CN101810939A - Preparation and application method of solid phase extractant capable of simultaneously accumulating multiple heavy metal ions - Google Patents
Preparation and application method of solid phase extractant capable of simultaneously accumulating multiple heavy metal ions Download PDFInfo
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Abstract
The invention relates to a preparation and application method of a solid phase extractant capable of simultaneously accumulating multiple heavy metal ions. Firstly, 2.5g of carboxylation carbon nano tube and 30 mL of anhydrous thionyl chloride react for 1-2 days at the temperature of 60-90 DEG C; pump filtration is carried out; after being cleaned, filter residue is dried in vacuum for the whole night to obtain an acylation carbon nano tube; the acylation carbon nano tube is dispersed in a solution composed of 1g of thiosemicarbazide and 100 mL of anhydrous N, N-dimethyl formamide; the mixture reacts under the protection of nitrogen with the temperature of 100 DEG C for 48 hours; pump filtration is carried out; after being cleaned, the filter residue is dried in vacuum for 1-2 days to obtain the solid phase extractant capable of simultaneously accumulating multiple heavy metal ions. The solid phase extractant serves as a column filler to dynamically accumulate 0.5-1 L of water samples to be detected, wherein the heavy metal ion content of the water samples is 1-5 mu g/L; and the solid phase extractant in which the heavy metal ions are accumulated is eluted and desorbed by utilizing dilute nitric acid, wherein the recovery rate is above 95%, and the desorbed solid phase extractant is repeatedly recycled for 2-3 times. The invention has high efficiency, is simple and can simultaneously accumulate various heavy metal ions, i.e. Cu (II), Ni (II), Zn (II), Cd (II) and Pb (II).
Description
Technical field
The present invention relates to the preparation and the application process thereof of the solid extracting agent that a kind of contents of many kinds of heavy metal ion of enrichment simultaneously uses, be specifically related to the preparation method of the functionalized carbon nano-tube of multiple trace heavy metal ion in a kind of SPE environment water and the fluid sample; Further relate to using method with this solid extracting agent extraction contents of many kinds of heavy metal ion.Belong to and separate and technical field of analysis and detection.
Background technology
Along with developing rapidly of industrial or agricultural, a large amount of pollutants enter environment, cause the environmental quality severe exacerbation, and wherein heavy metal pollution is one of the most serious pollution.Be different from other pollutant, heavy metal pollution has characteristics such as disguise, irreversibility and chronicity.In environment, easily accumulate, can be suppressed crop growth, promote early ageing, reduce output, and enter plant, by the transmission and the enrichment of food chain, finally be detrimental to health again by the root system of plant by absorptions such as soil crops.Be difficult in the heavy metal pollution short-term being discovered,, run up to a certain degree and just can show the harm of environment and human body by the people.Because rapid economy development, the heavy metal pollution problem of China is on the rise in recent years, and Chinese Ministry of Environmental Protection is informed of a case in 2009 just 12 heavy metals such as Fengxiang, Shaanxi, metalloid contamination accident.These incidents cause that 4035 people's blood leads exceed standard, 182 people's cadmiums exceed standard, and cause 32 Mass disturbances.Different heavy metals is different to human body harm, can damage nervous system as mercury, lead, causes slow in reacting, dull-witted; Cadmium can cause bone ailing downright bad; Nickel is then bigger to the liver function destructiveness.In addition, mercury, cadmium, arsenic, lead all can cause human body and suffer from cancer, cause diseases such as artery sclerosis, cardiovascular and cerebrovascular diseases, dementia.Therefore, as one of heavy metal pollution of water body thing research main contents, carry out about the fast enriching of trace in the water body or ultra trace heavy metal and the research work of detection receiving much concern always.
