CN102863070A - Ozonization water treatment method with NiFe2O4 magnetic nanometer material as catalyst - Google Patents
Ozonization water treatment method with NiFe2O4 magnetic nanometer material as catalyst Download PDFInfo
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- CN102863070A CN102863070A CN2012103841141A CN201210384114A CN102863070A CN 102863070 A CN102863070 A CN 102863070A CN 2012103841141 A CN2012103841141 A CN 2012103841141A CN 201210384114 A CN201210384114 A CN 201210384114A CN 102863070 A CN102863070 A CN 102863070A
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Abstract
Provided is an ozonization water treatment method with a NiFe2O4 magnetic nanometer material as a catalyst. The NiFe2O4 magnetic nanometer material is prepared through a hydrothermal method and used as the catalyst to be added in an ozonization water treatment system containing phenol waste water, degrading of phenol organic pollutant is promoted, and a novel ozonization water treatment method is provided. The method belongs to the technical field of water treatment and environment catalysis. The scale of the NiFe2O4 magnetic nanometer material is small, dispersibility of the NiFe2O4 magnetic nanometer material in a water solution is good, and the NiFe2O4 magnetic nanometer material can be separated and recycled by using an external magnetic field effectively and has wide prospects in ozonization water treatment application.
Description
Technical field
The present invention proposes a kind of with NiFe
2O
4Magnetic Nano material belongs to environmental catalysis and water treatment field as the ozonization water treatment method of catalyzer.
Background technology
Current, along with the fast development of industrial or agricultural, the trade effluent and the agricultural effluent quantity discharged that contain organic pollutant are increasing.Wherein large, the difficulty of many organic pollutant toxicity is biodegradable, and ecotope and human health have been caused serious threat, and therefore the effective processing for such organic waste water causes people's extensive concern.Ozone molecule has stronger oxidation capacity (En=2.07V), and ozonation carries out at normal temperatures and pressures, and mild condition, easy and simple to handle is thorough to organic pollutant removal, thereby has broad application prospects in water treatment.But the organic pollutant take aromatics and condensed ring compounds as representative has very high stability, and ozone degradation efficient is lower separately, and catalytic ozonation then is to utilize catalyzer to strengthen at normal temperatures and pressures a kind of advanced oxidation process of ozone oxidation.Studies show that the hydroxyl radical free radical that produces in the catalytic reaction process is very active, oxidizing potential is up to 2.33V, and the most stable of degrading is high, toxicity is large and the organic pollutant of difficult degradation.Therefore, the research of Catalytic Ozonation organic pollutants comes into one's own day by day.
Catalytic ozonation can be divided into homogeneous catalysis and heterogeneous catalyst.Multi-phase catalytic ozonation reacts at normal temperatures and pressures, and is easy to operate, oxidation capacity is strong, has a extensive future in treatment of Organic Wastewater.In recent years, along with the research of nano material and nanotechnology deepens continuously, the nano material technology of preparing is ripe day by day, and nano material has caused people's extensive concern in the research of catalytic field.
Magnetic nano-catalyst, yardstick is little on the one hand, specific surface large, good dispersity, is conducive to improve catalytic ozonation efficient.According to exterior magnetic field, can make things convenient on the other hand, be isolated rapidly, reclaim, recycle, overcome the difficult shortcoming that reclaims of non magnetic nanocatalyst.The use of magnetic nano-catalyst, improve catalyzer service efficiency, avoid catalyzer that water quality is polluted, reduces cost of sewage disposal.Therefore developing efficient magnetic nano-catalyst, is a kind of effective ways that advance the catalytic ozonation industrial applications.
Summary of the invention
The object of the present invention is to provide a kind of ozonization water treatment method of magnetic nano-catalyst, reduce water and pollute, improve the using value of catalytic ozonation.Purpose of the present invention can be achieved through the following technical solutions:
(1) NiFe
2O
4The preparation of magnetic Nano material: with Ni (NO
3)
26H
2O and Fe (NO
3)
39H
2O is dissolved in the water, wherein Fe: Ni=2: 1 (mol ratio).Adding volumetric molar concentration is the 4.4mol/L sodium hydroxide solution, transfers in the reactor behind the vigorous stirring number minute simultaneously, keeps 24h at 180 ℃ of lower seals, after finishing, reaction naturally cools to room temperature, the deionized water wash gained is precipitated to neutrality, and drying products obtains NiFe
2O
4Nano material.
