CN107469827A - A kind of magnetic type Fenton catalyst and preparation method thereof - Google Patents
A kind of magnetic type Fenton catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 65
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 61
- 230000015556 catabolic process Effects 0.000 claims abstract description 38
- 238000006731 degradation reaction Methods 0.000 claims abstract description 38
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 6
- -1 hydroxyl radical free radical Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 239000000975 dye Substances 0.000 claims description 21
- 239000001045 blue dye Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 13
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000010908 decantation Methods 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 239000008236 heating water Substances 0.000 claims description 7
- 238000012423 maintenance Methods 0.000 claims description 7
- 229910052603 melanterite Inorganic materials 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000004042 decolorization Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229940044927 ceric oxide Drugs 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- TZIBOXWEBBRIBM-UHFFFAOYSA-N cerium(3+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ce+3] TZIBOXWEBBRIBM-UHFFFAOYSA-N 0.000 abstract 1
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 238000002835 absorbance Methods 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002122 magnetic nanoparticle Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/33—Electric or magnetic properties
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C02F1/72—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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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The present invention protects a kind of magnetic Fe3O4/CeO2The preparation method of nano-complex and the method as class Fenton's reaction catalyst treatment methylene blue solution, the magnetic composite catalyst are made up of the nanometer titanium dioxide cerium material being coated on magnetic ferroferric oxide nanometer particle.The magnetic solid catalyst of the present invention can be used as heterogeneous catalysis catalyzing hydrogen peroxide to produce hydroxyl radical free radical degradation of methylene blue, and using the inventive method, 30 minutes methylene blue degradation rates are up to more than 90%.
Description
Technical field
The invention belongs to technical field of waste water processing, is related to magnetic Fe3O4/CeO2At nano-complex high-level oxidation technology
The method for managing dyeing waste water.
Background technology
Water pollution situation in China's is on the rise at present, raw by chemical industry, weaving, agricultural chemicals, biological medicine etc. in waste water control
Hard-degrading high concentrated organic wastewater caused by production process is the difficulties of sewage disposal technology.In order to administer such pollution,
Technology common at present mainly has Ozonation, active carbon adsorption, membrane separation process, wet oxidation process and Fenton oxidation method
Deng.Relative to other methods, Fenton oxidation method is because with the advantage such as oxidation rate is fast, cost and operating cost are low and by wide in the industry
General use.So far, one-hundred-year history in the research of Fenton, class Fenton's reaction.Fenton's reaction mainly utilizes H2O2In Fe2 +/Fe3+Catalytic action under generation with high reaction activity hydroxyl radical free radical, will be organic by the superpower oxidisability of free radical
Thing oxidation Decomposition is small molecule, in addition directly mineralising be converted into carbon dioxide and water, can effectively remove traditional water technology without
The hardly degraded organic substance that method removes.Class Fenton's reaction be mainly use iron ion outside transition-metal ion (such as copper, manganese,
Aluminium, chromium, cerium etc.) or transition group metallic oxide or by different transition-metal ions or oxide carried fixation, then with
Hydrogen peroxide or other strong oxidizers reaction generation free radical, so as to reach the purpose of oxide target thing.But sewage disposal
In, classical Fenton's reaction add hydrogen peroxide and ferrous ion and acidified, oxidation, in and and four steps of precipitation it
After have a generation of a large amount of iron cements, and due in reaction constantly caused by oxygen bubble cause Mud up-floating problem, make discharge water
Matter is not up to standard, influences to discharge.In addition the catalyst used in reacting can not recycle, and hamper Fenton's reaction in water process
Practical application.
In recent years, magnetic nanoparticle is more and more applied in wastewater treatment.Because magnetic nanoparticle has
Porous and the characteristic easily separated and recovered by magnet, therefore be considered as a kind of up-and-coming adsorbent and catalyst carrier.