Because most of heavy metals all exist with the inorganic matter ionic species in water, colorless and odorless generally is difficult to visual inspection, even instrument detecting also requires the instrument of pinpoint accuracy just can test out.How to the separation of trace in the complicated substrate or ultra trace heavy metal ion and carry out simply, the on-the-spot detection is problem demanding prompt solution quickly.Though various instrument analytical methods are along with the detection limit of its analytical method of scientific and technological progress is more and more lower, the content that directly analyze these heavy metal ion tends to meet difficulty, and even may not realize under the particular case.In order to improve the sensitivity and the selectivity of existing Instrumental Analysis, satisfy the demand of the existing detection of complex environment sample, the enrichment preconditioning technique of more and more heavy metal ion was constantly developed in the last few years.Common concentration and separation technology to heavy metal ion relates generally to coprecipitation, ion-exchange, electrodeposition process, liquid-liquid extraction method etc.In recent years, since have high enrichment multiple, easy and simple to handle, do not cause secondary pollution, can use repeatedly, easily characteristics such as unite with different modern analysis detection techniques, SPE (SPE) technology is subjected to extensive concern as a kind of novel enrichment preconditioning technique.But, till to the greatest extent, very Cheng Shu SPE product shortage relatively also, so development of new efficiently, simply fast little, trace heavy metal ion SPE material is still significant.
CNT (CNTs) is widely studied at enriching pollutants with in removing owing to its super large specific area, strong electrostatic adsorption, high chemical stability and heat endurance.In the last few years, CNT carry out appropriate functionalization, utilize the research of the coordination enriched in metals ion of active group also to cause extensive concern (Y.Liu, Y.Li, X.P.Yan, Adv.Funct.Mater.2008,18,1536-1543.), but this class material is because the coordination selectivity of part, only have selectivity preferably, be raising extraction efficiency, the requirement that need extract multiple metal simultaneously when can not satisfy some at certain metal.Though carboxylic carbon nano-tube can have enrichment simultaneously and absorption behavior to contents of many kinds of heavy metal ion, can realize contents of many kinds of heavy metal ion enrichment simultaneously extraction, but the restriction of the characteristics of carboxyl coordination, often limited the kind (A.Staffej of its adsorption capacity and adion, K.Pyrzynska, Microchem.J., 2008,89,29-33).Thiosemicarbazides often is applied in the analytical chemistry compartment analysis as the complexing agent of contents of many kinds of heavy metal ion, by chemical reaction it is bonded to carbon nano tube surface, will obtain a kind of extraction material that can be used for extracting simultaneously various heavy.
Summary of the invention
The objective of the invention is to disclose a kind of preparation method of solid extracting agent of the contents of many kinds of heavy metal ion of enrichment simultaneously, another object of the present invention is with the application process of this solid extracting agent as the heavy metal ion solid extracting agent of multiple little, the trace of enrichment.
To achieve these goals, the present invention has made full use of characteristics such as the super large specific surface of CNT and easy functionalization, and thiosemicarbazides all has characteristics such as strong coordination ability to common metal ion, studied the amido thiocarbamide chemical modification method of CNT, and applied it in the SPE of trace heavy metal in the water sample.Product of the present invention is an initiation material with commercially available carboxyl carbon nanotube and thiosemicarbazides, by simple synthesis step, obtain a kind of thiosemicarbazides functionalized carbon nanotube that contains, the range of application of CNT in heavy metal isolation technics enrichment field expanded in extraction when can be effectively applied to natural water trace heavy metal ion Cu (II), Ni (II), Zn (II), Cd (II), Pb (II).This material is in pH 〉=5.5 o'clock, 40,8,16,13,15mg/g high absorption capacity to Cu (II), Ni (II), Zn (II), Cd (II), Pb (II) is respectively:, antijamming capability to other water body common ion is stronger, heavy metal ion after the enrichment can reclaim with hydrochloric acid or the nitric acid of 1～2M, and the rate of recovery is all more than 95%.It is a kind of new and effective heavy metal ion solid extracting agent.
The concrete step is poly-as follows:
Anhydrous thionyl chloride with 2.5g carboxylic carbon nano-tube and 30mL places round-bottomed flask earlier, 60-90 ℃ of stirring and refluxing reacted 1-2 days, and reaction finishes the back suction filtration, and filter residue cleans 3 times with anhydrous tetrahydro furan, vacuum drying is spent the night again, gets acyl group carbon nano tube product; Then gained acyl group carbon nano tube is dispersed in by 1g thiosemicarbazides and the anhydrous N of 100mL; in the solution that dinethylformamide (DMF) is formed; under 100 ℃ of nitrogen protections; reaction 48h; suction filtration after reacting completely, filter residue absolute ethanol washing 3 times, vacuum drying 1-2 days; the final thiosemicarbazides modified carbon nano-tube product that gets, the solid extracting agent of the contents of many kinds of heavy metal ion of enrichment simultaneously.
