CN103007940B - Preparation method of catalyst in microwave-assisted catalytic oxidation treating process for imidacloprid pesticide waste water - Google Patents
Preparation method of catalyst in microwave-assisted catalytic oxidation treating process for imidacloprid pesticide waste water Download PDFInfo
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- CN103007940B CN103007940B CN201210560545.9A CN201210560545A CN103007940B CN 103007940 B CN103007940 B CN 103007940B CN 201210560545 A CN201210560545 A CN 201210560545A CN 103007940 B CN103007940 B CN 103007940B
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Abstract
The invention relates to a preparation method of a copper catalyst in a microwave-assisted catalytic oxidation treating process for imidacloprid pesticide waste water. The method comprises the process steps as follows: choosing cocoanut shell activated charcoal as a carrier of the catalyst, soaking the cocoanut shell activated charcoal washed by distilled water in an HNO3 solution with a mass fraction of 10%, oscillating at a constant temperature, drying to constant weight at the constant temperature, obtaining the activated catalyst carrier, weighing the activated carrier, adding a CuSO4 solution, impregnating, filtering, discarding filtrate, putting the treated catalyst carrier into an oxalic acid solution for a precipitation reaction, drying by thermostatic waterbath after filtering, drying in an electrothermal constant-temperature dry box, roasting at a high temperature after cooling, taking out, and obtaining the catalyst applicable to the microwave-assisted catalytic oxidation treating process for the imidacloprid pesticide waste water. The method is high in treating efficiency, simple in adding mode and equipment, and convenient to operate, the outlet water temperature is appropriate, a novel high-efficient process is provided for treating the organic pesticide waste water difficult to degrade, and the method has wide application prospects.
Description
Technical field
The present invention relates to a kind of micro ware auxiliary catalysis oxidation technology and process the preparation method of catalyst in imidacloprid pesticide waster water process, particularly for the preparation of the method for Cu-series catalyst in micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process.Belong to waste water advanced oxidization processing technology field.
Background technology
Agricultural chemicals waste water is the unmanageable organic chemical waste water of a class, has that mass concentration is high, colourity is dark, toxicity is large, pollutant component is complicated, be difficult to the features such as biodegradation.At present the most of agricultural chemicals waste water of China is processed and is conventionally only carried out entering biochemistry pool after simple pretreatment and carry out biochemical treatment again.Although biochemical process is the method for treating water of technology comparative maturity, and processing cost is lower, because agricultural chemicals waste water toxicity is high, and contains and be difficult to biodegradable organic matter and be often difficult to obtain desirable effect.And traditional physico-chemical process is being removed wastewater toxicity and is being improved the aspect Shortcomings such as biodegradability of waste water, some Physical preconditioning technique toxic component of can not thoroughly degrading, thus cause transfer and the secondary pollution etc. of polluting.Therefore, explore efficient agricultural chemicals waste water processing method and become a processing difficult problem and the study hotspot in environmental improvement field.
Microwave assisted oxidation technology is a brand-new high-level oxidation technology, is often referred under the auxiliary condition of microwave, and the hydroxyl radical free radical (HO) that has a high reaction activity by generation carrys out the treatment technology of oxidative degradation organic pollution.Microwave assisted oxidation technology is in having traditional high-level oxidation technology advantage, if do not produced a large amount of other chemical substances and biological sludge, most organic matter can be by permineralization, very strong etc. to the degradation capability of organic pollution that can not be biochemical in waste water, also there is the advantages such as the reaction time is short, efficiency is high, anti impulsion load ability is strong, thus bio-refractory waste water process in application study more and more come into one's own.
At present, application high-level oxidation technology is processed the existing bibliographical information of agricultural chemicals waste water.But due to the characteristic of agricultural chemicals waste water, high-level oxidation technology remains the deficiency of the aspect such as little in high, the applicable pH value scope of disposal cost, oxidant consumption amount is large in actual applications.
Summary of the invention
Object of the present invention is overcoming prior art deficiency, invents the technical method of catalyst in a kind of micro ware auxiliary catalysis oxidation technology processing imidacloprid pesticide waster water process.
The preparation method of catalyst in micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process of the present invention, is characterized in that containing following processing step:
Selecting diameter is the carriers of 300 order cocoanut active charcoals as catalyst, the HNO that is 10% with mass fraction
3solution 1000mL soaks 150g cocoanut active charcoal after distilled water cleans, and after 40 DEG C of vibration 20h of constant temperature, 70 DEG C of constant temperature dryings, to constant weight, obtain the catalyst carrier of activation;
Take the activated carrier of 100g, add the CuSO of 1000mL
4solution, dipping 24h;
Filter, discard filtrate, catalyst carrier after treatment is dropped into precipitation reaction 24h in oxalic acid solution, after filtration, through the dry 12h of 80 DEG C of waters bath with thermostatic control, then in 110 DEG C of Constant Temp. Oven inner drying 2h, after cooling, roasting 3-5h under the high temperature of 350-450 DEG C, takes out, and obtains being applicable to the catalyst of micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process.
