CN103274515B - Ozonization water treatment method taking ZnAl2O4 nano particle as catalyst - Google Patents
Ozonization water treatment method taking ZnAl2O4 nano particle as catalyst Download PDFInfo
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- CN103274515B CN103274515B CN201310260766.9A CN201310260766A CN103274515B CN 103274515 B CN103274515 B CN 103274515B CN 201310260766 A CN201310260766 A CN 201310260766A CN 103274515 B CN103274515 B CN 103274515B
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Abstract
The invention discloses an ozonization water treatment method taking a ZnAl2O4 nano particle as a catalyst, and provides a novel ozonization water treatment method on the basis that the ZnAl2O4 nano particle is prepared by a hydrothermal method and serves as the catalyst to be added to an ozonization water treatment system containing phenol-bearing wastewater, so as to facilitate degradation of phenol organic pollutants. The ozonization water treatment method belongs to the technical field of water treatment and environmental catalysis. The obtained ZnAl2O4 nano particle is small in scale, good in dispersity in an aqueous solution system, high in activity, and easy to separate and recover, and has wide application prospects in ozonization water treatment application.
Description
Technical field
The present invention proposes a kind of with ZnAl
2o
4nanoparticle, 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, therefore causes people's extensive concern for effective processing of such organic waste water.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.In homogeneous catalysis ozonize, catalyzer is dispersed in solution, difficult Separation and Recovery recycling, thereby limited it and processed organic waste water.Multi-phase catalytic ozonation is easy to operate, oxidation capacity is strong, and catalyzer easily reclaims, and has overcome the difficult shortcoming separating of catalyzer in homogeneous catalysis ozonize, 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.Nanocatalyst, yardstick is little on the one hand, specific surface large, good dispersity, is conducive to improve catalytic ozonation efficiency.On the other hand, change the size of nanocatalyst, shape, pattern, composition, electronic structure and heat and chemical stability, can obtain the heterogeneous catalyst of high reactivity, highly selective and high stability.Therefore develop efficient nanocatalyst, can advance the industrialized process of multi-phase catalytic ozonation.
Summary of the invention
The object of the present invention is to provide a kind of ozonization water treatment method of nanocatalyst, 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) ZnAl
2o
4the preparation of nanoparticle: by Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o and urea are dissolved in (V in water and alcohol mixeding liquid
water/ V
ethanol=1), Zn: Al wherein: urea=1: 2: 20 (mol ratio).After stirred for several minute, transfer in reactor, keep 12-24h at 150-220 DEG C of lower seal, after having reacted, naturally cool to room temperature, deionized water wash gained is precipitated to neutrality, and drying products obtains ZnAl
2o
4nanoparticle.
(2) ozonization water treatment: by the ZnAl obtaining
2o
4nanoparticle 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, find that catalyzer has significant catalyzed degradation effect while being 0.00025-0.002 with the mass ratio of the waste water of processing.Catalytic amount is more, and organic matter degradation effect is unreasonable to be thought.
Beneficial effect of the present invention: with Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o and urea are raw material, by the method for hydro-thermal, synthesize ZnAl
2o
4nanoparticle, sets it as ozonize catalyzer, more independent ozonize, and catalytic ozonation is obviously accelerated the degradation rate of dirty organic pollutants, and mineralization degree obviously improves.Compare with existing ozonization water treatment catalyzer, the present invention has outstanding feature:
(1) ZnAl
2o
4preparation method simple to operate, raw material is easy to get, the building-up process cycle is short, nontoxic pollution-free.
(2) ZnAl
2o
4nanoparticle 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) ZnAl
2o
4nanoparticle 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, accelerates phenol degrading, and then improves degradation efficiency.
Brief description of the drawings
Figure l is the TEM photo of EXAMPLE l 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 ZnAl in example 1
2o
4nano particle catalysis ozonize; (3) line is ZnAl in example l
2o
4nanoparticle absorption;
Fig. 4 is that in EXAMPLE l, phenol is with the concentration curve of ozonize time, and (1) line is independent ozonize (catalyst-free), and (2) line is ZnAl in example 1
2o
4nano particle catalysis ozonize, (3) line is that the trimethyl carbinol exists ZnAl in lower example 1
2o
4nanoparticle;
Fig. 5 is that in EXAMPLE l, 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 ZnAl in example l
2o
4nanoparticle (0.05g) catalytic ozonation, (3) line is ZnAl in example 1
2o
4nanoparticle (0.10g) catalytic ozonation, (4) line is ZnAl in example 1
2o
4nanoparticle (0.20g) catalytic ozonation, (5) line is ZnAl in example 1
2o
4nanoparticle (0.40g) catalytic ozonation.
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.
