CN106040240A - Nanometer Cu0/Fe3O4 compound, method for preparing same and application of nanometer Cu0/Fe3O4 compound to treating organic wastewater by means of catalytically activating molecular oxygen - Google Patents
Nanometer Cu0/Fe3O4 compound, method for preparing same and application of nanometer Cu0/Fe3O4 compound to treating organic wastewater by means of catalytically activating molecular oxygen Download PDFInfo
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- CN106040240A CN106040240A CN201610361759.1A CN201610361759A CN106040240A CN 106040240 A CN106040240 A CN 106040240A CN 201610361759 A CN201610361759 A CN 201610361759A CN 106040240 A CN106040240 A CN 106040240A
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 title claims abstract description 23
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910001882 dioxygen Inorganic materials 0.000 title claims abstract description 8
- -1 Fe3O4 compound Chemical class 0.000 title abstract description 18
- 230000003213 activating effect Effects 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract 6
- 238000004140 cleaning Methods 0.000 claims abstract 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 10
- 229950000845 politef Drugs 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract 6
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 abstract 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003570 air Substances 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 29
- 238000006731 degradation reaction Methods 0.000 description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 27
- 239000010949 copper Substances 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- 239000004098 Tetracycline Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 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 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 235000019364 tetracycline Nutrition 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- 230000003197 catalytic effect 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
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000002975 chemoattractant Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/40—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- 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
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
Abstract
The invention relates to a nanometer Cu0/Fe3O4 compound, a method for preparing the same and application of the nanometer Cu0/Fe3O4 compound to treating organic wastewater by means of catalytically activating molecular oxygen. The method for preparing the nanometer Cu0/Fe3O4 compound includes (1), adding Cu(NO3)2 3H2O and Fe (NO3)3 9H2O into ethylene glycol according to a molar ratio of (0.05-20):1, dissolving the Cu(NO3)2 3H2O and the Fe (NO3)3 9H2O in the ethylene glycol and stirring the Cu(NO3)2 3H2O and the Fe (NO3)3 9H2O at the temperature of 25-60 DEG C for 30-120 min to obtain mixed liquid; (2), transferring the mixed liquid obtained at the step (1) into a polytetrafluoroethylene reaction kettle and keeping the mixed liquid in the polytetrafluoroethylene reaction kettle at the temperature of 150-200 DEG C for 12-96 h to obtain black precipitates; (3), separating the black precipitates obtained at the step (2) by the aid of centrifugal separation processes, and cleaning the black precipitates by the aid of deionized water until cleaning liquid is neutral so as to obtain the nanometer Cu0/Fe3O4 compound. The nanometer Cu0/Fe3O4 compound, the method and the application have the advantages that the nanometer Cu0/Fe3O4 compound is used as a catalyst, air or oxygen is used as an oxidizing agent, the oxygen is activated to generate active oxygen such as H2O2 and hydroxyl radicals, organic pollutants in water can be degraded, and the nanometer Cu0/Fe3O4 compound and the method are high in efficiency, wide in pH (potential of hydrogen) application range (pH ranges from 3 to 11) and easy to implement and are environmentally friendly; processes for preparing nanometer Cu0/Fe3O4 compound which is the catalyst are simple, the nanometer Cu0/Fe3O4 compound and the method are low in cost, the nanometer Cu0/Fe3O4 compound is magnetic and can be recycled by the aid of magnets, and the like.
Description
Technical field
The present invention relates to the interdisciplinary field of the subjects such as material, chemistry and environment, specifically disclose a kind of nano zero-valence
Copper/ferroferric oxide (Cu0/Fe3O4) complex catalysts anakmetomeres oxygen process organic wastewater method.
