CN102863070B - 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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- CN102863070B CN102863070B CN201210384114.1A CN201210384114A CN102863070B CN 102863070 B CN102863070 B CN 102863070B CN 201210384114 A CN201210384114 A CN 201210384114A CN 102863070 B CN102863070 B CN 102863070B
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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, as the ozonization water treatment method of catalyzer, belongs to environmental catalysis and water treatment field.
Background technology
Current, along with the fast development of industrial or agricultural, increasing containing trade effluent and the agricultural effluent quantity discharged of organic pollutant.Wherein large, the difficulty of much organic pollutant toxicity is biodegradable, and ecotope and human health have been caused to 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 that aromatics and condensed ring compounds be representative of take has very high stability, and ozone degradation efficiency is lower separately, and catalytic ozonation is to utilize catalyzer to strengthen at normal temperatures and pressures a kind of advanced oxidation process of ozone oxidation.Research shows that the hydroxyl radical free radical producing in catalytic reaction process is very active, and oxidizing potential is up to 2.33V, and the most stable of degrading is high, toxicity 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, easy to operate, oxidation capacity is strong, in treatment of Organic Wastewater, has a extensive future.In recent years, along with the research of nano material and nanotechnology deepens continuously, 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 efficiency.According to exterior magnetic field, can facilitate on the other hand, be isolated rapidly, reclaim, recycle, overcome the difficult shortcoming reclaiming of non magnetic nanocatalyst.The use of magnetic nano-catalyst, improve catalyzer service efficiency, avoid catalyzer to pollute, reduce cost of sewage disposal to water quality.Therefore developing efficient magnetic nano-catalyst, is a kind of effective ways that advance 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.Object of the present invention can be achieved through the following technical solutions:
(1) NiFe
2o
4the preparation of magnetic Nano material: by 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 4.4mol/L sodium hydroxide solution, after vigorous stirring number minute, transfers in reactor simultaneously, at 180 ℃ of lower seals, keeps 24h, after having reacted, naturally cool to room temperature, deionized water wash gained is precipitated to neutrality, and drying products obtains NiFe
2o
4nano material.
(2) ozonization water treatment: by the NiFe obtaining
2o
4nano material joins in ozonization water treatment system as catalyzer, passes into ozone, stirs 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 while being 0.00025-0.002.Catalytic amount is more, and organic matter degradation effect is unreasonable to be thought.
(4) NiFe
2o
4nano material magnetic separability: by the NiFe of mass concentration 1.0 g/L
2o
4the aqueous solution is dispersed in reagent bottle, and magnet is placed in to reagent bottle wall, after very short for some time, and NiFe
2o
4nano material is inhaled well on reagent bottle wall, obtains a settled solution.
Beneficial effect of the present invention: the method by hydro-thermal, synthesizes NiFe
2o
4magnetic Nano material, using it as ozonize catalyzer, more independent ozonize, catalytic ozonation is accelerated the degradation rate of dirty organic pollutants to some extent, and mineralization degree increases.In addition NiFe
2o
4nano material has magnetic, and reaction finishes, and by external magnetic field, can effectively be isolated, and has overcome the difficult separated shortcoming of non magnetic nanocatalyst, is convenient to recycling.Compare with existing ozonization water treatment catalyzer, the present invention has outstanding feature:
(1) NiFe
2o
4preparation 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, is conducive to contacting of raising and ozone, water pollutant.Therefore in use, less input amount can obtain good catalytic effect.
(3) NiFe
2o
4nano material is very faint to the absorption property of phenol in water, and its katalysis, mainly from catalyst surface and ozonization, promotes the decomposition of ozone to produce hydroxyl radical free radical, and then improves degradation efficiency.
(4) NiFe
2o
4nano material has magnetic, by external magnetic field, can effectively be isolated, and is convenient to recycling.
Accompanying drawing explanation
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 in embodiment 1, phenol is with the concentration curve of ozonize time, and (1) line is independent ozonize (catalyst-free), and (2) line is NiFe in example 1
2o
4nano material catalytic ozonation;
Fig. 4 is that in embodiment 1, phenol is with the concentration curve of ozonize time, and (1) line is independent ozonize (catalyst-free), and (2) line is NiFe in example 1
2o
4nano material catalytic ozonation, (3) line is that the trimethyl carbinol exists NiFe in lower example 1
2o
4nano material;
Fig. 5 is that in embodiment 1, under different catalysts amount, phenol is with the concentration curve of ozonize time, and (1) line is independent ozonize (catalyst-free), and (2) line is NiFe in example 1
2o
4nano material (0.05g) catalytic ozonation, (3) line is NiFe in example 1
2o
4nano material (0.10g) catalytic ozonation, (4) line is NiFe in example 1
2o
4nano material (0.20g) catalytic ozonation, (5) line is NiFe in example 1
2o
4nano material (0.40g) catalytic ozonation.
Fig. 6 is the separated schematic diagram of the magnetic of gained catalyzer in embodiment 1.
Embodiment
For more specific description method of the present invention, provide embodiments of the invention below, but application of the present invention is not limited to this.
Embodiment 1
Take 2.04g Ni (NO
3)
26H
2o and 5.66g Fe (NO
3)
39H
2o is dissolved in 140ml distilled water, after solution mixes, adds 20ml, 4.4mol/L NaOH solution, vigorous stirring.Gained liquid is transferred in polytetrafluoroethyllining lining reactor, and 180 ℃ of lower seals keep 24h; After having reacted, naturally cool to room temperature, deionized water wash gained is precipitated to neutrality, and 80 ℃ dry, obtains NiFe
2o
4nano material.Fig. 1 is shown in by its TEM photo, and XRD figure spectrum is shown in Fig. 2.