Described CuSO
4the concentration of solution is: 0.3mol/L, 0.2mol/L or 0.4mol/L.
The concentration of described oxalic acid solution is: 0.3mol/L, 0.2mol/L or 0.4mol/L.
The inventive method is particularly suitable for for the preparation of Cu-series catalyst in micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process.
Microwave assisted oxidation process is a kind of novel advanced oxidation processes water treatment technology, has the features such as oxidation rate is fast, equipment is simple, easy to operate.This research is to carry out catalyst carrier activation, active component is selected, active component concentration and precipitating reagent are selected, on the basis of the research such as roasting condition optimization, selecting particle diameter is that 300 object cocoanut active charcoals are catalyst carrier, adopt mantoquita to flood the absorbent charcoal carrier activating, precipitation, dry, the processing such as roasting, prepare the catalyst that is applicable to micro ware auxiliary catalysis oxidation processes Imidacloprid waster water process, show by engineer testing, the activated-carbon catalyst preparing by said method is applied to micro ware auxiliary catalysis oxidation Imidacloprid waster water process, work as H
2o
2addition is 14.73g/L, catalyst addition 50g/L, and microwave irradiation power 119W, exposure time 4min, pH value is 6 o'clock, technique can reach 86.2% to the COD clearance of imidacloprid pesticide simulated wastewater.Microwave energy consumption is now 0.00793kWh, and wastewater temperature is 48 DEG C.
Treatment effeciency of the present invention is high, and leaving water temperature is suitable, and dosing method and equipment are simple, easy to operate, for the processing of agricultural chemicals organic wastewater with difficult degradation thereby provides a kind of new and effective technique, has broad application prospects.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Selecting diameter is the carriers of 300 order cocoanut active charcoals as catalyst, the HNO that is 10% with mass fraction
3solution 1000mL soaks 150g cocoanut active charcoal after distilled water cleans, and after 40 DEG C of vibration 20h of constant temperature, 70 DEG C of constant temperature dryings, to constant weight, obtain the catalyst carrier of activation.
Take the activated carrier of 100g, add the CuSO of 1000mL
4solution, dipping 24h;
Filter, discard filtrate, catalyst carrier after treatment is dropped into precipitation reaction 24h in oxalic acid solution, after filtration, through the dry 12h of 80 DEG C of waters bath with thermostatic control, then in 110 DEG C of Constant Temp. Oven inner drying 2h, after cooling, roasting 3-5h under the high temperature of 350-450 DEG C, takes out, and obtains being applicable to the catalyst of micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process.
Described CuSO
4the concentration of solution is: 0.2mol/L, 0.3mol/L or 0.4mol/L.
The concentration of described oxalic acid solution is: 0.2mol/L, 0.3mol/L or 0.4mol/L.
Research shows, combines with catalytic oxidation technology auxiliary microwave, and this used water difficult to degradate of imidacloprid pesticide is had to certain treatment effect, and wherein the preparation of catalyst is the most key.
Embodiment 1: selecting diameter is the carriers of 300 order cocoanut active charcoals as catalyst, uses 10%(mass fraction) HNO
3solution 1000mL soaks 150g cocoanut active charcoal after distilled water cleans, and after 40 DEG C of vibration 20h of constant temperature, 70 DEG C of constant temperature dryings, to constant weight, obtain the catalyst carrier of activation.Take the activated carrier of 100g, adding 1000mL concentration is the CuSO of 0.3mol/L
4solution, dipping 24h.Filter, discard filtrate, by precipitation reaction 24h in the oxalic acid solution of catalyst carrier input 0.3mol/L after treatment, after filtration, through the dry 12h of 80 DEG C of waters bath with thermostatic control, again in 110 DEG C of Constant Temp. Oven inner drying 2h, cooling after, roasting 4h under the high temperature of 400 DEG C, take out, obtain being applicable to the catalyst of micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process, this catalyst is 268mg/L at imidacloprid pesticide simulated wastewater COD, H
2o
2addition is 14.73g/L, catalyst addition 50g/L, and microwave irradiation power 119W, exposure time 4min, can reach 86.2% to the COD clearance of technique.