Technical background
Fenton reacts (Fe2+And H2O2) as the most commonly used a kind of high-level oxidation technology, generation Strong oxdiative can be catalyzed
The hydroxyl radical free radical (OH) of property, it is adaptable to the process of the multiple persistent organic pollutants such as dye class, phenols, antibiotic.But
Fenton reaction be typically only applicable to pH less than 3 acid system, and major part waste water pH between 6-9, therefore with
Before Fenton reaction treatment Organic substance, need waste water is acidified, thus add processing cost.Meanwhile, Fenton reaction
Generally with H2O2For the source of strong oxidizing property free radical, there is shortcoming expensive, that poor stability, utilization rate are low in it.And molecule
Oxygen is as a kind of Green Oxidant, and wide material sources, easy to use, price is inexpensive, can greatly reduce cost of water treatment.But,
Molecular oxygen oxidation is limited in one's ability, it is impossible to directly degradable organic pollutant.Accordingly, it would be desirable to use catalyst to make it activate, to produce
The free radical that oxidability is higher, such as hydroxy radical, ability degradable organic pollutant.
At present, existing document and patent report Zero-valent Iron (Fe0) and zerovalent copper (Cu0) can anakmetomeres oxygen oxidative degradation dirt
Dye thing.Such as, Christina E.Noradoun and I.Francis Cheng report Zero-valent Iron can activate oxygen in water product
Raw hydroxy radical, oxidative degradation ethylenediaminetetraacetic acid (Keenan Christina R, Sedlak David L,
Environ.Sci.Technol.,2008,42(18),6936–6941).The report zerovalent copper such as Dong can be to dissolve in activated water
Oxygen generation hydrogen peroxide and hydroxy radical, oxidative degradation azo dye (Dong Guohui, Ai Zhihui, Zhang Lizhi,
water research66(2014)22-30).CN 102173500A discloses entitled " the Fenton oxygen of a kind of anakmetomeres oxygen
Water chemical treatment method " patent of invention, the method use transition metal ions, transition metal, transition metal oxide as work
Chemoattractant molecule VPO catalysts generation hydroxyl radical free radical, thus the Organic substance in oxidation removal waste water.But these catalysts activate
Molecular oxygen is easily affected by factors such as pH, dissolved oxygen concentration, catalyst amount, water body coexisting substances, there is activation of catalyst effect
The problem that rate is the highest.
In order to construct efficient catalytic oxidation system, the part such as EDTA, citric acid and sodium polyphosphate is introduced into zeroth order
Ironwork O2System, improves the generation amount of hydroxy radical.But the introducing of part may bring secondary pollution.
Summary of the invention
The present invention is directed to catalyst activity during existing RAPD check catalyst uses the highest, the most at acidic
Effective problem, it is provided that a kind of preparation process is simple, cheaper starting materials is easy to get, it is active high-effect to be catalyzed, pH applied range, easily returns
Zeroth order copper/ferroferric oxide (the Cu received0/Fe3O4) complex catalyst, this catalyst can be under conditions of room temperature, pH3～11
Anakmetomeres oxygen efficiently, fast degradation and mineralising Some Organic Pollutants.Therefore, Cu0/Fe3O4Catalyst and O2The class constituted
Fenton catalyst system and catalyzing is widely used value in waste water control industry.
The technical scheme is that
Nanometer Cu0/Fe3O4Complex, it is characterised in that described nanometer Cu0/Fe3O4Complex is prepared according to the following steps:
(1) by Cu (NO3)2·3H2O Yu Fe (NO3)3·9H2O is (0.05～20) in molar ratio: the ratio of 1, adds second
In glycol dissolve, temperature be 25～60 DEG C stirring under 30～120min；
(2) mixed liquor that step (1) obtains is transferred in politef reactor, at 150～200 DEG C, keep 12
～96h obtains black precipitate；
(3) black precipitate obtained by centrifugal separation separating step (2), cleans black precipitate with deionized water, extremely
Cleanout fluid is neutral, prepares nanometer Cu0/Fe3O4Complex.
A kind of nanometer Cu0/Fe3O4The preparation method of complex, it is characterised in that sequentially include the following steps:
(1) by Cu (NO3)2·3H2O Yu Fe (NO3)3·9H2O is (0.05～20) in molar ratio: the ratio of 1, adds second
Glycol dissolves, at temperature is 25～60 DEG C, stirs 30～120min；
(2) mixed liquor that step (1) obtains is transferred in politef reactor, at 150～200 DEG C, keep 12
～96h obtains black precipitate；
(3) black precipitate obtained by centrifugal separation separating step (2), cleans black precipitate with deionized water, extremely
Cleanout fluid is neutral, prepares nanometer Cu0/Fe3O4Complex.