Magnetic nanoparticle synthetic method is a lot, such as co-precipitation, microemulsion phase, hydro-thermal method and sonochemistry etc., its synthesis technique nor
It is often easy, it is cheap, it is low for cost of sewage disposal.But it is single use magnetic nanoparticle as catalyst to be used at water
Manage it is inefficient, it is ineffective, it is necessary to further heuristic approach, improve performance, improve its catalytic performance.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of magnetic retention compound to urge
The Preparation method and use of agent, material requested of the present invention is cheap and easy to get, and synthesis technique is simple, the magnetic composite catalysis of preparation
Agent concerted catalysis effect is good, can effectively reduce the dosage of hydrogen peroxide, have the advantages that it is environment-friendly, recyclable, gram
Take and iron cement is also easy to produce in classical Fenton's reaction, catalyst reclaims the shortcomings that difficult.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation of magnetic type Fenton catalyst and its application method, the catalyst aoxidize three by being coated on magnetic four
Nano ceric oxide compound composition on iron nano-particle, hydroxyl free is produced as heterogeneous catalysis activated hydrogen peroxide
Base degradation of methylene blue dyestuff.
Catalyst of the present invention is compound by the nano ceric oxide being coated on magnetic ferroferric oxide nanometer particle
Thing forms.
The preparation method of catalyst of the present invention is as follows：Certain volume 0.2M NaOH solution is added three mouthfuls first
In flask, a certain amount of nano Ce O is added2, heating water bath is passed through nitrogen 3min to remove to after 75-85 DEG C in mixed liquor
Oxygen in solution, then under electric stirring, it is added dropwise and a certain amount of contains Fe2(SO4)3And FeSO4·7H2O mixed solution,
The maintenance reaction 1h at 75-85 DEG C of temperature and logical condition of nitrogen gas, after completion of the reaction, under externally-applied magnetic field, using decantation with secondary
Precipitation 5-6 times obtained by water washing is distilled, 12h is dried in vacuo at a temperature of 60 DEG C after washing, then takes out desciccate and exist
It is finely ground in mortar, produce.
The preparation method of preferable catalyst is as follows：Certain volume 0.2M NaOH are added in three-necked flask first, then
Add a certain amount of nano Ce O2, heating water bath is passed through nitrogen 3min to remove the oxygen in solution, so to after 80 DEG C in mixed liquor
Afterwards under electric stirring, it is added dropwise and a certain amount of contains Fe2(SO4)3And FeSO4·7H2O mixed solution, in 80 DEG C of temperature and
Maintenance reaction 1h under logical condition of nitrogen gas, after completion of the reaction, under externally-applied magnetic field, sunk using decantation obtained by second distillation water washing
Shallow lake 5-6 times, 12h is dried in vacuo at a temperature of 60 DEG C after washing, it is finely ground in mortar to then take out desciccate, produces.
Fe in preparation method2(SO4)3And FeSO4·7H2In O mixed solution, Fe3+And Fe2+The ratio between the amount of material
Preferably 1:4.
Fe in preparation method2(SO4)3And CeO2Mass ratio be preferably 1.8-3.4:1.
Fe in preparation method2(SO4)3And CeO2Mass ratio be 2.6:1.
The addition of NaOH solution in preparation method is preferably to make to prepare the control of compound reaction system solution ph
In the range of 12-13.
Application of the catalyst of the present invention preferably in degradation of methylene blue dyestuff.
Catalyst of the present invention is preferably as the application in the catalyst degradation methylene blue dye of class Fenton's reaction.
Preferable catalyst of the present invention is that the method for the catalyst degradation methylene blue dye as class Fenton's reaction is as follows：
Methylene blue dye solution is taken, the catalyst and hydrogen peroxide of preparation are added thereto, in 25 DEG C of thermostatic control oscillator vibration
Oscillating reactions, methylene blue dye is reacted degradation and decolorization, after reaction terminates, carry out separation of solid and liquid using externally-applied magnetic field, take
The concentration of clear liquid dyestuff after ultraviolet-uisible spectrophotometer measure degraded, dyestuff is calculated according to dye strength change before and after degraded
Degradation rate.
Preferable catalyst of the present invention is that the method for the catalyst degradation methylene blue dye as class Fenton's reaction is as follows：
Methylene blue dye solution is taken, dye solution pH is 4, initial concentration 10-50mg/L, adds be more than or equal to thereto
Catalyst and 0.5-1.0g/L hydrogen peroxide prepared by 0.25g/L, the oscillating reactions in 25 DEG C of thermostatic control oscillator vibration
30min, methylene blue dye is reacted degradation and decolorization, after reaction terminates, carry out separation of solid and liquid using externally-applied magnetic field, take supernatant
With the concentration of dyestuff after ultraviolet-uisible spectrophotometer measure degraded, change the drop for calculating dyestuff according to dye strength before and after degraded
Solution rate.