Embodiment 2
At 200ml, containing initial phenol concentration, be 300mg L
-1simulated wastewater in, add NiFe
2o
4nano material 0.20g, starts stirring, passes into the ozone of ozone flow 0.75mg/min at 20 ℃ of temperature of reaction, records the concentration of phenol under different time.Result respectively as shown in Figure 3.
In Fig. 3, (1) line is independent ozonize (catalyst-free), and (2) line is NiFe in example 1
2o
4nano material catalytic ozonation.Show in the situation that other are identical NiFe
2o
4nano material add the remarkable degraded that promotes phenol.
Embodiment 3
At 200ml, containing initial phenol concentration, be 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 at 20 ℃ of temperature of reaction, records the concentration of phenol under different time.Result respectively as shown in Figure 4.
In Fig. 4, (1) line is independent ozonize (catalyst-free), and (2) line is NiFe in example 1
2o
4nano material catalytic ozonation, (3) line is that the trimethyl carbinol exists NiFe in lower example 1
2o
4nano material catalytic ozonation.Show in the situation that other conditions are identical, the trimethyl carbinol add the obvious degraded that suppresses phenol.
Embodiment 4
At 200ml, containing initial phenol concentration, be 300mg L
-1simulated wastewater in, add different amount NiFe
2o
4nano material, adds respectively 0.05g, 0.10g, 0.20g and 0.40g, stirs, and passes into the ozone of ozone flow 0.75mg/min at 20 ℃ of temperature of reaction, records the concentration of phenol under different time.Result respectively as shown in Figure 5.
In Fig. 5, (1) line is independent ozonize (catalyst-free), and (2) line is NiFe in example 1
2o
4nano material (0.05g) catalytic ozonation, (3) line is NiFe in example 1
2o
4nano material (0.10g) catalytic ozonation, (4) line is NiFe in example 1
2o
4nano material (0.20g) catalytic ozonation, (5) line is NiFe in example 1
2o
4nano material (0.40g) catalytic ozonation.Show that, in the situation that other are identical, catalytic amount is more, the degradation effect of phenol is more remarkable.
Embodiment 5
By 10ml, the NiFe of 1g/L
2o
4the aqueous solution is as in a reagent bottle, ultrasonic dispersion.One magnet, as for by reagent bottle, is determined to the magnetic separation property of catalyzer.Result respectively as shown in Figure 6.
Fig. 6 has shown the process of catalyzer magnetic separation, shows NiFe
2o
4nano material has significant magnetic separation property.
Claims (1)
1. one kind with NiFe
2o
4magnetic Nano material, as the ozonization water treatment method of catalyzer, is characterized in that adding NiFe in the system of ozonization water treatment
2o
4magnetic Nano material, as catalyzer, promotes the degraded of phenol organic pollutant, based on NiFe
2o
4magnetic, can efficient recovery NiFe
2o
4nano material, step is:
(1) NiFe
2o
4the preparation of magnetic Nano material: take 2.04g Ni (NO
3)
26H
2o and 5.66gFe (NO
3)
39H
2o is dissolved in 140ml distilled water, after solution mixes, add 20ml, 4.4mol/L NaOH solution, vigorous stirring, gained liquid is transferred in polytetrafluoroethyllining lining reactor, 180 ℃ of lower seals keep 24h, after having reacted, naturally cool to room temperature, and deionized water wash gained is precipitated to neutrality, 80 ℃ dry, obtains NiFe
2o
4nano material;
(2) ozonization water treatment: be 300mg L containing initial phenol concentration at 200ml
-1simulated wastewater in, add the NiFe of above-mentioned preparation
2o
4nano material 0.20g, starts stirring, passes into the ozone of ozone flow 0.75mg/min at 20 ℃ of temperature of reaction, degraded organic pollutants;
(3) NiFe
2o
4nano material magnetic is separated: reaction finishes, and by external magnetic field, can effectively be isolated, and has overcome the difficult separated shortcoming of non magnetic nanocatalyst, is convenient to recycling.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103288202B (en) * | 2013-06-27 | 2015-04-22 | 江南大学 | Ozonization water treatment method taking iron-nickel magnetic composite material as catalyst |
| CN103611539B (en) * | 2013-12-02 | 2015-09-30 | 江南大学 | A kind of magnetic calcium based solid alkali method for preparing catalyst of biodiesel synthesis |
| 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 |
| CN105776498B (en) * | 2016-03-07 | 2019-05-03 | 浙江工业大学 | The method that magnetic order mesoporous nickel ferrite based magnetic loaded catalytic ozonation removes antineoplastic in water removal |
| 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 |
| CN108483517B (en) * | 2018-04-03 | 2020-01-03 | 山东大学 | Nickel ferrite nanosheet and preparation method and application thereof |
| CN109046368B (en) * | 2018-07-02 | 2021-07-16 | 大唐（北京）水务工程技术有限公司 | Coal chemical wastewater deep oxidation catalyst and preparation method thereof |
| 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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| CN102580663A (en) * | 2012-02-21 | 2012-07-18 | 上海大学 | Preparation method and application of high magnetic composite material |
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| CN102151567A (en) * | 2011-02-25 | 2011-08-17 | 哈尔滨工业大学 | Catalyst for oxidation and decomposition of organic pollutants in water with ozone and method thereof for catalyzing sewage treatment with ozone |
| CN102580663A (en) * | 2012-02-21 | 2012-07-18 | 上海大学 | Preparation method and application of high magnetic composite material |
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