In described step (2), reaction temperature is preferably 160～200 DEG C, and described reaction temperature is more preferably 180 DEG C；
Nanometer Cu0/Fe3O4Complex catalysts anakmetomeres oxygen processes the method for organic wastewater, it is characterised in that: organic
Waste water adds a certain amount of Cu0/Fe3O4Complex is as catalyst, under conditions of being passed through air or oxygen, lives under room temperature
Chemoattractant molecule oxygen, produces H2O2And/or hydroxy radical active oxygen, the organic pollution in water is degraded.
Described organic wastewater concentration is 1.0～50mg/L.
Described Cu0/Fe3O4Catalyst concn is 0.2～1g/L.
It is 0.5～3.0mg/L that described molecular oxygen is dissolved in concentration in waste water.
Cu0/Fe3O4Complex passes through Cu0And Fe3O4Compound, to improve its catalytic activation oxygen generation H2O2, hydroxy radical
Isoreactivity oxygen and oxidative degradation Organic substance performance.Cu0And Fe3O4Fe in lattice2+H can be produced with oxygen reaction2O2；Cu0And it is anti-
Answer the Cu that process produces+, Fe can be effectively facilitated3+/Fe2+Circulation, regenerate Fe3O4；Fe3O4Fe in crystal2+Can be with product in situ
Raw H2O2Hydroxyl radical free radical is produced, with the organic pollution in degradation water by Fenton's reaction.
The advantage of the present invention mainly has:
(1) utilize molecular oxygen as oxidant, it is not necessary to additional hydrogen peroxide, there are with low cost, environmental friendliness, wide material sources
Etc. advantage；
(2) reaction condition is gentle, organic contamination efficiently, in fast degradation water in wider pH scope (pH 3～11)
Thing, non-secondary pollution；
(3) Cu is passed through0And Fe3O4Synergism, improves H2O2With the yield of hydroxy radical, strengthen organic fall
Solve；
(4) catalyst has magnetic, it is easy to reclaims, repeatable utilization, has bigger application prospect.
Accompanying drawing explanation
Fig. 1 Cu0/Fe3O4The XRD figure spectrum of nano-particle.
Fig. 2 Cu0/Fe3O4The scanning electron microscope (SEM) photograph of nano-particle.
Fig. 3 Cu0/Fe3O4The ultraviolet-visible light spectrogram of nanoparticulate activated dissolved oxygen degraded rhodamine.
Detailed description of the invention
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further explained, but the present invention wants
Asking, the scope of protection is not limited to that.
Embodiment 1
By Cu (NO3)2·3H2O Yu Fe (NO3)3·9H2O mol ratio is the ratio of 1:3, weighs 5mmol Cu respectively
(NO3)2·3H2O and 15mmol Fe (NO3)3·9H2O, is dissolved in 55mL ethylene glycol, stirs 120min at temperature is 25 DEG C；
The mixed liquor obtained is transferred in the politef reactor that capacity is 100ml at 180 DEG C, react 24h, obtain black
Precipitation；Separated by centrifugal separation, clean the black precipitate obtained with deionized water, be neutral to cleanout fluid, be nanometer
Cu0/Fe3O4Complex (Cu0/ Fe mol ratio content is 1:3).Confirmed that by XRD and SEM the catalyst of preparation is strictly received
Rice Cu0/Fe3O4Complex, as it is shown in figure 1, particle diameter is about 50-70nm, as shown in Figure 2.
