CN103084138A - Application of zirconium dioxide microspheres prepared by using microchannel injection auxiliary method to adsorptive enrichment of organophosphorus pesticide - Google Patents
Application of zirconium dioxide microspheres prepared by using microchannel injection auxiliary method to adsorptive enrichment of organophosphorus pesticide Download PDFInfo
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- CN103084138A CN103084138A CN2013100210895A CN201310021089A CN103084138A CN 103084138 A CN103084138 A CN 103084138A CN 2013100210895 A CN2013100210895 A CN 2013100210895A CN 201310021089 A CN201310021089 A CN 201310021089A CN 103084138 A CN103084138 A CN 103084138A
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Abstract
The invention discloses an application of zirconium dioxide microspheres prepared by using a microchannel injection auxiliary method to adsorptive enrichment of organophosphorus pesticide. According to the application, the zirconium dioxide microspheres are obtained by forming a support substance by taking a chitosan material as an intermediate product, taking zirconium oxychloride octahydrate, acetic acid and sodium hydroxide as raw materials and adopting a microchannel auxiliary method under the room temperature. Each zirconium dioxide microsphere is of a mesoporous structure and can be used for carrying out adsorptive enrichment on the organophosphorus pesticide within a shorter time and is free of secondary pollution; and the zirconium dioxide microspheres subjected to adsorption are easy to be successfully separated from a solution so as to carry out effective desorption on the pesticide, so that detection of pesticide residues in vegetables, such as brassicae chinensis and cucumbers are successfully achieved. The application disclosed by the invention has the advantages of capability of obtaining raw materials easily, simple process, environmental friendliness and low cost; and the zirconium dioxide microspheres are large in adsorbing capacity to multiple organophosphorus pesticides and good in separating effect and the like, not only can be used for environment detection of a trace amount of residues of organophosphorus pesticides of agricultural produces, but also can be used for adsorptive treatment to waste liquor of organophosphorus pesticides and accords with the demands of practical production.
Description
Technical field
The present invention relates to a kind of zirconium dioxide method for preparing microsphere for the adsorption and enrichment organophosphorus pesticide, relate in particular to meso-hole structure, the micron order particle diameter to the selective adsorption and enrichment effect of organophosphorus pesticide, conveniently uses and the preparation method of the zirconium dioxide microballoon that separates.
Background technology
Organophosphorus pesticide grows up for replacing organo-chlorine pesticide, and it is than the easy degraded of organo-chlorine pesticide, to the pollution of ring and to the harm of the ecosystem with residually also all do not have organo-chlorine pesticide so general and outstanding; The advantages such as it is high that it has drug effect, wide in variety, and prevention and treatment range is wide, and cost is low, and the selection effect is high, and poisoning is little, and degraded is fast in environment, residual hazard is low, existing still worldwide extensive use has very consequence.But its shortcoming is higher to people, animal toxicity, and is often careless because of use, keeping etc., occurs poisoning.Organophosphorus pesticide is often used as insecticide spraying on fruit tree, vegetables, although it is more easily degraded than organo-chlorine pesticide, residual life, is shorter, but organophosphorus pesticide toxicity is also higher, if remain in agricultural chemicals on fruit, vegetables or the agricultural chemicals of entered environment enters organism, most of have inhibitory action to cholinesterase in organism, suppressing cholinesterase makes it lose the ability of decomposing acetylcholine, cause the acetylcholine accumulation, cause nerve dysfunction, thereby cause the infringement of human body.In recent years, along with growth in the living standard, therefore people seek a kind of fast and convenient feasible detection of organic phosphorus pesticide and the method for removal and hold the balance environment, health, food security growing interest.
