CN102249395B - Water ozonization treatment method by taking cerium oxide nanomaterial as catalyst - Google Patents
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Abstract
The invention discloses a water ozonization treatment method by taking a cerium oxide nanomaterial as a catalyst. According to the method, different cerium oxide nanomaterials are prepared by adjusting and controlling the synthesis reaction conditions, and are taken as catalysts for adding into a water ozonization treatment system of phenol containing waste water, so that the degradation of phenol organic pollutants is facilitated. On the basis, a novel water ozonization treatment method is provided. The method belongs to the technical fields of water treatment and environmental catalysis. The prepared cerium oxide nanomaterial has the characteristics of small size, high dispersity in a water solution system, easiness for separation and recovery and the like, and has a wide application prospect in the application of water ozonization treatment.
Description
Technical field
The invention belongs to water treatment and environmental catalysis field, relate to a kind of with the ozonization water treatment method of cerium oxide nano materials as catalyzer.
Background technology
Increase and industrial or agricultural constant development of economy along with the density of population; The mankind consume great amount of water resources day by day; Trade effluent and undressed sewage directly enter river, lake and underground; Cause the water body pollution in wide area, brought great threat for ecotope and human life's safety.Organic wastewater quantity discharged in the industrial production is big, distributes extensively, complicated component, strong toxicity, is difficult for purifying, is difficult to handle.In current Industrial processes, the quantity discharged of organic wastewater is increasing, and therefore wherein mostly toxic and difficult degradation of organism adopts water treatment method to change water quality, make it innoxious or the resource recoveryization significant to the social harmony development.Chemical oxidation method comprises wet oxidation process, and photocatalytic degradation method and catalytic ozonation method are applicable to that the organic contamination substrate concentration is lower, lack the situation about being worth of recycling.Wherein the catalytic ozonation process is to utilize catalyzer to strengthen the advanced oxidation process of ozone oxidation at normal temperatures and pressures, compares with independent ozonize, has improved to a great extent organic degraded.This process condition is gentle, easy and simple to handle, and especially high to some stability, the organic oxidative degradation that toxicity is big is more thorough, in the processing research of organic wastewater, comes into one's own day by day.
In water treatment research, mainly use of the catalyst ozonize of three types of (nano metal and oxide compound thereof, ceramic honey comb and gac) materials as catalytic ozonation, such catalyzer can repeatedly use, avoid secondary pollution, thereby enjoys favor.
Because nanoparticle surface is long-pending greatly, the surfactivity center is many, nanocatalyst has surface effects, characteristics such as characterization of adsorption and surface reaction, so nanocatalyst is very extensive in the application of catalytic field.In catalytic ozonation, studying more nanocatalyst component is transition metal oxide.Cerium oxide mainly as decolouring, finings, the senior polishing powder of glass, also is applied to industries such as ceramic electrician, chemical industry.In recent years, adopt various technology to synthesize pattern cerium oxide preferably, the cerium oxide of these forms is widely used as electro-conductive material, catalyzer etc.Also there is certain achievement catalytic performance research aspect for nano-cerium oxide both at home and abroad; In catalytic ozonation is used, certain research has been arranged also; For example, people such as P.C.Isolani synthesize three kinds of cerium oxide through hydrothermal method with different cerium citrate source precursors; Cerium oxide is applied in the catalytic ozonation phenol process, and the result finds the difference of catalytic activity and the Ce on cerium oxide surface
3+Amount relevant (M.F.Pinheiro da Silva, L.S.Soeira, K.R.P.Daghastanli.CeO
2-catalyzed ozonation of phenol.J Therm Anal Calorim.2010,102:907-913).More than research explanation cerium oxide nano materials has certain application prospect as the ozonize catalyzer.
Summary of the invention
The objective of the invention is to develop the cerium oxide nano materials of practicality and high efficiency more, and its method of use is provided through the regulation and control synthetic reaction condition.The object of the invention can be realized through following technical scheme:
(1) preparation of cerium oxide nano materials: seven water Cerium II Chlorides or six water cerous nitrates are dissolved in the zero(ppm) water, add solid sodium hydroxide rapidly, simultaneously vigorous stirring.Cerium ion and naoh concentration are respectively 0.1mol L
-1, 2.5mol L
-1Mix the back and form lilac solution, transfer to again in the reaction kettle, keep 14-22h, naturally cool to room temperature after the reaction completion at 100-160 ℃ of lower seal, deionized water wash gained deposition, dry back is calcined 4h down at 300 ℃, obtains cerium oxide nano materials.