Embodiment 2
It is 5mg L in 50mL concentration-1Rhodamine B aqueous solution in add HNO3Or NaOH regulation pH value is 7.0, and it is passed through
Air, making water Middle molecule oxygen concentration is 2.0mg/L, adds the Cu that 50mg embodiment 1 prepares0/Fe3O4Composite catalyst (Cu0/Fe
Mol ratio content is 1:3), mechanical agitation under room temperature.After 40min, rhodamine B degradation rate is 99%, as it is shown on figure 3, the most organic
Carbon amounts (TOC) have dropped 55%.
Under same experimental conditions, it is 5mg L in two glasss of 50mL concentration-1Rhodamine B in be separately added into 50mg
Cu0With 50mg Fe3O4Catalyst, after reaction 40min, Cu0Catalyst is 25% to rhodamine B degradation rate, Fe3O4Catalyst pair
Rhodamine B degradation rate is 33%, Cu0Catalyst correspondence total organic carbon amount (TOC) have dropped 6%, Fe3O4Catalyst correspondence always has
Machine carbon amounts (TOC) have dropped 14%.
Embodiment 3
By Cu (NO3)2·3H2O Yu Fe (NO3)3·9H2O mol ratio is the ratio of 1:7, weighs 2.5mmol Cu respectively
(NO3)2·3H2O and 17.5mmol Fe (NO3)3·9H2O, is dissolved in 55mL ethylene glycol, stirs 30min at temperature is 60 DEG C；
The mixed liquor obtained is transferred in the politef reactor that capacity is 100ml at 150 DEG C, react 96h, obtain black
Precipitation；Separated by centrifugal separation, clean the black precipitate obtained with deionized water, be neutral to cleanout fluid, be nanometer
Cu0/Fe3O4Complex (Cu0/ Fe mol ratio content is 1:7).
Embodiment 4
It is 2mg L in 50mL concentration-1Rhodamine B aqueous solution in add HNO3Or NaOH regulation pH value is 10.0, and lead to
Entering air, making water Middle molecule oxygen concentration is 3.0mg/L, adds the Cu that 50mg embodiment 3 prepares0/Fe3O4Composite catalyst (Cu0/
Fe mol ratio content is 1:7), mechanical agitation under room temperature.After 60min, rhodamine B degradation rate is 91%, total organic carbon amount (TOC)
Have dropped 42%.
Under same experimental conditions, it is 2mg L in two glasss of 50mL concentration-1Rhodamine B in be separately added into 50mg
Cu0With 50mg Fe3O4Catalyst, after reaction 60min, Cu0Catalyst is 13% to rhodamine B degradation rate, Fe3O4Catalyst pair
Rhodamine B degradation rate is 24%, Cu0Catalyst correspondence total organic carbon amount (TOC) have dropped 4%, Fe3O4Catalyst correspondence always has
Machine carbon amounts (TOC) have dropped 9%.
Embodiment 5
By Cu (NO3)2·3H2O Yu Fe (NO3)3·9H2O mol ratio is the ratio of 7:1, weighs 17.5mmol Cu respectively
(NO3)2·3H2O and 2.5mmol Fe (NO3)3·9H2O, is dissolved in 55mL ethylene glycol, stirs 50min at temperature is 40 DEG C；
The mixed liquor obtained is transferred in the politef reactor that capacity is 100ml at 200 DEG C, react 12h, obtain black
Precipitation；Separated by centrifugal separation, clean the black precipitate obtained with deionized water, be neutral to cleanout fluid, be nanometer
Cu0/Fe3O4Complex (Cu0/ Fe mol ratio content is 7:1).
Embodiment 6
It is 5mg L in 50mL concentration-1Rhodamine B aqueous solution in add HNO3Or NaOH regulation pH value is 3.0, and it is passed through
Air, making water Middle molecule oxygen concentration is 1.0mg/L, adds the Cu that 50mg embodiment 5 prepares0/Fe3O4Composite catalyst (Cu0/Fe
Mol ratio content is 7:1), mechanical agitation under room temperature.After 30min, rhodamine B degradation rate is 100%, total organic carbon amount (TOC)
Have dropped 67%.