(2) ozonization water treatment: with the NiFe that obtains
2O
4Nano material joins in the ozonization water treatment system as catalyzer, passes into ozone, stirs the degraded organic pollutants.
(3) the ozonize effect of different catalysts amount: by comparing the consumption of catalyzer, the mass ratio of discovery catalyzer and the waste water of processing has significant catalyzed degradation effect when being 0.00025-0.002.Catalytic amount is more, and the organic matter degradation effect is unreasonable to be thought.
(4) NiFe
2O
4Nano material magnetic separability: with the NiFe of mass concentration 1.0 g/L
2O
4The aqueous solution is dispersed in the reagent bottle, and magnet is placed the reagent bottle wall, after very short for some time, and NiFe
2O
4Nano material is inhaled well on the reagent bottle wall, obtains a settled solution.
Beneficial effect of the present invention: the method by hydro-thermal synthesizes NiFe
2O
4Magnetic Nano material, with it as the ozonize catalyzer, more independent ozonize, catalytic ozonation makes in the sewage degradation rate of organic pollutant accelerate to some extent, mineralization degree increases.In addition NiFe
2O
4Nano material has magnetic, and reaction finishes, and can effectively be isolated by external magnetic field, has overcome the difficult shortcoming of separating of non magnetic nanocatalyst, is convenient to recycling.Compare with existing ozonization water treatment catalyzer, the present invention has outstanding feature:
(1) NiFe
2O
4The preparation method simple to operate, raw material is easy to get, the building-up process cycle is short, nontoxic pollution-free.
(2) nano-Ni/Fe
2O
4Particle has good dispersiveness in water, be conducive to improve and the contacting of ozone, water pollutant.Therefore in use, less input amount can obtain preferably catalytic effect.
(3) NiFe
2O
4Nano material is very faint to the absorption property of phenol in the water, and its katalysis promotes the decomposition of ozone to produce hydroxyl radical free radical, and then improves degradation efficiency mainly from catalyst surface and ozonization.
(4) NiFe
2O
4Nano material has magnetic, can effectively be isolated by external magnetic field, is convenient to recycling.
Description of drawings
Fig. 1 is the TEM photo of embodiment 1 products obtained therefrom;
Fig. 2 is the XRD figure spectrum of embodiment 1 products obtained therefrom;
Fig. 3 is that phenol is with the concentration curve of ozonize time among the embodiment 1, and (1) line is independent ozonize (catalyst-free), and (2) line is NiFe in the example 1
2O
4The nano material catalytic ozonation;
Fig. 4 is that phenol is with the concentration curve of ozonize time among the embodiment 1, and (1) line is independent ozonize (catalyst-free), and (2) line is NiFe in the example 1
2O
4Nano material catalytic ozonation, (3) line are that the trimethyl carbinol exists NiFe in the lower example 1
2O
4Nano material;
Fig. 5 is that phenol is with the concentration curve of ozonize time under the different catalysts amount among the embodiment 1, and (1) line is independent ozonize (catalyst-free), and (2) line is NiFe in the example 1
2O
4Nano material (0.05g) catalytic ozonation, (3) line is NiFe in the example 1
2O
4Nano material (0.10g) catalytic ozonation, (4) line is NiFe in the example 1
2O
4Nano material (0.20g) catalytic ozonation, (5) line is NiFe in the example 1
2O
4Nano material (0.40g) catalytic ozonation.
Fig. 6 is that the magnetic of gained catalyzer among the embodiment 1 separates synoptic diagram.
Embodiment
For more specific description method of the present invention, the below provides embodiments of the invention, but application of the present invention is not limited to this.
Embodiment 1
Take by weighing 2.04g Ni (NO
3)
26H
2O and 5.66g Fe (NO
3)
39H
2O is dissolved in the 140ml distilled water, after solution mixes, adds 20ml, 4.4mol/L NaOH solution, vigorous stirring.Gained liquid is transferred in the polytetrafluoroethyllining lining reactor, and 180 ℃ of lower seals keep 24h; Naturally cool to room temperature after reaction is finished, the deionized water wash gained is precipitated to neutrality, and 80 ℃ of dryings obtain NiFe
2O
4Nano material.Its TEM photo is seen Fig. 1, and the XRD figure spectrum is seen Fig. 2.