In existing technology, there is several different methods can realize the removal of organophosphorus pesticide.The method of removing mainly can be divided into absorption and degraded, and wherein degradation process can be divided into biodegradation and non-biodegradation again.Nonbiodegradable method has absorption, catalytic degradation and light degradation substantially.In the process that organophosphorus pesticide is degraded, the toxicity that its catabolite has reduces, and the toxicity that has strengthens.And these degraded modes are at cost, efficient, complexity and cause the secondary pollution aspect to exist limitation.Therefore absorption is widely used as the simple and convenient and economic method of organic agricultural chemicals pollutant in a kind of removal and enrichment detection polluted-water.And various adsorbents be chosen in determining to a great extent absorption feasibility.In the past ten years, the researcher is exploitation new adsorbent such as active carbon, nano-aluminium oxide, and silicon adsorption material, carbon nanotube adsorption material, molecular engram sorbing material, and the macroporous resin adsorption material etc.But because their complicated loaded down with trivial details Separation of Solid and Liquid programs are very limited its application.Zirconium dioxide is as a kind of novel surrounding purifying material, it has, and molten boiling point is high, and hardness is large, and many strong acid and strong base solution are had enough advantages such as stability, and because there are a lot of bonded hydroxies on the zirconium dioxide surface, make it to organophosphorus pesticide, good selective absorption effect be arranged.In recent years, when carrying out waste water control, micron order or the grade structure that only need to be made into macroscopic view just can realize quick separation, and can not produce secondary pollution because of it.Simultaneously also can realize the recovery of precious absorbate, and the regeneration of adsorbent.Zirconium dioxide becomes the object of increasing scholar expert's research also because of its plurality of advantages.Xu Li (Anal. Chem. 2007,79,5,241 5248) be all etc. the zirconium dioxide hollow pipe that utilizes biological template to prepare to have macroscopical Centimeter Level structure, then the zirconium dioxide material that obtains be used for enrichment and detect solution trace organophosphorus pesticide pollution thing.But the preparation process of these magnetic materials is very complicated, and adsorption capacity is not very strong, although can realize organophosphorus pesticide pollution thing trace detection, can not be used for effective Adsorption of high concentration organophosphorus pesticide pollution thing.
The present invention adopts cheap shitosan as intermediate product moulding backing material, take eight water basic zirconium chlorides as the zirconium source.With both are simple mix after, rely on microchannel, then carry out gentle calcination process and just can obtain the zirconium dioxide micro-sphere material that has the micron order macrostructure and have meso-hole structure a step.A large amount of organophosphorus pesticide pollution thing in this zirconium dioxide micro-sphere material energy within a short period of time adsorbent solution of preparing, and the pH value that does not need to regulate contaminated solution.Zirconium dioxide bead after the absorption agricultural chemicals is carried out desorption, and desorption rate can reach 97%, illustrates that the enrichment that can be applied to the trace organophosphorus pesticide fully detects.Technique of the present invention is simple, and cost is low, and environmental friendliness is convenient to further expanding production.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of zirconium dioxide micro-sphere material.This preparation method is simple, and the zirconium dioxide micro-sphere material of preparation is better to the adsorption effect of organophosphorus pesticide.
Realize technical scheme of the present invention:
A kind of zirconium dioxide micro-sphere material, this material macroscopic view has micro-sphere structure, and microcosmic has meso-hole structure.
The preparation method of zirconium dioxide microballoon of the present invention comprises the following steps:
1), 3.0 gram shitosans are joined 100 mL volumetric concentrations is in 3% aqueous acetic acid, forms homogeneous phase solution under magnetic agitation;
2), under magnetic agitation, 0.3 g eight water basic zirconium chlorides are joined in the solution that step 1) obtains, continue magnetic agitation and be mixed into homogeneous phase solution;
3), use the syringe of 2mL, step 2 is got in gradation) resulting solution, be added drop-wise in 3 mol/L sodium hydroxide solutions, form spherical products;
4), with step 3) product that obtains filters, filter cake is dried under 50 ℃ of conditions, calcines under 600 ℃ of conditions in Muffle furnace, namely obtains the zirconium dioxide microballoon.
Above-mentioned preparation method's step 4) in, filter cake is dried under 50 ℃ of conditions, and with the programming rate to 600 of 5 ℃/min ℃, calcining is 6 hours under 600 ℃ of conditions in Muffle furnace.
Effect of the present invention and advantage:
1. the zirconium dioxide micro-sphere material that obtains of the inventive method, macroscopic view has particle diameter and is the micro-sphere structure of micron, and microcosmic has meso-hole structure.
2. whole technical process is simple and easy to control, and power consumption is few, and productive rate is high, and cost is low, realistic need of production.
3. compare with existing synthetic adsorption and enrichment material technology, synthesis condition is gentle, and power consumption is few, and simple, product purity is high, steady quality.The absorption organophosphorus pesticide only just can reach adsorption equilibrium about 10 minutes, the DDVP about 10 minutes more than 98% has removed.Zirconium dioxide microballoon after the absorption organophosphorus pesticide is carried out desorption, and desorption rate can reach 97%.Realizing suitability for industrialized production and actual detection application for it provides the foundation.