Under same experimental conditions, it is 5mg L in two glasss of 50mL concentration-1Rhodamine B in be separately added into 50mg
Cu0With 50mg Fe3O4Catalyst, after reaction 30min, Cu0Catalyst is 35% to rhodamine B degradation rate, Fe3O4Catalyst pair
Rhodamine B degradation rate is 57%, Cu0Catalyst correspondence total organic carbon amount (TOC) have dropped 24%, Fe3O4Catalyst correspondence always has
Machine carbon amounts (TOC) have dropped 37%.
Embodiment 7
It is 20mg L in 50mL concentration-1Phenol solution in add HNO3Or NaOH regulation pH value is 7.0, and it is passed through sky
Gas, making water Middle molecule oxygen concentration is 2.0mg/L, adds the Cu that 50mg embodiment 1 prepares0/Fe3O4Composite catalyst (Cu0/ Fe rubs
You are 1:3 than content), mechanical agitation under room temperature.After 60min, the degradation rate of phenol is 95%, and total organic carbon amount (TOC) declines
35%.
Under same experimental conditions, it is 20mg L in two glasss of 50mL concentration-1Phenolic waste water is separately added into 50mg Cu0With
Fe3O4Catalyst, after reaction 60min, Cu0The degradation rate of catalyst Pyrogentisinic Acid is 11%, Fe3O4The degradation rate of catalyst Pyrogentisinic Acid
It is 20%.Cu0Catalyst correspondence total organic carbon amount (TOC) have dropped 5%, Fe3O4Under catalyst correspondence total organic carbon amount (TOC)
Drop 11%.
Embodiment 8
It is 20mg L in 50mL concentration-14-chlorophenol aqueous solution in add HNO3Or NaOH regulation pH value is 7.0, and it is passed through
Air, making water Middle molecule oxygen concentration is 3.0mg/L, adds 50mg embodiment 1 and prepares Cu0/Fe3O4Composite catalyst (Cu0/ Fe rubs
You are 1:3 than content), mechanical agitation under room temperature.After 60min, the degradation rate of 4-chlorophenol is 98%, under total organic carbon amount (TOC)
Drop 44%.
Under same experimental conditions, it is 20mg L in two glasss of 50mL concentration-14-Chlorophenol in be separately added into 50mg
Cu0And Fe3O4Catalyst, after reaction 60min, Cu0Catalyst is 15% to the degradation rate of 4-chlorophenol, Fe3O4Catalyst is to 4-chlorine
The degradation rate of phenol is 28%.Cu0Catalyst correspondence total organic carbon amount (TOC) have dropped 7%, Fe3O4Catalyst correspondence total organic carbon
Amount (TOC) have dropped 16%.
Embodiment 9
It is 10mg L in 50mL concentration-1Tetracycline aqueous solution in add HNO3Or NaOH regulation pH value is 5.0, and it is passed through
Air, making water Middle molecule oxygen concentration is 2.0mg/L, adds the Cu that 50mg embodiment 3 prepares0/Fe3O4Composite catalyst (Cu0/Fe
Mol ratio content is 1:7), mechanical agitation under room temperature.After 60min, the degradation rate of tetracycline is 93%, total organic carbon amount (TOC)
Have dropped 32%.
Under same experimental conditions, it is 10mg L in two glasss of 50mL concentration-1Tetracycline wastewater in be separately added into 50mg
Cu0And Fe3O4Catalyst, after reaction 60min, Cu0Catalyst is 12% to the degradation rate of tetracycline, Fe3O4Catalyst is to Fourth Ring
The degradation rate of element is 23%.Cu0Catalyst correspondence total organic carbon amount (TOC) have dropped 6%, Fe3O4Catalyst correspondence total organic carbon
Amount (TOC) have dropped 13%.
Embodiment 10
It is 20mg L in 50mL concentration-1Bisphenol-A aqueous solution in add HNO3Or NaOH regulation pH value is 6.0, and it is passed through
Air, making water Middle molecule oxygen concentration is 2.0mg/L, adds the Cu that 50mg embodiment 3 prepares0/Fe3O4Composite catalyst (Cu0/Fe
Mol ratio content is 1:7), mechanical agitation under room temperature.After 60min, the degradation rate of bisphenol-A is 96%, under total organic carbon amount (TOC)
Drop 35%.