Degradation rate (%)=[(C0–C)/C0] × 100%=[(A0–A)/A0] × 100%
In formula：C0For the initial concentration of methylene blue dye；C is degraded certain time (min) methylene blue dye afterwards
Concentration；A0For C0Corresponding absorbance；A is absorbance corresponding to C.
The beneficial effects of the invention are as follows：
(1) catalyst of the present invention is Fe3O4/CeO2Compound, material source is extensive, cheap and easy to get, has concerted catalysis effect
Should, excellent catalytic effect.
(2) using hydrogen peroxide as primary oxidizers, dosage reduce further the present invention far fewer than similar Fenton's reaction
Cost.
(3) magnetic Fe3O4/CeO2Complex catalyst easily realizes separation of solid and liquid very much using externally-applied magnetic field, not only avoid one
As catalyst easily generate iron containing sludge and reluctant phenomenon in use, and solve that catalyst is difficult to reclaim asks
Topic.
(4) method of the invention is easy, easy to operate, and the catalyst of preparation has surface-active high, dispersiveness in the aqueous solution
Well, the features such as stability is good, cost of material cost is low, is adapted to industrialized production, has certain application prospect.
Brief description of the drawings
Fig. 1 is the magnetic Fe prepared3O4/CeO2The electron scanning micrograph of nano-complex.
Fig. 2 is color contrast before and after methylene blue dye degraded, wherein left side is methylene blue dye
Scheme before expecting degraded, right side is to scheme after methylene blue dye is degraded.
Embodiment
To make the object, technical solutions and advantages of the present invention of greater clarity, with reference to embodiment, to this
Invention is described in further detail.These descriptions are merely illustrative, but the implementation of the present invention is not limited to this.
Embodiment 1：Magnetic Fe3O4/CeO2The preparation of nano-complex catalyst
100mL 0.2M NaOH are added in three-necked flask first, add 0.154g nano Ces O2, heating water bath to 80
Nitrogen 3min is passed through after DEG C, in mixed liquor to remove the oxygen in solution.Then under electric stirring, 100mL is added dropwise and contains
0.400g Fe2(SO4)3With 2.224g FeSO4·7H2O mixed solution, the maintenance reaction at 80 DEG C of temperature and logical condition of nitrogen gas
1h.After completion of the reaction, under externally-applied magnetic field, precipitated using decantation (5-6 times) gained of second distillation water washing, washing finishes
12h is dried in vacuo at a temperature of 60 DEG C afterwards, finally taking-up desciccate is finely ground in mortar, weighs product quality and simultaneously loads weighing
It is standby in bottle.
The catalyst prepared with embodiment 1, following experiment is carried out, is specifically shown in experimental example 1-5：
Experimental example 1
Under normal temperature and pressure, a certain amount of methylene blue storing solution is taken in the 50mL water of certain pH value, prepares initial concentration
For the methylene blue solution of 20mg/L difference pH value, solution pH value is respectively 2-7.Respectively two parts of the preparation of the solution of same pH, one
Part uses the initial absorbance (A of determined by ultraviolet spectrophotometry solution0)；Another solution adds a certain amount of complex catalyst
And H2O2, it is 0.5g/L, H to make addition rear catalyst concentration2O2Concentration is 1.0 × 10-3Mol/L, it is placed in 250mL conical flasks
30min is vibrated with 180r/min in controllable temperature shaking table, after completion of the reaction, Magneto separate is carried out with strong magnet, supernatant with
6000r/min is centrifuged, and takes methylene blue absorbance (A) after secondary supernatant ultraviolet specrophotometer measure degraded, root
Result calculates its degradation rate according to surveying and determination.Each experimental point does three Duplicate Samples.
