CN106179237A - A kind of nanofiber of extracting and enriching heavy metal ion and preparation method thereof - Google Patents

A kind of nanofiber of extracting and enriching heavy metal ion and preparation method thereof Download PDF

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CN106179237A
CN106179237A CN201610546868.0A CN201610546868A CN106179237A CN 106179237 A CN106179237 A CN 106179237A CN 201610546868 A CN201610546868 A CN 201610546868A CN 106179237 A CN106179237 A CN 106179237A
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heavy metal
nanofiber
ion
metal ion
extracting
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CN106179237B (en
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赵孔银
秦志
李金刚
刘亮
魏梦梦
郭杰
蔡志江
魏俊富
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Experiment Animals Centre, Military Medical Science Inst., of PLA
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Tianjin Polytechnic University
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    • C02F1/00—Treatment of water, waste water, or sewage
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
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Abstract

It is difficult to eluting after, adsorption time length low for common material heavy metal ionic adsorption amount, absorption and causes the problems such as extraction difficulty, the present invention is with sodium alginate and carboxymethyl chitosan as primary raw material, it is dissolved in the water together with the auxiliary macromolecule of spinning and porogen, it is configured to spinning liquid, electrostatic spinning technique is used to obtain nanofiber, through calcium ion crosslinking molding, obtain the nanofiber of a kind of extracting and enriching heavy metal ion.Being put in complexing of metal ion agent by nanofiber after Adsorption of Heavy Metal Ions, utilize the stronger adhesion of metal chelating agent to make alginate/carboxymethyl chitosan composite aquogel dissolve, heavy metal ion is dispersed in the solution.Before and after being adsorbed by test nanofiber, the concentration change of heavy metal ion calculates adsorbance, calculates the enrichment multiplying power of nanofiber heavy metal according to the volume ratio of solution and complexing of metal ion agent solution before absorption.The present invention has applications well prospect in heavy metal ion enrichment detects.

