CN102284275B - Preparation method of heavy metal ion solid-phase extraction agent - Google Patents
Preparation method of heavy metal ion solid-phase extraction agent Download PDFInfo
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- CN102284275B CN102284275B CN2011101567557A CN201110156755A CN102284275B CN 102284275 B CN102284275 B CN 102284275B CN 2011101567557 A CN2011101567557 A CN 2011101567557A CN 201110156755 A CN201110156755 A CN 201110156755A CN 102284275 B CN102284275 B CN 102284275B
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Abstract
The invention relates to a preparation method of a heavy metal ion solid-phase extraction agent. In the method, a multi-walled carbon nano-tube is used as a main body, a phenyliminodiacetic acid ligand is introduced to the surface of the carbon nano-tube by virtue of a mild diazotization reaction so as to obtain a phenyliminodiacetic acid modified carbon nano-tube; and the phenyliminodiacetic acid modified carbon nano-tube serving as a heavy metal ion solid-phase extraction agent is filled in a 6mL SPE (solid phase extraction) column, a mixed water sample containing Pb(II), Cu(II) and Fe(III)is dynamically enriched by using an SPE device, the adsorption rate reaches 95 to 97 percent when the pH is 6, and the recovery rate is more than 97 percent. The heavy metal ion solid-phase extraction agent has a mild and quick reaction and a high functional modification degree by using water as a solvent, and has the characteristics of capabilities of simultaneously adsorbing Pb(II), Cu(II) and Fe(III) in the water body, high adsorption capacity, strong interference resistance, recyclability and the like.
Description
Technical field
The present invention relates to a kind of preparation method of heavy metal ion solid-phase extraction agent, specifically prepare the technique of phenylimino oxalic acid modified carbon nano-tube by diazo-reaction.The heavy metal ion pre-separation beneficiation technologies field that belongs to trace in the fluid sample.
Background technology
At present, the harm of heavy metal is paid close attention to by the people more and more, and heavy metal is as the most dangerous pollutant of a class, the serious ecological environment and human healthy and safe that threatens.Because heavy metal has irreversibility and accumulation property, even in the situation of trace, also can produce adverse consequences, therefore, content of beary metal seems further necessary in concentration and separation and the testing environment effectively.
Solid phase extraction techniques (Solid phase extraction, be called for short SPE) be a kind of novel pre-separation beneficiation technologies that grows up the seventies in last century, be widely used in all trades and professions because have the following advantages: 1) organic solvent consumption is few, composition to be measured is in the SPE post after the enrichment, eluant, eluent that only need to be few just can be the complete wash-out of composition to be measured in fixing mutually, and the consumption of organic solvent is well below traditional liquid-liquid extraction.2) can carry out the pre-separation of purifying and the interfering component of sample, in conjunction with the characteristics of composition to be measured, select targetedly extractant, thereby selectively enrichment composition to be measured, also can allow interfering component be retained on the extractant, allow composition to be measured pass through, thereby separate interfering component.Therefore, the SPE technology can effectively be carried out Sample Purification on Single and interfering component pre-separation.3) enrichment times is high, and to environmental water sample, the SPE technology can be enriched to several milliliters to tens compositions to be measured to hundreds of ml samples, and enrichment times reaches decades of times to hundreds of times, and this advantage when concentration of component to be measured is lower, show more obvious.4) the SPE technology can be enriched in composition to be measured in the SPE post, is convenient to the storage of sample and transports, and is highly suitable for the spot sampling in the environmental monitoring.5) easily realize automation mechanized operation, energy and various detecting instrument such as ICP, HPLC etc. link to each other, and reach the purpose of rapid analysis.