As a result show, for the methylene blue solution that initial concentration is 20mg/L, catalyst concn 0.5g/L, H2O2It is dense
Spend for 1.0 × 10-3Mol/L, the initial pH of solution are respectively 2,3,4,5,6,7 methylene blue solution class Fenton's reaction system, instead
Solution degradation rate is respectively 92.8,96.7,99.0,91.0,88.6 and 88.1% after answering.
Experimental example 2
Under normal temperature and pressure, a certain amount of methylene blue storing solution is taken respectively in 50mL water, and preparation initial concentration is 20mg/
L, pH value are 4 methylene blue solution several pieces.A certain amount of complex catalyst and not is added in every part of methylene blue solution
With the H of concentration2O2, it is 0.5g/L, H to make addition rear catalyst concentration2O2Concentration be respectively 0.2,0.5,1.0,2.0 and 3.0 (×
10-3Mol/L), it is placed in 250mL conical flasks in controllable temperature shaking table and 30min is vibrated with 180r/min, after completion of the reaction, uses
Strong magnet carries out Magneto separate, and supernatant is centrifuged with 6000r/min, takes secondary supernatant to be determined with ultraviolet specrophotometer
Methylene blue absorbance (A) after degraded, while determine the absorbance (A of initial methylene blue solution0), calculated according to measurement result
Its degradation rate.Each experimental point does three Duplicate Samples.
As a result show, be for the methylene blue solution that initial concentration is 20mg/L, pH value of solution 4, catalyst concn
0.5g/L, H2O2Concentration is respectively 0.2,0.5,1.0,2.0 and 3.0 (× 10-3Mol/L methylene blue solution class Fenton) is anti-
System is answered, solution degradation rate is respectively 89.3,95.7,98.6,85.6 and 81.0% after reaction.
Experimental example 3
Under normal temperature and pressure, a certain amount of methylene blue storing solution is taken respectively in 50mL water, and preparation initial concentration is 20mg/
L, pH value are 4 methylene blue solution several pieces.A certain amount of H is added in every part of methylene blue solution2O2With answering for various concentrations
Mixture catalyst, make H after addition2O2Concentration is 1.0 × 10-3Mol/L, complex catalysts agent concentration is respectively 0.25,0.5,
1.0g/L, it is placed in 250mL conical flasks in controllable temperature shaking table and 30min is vibrated with 180r/min, after completion of the reaction, with strong magnetic
Iron carries out Magneto separate, and supernatant is centrifuged with 6000r/min, takes secondary supernatant ultraviolet specrophotometer measure degraded
Methylene blue absorbance (A) afterwards, while determine the absorbance (A of initial methylene blue solution0), its drop is calculated according to measurement result
Solution rate.Each experimental point does three Duplicate Samples.
As a result show, catalyst amount has considerable influence to methylene blue dye degradation time and degradation rate, with catalysis
The increase of agent dosage, the degradation rate increase of dyestuff, degradation time shorten.It is molten for 20mg/L methylene blue for initial concentration
Liquid, pH value of solution 4, H2O2Concentration is 1.0 × 10-3Mol/L and different catalysts dosage class Fenton's reaction system, the drop of dyestuff
Solution situation is as follows：(1) catalyst concn is 0.25g/L, reaction time 30min, and the degradation rate of methylene blue solution is
98.2%；(2) catalyst concn is 0.5g/L, and reaction time 10min, the degradation rate of methylene blue solution is 99.0%；(3)
Catalyst concn is 1.0 g/L, and reaction time 2min, the degradation rate of methylene blue solution is 100%.
Experimental example 4
Under normal temperature and pressure, a certain amount of methylene blue storing solution is taken respectively in 50mL water, and preparation initial concentration is 20mg/
L, pH value are 4 methylene blue solution several pieces.A certain amount of H is added in every part of methylene blue solution2O2(or it is not added with H2O2It is right
According to) and different types of catalyst (or being not added with catalyst control), make H after addition2O2Concentration is 1.0 × 10-3Mol/L, catalysis
Agent concentration is 0.5g/L, is placed in 250mL conical flasks in controllable temperature shaking table and vibrates 30min with 180 r/min, and reaction finishes
Afterwards, Magneto separate is carried out with strong magnet, supernatant is centrifuged with 6000r/min, takes secondary supernatant ultraviolet specrophotometer
Methylene blue absorbance (A) after measure degraded, while determine the absorbance (A of initial methylene blue solution0), tied according to measure
Fruit calculates its degradation rate.Each experimental point does three Duplicate Samples.