Further the present invention will be described below in conjunction with drawings and Examples.
Description of drawings
Fig. 1 is the XRD diffraction maximum of the prepared zirconium dioxide sample of embodiment 1;
The XRD collection of illustrative plates of diffraction maximum and zirconium dioxide standard contrast in figure, the zirconium dioxide sample that can find out preparation is pure zirconium dioxide crystal (JCPDS file No. 81-1544).
Fig. 2-1, Fig. 2-2 are respectively that embodiment 1 products therefrom is the XPS spectrum figure of phosphorus 2p track before and after absorption DDVP, as can be seen from the figure adsorb the characteristic peak that apparent in view phosphorus appears in phosphorus 2p track spectrogram after DDVP.
Fig. 3 and 4 is phosphorus 2p track before and after embodiment 1 products therefrom absorption DDVP and the spectrogram of oxygen 1s track, and as can be seen from Figure 4, the characteristic peak of apparent in view phosphorus-to-oxygen bonds appears in the oxygen 1s track spectrogram after absorption DDVP.
Fig. 5-1, Fig. 5-2 are respectively the overall picture of embodiment 1 gained zirconium dioxide microballoon and local pattern SEM figure, can find out significantly that from the SEM picture prepared zirconium dioxide micro-sphere material surface has meso-hole structure.
Fig. 6 is the N of embodiment 1 gained zirconium dioxide microballoon
2Adsorption-desorption curve and graph of pore diameter distribution.
Fig. 7 be the zirconium dioxide microballoon of embodiment 1 gained to the dynamics absorption figure of the DDVP of variable concentrations, can see about 10 minutes from figure just can reaching adsorption equilibrium.The speed that adsorbent absorption DDVP is described is very fast, and respectively has the DDVP more than 98% to be removed about 10 minutes.
Fig. 8 is that embodiment 1 gained zirconium dioxide microballoon has adsorbed the chromatograms that carries out desorption after organophosphorus pesticide DDVP, and as can be seen from the figure the zirconium dioxide microballoon has good desorption performance, can be applied to the detection of actual sample.
Fig. 9 is that the zirconium dioxide microballoon of embodiment 1 gained is to the comparison diagram of organophosphorus pesticide and non-organophosphorus pesticide adsorption effect, as can be seen from the figure, the zirconium dioxide microballoon is only to organophosphorus pesticide DDVP and the selective suction-operated of phoxim, and to non-organophosphorus pesticide 2,4-drips does not have suction-operated.
The specific embodiment
Embodiment 1
The preparation of zirconium dioxide micro-sphere material
Preparation process is as follows successively:
1), 3.0 gram shitosans are joined the 100mL volumetric concentration is in 3% aqueous acetic acid, forms homogeneous phase solution under magnetic agitation; Under magnetic agitation, 0.3 g eight water basic zirconium chloride solids are joined in the acetum of shitosan, continue magnetic agitation and be mixed into homogeneous phase solution;
2) the 2 mL syringes that are, 0. 5mm with the syringe needle diameter are drawn full packages homogeneous phase solution (2 mL), dropwise be added drop-wise to take the height of 6 about cm and be loaded with volume in the culture dish of the 3 mol/L sodium hydroxide solutions of 55 mL, wherein the culture dish diameter is 8.7 cm, this moment, the volume of the sodium hydroxide solution that fills just accounted for more than 2/3 of culture dish volume, at this moment sodium hydroxide solution will be greatly excessive, will form spherical products at once in the dropping process.The sodium hydroxide solution of surface plate institute splendid attire can make 2 mL full packages homogeneous phase solution balling-up about 20 pipes.
3), the product that obtains is filtered, and wash more than 3 times with distilled water, to remove the NaOH of product remained on surface, products therefrom after washing is dried under 50 ℃ of conditions, in Muffle furnace with the programming rate of 5 ℃/min, calcined 6 hours, and just can obtain the zirconium dioxide micro-sphere material for 600 ℃.
The XRD of product zirconium dioxide sample sees Fig. 1; Phosphorus 2p track before and after absorption DDVP and the spectrogram of oxygen 1s track are seen Fig. 2-1,2-2, Fig. 3 and 4; Zirconium dioxide microballoon overall picture and local pattern SEM figure see Fig. 5-1, Fig. 5-2, the N of zirconium dioxide microballoon
2Adsorption-desorption curve and graph of pore diameter distribution are seen Fig. 6.