Under same experimental conditions, it is 20mg L in two glasss of 50mL concentration-1Bisphenol-A waste water in be separately added into 50mg Cu0
And Fe3O4Catalyst, after reaction 60min, Cu0Catalyst is 18% to the degradation rate of bisphenol-A, Fe3O4The catalyst fall to bisphenol-A
Solution rate is 27%.Cu0Catalyst correspondence total organic carbon amount (TOC) have dropped 9%, Fe3O4Catalyst correspondence total organic carbon amount
(TOC) have dropped 12%.
Embodiment 11
It is 5mg L in 50mL concentration-1Phenol solution in add HNO3Or NaOH regulation pH value is 11.0, and it is passed through sky
Gas, making water Middle molecule oxygen concentration is 0.5mg/L, adds the Cu that 10mg embodiment 1 prepares0/Fe3O4Composite catalyst (Cu0/ Fe rubs
You are 1:3 than content), magnetic agitation under room temperature.After 60min, the degradation rate of phenol is 92%, and total organic carbon amount (TOC) declines
33%.
Under same experimental conditions, it is 5mg L in two glasss of 50mL concentration-1Phenolic waste water is separately added into 10mg Cu0With
Fe3O4Catalyst, after reaction 60min, Cu0The degradation rate of catalyst Pyrogentisinic Acid is 9%, Fe3O4The degradation rate of catalyst Pyrogentisinic Acid
It is 18%.Cu0Catalyst correspondence total organic carbon amount (TOC) have dropped 4%, Fe3O4Under catalyst correspondence total organic carbon amount (TOC)
Drop 10%.
Embodiment 12
It is 10mg L in 50mL concentration-1Tetracycline aqueous solution in add HNO3Or NaOH regulation pH value is 5.0, and it is passed through
Air, making water Middle molecule oxygen concentration is 1.0mg/L, adds the Cu that 30mg embodiment 1 prepares0/Fe3O4Composite catalyst (Cu0/Fe
Mol ratio content is 1:3), magnetic agitation under room temperature.After 60min, the degradation rate of tetracycline is 93%, total organic carbon amount (TOC)
Have dropped 32%.
Under same experimental conditions, it is 10mg L in two glasss of 50mL concentration-1Tetracycline wastewater in be separately added into 30mg
Cu0And Fe3O4Catalyst, after reaction 60min, Cu0Catalyst is 10% to the degradation rate of tetracycline, Fe3O4Catalyst is to Fourth Ring
The degradation rate of element is 21%.Cu0Catalyst correspondence total organic carbon amount (TOC) have dropped 5%, Fe3O4Catalyst correspondence total organic carbon
Amount (TOC) have dropped 12%.
Claims (8)
1. nanometer Cu0/Fe3O4Complex, it is characterised in that described nanometer Cu0/Fe3O4Complex is prepared according to the following steps:
(1) by Cu (NO3)2·3H2O Yu Fe (NO3)3·9H2O is (0.05～20) in molar ratio: the ratio of 1, adds ethylene glycol
Middle dissolving, stirs 30～120min at temperature is 25～60 DEG C；
(2) mixed liquor that step (1) obtains is transferred in politef reactor, at 150～200 DEG C keep 12～
96h obtains black precipitate；
(3) black precipitate obtained by centrifugal separation separating step (2), cleans black precipitate with deionized water, to cleaning
Liquid is neutral, prepares nanometer Cu0/Fe3O4Complex.
2. nanometer Cu0/Fe3O4The preparation method of complex, it is characterised in that sequentially include the following steps:
(1) by Cu (NO3)2·3H2O Yu Fe (NO3)3·9H2O is (0.05～20) in molar ratio: the ratio of 1, adds ethylene glycol
Middle dissolving, stirs 30～120min at temperature is 25～60 DEG C；
(2) mixed liquor that step (1) obtains is transferred in politef reactor, at 150～200 DEG C keep 12～
96h obtains black precipitate；
(3) black precipitate obtained by centrifugal separation separating step (2), cleans black precipitate with deionized water, to cleaning
Liquid is neutral, prepares nanometer Cu0/Fe3O4Complex.