As a result show, for the methylene blue solution that initial concentration is 20mg/L, pH value of solution 4, H2O2Concentration be 1.0 ×
10-3Mol/L, catalyst concn are the methylene blue solution class Fenton's reaction of 0.5g/L different systems, react each body after 30min
The degraded situation of based dye is as follows：(1) for Fe3O4-H2O2- methylene blue system, solution degradation rate is 40.6% after reaction；
(2) for CeO2-H2O2- methylene blue system, solution degradation rate is 30.4% after reaction；(3) for Fe3O4+CeO2-H2O2- sub-
Methyl blue system (Fe3O4 +CeO2Refer to Fe3O4With CeO2Simply mix), solution degradation rate is 75.3% after reaction；(4)
For Fe3O4/CeO2-H2O2- methylene blue system, solution degradation rate is 99.2% after reaction；(5) for Fe3O4/CeO2- sub-
Methyl blue system, solution degradation rate is 11.2% after reaction；(6) for H2O2- methylene blue system, solution degradation rate after reaction
For 16.5%；
Experimental example 5
Under normal temperature and pressure, a certain amount of methylene blue storing solution is taken respectively in 50mL water, and preparing initial concentration is respectively
10th, 20,50,100 and 150mg/L, pH value are 4 methylene blue solution several pieces.Added in every part of methylene blue solution certain
The H of amount2O2And complex catalyst, make H after addition2O2Concentration is 1.0 × 10-3Mol/L, catalyst concn 0.5g/L, is placed in
30min is vibrated with 180r/min in controllable temperature shaking table in 250mL conical flasks, after completion of the reaction, magnetic point is carried out with strong magnet
From supernatant is centrifuged with 6000r/min, and methylene blue is inhaled after taking secondary supernatant ultraviolet specrophotometer measure degraded
Luminosity (A), while determine the absorbance (A of initial methylene blue solution0), its degradation rate is calculated according to measurement result.It is each real
Test and a little do three Duplicate Samples.
As a result show, be respectively 10,20,50,100 and 150mg/L methylene blue solution for initial concentration, solution
PH is 4, catalyst concn 0.5g/L, H2O2Concentration is 1.0 × 10-3Mol/L methylene blue solution class Fenton's reaction body
System, solution degradation rate is respectively 100,99.4,93.6,70.8 and 48.9% after reaction.
Embodiment 2：Magnetic Fe3O4/CeO2The preparation of nano-complex catalyst
100mL 0.2M NaOH are added in three-necked flask first, add 0.222g nano Ces O2, heating water bath to 75
Nitrogen 3min is passed through after DEG C, in mixed liquor to remove the oxygen in solution.Then under electric stirring, 100mL is added dropwise and contains
0.400g Fe2(SO4)3With 2.224g FeSO4·7H2O mixed solution, the maintenance reaction at 75 DEG C of temperature and logical condition of nitrogen gas
1h.After completion of the reaction, under externally-applied magnetic field, precipitated using decantation (5-6 times) gained of second distillation water washing, washing finishes
12h is dried in vacuo at a temperature of 60 DEG C afterwards, finally taking-up desciccate is finely ground in mortar, weighs product quality and simultaneously loads weighing
It is standby in bottle.
Embodiment 3：Magnetic Fe3O4/CeO2The preparation of nano-complex catalyst
100mL 0.2M NaOH are added in three-necked flask first, add 0.116g nano Ces O2, heating water bath to 85
Nitrogen 3min is passed through after DEG C, in mixed liquor to remove the oxygen in solution.Then under electric stirring, 100mL is added dropwise and contains
0.400g Fe2(SO4)3With 2.224g FeSO4·7H2O mixed solution, the maintenance reaction at 85 DEG C of temperature and logical condition of nitrogen gas
1h.After completion of the reaction, under externally-applied magnetic field, precipitated using decantation (5-6 times) gained of second distillation water washing, washing finishes
12h is dried in vacuo at a temperature of 60 DEG C afterwards, finally taking-up desciccate is finely ground in mortar, weighs product quality and simultaneously loads weighing
It is standby in bottle.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, in the case of without departing from the method and scope of the present invention, embodiments of the present invention can be made with various changes, replaced
Change and change.
