CN105251499A - Method for preparing iron and cerium compound by means of ultrasonic infiltration and application of method in fenton-like water treatment - Google Patents
Method for preparing iron and cerium compound by means of ultrasonic infiltration and application of method in fenton-like water treatment Download PDFInfo
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Abstract
The invention discloses a method for preparing an iron and cerium compound oxide by means of ultrasonic infiltration and application of the method in fenton-like water treatment. The method for preparing the iron and cerium compound oxide by means of ultrasonic infiltration comprises the following steps that after cerium metal salt is dissolved in water, an alkaline aqueous solution is added for precipitation reaction, precipitation obtained after the reaction is completed is dried and ground, and cerium dioxide powder is obtained after natural cooling to the room temperature is conducted; after iron metal salt is dissolved in water, the cerium dioxide powder is added for ultrasonic infiltration, precipitation obtained after the reaction is completed is filtered and calcined, natural cooling to the room temperature is conducted, and the iron and cerium compound oxide is obtained. The iron and cerium compound oxide prepared through the ultrasonic infiltration method is simple in structure, higher in activity, the preparation method is simple in operation step and short in reaction time, the reaction condition is easy to control, and practical application value is achieved. After a catalytic reaction is conducted for 20 min in a fenton-like water treatment system, the removal effects on pharmaceutical waste water and antibiotic waste water can reach 81% and 87% respectively.
Description
Technical field
The invention belongs to environmentally conscious materials, environmental catalysis and environmental protection technical field, relate to a kind of ultrasonic immersing and prepare the method for iron cerium compound and the application in the water treatment of class Fenton thereof.
Background technology
The process of indegradable industrial effluent is the difficult problem that sewage disposal circle both at home and abroad is at present generally acknowledged.For this kind of waste water, what research was more both at home and abroad has the professional waste water such as dyeing waste water, pharmacy waste water, antibiotic waste water.In this kind of waste water, the hardly degraded organic substance often containing higher concentration, or even biological toxants, and also kind is more.Therefore, bioanalysis is difficult to the organic wastewater with difficult degradation thereby processing high concentration, and physical method such as absorption method, extraction, membrane separation process etc. do not realize removing to organic degraded but to organic, can bring serious secondary pollution like this.So chemical method especially advanced oxidation processes has larger application potential in process organic wastewater with difficult degradation thereby.
At present, advanced oxidation processes is because its Strong oxdiative ability obtains practical application in indegradable industrial effluent process, in the removal of wherein class Fenton technology Recalcitrant chemicals in industrial wastewater, research widely, and it forms heterogeneous Fenton reaction system by solid ferruginous thing or by the method for carrier immobilized iron ion and hydrogen peroxide.Adopt class Fenton technical finesse water Chinese traditional medicine pollutant can realize organic effective removal in industrial wastewater, can not secondary pollution be caused simultaneously, effectively can improve the shortcoming and defect existed in the method such as general materialization and biochemistry.But still exist some problems need research and solve: (1) can detect the stripping of iron ion for a lot of class Fenton's reaction, and the stripping of iron ion can affect activity and the effluent quality of catalyst, further development structure is needed to stablize and the catalyst of high catalytic activity can be kept; (2) catalytic efficiency of existing class Fenton's reaction is often low than Fenton's reaction, therefore need improve catalyst activity further, thus reduces the cost in technology application.
Therefore, in class Fenton water treatment system, need development structure to stablize, active high catalyst.The catalyst mainly compound such as iron and rare-earth oxide, noble metal, molecular sieve, heteropoly acid that current research is more.Wherein, the oxide of rare earth metal cerium because rich reserves, and has stronger oxygen storage capacity and redox property, also has the ability of good chemical stability and the quick Lacking oxygen diffusion of high temperature simultaneously, is thus extensively studied.Due to the difference of iron ion and cerium ion radius, when both form composite oxides, stable composite construction can suppress the stripping of ferro element in water, simultaneously, this compound will have higher mechanical strength, can extend its service life, and because of compound produce lattice defect, to electro transfer be promoted and the formation of the more active species of initiation, therefore be applicable to class Fenton water treatment system.