Embodiment 2: selecting diameter is the carriers of 300 order cocoanut active charcoals as catalyst, uses 10%(mass fraction) HNO
3solution 1000mL soaks 150g cocoanut active charcoal after distilled water cleans, and after 40 DEG C of vibration 20h of constant temperature, 70 DEG C of constant temperature dryings, to constant weight, obtain the catalyst carrier of activation.Take the activated carrier of 100g, adding 1000mL concentration is the CuSO of 0.2mol/L
4solution, dipping 24h.Filter, discard filtrate, by precipitation reaction 24h in the oxalic acid solution of catalyst carrier input 0.2mol/L after treatment, after filtration, through the dry 12h of 80 DEG C of waters bath with thermostatic control, then in 110 DEG C of Constant Temp. Oven inner drying 2h, cooling after, roasting 5h under the high temperature of 350 DEG C, take out, obtain being applicable to the catalyst of micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process, or Cu-series catalyst, this catalyst is 268mg/L at imidacloprid pesticide simulated wastewater COD, H
2o
2addition is 14.73g/L, catalyst addition 50g/L, and microwave irradiation power 119W, exposure time 4min, can reach 61.3% to the COD clearance of technique.
Embodiment 3: selecting diameter is the carriers of 300 order cocoanut active charcoals as catalyst, uses 10%(mass fraction) HNO
3solution 1000mL soaks 150g cocoanut active charcoal after distilled water cleans, and after 40 DEG C of vibration 20h of constant temperature, 70 DEG C of constant temperature dryings, to constant weight, obtain the catalyst carrier of activation.Take the activated carrier of 100g, adding 1000mL concentration is the CuSO of 0.4mol/L
4solution, dipping 24h.Filter, discard filtrate, by precipitation reaction 24h in the oxalic acid solution of catalyst carrier input 0.4mol/L after treatment, after filtration, through the dry 12h of 80 DEG C of waters bath with thermostatic control, then in 110 DEG C of Constant Temp. Oven inner drying 2h, cooling after, roasting 3h under the high temperature of 450 DEG C, take out, obtain being applicable to the catalyst of micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process, or Cu-series catalyst, this catalyst is 268mg/L at imidacloprid pesticide simulated wastewater COD, H
2o
2addition is 14.73g/L, catalyst addition 50g/L, and microwave irradiation power 119W, exposure time 4min, can reach 78.6% to the COD clearance of technique.
The present invention has carried out the experiment of traditional catalytic oxidation processing imidacloprid pesticide waste water, and by comparison, micro ware auxiliary catalysis oxidation technology has oxidant H
2o
2consumption is few, its consumption saves approximately 2/5, and reaction speed is fast, by within traditional tens minutes, shortening to 5min, widen the scope of application of pH value, be extended to pH3-9 by traditional pH3-7, treatment effeciency is high, and leaving water temperature is suitable, dosing method and equipment are simple, the advantage such as easy to operate, for the processing of this class organic wastewater with difficult degradation thereby of agricultural chemicals provides a kind of new and effective technique, has broad application prospects.
Claims (1)
1. micro ware auxiliary catalysis oxidation technology is processed a preparation method for catalyst in imidacloprid pesticide waster water process, it is characterized in that containing following processing step: selecting diameter is the carriers of 300 order cocoanut active charcoals as catalyst, the HNO that is 10% with mass fraction
3solution 1000mL soaks 150g cocoanut active charcoal after distilled water cleans, and after 40 DEG C of vibration 20h of constant temperature, 70 DEG C of constant temperature dryings, to constant weight, obtain the catalyst carrier of activation;
Take the activated carrier of 100g, add the CuSO of 1000mL
4solution, dipping 24h;
Filter, discard filtrate, catalyst carrier after treatment is dropped into precipitation reaction 24h in oxalic acid solution, after filtration, through the dry 12h of 80 DEG C of waters bath with thermostatic control, then in 110 DEG C of Constant Temp. Oven inner drying 2h, after cooling, roasting 3-5h under the high temperature of 350-450 DEG C, takes out, and obtains being applicable to the catalyst of micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process;
The concentration of described oxalic acid solution is: 0.3mol/L, 0.2mol/L or 0.4mol/L.
2. the preparation method of catalyst in micro ware auxiliary catalysis oxidation processes imidacloprid pesticide waster water process according to claim 1, is characterized in that described CuSO
4the concentration of solution is: 0.3mol/L, 0.2mol/L or 0.4mol/L.
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| CN1330584C (en) * | 2004-09-20 | 2007-08-08 | 王君 | Method of fast degradation of organic phosphorus pesticide |
| CN100336721C (en) * | 2005-08-15 | 2007-09-12 | 昆明理工大学 | Super active carbon preparation method |
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| CN100395022C (en) * | 2006-07-04 | 2008-06-18 | 北京交通大学 | Activated charcoal carried copper oxide catalyst and process for preparing same |
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