Claims (10)
1. a kind of magnetic type Fenton catalyst, it is characterised in that the catalyst is by being coated on magnetic ferroferric oxide nanometer
Nano ceric oxide compound composition on grain.
2. the preparation method of catalyst according to claim 1, it is characterised in that the preparation method is as follows：First will
Certain volume 0.2M NaOH solutions are added in three-necked flask, add a certain amount of nano Ce O2, heating water bath is to 75-85 DEG C
Afterwards, nitrogen 3min is passed through in mixed liquor to remove the oxygen in solution, then under electric stirring, a certain amount of contain is added dropwise
Fe2(SO4)3And FeSO4·7H2O mixed solution, the maintenance reaction 1h at 75-85 DEG C of temperature and logical condition of nitrogen gas, reaction finish
Afterwards, under externally-applied magnetic field, precipitation 5-6 times obtained by second distillation water washing using decantation, after washing at a temperature of 60 DEG C
12h is dried in vacuo, it is finely ground in mortar to then take out desciccate, produces.
3. the preparation method of catalyst according to claim 2, it is characterised in that the preparation method is as follows：First will
Certain volume 0.2M NaOH are added in three-necked flask, add a certain amount of nano Ce O2, heating water bath is to after 80 DEG C, mixing
Nitrogen 3min is passed through in liquid to remove the oxygen in solution, then under electric stirring, is added dropwise and a certain amount of contains Fe2(SO4)3
And FeSO4·7H2O mixed solution, the maintenance reaction 1h at 80 DEG C of temperature and logical condition of nitrogen gas, after completion of the reaction, externally-applied magnetic field
Under, using decantation, precipitation 5-6 times obtained by second distillation water washing, 12h is dried in vacuo after washing at a temperature of 60 DEG C,
It is finely ground in mortar to then take out desciccate, produces.
4. the preparation method of the catalyst according to claim any one of 2-3, it is characterised in that the Fe2(SO4)3With
FeSO4·7H2In O mixed solution, Fe3+And Fe2+The ratio between the amount of material be 1:4.
5. the preparation method of the catalyst according to claim any one of 2-3, it is characterised in that the Fe2(SO4)3With
CeO2Mass ratio be 1.8-3.4:1.
6. the preparation method of the catalyst according to claim any one of 2-3, it is characterised in that the Fe2(SO4)3With
CeO2Mass ratio be 2.6:1.
7. the preparation method of the catalyst according to claim any one of 2-3, it is characterised in that the NaOH solution adds
Enter amount to make to prepare the control of compound reaction system solution ph in the range of 12-13.
8. application of the catalyst according to claim 1 in degradation of methylene blue dyestuff, it is characterised in that the catalysis
Agent is the application in the catalyst degradation methylene blue dye as class Fenton's reaction.
9. application according to claim 8, it is characterised in that the catalyst is the catalyst drop as class Fenton's reaction
The method for solving methylene blue dye is as follows：Methylene blue dye solution is taken, adds the catalyst and hydrogen peroxide of preparation thereto,
The oscillating reactions in 25 DEG C of thermostatic control oscillator vibration, methylene blue dye is set to react degradation and decolorization, after reaction terminates, using outer
Add magnetic field to carry out separation of solid and liquid, the concentration of dyestuff after the measure degraded of supernatant ultraviolet-uisible spectrophotometer is taken, according to degraded
Front and rear dye strength change calculates the degradation rate of dyestuff.