Embodiment 2
Organophosphorus pesticide DDVP experiment in the zirconium dioxide micro-sphere material adsorbent solution of embodiment 1 preparation
1, take 30 milligrams, the zirconium dioxide micro-sphere material adsorbent of gained;
2, take DDVP agricultural chemicals solid dissolve with methanol solution, being mixed with concentration is 1000 mg L
-1The standard liquid of DDVP (DDVP):
3, the standard liquid of removing step 2 be diluted to respectively 150,200,270 and 300 mg/L simulating pollution solution each 50 milliliters standby:
4, DDVP experiment in the contaminated solution of absorption.Experiment is carried out at ambient temperature, do not need to regulate the pH value of sewage, zirconium dioxide material concentration 0.6 g/L, begin timing after evenly spreading to adsorbent in sewage, what whole adsorption process kept oscillator is 120 rev/mins, and a minute different time is taken a sample, and the liquid diameter of taking a sample is the membrane filtration of 0.25 μ m, filtrate uses high performance liquid chromatography (model is LC-20A, Japanese Shimadzu) to analyze at once.Analysis result is depicted as dynamics absorption figure such as Fig. 7.
5, with 0.03 g embodiment 1 system the DDVP solution absorption after 30 minutes of putting into 50 milliliter of 150 mg/L of zirconium dioxide microballoon, take out the zirconium dioxide microballoon, the methanol solution of putting into 50 milliliters of pH=10 carries out desorption.Before absorption and the DDVP solution after desorption take a sample respectively, be the membrane filtration of 0.25 μ m with diameter, filtrate horse back is analyzed with high performance liquid chromatography, can get desorption rate and reach 97%.The contrast of gained chromatograms as shown in Figure 8.
6, the zirconium dioxide microballoon of getting respectively 0.03 g embodiment 1 gained is put into the DDVP of 50 milliliter of 150 mg/L, phoxim and 2,4-drip in solution, and a minute different time is taken a sample, the liquid diameter of taking a sample is the membrane filtration of 0.25 μ m, and filtrate is analyzed with high performance liquid chromatography at once.Figure is as Fig. 9 in analysis result absorption.
Embodiment 3
1, take little green vegetables and each 25g of cucumber slice sample as actual sample;
2, the sample that takes is added respectively in mortar, respectively add 5 g NaCl to grind broken;
3, will grind broken sample and transfer in conical flask, add 30 ml acetonitriles, ultrasonic 15 minutes, cooling rear centrifugal, standing with centrifuge; Organic phase is transferred in 100 ml volumetric flasks; Remaining mother liquor continues to use the acetonitrile extracting twice, and organic phase solution is continued to transfer in volumetric flask.Extraction adds acetonitrile to graduation mark after finishing in the volumetric flask that fills acetonitrile solution;
4, previous step gained acetonitrile solution is transferred in 150 ml conical flasks, added the prepared zirconium dioxide microballoon of 0.1 g embodiment 1, vibration absorption 90 minutes;
5, after absorption is completed, take out the zirconium dioxide bead, join desorption in the methanol solution of 25 ml pH=10, respectively get gained solution 5 ml after desorption, the DDVP standard liquid that adds respectively 10,20,30 μ L 1000 mg/L, after 0.25 μ m membrane filtration, inject high performance liquid chromatograph and detect;
6, above experiment is parallel does 3 times, averages.Actual sample detects the data obtained and is respectively in table 1,2, and by can be calculated, this content with DDVP in the measured little green vegetables of standard addition method is 0.0412 mg/g, and in cucumber slice, the content of DDVP is 0.0359 mg/g, all meets national standard.
In the little green vegetables sample of table 1, the DDVP agricultural chemicals reclaims and detects test (n=3)
Sample; Mark-on concentration (mg/L); Detectable concentration (mg/L); The rate of recovery (%); Relative standard deviation (%)
1 2 2.0545 105.8 4.3
2 4 4.0495 104.0 3.5
3 6 6.0555 101.9 1.7。
In table 2 cucumber sample, the DDVP agricultural chemicals reclaims and detects test (n=3)
Sample; Mark-on concentration (mg/L); Detectable concentration (mg/L); The rate of recovery (%); Relative standard deviation (%)
1 2 2.0435 103.2 3.7
2 4 4.0454 98.9 2.5
3 6 6.0458 98.0 2.9。
Claims (3)
1. zirconium dioxide microballoon, it is characterized in that: particle diameter is micron order, has meso-hole structure, and organophosphorus pesticide is had good selective absorption effect.