Containing initial phenol concentration at 200ml is 300mg L
-1Simulated wastewater in, add NiFe
2O
4Nano material 0.20g starts stirring, passes into the ozone of ozone flow 0.75mg/min under 20 ℃ of temperature of reaction, the concentration of phenol under the record different time.The result respectively as shown in Figure 3.
(1) line is independent ozonize (catalyst-free) among Fig. 3, and (2) line is NiFe in the example 1
2O
4The nano material catalytic ozonation.Show in other identical situations NiFe
2O
4The adding of nano material has significantly promoted the degraded of phenol.
Embodiment 3
Containing initial phenol concentration at 200ml is 300mg L
-1Simulated wastewater in, add NiFe
2O
4Nano material 0.20g adds the trimethyl carbinol, and mass concentration is 10g/L, stirs, and passes into the ozone of ozone flow 0.75mg/min under 20 ℃ of temperature of reaction, the concentration of phenol under the record different time.The result respectively as shown in Figure 4.
(1) line is independent ozonize (catalyst-free) among Fig. 4, and (2) line is NiFe in the example 1
2O
4Nano material catalytic ozonation, (3) line are that the trimethyl carbinol exists NiFe in the lower example 1
2O
4The nano material catalytic ozonation.Show that the adding of the trimethyl carbinol has obviously suppressed the degraded of phenol in the identical situation of other conditions.
Containing initial phenol concentration at 200ml is 300mg L
-1Simulated wastewater in, add different amount NiFe
2O
4Nano material is added respectively 0.05g, 0.10g, 0.20g and 0.40g, stirs, and passes into the ozone of ozone flow 0.75mg/min under 20 ℃ of temperature of reaction, the concentration of phenol under the record different time.The result respectively as shown in Figure 5.
(1) line is independent ozonize (catalyst-free) among Fig. 5, and (2) line is NiFe in the example 1
2O
4Nano material (0.05g) catalytic ozonation, (3) line is NiFe in the example 1
2O
4Nano material (0.10g) catalytic ozonation, (4) line is NiFe in the example 1
2O
4Nano material (0.20g) catalytic ozonation, (5) line is NiFe in the example 1
2O
4Nano material (0.40g) catalytic ozonation.Show that catalytic amount is more in other identical situations, the degradation effect of phenol is more remarkable.
Embodiment 5
With 10ml, the NiFe of 1g/L
2O
4The aqueous solution is as in the reagent bottle, ultra-sonic dispersion.One magnet as for by the reagent bottle, is determined the magnetic separation property of catalyzer.The result respectively as shown in Figure 6.
Fig. 6 has showed the process that catalyzer magnetic separates, and shows NiFe
2O
4Nano material has significant magnetic separation property.
Claims (2)
1. one kind with NiFe
2O
4Magnetic Nano material is characterized in that adding NiFe in the system of ozonization water treatment as the ozonization water treatment method of catalyzer
2O
4Magnetic Nano material promotes the degraded of phenol organic pollutant, based on NiFe as catalyzer
2O
4Magnetic, can efficient recovery NiFe
2O
4Nano material, step is:
(1) NiFe
2O
4The preparation of magnetic Nano material: with Ni (NO
3)
26H
2O and Fe (NO
3)
39H
2O is dissolved in the water, wherein Fe: Ni=2: 1 (mol ratio).Adding volumetric molar concentration is the 4.4mol/L sodium hydroxide solution, transfers in the reactor behind the vigorous stirring number minute simultaneously, keeps 24h at 180 ℃ of lower seals, after finishing, reaction naturally cools to room temperature, the deionized water wash gained is precipitated to neutrality, and drying products obtains NiFe
2O
4Nano material.
(2) ozonization water treatment: with the NiFe that obtains
2O
4Nano material joins in the ozonization water treatment system as catalyzer, passes into ozone, stirs the degraded organic pollutants.
(3) NiFe
2O
4Nano material magnetic separates: reaction finishes, and can effectively be isolated by external magnetic field, has overcome the difficult shortcoming of separating of non magnetic nanocatalyst, is convenient to recycling.