Description

A kind of nanofiber of extracting and enriching heavy metal ion and preparation method thereof
Technical field
The present invention relates to preparation and the heavy metal accumulation method of the nanofiber of a kind of extracting and enriching heavy metal ion, belong to Functional material, environmentally conscious materials and chemical field.
Background technology
Along with China's fast industrialization and urbanization, plurality of heavy metal is discharged into by all means in environment, adds The heavy metal burden of environment, causes serious heavy metal pollution.Heavy metal is mainly by artificial pollution and geologic erosion, wind The forms such as change enter water body, are difficult to be metabolized, be easily bioaccumulation, the serious threat mankind and hydrobiological life in biological chain Deposit.
The analyzing detecting method of heavy metal mainly has atomic adsorption spectrographic method, atomic emission spectrometry, atomic fluorescence spectrophotometry Method, ICP-OES, ICP-MS, the chromatography of ions, electrochemical analysis method etc..But these methods need technician to go to scene to take Sample, is then return to laboratory and detects.This process detecting step is loaded down with trivial details, and the time is longer, expensive, and analyzing work can only be Indoor laboratory is carried out, and easily occurs mistake in sample transportation, limits the application of Site Detection, many large-scale The application of instrument is also only limitted to research field, and medium-sized and small enterprises and small-size laboratory in general district class all cannot be popularized, Especially in the application of remote districts.Many portable sets have been applied to the detection such as uv-spectrophotometric of heavy metal in recent years Method, electrochemical method and metal sensor etc. [Electrochimica Acta, 2011,56 (9): 3139-3146].And by In the complexity of sample, there is directly measuring of substantial amounts of interference factor, trace and micro heavy and there is also certain difficulty, need Sample is carried out preenrichment, removes matrix effect, improve detection sensitivity.
At present, the method for separating and concentrating that metal ion is conventional has coprecipitation, absorption and ion exchange, supercritical fluid Extraction, emulsion liquid membrane extraction, cloud point extraction method, solid phase extraction, Solid-phase Microextraction, liquid-phase extraction method, liquid-phase micro-extraction method Deng.Absorption and the selection that it is critical only that adion exchanger of ion exchange, can be used for element morphology and divide the analysis of variance, point Higher from efficiency, can be used for the preparation of microcomponent enrichment and high purity material, but operating process is loaded down with trivial details, regenerative process is the longest.
Solid-Phase Extraction (SPE) technology uses the fixing phase of efficient absorption, utilizes the pollutant in fixing relative water body to add richness Collection, the most again by elution or the method for heating desorption, due to have simple to operate, the response rate is high, enrichment multiplying power is big, The advantages such as solvent load is little and be widely used in separating and enriching trace element.Solid-phase microextraction (SPME) is that nineteen ninety is by adding It is a kind of new that pawliszyn research group [Analytical chemistry, 1990,62 (19): 2145-2148] of putting on airs proposes The Sample Pretreatment Technique integrating extraction, concentration, desorbing of type, is by either physically or chemically, will have absorption extraction The coating material taking function is supported on stromal surface, target analytes enrichment is concentrated, sample introduction or and auto injection after desorbing Device is directly combined, thus accurately detects object analyte.By 1993, first Supelco company of the U.S. released The portable solid-phase microextraction handle of commercialization, it is achieved that the commercialization of SPME, has expanded its range of application.Solid phase in pipe Micro-extraction is a kind of can be realized consolidating of automation mechanized operation associated with HPLC, GC by what Pawliszyn et al. grew up Phase extraction technology [Analytical Chemistry, 1997,69 (16): 3140-3147].The method is by fixing for extraction phase Being coated in one section of capillary tube (such as quartz capillary), when sample flows through in managing, component is extracted to fix in pipe and goes up mutually.In pipe admittedly Phase extraction method is in static according to determinand or being driven through fiber pipe by external force is divided into two kinds: static method is with dynamic Method.It is fixing long-pending with bigger extraction surface mutually that In-tube SPME has thinner extraction, can be rapidly achieved extraction equilibrium, Desorption is relatively easy to.
Being difficult to eluting after, adsorption time length low for common material heavy metal ionic adsorption amount, absorption causes extraction tired The problem such as difficult, the present invention is with sodium alginate and carboxymethyl chitosan as primary raw material, by its macromolecule with auxiliary spinning with cause Hole agent is dissolved in the water together, is configured to spinning liquid, uses electrostatic spinning technique to obtain nanofiber, through calcium ion crosslinking Molding, obtains the nanofiber of a kind of extracting and enriching heavy metal ion.Nanofiber after Adsorption of Heavy Metal Ions is put into from In sub-chelating agent, the stronger adhesion of metal chelating agent is utilized to make alginate/carboxymethyl chitosan composite aquogel dissolve, with much money Belong to uniform ion to disperse in the solution.Before and after being adsorbed by test nanofiber, the concentration change of heavy metal ion calculates absorption Amount, calculates the enrichment multiplying power of nanofiber heavy metal according to the volume ratio of solution and ion complexation agent solution before absorption.This Bright porous nano-fibre has good application prospect at heavy metal ion adsorbed detection field.
Summary of the invention
Being difficult to eluting after, adsorption time length low for common material heavy metal ionic adsorption amount, absorption causes extraction tired The problems such as difficulty, the present invention develops the nanofiber of a kind of extracting and enriching heavy metal ion.