2. the preparation method of zirconium dioxide microballoon as claimed in claim 1 is characterized in that comprising the following steps:
1), 3.0 gram shitosans are joined 100 mL volumetric concentrations is in 3% aqueous acetic acid, forms homogeneous phase solution under magnetic agitation;
2), under magnetic agitation, 0.3 g eight water basic zirconium chlorides are joined in the solution that step 1) obtains, continue magnetic agitation and be mixed into homogeneous phase solution;
3), use the syringe of 2mL, step 2 is got in gradation) resulting solution, being added drop-wise to concentration is in 3 mol/L sodium hydroxide solutions, forms spherical products;
4), with step 3) product that obtains filters, filter cake is dried under 50 ℃ of conditions, calcines under 600 ℃ of conditions in Muffle furnace, namely obtains the zirconium dioxide microballoon.
3. the preparation method of zirconium dioxide microballoon as claimed in claim 2, is characterized in that step 4) in, filter cake is dried under 50 ℃ of conditions, and with the programming rate to 600 of 5 ℃/min ℃, calcining is 6 hours under 600 ℃ of conditions in Muffle furnace.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103706333A (en) * | 2013-09-26 | 2014-04-09 | 燕山大学 | Preparation method and phosphorus removal method of zirconium oxide-loading phosphorus removal biological composite material |
| CN106376992A (en) * | 2016-10-26 | 2017-02-08 | 广西大学 | Agricultural protective mask material |
| CN106902729A (en) * | 2017-03-31 | 2017-06-30 | 华中师范大学 | A kind of Zr La metal composite oxides, preparation and its control body eutrophication remove phosphatic application |
| CN111207958A (en) * | 2020-01-08 | 2020-05-29 | 中国农业科学院农业质量标准与检测技术研究所 | Pretreatment agent and pretreatment package for organophosphorus pesticide detection and application thereof |
| CN114262646A (en) * | 2021-12-28 | 2022-04-01 | 山东中大药业有限公司 | Detergent for removing pesticide residues of traditional Chinese medicine plants and preparation method thereof |
| CN115722213A (en) * | 2022-11-29 | 2023-03-03 | 浙江工业大学 | Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater |
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2013
- 2013-01-21 CN CN201310021089.5A patent/CN103084138B/en not_active Expired - Fee Related
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| ABDELKRIM EL KADIB ET AL.: "Chitosan templated synthesis of porous metal oxide microspheres with filamentary nanostructures", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
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| CN103706333A (en) * | 2013-09-26 | 2014-04-09 | 燕山大学 | Preparation method and phosphorus removal method of zirconium oxide-loading phosphorus removal biological composite material |
| CN103706333B (en) * | 2013-09-26 | 2016-08-17 | 燕山大学 | A kind of preparation carrying zirconium oxide phosphorus removal bio composite and phosphorus removing method |
| CN106376992A (en) * | 2016-10-26 | 2017-02-08 | 广西大学 | Agricultural protective mask material |
| CN106902729A (en) * | 2017-03-31 | 2017-06-30 | 华中师范大学 | A kind of Zr La metal composite oxides, preparation and its control body eutrophication remove phosphatic application |
| CN106902729B (en) * | 2017-03-31 | 2019-11-26 | 华中师范大学 | A kind of Zr-La metal composite oxide, preparation and its control water eutrophication remove phosphatic application |
| CN111207958A (en) * | 2020-01-08 | 2020-05-29 | 中国农业科学院农业质量标准与检测技术研究所 | Pretreatment agent and pretreatment package for organophosphorus pesticide detection and application thereof |
| CN111207958B (en) * | 2020-01-08 | 2022-08-02 | 中国农业科学院农业质量标准与检测技术研究所 | Pretreatment agent and pretreatment package for organophosphorus pesticide detection and application thereof |
| CN114262646A (en) * | 2021-12-28 | 2022-04-01 | 山东中大药业有限公司 | Detergent for removing pesticide residues of traditional Chinese medicine plants and preparation method thereof |
| CN114262646B (en) * | 2021-12-28 | 2024-04-16 | 山东中大药业有限公司 | Detergent for removing pesticide residues of traditional Chinese medicine plants and preparation method thereof |
| CN115722213A (en) * | 2022-11-29 | 2023-03-03 | 浙江工业大学 | Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater |
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