At present, iron cerium compound preparation method mainly contain coprecipitation, hydro-thermal method, sol-gal process and infusion process, wherein infusion process is flooded for crucial and specific step, is also the method for extensive use during current Catalyst is produced.Infusion process to be impregnated on porous carrier with salting liquid form based on active component and to penetrate into inner surface, metal or metal oxide is distributed in carrier surface or pore, and forms the principle of effective catalyst.Therefore, infusion process is a kind of simple and economic method, is widely used in preparing loaded catalyst.But due to the restriction of impregnation steps, there is the shortcoming that active constituent loading is uneven, dip time is long, product efficiency is low in traditional infusion process.And ultrasonic immersing method can make the active component in solution be evenly distributed in the carrier by hyperacoustic concussion effect, the phenomenon avoiding active component to reunite occurs, simultaneously due to the high efficiency of ultrasonic vibration, also can save the reaction time of impregnation steps.Compared with traditional infusion process, use ultrasonic immersing method can improve preparation speed and the catalytic performance of catalyst.At present, there is no and adopt ultrasonic immersing legal system for iron cerium compound and the report applied in class Fenton water treatment system thereof.Therefore, ultrasonic technique be applied in impregnation steps, the preparation method for iron cerium compound is a kind of innovation, has also widened the application of ultrasonic wave in material preparation and water treatment field simultaneously.
Summary of the invention
The object of the invention is to solve that catalyst activity component in class Fenton water treatment system easily runs off, method that iron cerium compound is prepared in structural instability, the active problem such as low and a kind of ultrasonic immersing of providing.
The method of iron cerium compound is prepared in ultrasonic immersing provided by the invention, comprises the steps:
After water-soluble for the slaine of Ce elements, the aqueous solution adding alkali carries out precipitation reaction, reacts complete and gained is precipitated drying grinds, naturally cool to room temperature and obtain cerium oxide powder; After water-soluble for the slaine of ferro element, add above-mentioned cerium oxide powder and carry out ultrasonic immersing, react complete and gained sedimentation and filtration is calcined again, naturally cool to room temperature and obtain described iron cerium compound;
In said method, the mol ratio of Ce elements and alkali is 0.05 ~ 0.15: 0.1 ~ 0.3; The aqueous solution of alkali is the aqueous solution of NaOH or the aqueous solution of potassium hydroxide, and concentration is 0.1 ~ 1.0mol/L; The slaine of Ce elements is cerous nitrate, and the slaine of ferro element is frerrous chloride, and the mol ratio of iron and Ce elements is 1 ~ 9: 9 ~ 1; In precipitation reaction step, temperature is 30 ~ 40 DEG C, and the reaction time is 3h ~ 5h; In drying steps, temperature is 100 ~ 120 DEG C, and the time is 2h ~ 10h.In ultrasonic immersing step, ultrasonic power is 65W ~ 650W, and frequency is 20 ~ 25KHz, and the time is 5min ~ 30min; In calcining step, temperature is 400 ~ 600 DEG C, and the time is 1h ~ 5h.
The iron cerium compound that ultrasonic immersing legal system provided by the invention is standby, operating procedure is simple, and the impregnation time is short, easily-controlled reaction conditions, shows good stability and activity, have the value of practical application in class Fenton water treatment system.
(1) ultrasonic immersing method of the present invention and traditional infusion process contrast
(2) ultrasonic immersing method of the present invention and traditional infusion process are prepared iron cerium compound and are contrasted
Accompanying drawing explanation
Fig. 1 is the removal effect of embodiment 1, embodiment 2 and comparative example 1 ~ 4 pair of pharmacy waste water and antibiotic waste water.
Detailed description of the invention
Below with the practical application of the method for the invention in class Fenton water treatment system for embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.
Embodiment 1
Simulation pharmacy waste water composition: distilled water 100mL and C14H10Cl2NNaO2 2mg.
Iron cerium compound 0.1g is added in simulation pharmacy waste water, the concentration adding hydrogen peroxide is 100mmol/L, regulate initial pH value 5, after reaction 20min, after reacting, solution is after 0.22 micron of PTFE material filter filters, and collects filtrate and uses the concentration of high-performance liquid chromatogram determination C14H10Cl2NNaO2 and calculate clearance.
High performance liquid chromatography testing conditions: adopt U.S. Waterse2695 high performance liquid chromatography, is equipped with C18 reversed-phase column and the UV-detector of 250mm × 4.6mm.UV detect wavelength is 275nm; Elution requirement: mobile phase is that the glacial acetic acid aqueous solution of 0.05mol/L and acetonitrile form by concentration, and volume ratio is 30%: 70%, and flow velocity is 1ml/min, and sample size is 10 μ L, and column temperature is 30 DEG C.
Embodiment 2
Simulation antibiotic waste water composition: distilled water 100mL and Amoxicillin 2mg.
Iron cerium compound 0.1g is added in simulation antibiotic waste water, the concentration adding hydrogen peroxide is 100mmol/L, regulate initial pH value 5, after reaction 20min, after reacting, solution is after 0.22 micron of PTFE material filter filters, and collects filtrate and uses the concentration of high-performance liquid chromatogram determination Amoxicillin and calculate clearance.