Application SPE technology Preconcentration and Separation trace metal ion has obtained the concern of vast scientific researcher, Liu Yongwen etc. are with 2,6-dihydroxy benzenes-diazoaminoazobenzene (DHDAA) and 2-thiuretic acid benzene diazoaminoazobenzene (AMPDAA) modification Ambcrlitc XAD-4 pre-separation enrichment Cd (II), Co (II), Cu (II), the metal ions such as Zn (II), and for these Enrichment of trace ions mensuration of environmental water sample (Liu Y, Guo Y, Meng S, FengF, Chang X.Microchemical Atca, 2007,157:209.).Cr (III), Pb (II), Fe (III) that active carbon after the human ethylenediamine modifications such as Chang Xijun adsorbs in the water sample have simultaneously obtained good effect (Chang X J, Li ZH, Zou X J, et al.Analytica ChimicaActa, 2009,632:272-277).The development of SPE technology has promoted the development of SPE material.
In recent years, CNT is because its excellent physicochemical properties have been subject to extensive concern.Huge specific area wherein, excellent chemical stability, and easily the advantage such as functionalization has CNT to become the prerequisite of SPE material.Cd (II) in the carbon nanotube adsorption environmental water sample of the people such as Yan after with the Cys modification has obtained satisfied result (Y Liu, Y Li, X P Yan, Adv Funct Mater, 18 (2008) 1536-1543.).The humans such as Cui three-(2-aminoethyl) amine modified carbon nano-tube, and with its solid extracting agent as Pb (II), adsorption capacity reaches 38mg/g (Y Cui, S Liu, et al.Microchim Acta, 2011, DOI10.1007/s00604-011-0601-8).
But above-mentioned two kinds material modified be by CNT by under hot conditions with strong acid reaction after, use the thionyl chloride chloride, obtain under the process conditions by acid amides reaction introducing part again, therefore there is severe reaction conditions, complex process, contaminated environment and can only adsorb the shortcoming and defect such as single heavy metal ion.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of phenylimino oxalic acid chemical modification CNT (MWCNTs-PIAD), this MWCNTs-PIAD can adsorb contents of many kinds of heavy metal ion simultaneously as heavy metal ion solid-phase extraction agent, and synthesis step environmental protection, simple to operate.
In order to achieve the above object, the present invention is take multi-walled carbon nano-tubes as main body, diazo-reaction by gentleness is introduced phenylimino oxalic acid part in carbon nano tube surface, the MWCNTs-PIAD that obtains is as a kind of novel sorbing material of SPE, when this material is used for the heavy metal ion enrichment of environment water, when pH=6, the adsorption capacity of Pb (II), Cu (II), Fe (III) is reached maximum, be respectively 16.9mg/g, 30.5mg/g, 64.8mg/g.Its strong interference immunity simultaneously, the metal ion after the enrichment can be with rare nitric acid or hydrochloric acid wash-out, and the rate of recovery reaches more than 95%.
MWNCTs-PIAD synthetic method of the present invention is the benzoic acid modified CNT of first synthesizing amino (MWCNTs-PA), again the CNT of synthesis of phenyl iminodiacetic acid modification (MWCNTs-PIAD).Concrete technology is as follows:
The first step, be in 10% the sodium dodecyl benzene sulfonate aqueous solution with the 0.3-0.5g multi-walled carbon nano-tubes in the ultrasonic lower weight percent concentration that is dispersed in first, then add rapidly 1 of 740-760mg, PABA, 480-500mg natrium nitrosum and 6-10ml HCl, behind 80 ℃ of stirring reaction 24h with 45 μ m filtering with microporous membrane, filter residue DMF supersound washing, until filtrate is without color, use ethanol, acetone and water wash respectively and obtain solid again, and solid is spent the night 80 ℃ of vacuum drying, obtain the amino benzoic Acid modified carbon nano-tube, for subsequent use;
Second step, get the amino benzoic Acid modified carbon nano-tube 0.1-0.3g that the first step obtains, it is dispersed in the 300-500ml absolute ethyl alcohol, ultrasonic dispersion 30min, add 1-3g NaOH, add the 1.5-3.0g sodium chloroacetate behind 78 ℃ of heating 45min, use the 45mm filtering with microporous membrane behind the reaction 24h, filter residue wash with DMF until cleaning solution without color, use respectively more afterwards ethanol, water and acetone washing, last 80 ℃ of vacuum drying get end product phenylimino oxalic acid modified carbon nano-tube;
160w 59Hz SK-3300H type Ultrasound Instrument (Shanghai High Kudos Science Instrument Co., Ltd.) is all adopted in above-mentioned ultrasonic employing;
It is pure that above-mentioned raw materials is commercially available analysis.