(2) ozonization water treatment: the cerium oxide nano materials that obtains is joined in the ozonization water treatment system as catalyzer, feed ozone, start stirring simultaneously, organic pollutant in the beginning degradation water;
(3) recovery of cerium oxide nano materials: ozonation treatment finishes, through leave standstill, centrifugal or filter, cerium oxide nano materials is separated from the aqueous solution, be used for catalytic process next time after the washing drying.
In experimentation, the amount that we find to add catalyzer is 0.001 with the ratio of the quality of processing waste water, and temperature of reaction can reach catalytic effect preferably in the time of 20 ℃.
Beneficial effect of the present invention: adopt identical proportioning raw materials,, synthesize precursor with different cerium sources, hydrothermal temperature, hydro-thermal time; Through the calcining after obtain dissimilar cerium oxide nano materials, with these nano-cerium oxides as catalyzer after, in identical ozone input amount; Catalytic amount; Temperature of reaction is following, and the degradation rate of organic pollutant in the sewage is accelerated to some extent, and mineralization degree increases.Be the cerium source wherein with seven water Cerium II Chlorides, 130 ℃ of hydrothermal temperatures, the cerium oxide particle catalyzed degradation effect that synthesizes under the preparation condition of hydro-thermal time 14h is best.Compare with existing treatment process, the water treatment method that the present invention proposes has outstanding feature:
(1) preparation method of cerium oxide is simple to operate, and raw material is easy to get, and the building-up process cycle is short, nontoxic pollution-free.
(2) the nano-cerium oxide particle scale is less, in water, has good dispersiveness, helps improving and the contacting of ozone, water pollutant.Therefore in use, less input amount can obtain catalytic effect preferably.
(3) cerium oxide nano materials has physical strength preferably, under the catalytic ozonation condition, has stability preferably, is repeatedly used, and catalytic effect can both be kept preferably, and this carries out practical application for it.
Description of drawings
Fig. 1 is embodiment 1,2, the TEM photo of 3,4,5,6 products obtained therefroms;
Fig. 2 is embodiment 1,2, the XRD figure spectrum of 3,4,5,6 products obtained therefroms;
Fig. 3 is that phenol is with the concentration curve of ozonize time among the embodiment 7, and (1) line is independent ozonize (catalyst-free), and (2) line is a cerium oxide nano materials catalytic ozonation in the instance 1, and (3) line is a cerium oxide nano materials catalytic ozonation in the instance 2;
Fig. 4 be among the embodiment 7 phenol with the concentration curve of ozonize time; (1) line is independent ozonize (catalyst-free); (2) line is a cerium oxide nano materials catalytic ozonation in the instance 3; (3) line is a cerium oxide nano materials catalytic ozonation in the instance 1, and (4) line is a cerium oxide nano materials catalytic ozonation in the instance 4;
Fig. 5 be among the embodiment 7 phenol with the concentration curve of ozonize time; (1) line is independent ozonize (catalyst-free); (2) line is a cerium oxide nano materials catalytic ozonation in the instance 5; (3) line is a cerium oxide nano materials catalytic ozonation in the instance 1, and (4) line is a cerium oxide nano materials catalytic ozonation in the instance 6.
Embodiment
For method of the present invention is described more specifically, provide embodiments of the invention below, but application of the present invention is not limited thereto.
Take by weighing 4.50g seven water Cerium II Chlorides and be dissolved in the 120ml zero(ppm) water, after solution mixes, add the 12g solid sodium hydroxide rapidly, simultaneously vigorous stirring.Gained lilac solution is transferred in the polytetrafluoroethyllining lining reaction kettle, keeps 18h at 130 ℃ of lower seals; Reaction naturally cools to room temperature after accomplishing, and deionized water wash gained deposition is at room temperature dry, and calcining 4h under 300 ℃ obtains cerium oxide nano materials then.Its TEM photo is seen Fig. 1 (a), and the XRD figure spectrum is seen Fig. 2 (a).