The application process of the solid extracting agent of the contents of many kinds of heavy metal ion of enrichment simultaneously is: earlier with the column packing of 5～20mg thiosemicarbazides modified carbon nano-tube product as solid-phase extraction device, be filled in the solid phase extraction column of 6mL of solid-phase extraction device, with solid-phase extraction device 0.5～1L water sample to be measured is carried out dynamic enrichment again, water sample to be measured is that heavy metal ion content is the water sample of 1～5 μ g/L, and heavy metal ion comprises Cu (II), Ni (II), Zn (II), Cd (II) and Pb (II); Then with the molar concentration of 5mL be rare nitric acid of 1～3M to enrichment the solid extracting agent of heavy metal ion carry out wash-out and desorb, the rate of recovery of heavy metal ion is more than 95%, separate attached solid extracting agent and still have preferably adsorption capacity again, can recycle repeatedly 2～3 times.
Major advantage of the present invention is as follows:
1, the present invention successfully utilizes little molecular function part thiosemicarbazides that the absorption property of material is regulated and control, extracting power when making CNT after the functionalization possess Cu (II), Ni (II), Zn (II), Cd (II) and Pb (II) contents of many kinds of heavy metal ion.
2, the CNT pH scope of application that the inventive method obtains is wide, o'clock all can guarantee the adsorption efficiency of above-mentioned metal ion (95%) preferably in pH 〉=5.5; The Ca of common concentration in the water body
2+, Mg
2+, Mn
2+, Co
2+And Fe
3+All to the not influence of material absorption contents of many kinds of heavy metal ion; The heavy metal ion of absorption can desorb with diluted acid, and the rate of recovery can reach 95%, separates attached material and still has preferably adsorption capacity again, can recycle repeatedly 2～3 times, has certain chemistry, physical stability.
3, the functionalized carbon nano-tube solid extracting agent that the inventive method obtains, for a kind of novel be the efficient, fast simple of carrier based on CNT, can be used for the solid extracting agent that contents of many kinds of heavy metal ion extracts simultaneously, the solid-phase extraction column that can be used for packed goodsization, utilizing solid-phase extraction device to carry out the dynamic enrichment operation of actual water sample, is a kind of heavy metal extractant with practicability potentiality.
The specific embodiment
Embodiment 1
Take by weighing the commercially available multi-carboxylation CNT of 2.5g (MC3, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) and the 20mL thionyl chloride place round-bottomed flask, 60-90 ℃ of stirring and refluxing reacted 1-2 days, reaction finishes the back suction filtration, filter residue cleans 3 times with anhydrous tetrahydro furan, vacuum drying is spent the night again, gets acyl group carbon nano tube product; Again gained acyl group carbon nano tube is dispersed in by 1g thiosemicarbazides and the anhydrous N of 100mL; in the solution that dinethylformamide is formed; under 100 ℃ of nitrogen protections; reaction 48h; suction filtration after reacting completely, filter residue absolute ethanol washing 3 times, vacuum drying 1～2 day; the final thiocarbamide modified carbon nano-tube product that gets, the i.e. solid extracting agent of the contents of many kinds of heavy metal ion of enrichment simultaneously.
Embodiment 2
The solid extracting agent of enrichment contents of many kinds of heavy metal ion carries out every index experiment in the time of with embodiment 1 gained:
1) 20mg solid extracting agent product, the Cu of 20mL (II), Ni (II), Zn (II), Cd (II), Pb (II) (being 1mg/L) solution, condition of different pH is fully vibration down, carry out the adsorption experiment of Cu (II), experimental results show that: when system pH 〉=5.5, its adsorption rate improves rapidly, reaches more than 95%.For reaching the absorption fully of Cu (II), it is the pH condition that other condition experiment is all selected pH=6.
2) selecting pH=6 is system pH condition, 20mg solid extracting agent product, 10mL with 1) identical Cu (II), Ni (II), Zn (II), Cd (II) and Pb (II) solion (1mg/L), carry out Cu (II), Ni (II), Zn (II), Cd (II) and Pb (II) ionic adsorption time and test, test only show need the 3min product just can reach to adsorb saturated;
40,8,16,13,15mg/g 3) by the adsorbance change curve of product under the different above-mentioned several heavy metal ion initial concentrations of research, obtain product the high absorption capacity of Cu (II), Ni (II), Zn (II), Cd (II) and Pb (II) is respectively:;
In the above-mentioned 1-3 step, all adopt suitable Cu (II), Ni (II), Zn (II), Cd (II) and Pb (II) mixed solution, after solid extracting agent absorption,, got cleaner liquid and measure several heavy metal concentrations and calculate accordingly result through 0.45 μ m membrane filtration.