Major advantage of the present invention and effect are as follows:
1, compare with CNT and three after the existing Cys modification-(2-aminoethyl) amine modified carbon nano-tube, because part is different to the metal-complexing performance, therefore, the present invention can be adsorbed Pb (II), Cu (II) and Fe (III) three metal ion species simultaneously, and synthesis step environmental protection, simple to operate.
2, because the present invention utilizes gentle diazo-reaction to introduce phenylimino oxalic acid part in carbon nano tube surface, the MWCNTs-PIAD that obtains, CNT has nanometer and micron double scales characteristics, with it as modified support, both effectively utilize the advantage of its super large specific area, guaranteed again the separability of material and collection property.
3, product of the present invention is just effectively enriched with trace metal Pb (II), Cu (II), Fe (III) from water body at short notice, and it is moderate that material also has absorption pH, and adsorption capacity is large, antijamming capability is strong, the various features such as can repeatedly recycle.
4, the product that the present invention is obtained is filled in the dynamic enrichment operation of carrying out actual water sample in the SPE pillar, lays a good foundation for it is practical.
The specific embodiment
Instantiation is explained the synthetic and application in Pb (II), Cu (II), Fe (III) SPE in water body that relates to MWNCTs-PIAD in detail.
Embodiment 1:
The first step, amino benzoic Acid modified carbon nano-tube (MWCNTs-PA) synthetic.
Taking by weighing commercially available model is the multi-walled carbon nano-tubes 0.3-0.5g of M210, making it be dispersed in weight percent concentration under the 50Hz ultrasound condition is in 10% the sodium dodecyl benzene sulfonate aqueous solution, add rapidly again 740-760mg 1, PABA, 480-500mg natrium nitrosum and 6-10ml HCl, 80 ℃ of stirring reaction 24h, reaction finishes rear with 45 μ m filtering with microporous membrane, filter residue DMF supersound washing, until filtrate without color, is used ethanol again, acetone and water wash respectively, 80 ℃ of vacuum drying are spent the night, and it is for subsequent use to obtain MWCNTs-PA;
Second step, phenylimino oxalic acid modified carbon nano-tube (MWCNTs-PIAD) is synthetic.Getting 0.1-0.3g MWCNTs-PA is dispersed in the 300-500ml absolute ethyl alcohol, ultrasonic dispersion 30min adds 1-3g NaOH, 78 ℃ of heating 45min, add afterwards the 1.5-3.0g sodium chloroacetate, reaction 24h use the 45mm filtering with microporous membrane after reaction finishes, filter residue wash with DMF until cleaning solution without color, use respectively more afterwards ethanol, water and acetone washing, 80 ℃ of vacuum drying get end product MWCNTs-PIAD.
160w 59Hz SK-3300H type Ultrasound Instrument (Shanghai High Kudos Science Instrument Co., Ltd.) is all adopted in above-mentioned ultrasonic employing;
It is pure that above-mentioned raw materials is commercially available analysis.
Embodiment 2:
MWCNTs-PIAD30-50mg with embodiment 1 gained, be filled in the SPE pillar of 6mL, with the SPE device 300-500mL contained Pb (II), Cu (II) and Fe (III), the mixed sample that the content of every heavy metal species ion is 1～5 μ g/L carries out dynamic enrichment, and with the HNO of 5mL 2M
3Wash-out, adsorption rate all reach 95%-97%, and when mixed sample pH=6, all greater than 97%, and adsorption time only needs 15min to Pb (II), Cu (II), Fe (III) heavy metal removal rate, and it is saturated just to reach absorption; Common ion does not affect the enrichment of Pb (II), Cu (II), Fe (III) in the interfering ion experiment discovery natural water, and the rate of recovery is all greater than 97%.
MWCNTs-PIAD to embodiment 1 gained carries out the adsorption capacity experiment, and the saturated extent of adsorption that draws Pb (II), Cu (II), Fe (III) is respectively 16.9mg/g, 30.5mg/g, 64.8mg/g.