Take by weighing 5.22g seven water Cerium II Chlorides and be dissolved in the 120ml zero(ppm) water, after solution mixes, add the 12g solid sodium hydroxide rapidly, simultaneously vigorous stirring.Gained lilac solution is transferred in the polytetrafluoroethyllining lining reaction kettle, keeps 18h at 130 ℃ of lower seals; Reaction naturally cools to room temperature after accomplishing, and deionized water wash gained deposition is at room temperature dry, and calcining 4h under 300 ℃ obtains cerium oxide nano materials then.Its TEM photo is seen Fig. 1 (b), and the XRD figure spectrum is seen Fig. 2 (b).
Take by weighing 4.50g seven water Cerium II Chlorides and be dissolved in the 120ml zero(ppm) water, after solution mixes, add the 12g solid sodium hydroxide rapidly, simultaneously vigorous stirring.Gained lilac solution is transferred in the polytetrafluoroethyllining lining reaction kettle, keeps 18h at 100 ℃ of lower seals; Reaction naturally cools to room temperature after accomplishing, and deionized water wash gained deposition is at room temperature dry, and calcining 4h under 300 ℃ obtains cerium oxide nano materials then.Its TEM photo is seen Fig. 1 (c), and the XRD figure spectrum is seen Fig. 2 (c).
Take by weighing 4.50g seven water Cerium II Chlorides and be dissolved in the 120ml zero(ppm) water, after solution mixes, add the 12g solid sodium hydroxide rapidly, simultaneously vigorous stirring.Gained lilac solution is transferred in the polytetrafluoroethyllining lining reaction kettle, keeps 18h at 160 ℃ of lower seals; Reaction naturally cools to room temperature after accomplishing, and deionized water wash gained deposition is at room temperature dry, and calcining 4h under 300 ℃ obtains cerium oxide nano materials then.Its TEM photo is seen Fig. 1 (d), and the XRD figure spectrum is seen Fig. 2 (d).
Embodiment 5
Take by weighing 4.50g seven water Cerium II Chlorides and be dissolved in the 120ml zero(ppm) water, after solution mixes, add the 12g solid sodium hydroxide rapidly, simultaneously vigorous stirring.Gained lilac solution is transferred in the polytetrafluoroethyllining lining reaction kettle, keeps 14h at 130 ℃ of lower seals; Reaction naturally cools to room temperature after accomplishing, and deionized water wash gained deposition is at room temperature dry, and calcining 4h under 300 ℃ obtains cerium oxide nano materials then.Its TEM photo is seen Fig. 1 (e), and the XRD figure spectrum is seen Fig. 2 (e).
Embodiment 6
Take by weighing 4.50g seven water Cerium II Chlorides and be dissolved in the 120ml zero(ppm) water, after solution mixes, add the 12g solid sodium hydroxide rapidly, simultaneously vigorous stirring.Gained lilac solution is transferred in the polytetrafluoroethyllining lining reaction kettle, keeps 22h at 130 ℃ of lower seals; Reaction naturally cools to room temperature after accomplishing, and deionized water wash gained deposition is at room temperature dry, and calcining 4h under 300 ℃ obtains cerium oxide nano materials then.Its TEM photo is seen Fig. 1 (f), and the XRD figure spectrum is seen Fig. 2 (f).
Embodiment 7
Containing initial phenol concentration at 200ml is 100mg L
-1Simulated wastewater in, add different oxidation cerium nano material 0.20g, start stirring, feed ozone flow 0.50mg min down 20 ℃ of temperature of reaction
-1Ozone, the concentration of phenol under the record different time.The result is respectively like Fig. 3, shown in 4,5.
