than being 80~160:1g/mol.
6. a kind of S-Cu1-XCoXFe2O4Class fenton catalyst, which is characterized in that pass through any preparation side of Claims 1 to 5
Method is prepared.
7. S-Cu according to claim 61-XCoXFe2O4Class fenton catalyst, which is characterized in that the S-Cu1-XCoXFe2O4
The mass fraction of S is 2.0~4.0% in class fenton catalyst.
8. any S-Cu of claim 6~71-XCoXFe2O4Class fenton catalyst processing drug containing, personal-care supplies,
Application in the sewage of incretion interferent or perfluorinated compound.
9. a kind of catalyst system, which is characterized in that including any S-Cu of claim 6~71-XCoXFe2O4Class Fenton is urged
Agent and HCO3 -/H2O2。
10. catalyst system according to claim 9, which is characterized in that S-Cu in the catalyst system1-XCoXFe2O4Class
Fenton catalyst, HCO3 -And H2O2Molar ratio be 3~10:1:6.8~20.4.
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