4) 1mg/L Cu (II) solution has been carried out the common ion interference test, when relative error is 5%, 750mg/L Ca
2+, 800mg/L Mg
2+, 100mg/L Fe
3+, 10mg/L Mn
2+With 10mg/L Co
2+Absorption to above-mentioned several heavy metal ion does not exert an influence, and with rare nitric acid (1M) wash-out, measures several concentration of heavy metal ion of eluent, and calculate recovery rate, and the rate of recovery is all greater than 95%;
5) functionalized carbon nano-tube of embodiment 1 gained, promptly the solid extracting agent 5～20mg of the contents of many kinds of heavy metal ion of enrichment simultaneously is a column packing, be filled in the solid phase extraction column of 6mL of solid-phase extraction device, with solid-phase extraction device 0.5～1L is simulated Cu (II), Ni (II), Zn (II), Cd (II) and Pb (II) water sample (each concentration of metal ions is 1～5 μ g/L) carry out dynamic enrichment, and with rare nitric acid of 5mL (1～3M) wash-out desorbs, directly measure the concentration of each metal ion species of eluting liquid, and calculate recovery rate, its optimum recovery rate can reach 95%, separate attached solid extracting agent and still have preferably adsorption capacity again, can recycle repeatedly 2～3 times.
Annotate: the instrument that is used for measuring simultaneously various tenors and concentration among the embodiment 2 is: the Optima 2100 DV plasma emission spectrometers of U.S. PE company.
Claims (2)
1. the preparation method of the solid extracting agent of enrichment contents of many kinds of heavy metal ion simultaneously, it is characterized in that: the anhydrous thionyl chloride with 2.5g carboxylic carbon nano-tube and 30mL places round-bottomed flask earlier, 60-90 ℃ of stirring and refluxing reacted 1-2 days, reaction finishes the back suction filtration, filter residue cleans 3 times with anhydrous tetrahydro furan, vacuum drying is spent the night again, gets acyl group carbon nano tube product; Then gained acyl group carbon nano tube is dispersed in by 1g thiosemicarbazides and the anhydrous N of 100mL; in the solution that dinethylformamide is formed; under 100 ℃ of nitrogen protections; reaction 48h; suction filtration then, filter residue was with absolute ethanol washing 3 times, vacuum drying 1-2 days; the final thiosemicarbazides modified carbon nano-tube product that gets, the solid extracting agent of the contents of many kinds of heavy metal ion of enrichment simultaneously.
2. the application process of the solid extracting agent of the contents of many kinds of heavy metal ion of enrichment simultaneously of claim 1, it is characterized in that: earlier with the column packing of 5～20mg thiosemicarbazides modified carbon nano-tube product as solid-phase extraction device, be filled in the solid phase extraction column of 6mL of solid-phase extraction device, with solid-phase extraction device 0.5～1L water sample to be measured is carried out dynamic enrichment again, heavy metal ion comprises Cu (II), Ni (II), Zn (II), Cd (II) and Pb (II) in the water sample to be measured, and content is 1～5 μ g/L; Then with the molar concentration of 5mL be rare nitric acid of 1～3M to enrichment the solid extracting agent of heavy metal ion carry out wash-out and desorb, the rate of recovery of heavy metal ion is more than 95%, separate attached solid extracting agent and still have preferably adsorption capacity again, can recycle repeatedly 2～3 times.
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| CN102284275A (en) * | 2011-06-13 | 2011-12-21 | 同济大学 | Preparation method of heavy metal ion solid-phase extraction agent |
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| CN102284275B (en) * | 2011-06-13 | 2013-01-02 | 同济大学 | Preparation method of heavy metal ion solid-phase extraction agent |
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| CN102500318B (en) * | 2011-09-28 | 2013-10-30 | 武汉工程大学 | Surface modification method of carbon nanotube, carbon nanotube and application thereof |
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