(1) line is independent ozonize (catalyst-free) among Fig. 3, and (2) line is a cerium oxide nano materials catalytic ozonation in the instance 1, and (3) line is a cerium oxide nano materials catalytic ozonation in the instance 2.Being illustrated under the identical situation of other synthesis conditions, is the degraded that the adding of the cerium oxide nano materials prepared of cerium source has significantly promoted phenol with seven water Cerium II Chlorides;
(1) line is independent ozonize (catalyst-free) among Fig. 4, and (2) line is a cerium oxide nano materials catalytic ozonation in the instance 3, and (3) line is a cerium oxide nano materials catalytic ozonation in the instance 1, and (4) line is a cerium oxide nano materials catalytic ozonation in the instance 4.Be illustrated under the identical situation of other synthesis conditions, the adding of the cerium oxide nano materials of when hydrothermal temperature is 130 ℃, preparing has significantly promoted the degraded of phenol;
(1) line is independent ozonize (catalyst-free) among Fig. 5, and (2) line is a cerium oxide nano materials catalytic ozonation in the instance 5, and (3) line is a cerium oxide nano materials catalytic ozonation in the instance 1, and (4) line is a cerium oxide nano materials catalytic ozonation in the instance 6.Be illustrated under the identical situation of other synthesis conditions, the adding of the cerium oxide nano materials of preparing during for 14h in the hydro-thermal time has significantly promoted the degraded of phenol.
Claims (2)
1. one kind with the ozonization water treatment method of cerium oxide nano materials as catalyzer, it is characterized in that in the system of ozonization water treatment, adding cerium oxide nano materials as catalyzer, promotes the degraded of phenol organic pollutant, and step is:
(1) preparation of cerium oxide nano materials: seven water Cerium II Chlorides or six water cerous nitrates are dissolved in the zero(ppm) water, add solid sodium hydroxide rapidly, simultaneously vigorous stirring; Cerium ion and naoh concentration are respectively 0.1mol L
-1, 2.5molL
-1Mix the back and form lilac solution, transfer to again in the reaction kettle, keep 14-22h at 100-160 ℃ of lower seal; Reaction naturally cools to room temperature after accomplishing; Deionized water wash, dry gained deposition are calcined 4h down at 300 ℃ then, obtain cerium oxide nano materials;
(2) ozonization water treatment: the cerium oxide nano materials that obtains is joined in the ozonization water treatment system as catalyzer, feed ozone, start stirring simultaneously, organic pollutant in the beginning degradation water;
(3) recovery of cerium oxide nano materials: ozonation treatment finishes, through leave standstill, centrifugal or filter, cerium oxide nano materials is separated from the aqueous solution, be used for catalytic process next time after the washing drying.
2. according to claim 1 with the ozonization water treatment method of cerium oxide nano materials as catalyzer, the amount of interpolation catalyzer is 0.001 with the ratio of the quality of processing waste water.
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| CN102491490A (en) * | 2011-12-06 | 2012-06-13 | 江南大学 | Ozonated water treatment method with nano ceria as catalyst |
| CN102583699A (en) * | 2011-12-06 | 2012-07-18 | 江南大学 | Method for ozonizing water by using nano neodymium oxide as catalyst |
| CN103100389B (en) * | 2013-02-07 | 2015-01-28 | 浙江工业大学 | Magnetic nano cerium dioxide ozone catalyst, preparation method and application |
| CN103570120B (en) * | 2013-03-27 | 2015-09-23 | 北京林业大学 | A kind of preparation of cerium oxide changed red mud catalyzer and the application in water technology thereof |
| CN103787488B (en) * | 2014-02-10 | 2015-10-28 | 同济大学 | A kind of method utilizing pyrite cinder O3 catalytic oxidation process waste water |
| CN106732625B (en) * | 2016-12-09 | 2019-03-05 | 中南大学 | A kind of Copper-cladding Aluminum Bar cerium oxide nano materials of cyclic structure and its preparation and application |
| CN108249468A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子科技（上海）股份有限公司 | A kind of preparation method of cerium oxide crystalline and its application in chemical mechanical polishing liquid |
| CN107456993B (en) * | 2017-07-24 | 2019-11-29 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of water process ozone catalyst and products thereof and application |
| CN108046407B (en) * | 2017-11-13 | 2021-02-02 | 浙江工业大学 | Adopts nano-CeO2/H2O2/O3Method for treating acidic degradation-resistant wastewater by system |
| CN113842907A (en) * | 2021-11-03 | 2021-12-28 | 长沙蓝思新材料有限公司 | Method for treating waste residue and waste liquid of cerium oxide polishing powder, cerium oxide polishing recovery powder and application thereof |
| CN115215499A (en) * | 2022-07-18 | 2022-10-21 | 北京师范大学 | Household multi-effect ceramic water purifier and manufacturing method thereof |
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