The present invention has adopted portable solid-phase extractor (GE PSPE-01, upper sea green Supreme Being Environmental Protection Technology Co., Ltd)
Annotate: being used in the example measuring Pb (II), Cu (II), the content of Fe (III) and the instrument of concentration is the inductively coupled plasma emission spectrometer of U.S. PE company.
Claims (1)
1. the preparation method of a heavy metal ion solid-phase extraction agent is characterized in that:
The first step, first the 0.3-0.5g multi-walled carbon nano-tubes is dispersed in weight percent concentration is under ultrasound condition in 10% the sodium dodecyl benzene sulfonate aqueous solution, then add rapidly 1 of 740-760mg, PABA, 480-500mg natrium nitrosum and 6-10ml HCl, behind 80 ℃ of stirring reaction 24h with 45 μ m filtering with microporous membrane, filter residue N, the dinethylformamide supersound washing is until filtrate without color, is used ethanol again, acetone and water wash respectively and obtain solid, solid is spent the night 80 ℃ of vacuum drying, obtain the amino benzoic Acid modified multiwalled carbon nanotube, for subsequent use;
Second step, get the amino benzoic Acid modified multiwalled carbon nanotube 0.1-0.3g that the first step obtains, it is dispersed in the 300-500ml absolute ethyl alcohol, ultrasonic dispersion 30min, add 1-3g NaOH, add the 1.5-3.0g sodium chloroacetate behind 78 ℃ of heating 45min, behind the reaction 24h with 45 μ m filtering with microporous membrane, filter residue N, the dinethylformamide washing is until cleaning solution without color, is used respectively ethanol afterwards again, and water and acetone wash, last 80 ℃ of vacuum drying get end product phenylimino oxalic acid modified carbon nano-tube heavy metal ion solid-phase extraction agent;
Above-mentioned ultrasonic employing 160w 59Hz SK-3300H type Ultrasound Instrument, Shanghai High Kudos Science Instrument Co., Ltd.;
Above-mentioned raw materials is that commercially available analysis is pure.
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| CN110170307B (en) * | 2019-06-02 | 2021-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of coconut shell activated carbon through ozone surface treatment and para aminobenzoic acid modification treatment, product and application |
| CN110170306B (en) * | 2019-06-02 | 2021-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Process for preparing adsorbent for efficiently removing low-concentration formaldehyde in air at normal temperature by two-step modification method, product and application thereof |
| CN110559992B (en) * | 2019-09-06 | 2021-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation process of inorganic strong acid ammonium salt modified coconut shell activated carbon for removing formaldehyde in air at normal temperature, product and application thereof |
| CN111349445B (en) * | 2020-04-02 | 2021-07-09 | 山东省神农生态科技股份有限公司 | Slow-release repairing agent for soil pollution and preparation method thereof |
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| EP2075337A1 (en) * | 2007-12-27 | 2009-07-01 | Wageningen Universiteit | Method for the enzymatic production of fatty alcohol and/or fatty acid |
| CN101810939A (en) * | 2010-04-02 | 2010-08-25 | 同济大学 | Preparation and application method of solid phase extractant capable of simultaneously accumulating multiple heavy metal ions |
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| JPH03175985A (en) * | 1989-12-05 | 1991-07-31 | Kyoichi Kobashi | Acidic urethanase |
| US6756486B1 (en) * | 2003-09-18 | 2004-06-29 | Engelhard Corporation | Non-migrating metallized disazo green shade yellow pigment |
| US20090203145A1 (en) * | 2008-02-07 | 2009-08-13 | Min Huang | Methods for analysis of vitamins |
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| EP2075337A1 (en) * | 2007-12-27 | 2009-07-01 | Wageningen Universiteit | Method for the enzymatic production of fatty alcohol and/or fatty acid |
| CN101810939A (en) * | 2010-04-02 | 2010-08-25 | 同济大学 | Preparation and application method of solid phase extractant capable of simultaneously accumulating multiple heavy metal ions |
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