10. application according to claim 8, it is characterised in that the catalyst is the catalyst as class Fenton's reaction
The method of degradation of methylene blue dyestuff is as follows：Methylene blue dye solution is taken, dye solution pH is 4, initial concentration 10-
50mg/L, the hydrogen peroxide of the catalyst and 0.5-1.0g/L that are more than or equal to 0.25g/L preparations is added thereto, at 25 DEG C
Oscillating reactions 30min in thermostatic control oscillator vibration, methylene blue dye is set to react degradation and decolorization, after reaction terminates, utilization is additional
Magnetic field carries out separation of solid and liquid, the concentration of dyestuff after the measure degraded of supernatant ultraviolet-uisible spectrophotometer is taken, before degraded
Dyestuff change in concentration calculates the degradation rate of dyestuff afterwards.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108339515A (en) * | 2018-03-22 | 2018-07-31 | 上海应用技术大学 | A kind of preparation method convenient for recovery processing waste water from dyestuff material |
| CN109046373A (en) * | 2018-07-24 | 2018-12-21 | 成都信息工程大学 | Heterogeneous class Fenotn catalyst CeO capable of magnetic separating2The preparation method and application of/MZFS |
| CN109603836A (en) * | 2019-01-09 | 2019-04-12 | 广州桑尼环保科技有限公司 | A kind of recyclable magnetic powdery ozone catalyst and preparation method thereof |
| CN110759544A (en) * | 2019-12-02 | 2020-02-07 | 沈阳环境科学研究院 | Fenton-like catalytic degradation method for pesticide wastewater |
| CN111889126A (en) * | 2020-06-28 | 2020-11-06 | 南昌大学 | Preparation method and application of Fenton-like material with visible light response |
| US11065610B2 (en) | 2018-11-06 | 2021-07-20 | Nanjing University | Fenton-like catalytic material with dual reaction centers and preparation method thereof |
| CN114471716A (en) * | 2022-03-11 | 2022-05-13 | 北京师范大学珠海校区 | Preparation method, product and application of gradient-adjustable high-strength anti-deposition long-acting catalytic membrane |
| CN115176816A (en) * | 2022-08-30 | 2022-10-14 | 河北科技师范学院 | Fe 3 O 4 @CuO x Composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102327773A (en) * | 2011-06-13 | 2012-01-25 | 清华大学 | Preparation method of nano Fe3O4/CeO2 composite material and application thereof |
-
2017
- 2017-07-24 CN CN201710605062.9A patent/CN107469827A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102327773A (en) * | 2011-06-13 | 2012-01-25 | 清华大学 | Preparation method of nano Fe3O4/CeO2 composite material and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| KEYAN LI, ET AL.: "Magnetic ordered mesoporous Fe3O4/CeO2 composites with synergy of adsorption and Fenton catalysis", 《APPLIED SURFACE SCIENCE》 * |
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| CN108339515A (en) * | 2018-03-22 | 2018-07-31 | 上海应用技术大学 | A kind of preparation method convenient for recovery processing waste water from dyestuff material |
| CN109046373A (en) * | 2018-07-24 | 2018-12-21 | 成都信息工程大学 | Heterogeneous class Fenotn catalyst CeO capable of magnetic separating2The preparation method and application of/MZFS |
| CN109046373B (en) * | 2018-07-24 | 2021-02-05 | 成都信息工程大学 | Magnetically separable heterogeneous Fenton-like catalyst CeO2Preparation method and application of/MZFS |
| US11065610B2 (en) | 2018-11-06 | 2021-07-20 | Nanjing University | Fenton-like catalytic material with dual reaction centers and preparation method thereof |
| CN109603836A (en) * | 2019-01-09 | 2019-04-12 | 广州桑尼环保科技有限公司 | A kind of recyclable magnetic powdery ozone catalyst and preparation method thereof |
| CN110759544A (en) * | 2019-12-02 | 2020-02-07 | 沈阳环境科学研究院 | Fenton-like catalytic degradation method for pesticide wastewater |
| CN111889126A (en) * | 2020-06-28 | 2020-11-06 | 南昌大学 | Preparation method and application of Fenton-like material with visible light response |
| CN114471716A (en) * | 2022-03-11 | 2022-05-13 | 北京师范大学珠海校区 | Preparation method, product and application of gradient-adjustable high-strength anti-deposition long-acting catalytic membrane |
| US11746026B1 (en) | 2022-03-11 | 2023-09-05 | Beijing Normal University, Zhuhai | Preparation and application of gradient long-effective catalytic membrane with high-strength and anti-deposition property |
| CN115176816A (en) * | 2022-08-30 | 2022-10-14 | 河北科技师范学院 | Fe 3 O 4 @CuO x Composite material and preparation method and application thereof |
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