2. according to claim 1 with NiFe
2O
4Magnetic Nano material is as the ozonization water treatment method of catalyzer, and the mass ratio that it is characterized in that catalyzer and the waste water of processing has significant catalyzed degradation effect when being 0.00025-0.002.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288202A (en) * | 2013-06-27 | 2013-09-11 | 江南大学 | Ozonization water treatment method taking iron-nickel magnetic composite material as catalyst |
| CN103611539A (en) * | 2013-12-02 | 2014-03-05 | 江南大学 | Preparation method of magnetic calcium based solid base catalyst used for synthesizing biodiesel |
| CN104028281A (en) * | 2014-06-27 | 2014-09-10 | 北京林业大学 | Multiphase catalytic ozone oxidation depollution technology based on enhanced ozone adsorption and application thereof |
| CN105776498A (en) * | 2016-03-07 | 2016-07-20 | 浙江工业大学 | Method for removing anti-tumor medicine in water through catalytic ozonation of magnetic ordered mesopore nickel ferrite |
| CN106669727A (en) * | 2016-12-28 | 2017-05-17 | 华南理工大学 | Preparation method and application of sludge carbonization and modification magnetic nanometer material capable of activating persulfate to realize printing and dyeing wastewater treatment |
| CN108483517A (en) * | 2018-04-03 | 2018-09-04 | 山东大学 | A kind of ferrous acid nickel nano film and its preparation method and application |
| CN109046368A (en) * | 2018-07-02 | 2018-12-21 | 大唐（北京）水务工程技术有限公司 | A kind of coal chemical industrial waste water deep oxidation catalyst and preparation method thereof |
| CN110342725A (en) * | 2019-08-19 | 2019-10-18 | 中国十七冶集团有限公司 | A kind of emergency method for strengthening in-situ treatment black and odorous water |
| CN110479282A (en) * | 2019-08-13 | 2019-11-22 | 北京航空航天大学 | A kind of preparation method and application of the Ni substrate load ferrous acid nickel-nickel oxide composite catalyst of catalytic ozonation Organic substance in water |
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Cited By (13)
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| CN103288202A (en) * | 2013-06-27 | 2013-09-11 | 江南大学 | Ozonization water treatment method taking iron-nickel magnetic composite material as catalyst |
| CN103288202B (en) * | 2013-06-27 | 2015-04-22 | 江南大学 | Ozonization water treatment method taking iron-nickel magnetic composite material as catalyst |
| CN103611539A (en) * | 2013-12-02 | 2014-03-05 | 江南大学 | Preparation method of magnetic calcium based solid base catalyst used for synthesizing biodiesel |
| CN104028281A (en) * | 2014-06-27 | 2014-09-10 | 北京林业大学 | Multiphase catalytic ozone oxidation depollution technology based on enhanced ozone adsorption and application thereof |
| CN104028281B (en) * | 2014-06-27 | 2016-12-07 | 北京林业大学 | A kind of heterogeneous catalytic ozonation depollution technology based on strengthening ozone absorption and application thereof |
| CN105776498A (en) * | 2016-03-07 | 2016-07-20 | 浙江工业大学 | Method for removing anti-tumor medicine in water through catalytic ozonation of magnetic ordered mesopore nickel ferrite |
| CN106669727A (en) * | 2016-12-28 | 2017-05-17 | 华南理工大学 | Preparation method and application of sludge carbonization and modification magnetic nanometer material capable of activating persulfate to realize printing and dyeing wastewater treatment |
| CN108483517A (en) * | 2018-04-03 | 2018-09-04 | 山东大学 | A kind of ferrous acid nickel nano film and its preparation method and application |
| CN108483517B (en) * | 2018-04-03 | 2020-01-03 | 山东大学 | Nickel ferrite nanosheet and preparation method and application thereof |
| CN109046368A (en) * | 2018-07-02 | 2018-12-21 | 大唐（北京）水务工程技术有限公司 | A kind of coal chemical industrial waste water deep oxidation catalyst and preparation method thereof |
| CN110479282A (en) * | 2019-08-13 | 2019-11-22 | 北京航空航天大学 | A kind of preparation method and application of the Ni substrate load ferrous acid nickel-nickel oxide composite catalyst of catalytic ozonation Organic substance in water |
| CN110479282B (en) * | 2019-08-13 | 2020-09-22 | 北京航空航天大学 | Preparation method and application of nickel-based body-loaded nickel ferrite-nickel oxide composite catalyst for catalyzing and ozonizing organic matters in water |
| CN110342725A (en) * | 2019-08-19 | 2019-10-18 | 中国十七冶集团有限公司 | A kind of emergency method for strengthening in-situ treatment black and odorous water |
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