Nanometer Cu the most according to claim 20/Fe3O4The preparation method of complex, it is characterised in that: described step (2)
Middle reaction temperature is preferably 160～200 DEG C.
Nanometer Cu the most according to claim 30/Fe3O4The preparation method of complex, it is characterised in that: described reaction temperature
It is preferably 180 DEG C.
5. utilize nanometer Cu described in claim 10/Fe3O4Complex catalysts anakmetomeres oxygen processes the method for organic wastewater,
It is characterized in that: in organic wastewater, add a certain amount of Cu0/Fe3O4Complex, as catalyst, is being passed through air or oxygen
Under conditions of, anakmetomeres oxygen under room temperature, produce H2O2And/or hydroxy radical active oxygen, the organic pollution in water is dropped
Solve.
Nanometer Cu the most according to claim 50/Fe3O4Complex catalysts anakmetomeres oxygen processes the method for organic wastewater,
It is characterized in that: described organic wastewater concentration is 1.0～50mg/L.
Nanometer Cu the most according to claim 50/Fe3O4Complex catalysts anakmetomeres oxygen processes the method for organic wastewater,
It is characterized in that: Cu0/Fe3O4Catalyst concn is 0.2～1g/L.
Nanometer Cu the most according to claim 50/Fe3O4Complex catalysts anakmetomeres oxygen processes the method for organic wastewater,
It is characterized in that: it is 0.5～3.0mg/L that molecular oxygen is dissolved in concentration in waste water.
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| CN110205095A (en) * | 2019-06-10 | 2019-09-06 | 南京航空航天大学 | One kind being directed to the efficient wave absorbing agent and preparation method thereof of 2 ~ 18GHz frequency range |
| CN112473746A (en) * | 2020-12-08 | 2021-03-12 | 东华大学 | Cu0Preparation method and application of (E) -ferroferric oxide @ chitosan nano material |
| CN114908598A (en) * | 2022-02-26 | 2022-08-16 | 北京林业大学 | Oxygen bleaching method for paper pulp |
| CN115072856A (en) * | 2022-04-27 | 2022-09-20 | 赣南医学院 | Application of copper-iron-oxygen nanoenzyme in removing colored printing and dyeing dye and kit for removing printing and dyeing dye |
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| CN109806868A (en) * | 2018-07-02 | 2019-05-28 | 陈天仪 | A kind of organic wastewater degraded agent of recyclable recycling |
| CN109806868B (en) * | 2018-07-02 | 2021-10-26 | 陈天仪 | Recyclable and reusable organic wastewater degrading agent |
| CN110205095A (en) * | 2019-06-10 | 2019-09-06 | 南京航空航天大学 | One kind being directed to the efficient wave absorbing agent and preparation method thereof of 2 ~ 18GHz frequency range |
| CN110205095B (en) * | 2019-06-10 | 2020-10-16 | 南京航空航天大学 | Efficient wave absorbing agent for 2-18 GHz frequency band and preparation method thereof |
| CN112473746A (en) * | 2020-12-08 | 2021-03-12 | 东华大学 | Cu0Preparation method and application of (E) -ferroferric oxide @ chitosan nano material |
| CN112473746B (en) * | 2020-12-08 | 2022-03-04 | 东华大学 | Cu0Preparation method and application of (E) -ferroferric oxide @ chitosan nano material |
| CN114908598A (en) * | 2022-02-26 | 2022-08-16 | 北京林业大学 | Oxygen bleaching method for paper pulp |
| CN114908598B (en) * | 2022-02-26 | 2022-12-09 | 北京林业大学 | Oxygen bleaching method for paper pulp |
| CN115072856A (en) * | 2022-04-27 | 2022-09-20 | 赣南医学院 | Application of copper-iron-oxygen nanoenzyme in removing colored printing and dyeing dye and kit for removing printing and dyeing dye |
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