High performance liquid chromatography testing conditions: adopt U.S. Waterse2695 high performance liquid chromatography, is equipped with C18 reversed-phase column and the UV-detector of 250mm × 4.6mm.UV detect wavelength is 225nm; Elution requirement: mobile phase is that ultra-pure water and methyl alcohol form by concentration, and volume ratio is 90%: 10%, and flow velocity is 1ml/min, and sample size is 10 μ L, and column temperature is 30 DEG C.
Comparative example 1
In simulation pharmacy waste water, do not add iron cerium compound, all the other steps are identical with embodiment 1.
Comparative example 2
In simulation pharmacy waste water, do not add hydrogen peroxide, all the other steps are identical with embodiment 1.
Comparative example 3
In simulation antibiotic waste water, do not add iron cerium compound, all the other steps are identical with embodiment 2.
Comparative example 4
In simulation antibiotic waste water, do not add hydrogen peroxide, all the other steps are identical with embodiment 2.
From in Fig. 1, iron cerium compound catalytic reaction 20min in Fenton-like that the present invention adopts ultrasonic immersing legal system standby, can reach 81% and 87% respectively to the removal effect of pharmacy waste water and antibiotic waste water.Without significant change before and after the iron cerium compound reaction that ultrasonic immersing legal system of the present invention is standby, Stability Analysis of Structures, activity is higher, and preparation method's operating procedure is simple, and the reaction time is short, easily-controlled reaction conditions, has the value of practical application.
Claims (3)
1. a method for iron cerium composite oxides is prepared in ultrasonic immersing, comprises the steps:
After water-soluble for the slaine of Ce elements, the aqueous solution adding alkali carries out precipitation reaction, reacts complete and gained is precipitated drying grinds, naturally cool to room temperature and obtain cerium oxide powder; After water-soluble for the slaine of ferro element, add above-mentioned cerium oxide powder and carry out ultrasonic immersing, react complete and gained sedimentation and filtration is calcined again, naturally cool to room temperature and obtain described iron cerium composite oxides.
2. method according to claim 1, is characterized in that:
The mol ratio of described Ce elements and alkali is 0.05 ~ 0.15: 0.1 ~ 0.3; The aqueous solution of alkali is the aqueous solution of NaOH or the aqueous solution of potassium hydroxide, and concentration is 0.1 ~ 1.0mol/L; The slaine of Ce elements is cerous nitrate, and the slaine of ferro element is frerrous chloride, and the mol ratio of iron and Ce elements is 1 ~ 9: 9 ~ 1.
3. method according to claim 1 and 2, is characterized in that:
In described precipitation reaction step, temperature is 30 ~ 40 DEG C, and the reaction time is 3h ~ 5h; In drying steps, temperature is 100 ~ 120 DEG C, and the time is 2h ~ 10h; In ultrasonic immersing step, ultrasonic power is 65W ~ 650W, and frequency is 20 ~ 40KHz, and the time is 5min ~ 30min; In calcining step, temperature is 400 ~ 600 DEG C, and the time is 1h ~ 5h.
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Cited By (5)
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| CN105753231A (en) * | 2016-04-13 | 2016-07-13 | 东莞市联洲知识产权运营管理有限公司 | Method of utilizing Fenton reaction to remove organic pollutants in wastewater |
| CN106040250A (en) * | 2016-06-21 | 2016-10-26 | 沈阳建筑大学 | Heterogeneous Fe-Ce fenton-like catalyst and preparation method and use thereof |
| CN107537491A (en) * | 2017-10-09 | 2018-01-05 | 华东交通大学 | A kind of metallic catalyst preparation method for coking wastewater deep treatment |
| CN112264096A (en) * | 2020-11-23 | 2021-01-26 | 陕西科技大学 | Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof |
| CN113800552A (en) * | 2021-08-12 | 2021-12-17 | 淮阴师范学院 | Novel cerium dioxide, preparation method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105753231A (en) * | 2016-04-13 | 2016-07-13 | 东莞市联洲知识产权运营管理有限公司 | Method of utilizing Fenton reaction to remove organic pollutants in wastewater |
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| CN106040250A (en) * | 2016-06-21 | 2016-10-26 | 沈阳建筑大学 | Heterogeneous Fe-Ce fenton-like catalyst and preparation method and use thereof |
| CN107537491A (en) * | 2017-10-09 | 2018-01-05 | 华东交通大学 | A kind of metallic catalyst preparation method for coking wastewater deep treatment |
| CN112264096A (en) * | 2020-11-23 | 2021-01-26 | 陕西科技大学 | Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof |
| CN112264096B (en) * | 2020-11-23 | 2023-02-03 | 陕西科技大学 | Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof |
| CN113800552A (en) * | 2021-08-12 | 2021-12-17 | 淮阴师范学院 | Novel cerium dioxide, preparation method and application |
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