EXAMPLE l
Take 2.38g Zn (NO
3)
26H
2o, 6.00g Al (NO
3)
39H
2o and 9.60g urea are dissolved in (V in 160ml water and alcohol mixeding liquid
water/ V
ethanol=1), be stirred to dissolving.Gained liquid is transferred in polytetrafluoroethyllining lining reactor, and 200 DEG C of lower seals keep 18h; After having reacted, naturally cool to room temperature, deionized water wash gained is precipitated to neutrality, and 90 DEG C dry, obtains ZnAl
2o
4nanoparticle.Fig. 1 is shown in by its TEM photo, and XRD figure spectrum is shown in Fig. 2.
Embodiment 2
Be 300mg L at 200ml containing initial phenol concentration
-1simulated wastewater in, add ZnAl
2o
4nanoparticle 0.20g, stirs, and passes into the ozone of ozone flow 0.75mg/min at 25 DEG C 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 ZnAl in example 1
2o
4nano particle catalysis ozonize.Show in the situation that other are identical ZnAl
2o
4nanoparticle add the remarkable degraded that promotes phenol.
Embodiment 3
Be 300mg L at 200ml containing initial phenol concentration
-1simulated wastewater in, add ZnAl
2o
4nanoparticle 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 25 DEG C 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 ZnAl in example l
2o
4nano particle catalysis ozonize, (3) line is that the trimethyl carbinol exists ZnAl in lower example 1
2o
4nano particle catalysis ozonize.Show in the situation that other conditions are identical, the trimethyl carbinol add the obvious degraded that suppresses phenol.
Embodiment 4
Be 300mg L at 200ml containing initial phenol concentration
-1simulated wastewater in, add different amount ZnAl
2o
4nanoparticle, adds respectively 0.05g, 0.10g, 0.20g and 0.40g, stirs, and passes into the ozone of ozone flow 0.75mg/min at 25 DEG C 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 ZnAl in example 1
2o
4nanoparticle (0.05g) catalytic ozonation, (3) line is ZnAl in example 1
2o
4nanoparticle (0.10g) catalytic ozonation, (4) line is ZnAl in example 1
2o
4nanoparticle (0.20g) catalytic ozonation, (5) line is ZnAl in example 1
2o
4nanoparticle (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.
Claims (2)
1. one kind with ZnAl
2o
4nanoparticle, as the ozonization water treatment method of catalyzer, is characterized in that adding ZnAl in the system of ozonization water treatment
2o
4nanoparticle, as catalyzer, promotes the degraded of phenol organic pollutant, and step is:
(1) ZnAl
2o
4the preparation of nanoparticle: by Zn (NO
3)
26H
2o, Al (NO
3)
39H
2it is that in the water/alcohol mixeding liquid of 1: 1, wherein three's mol ratio is Zn: Al: urea=1: 2: 20 that O and urea are dissolved in volume ratio; After stirred for several minute, transfer in reactor, keep 12-24h at 150-220 DEG C of lower seal, after having reacted, naturally cool to room temperature, deionized water wash gained is precipitated to neutrality, and drying products obtains ZnAl
2o
4nanoparticle;
(2) ozonization water treatment: by the ZnAl obtaining
2o
4nanoparticle joins in ozonization water treatment system as catalyzer, passes into ozone, stirs degraded organic pollutants.
2. according to claim 1 with ZnAl
2o
4nanoparticle, as the ozonization water treatment method of catalyzer, is characterized in that catalyzer has significant catalyzed degradation effect while being 0.00025-0.002 with the mass ratio of the waste water of processing.
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| CN103274515B true CN103274515B (en) | 2014-08-06 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113452A (en) * | 1994-04-08 | 1995-12-20 | 罗纳·布朗克化学公司 | Spinel based catalysts for reducing emissions of oxides of nitrogen |
| CN1181283A (en) * | 1996-10-30 | 1998-05-13 | 菲利浦石油公司 | Hydrogenation catalysts and processes therewith |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100525465B1 (en) * | 2002-12-27 | 2005-11-02 | 한국과학기술연구원 | Method of water treatment for drinking water using supported nano-sized iron catalyst |
-
2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113452A (en) * | 1994-04-08 | 1995-12-20 | 罗纳·布朗克化学公司 | Spinel based catalysts for reducing emissions of oxides of nitrogen |
| CN1181283A (en) * | 1996-10-30 | 1998-05-13 | 菲利浦石油公司 | Hydrogenation catalysts and processes therewith |
Non-Patent Citations (2)
| Title |
|---|
| Photocatalytic degradation of gaseous toluene over ZnAl2O4 prepared by different methods: A comparative study;Xinyong Li 等;《Journal of Hazardous Materials》;20110228;第186卷(第2-3期);第2089-2096页 * |
| Xinyong Li 等.Photocatalytic degradation of gaseous toluene over ZnAl2O4 prepared by different methods: A comparative study.《Journal of Hazardous Materials》.2011,第186卷(第2-3期),第2089-2096页. |
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