The invention provides nanofiber of a kind of extracting and enriching heavy metal ion and preparation method thereof, it is characterized in that component As follows with weight/mass percentage composition:
The preparation of the nanofiber of a kind of extracting and enriching heavy metal ion and heavy metal accumulation method, it is characterized in that including with Lower step:
A) sodium alginate, carboxymethyl chitosan, the macromolecule of auxiliary spinning and porogen are successively dissolved in deionized water In, ultrasonic disperse is uniform, obtains spinning liquid after deaeration；Spinning liquid is injected in needle tubing, is obtained by high-voltage electrostatic spinning technology To nanofiber, controlling the thickness of chien shih nano fibrous membrane during spinning is 50-300 micron；
B) preparing metal mass of ion percentage ratio is the aqueous metal salt of 2%-30%, as ion crosslinking agent；
C) nano fibrous membrane that step a) obtains is dipped in the aqueous metal salt that step b) obtains crosslinking 0.5- 24h, is washed with deionized water surface metal salt, obtains macroporous structure through lyophilization, then by the nanometer after lyophilization Fibrous membrane is dipped into 2-24h in deionized water again, washes away porogen and obtains microcellular structure, thus obtains a kind of extracting and enriching The nanofiber of heavy metal ion；
D) nanofiber of the extracting and enriching heavy metal ion obtained by step c) is put in extracting tube, makes heavy metal ion Solution flows through, and the nanofiber after Adsorption of Heavy Metal Ions is put into stirring 1-24h in ionic complexing agent, utilizes metal chelating agent Stronger adhesion makes alginate/carboxymethyl chitosan composite aquogel dissolve, and heavy metal ion is dispersed in the solution；Logical Cross the concentration change of heavy metal ion before and after test nanofiber adsorbs and calculate adsorbance, according to solution and ion complexation before absorption The volume ratio of agent solution calculates the enrichment multiplying power of nanofiber heavy metal.
The macromolecule of auxiliary spinning of the present invention is in polyoxyethylene ether, polyvinyl alcohol, water-soluble cellulose, sericin Any one or two or more mixture；Described aqueous metal salt is calcium chloride, dalcium biphosphate, calcium nitrate, carbonic acid Any one or two or more mixture in hydrogen calcium aqueous solution；Described porogen is polyvinyl pyrrolidone, poly-second two Any one in alcohol, polyacrylamide, carbamide；Described ionic complexing agent is ethylenediamine, sodium citrate, ethylenediamine tetrem Any one in acid disodium salt, thiourea.Described heavy metal ion be copper ion, cadmium ion, lead ion, zinc ion, nickel from Any one or two or more mixture in son, its enrichment multiplying power is 5-50 times.
Detailed description of the invention
The specific embodiment of the present invention is described below, but the present invention should not be limited by the examples.
Embodiment 1.
A) sodium alginate, carboxymethyl chitosan, polyoxyethylene ether and polyacrylamide are successively dissolved in deionized water, Ultrasonic disperse is uniform, obtains spinning liquid after deaeration；Spinning liquid is injected in needle tubing, is received by high-voltage electrostatic spinning technology Rice fiber, controlling the thickness of chien shih nano fibrous membrane during spinning is 300 microns；
B) preparing metal mass of ion percentage ratio is the calcium chloride water of 30%, as ion crosslinking agent；
C) nano fibrous membrane that step a) obtains is dipped in the calcium chloride water that step b) obtains crosslinking 24h, uses Deionized water washes away surface chlorination calcium, obtains macroporous structure through lyophilization, then by the nano fibrous membrane after lyophilization Again it is dipped into 24h in deionized water, washes away polyacrylamide and obtain microcellular structure, thus obtain an a kind of extracting and enriching huge sum of money Belong to the nanofiber of ion；
D) nanofiber of the extracting and enriching heavy metal ion obtained by step c) is put in extracting tube, makes cadmium-ion solution Flow through, the nanofiber after Adsorption of Cadmium is put into stirring 24h in ethylenediamine, utilizes the stronger adhesion of metal chelating agent to make sea Alginate/carboxymethyl chitosan composite aquogel dissolves, and cadmium ion is dispersed in the solution；Adsorbed by test nanofiber Front and back the concentration change of cadmium ion calculates adsorbance, calculates nanofiber according to the volume ratio of solution and ethylenediamine solution before absorption Enrichment multiplying power to cadmium, result is 10 times to the enrichment multiplying power of cadmium ion.
Embodiment 2.
A) sodium alginate, carboxymethyl chitosan, polyvinyl alcohol and polyvinyl pyrrolidone are successively dissolved in deionization In water, ultrasonic disperse is uniform, obtains spinning liquid after deaeration；Spinning liquid is injected in needle tubing, by high-voltage electrostatic spinning technology Obtaining nanofiber, controlling the thickness of chien shih nano fibrous membrane during spinning is 50 microns；
B) preparing metal mass of ion percentage ratio is the calcium nitrate aqueous solution of 2%, as ion crosslinking agent；
C) nano fibrous membrane that step a) obtains is dipped in the calcium nitrate aqueous solution that step b) obtains crosslinking 24h, uses Deionized water washes away surface calcium nitrate, obtains macroporous structure through lyophilization, then by the nano fibrous membrane after lyophilization Again it is dipped into 2h in deionized water, washes away polyvinyl pyrrolidone and obtain microcellular structure, thus obtain a kind of extraction richness The nanofiber of collection heavy metal ion；
D) nanofiber of the extracting and enriching heavy metal ion obtained by step c) is put in extracting tube, makes lead ion solution Flow through, the nanofiber after adsorpting lead ion is put into stirring 1h in sodium citrate, utilizes the stronger adhesion of metal chelating agent to make Alginate/carboxymethyl chitosan composite aquogel dissolves, and lead ion is dispersed in the solution；Inhaled by test nanofiber Before and after attached, the concentration change of lead ion calculates adsorbance, calculates nanometer according to the volume ratio of solution and sodium citrate solution before absorption The fiber enrichment multiplying power to lead, result is 50 times to the enrichment multiplying power of lead.
Embodiment 3.
A) sodium alginate, carboxymethyl chitosan, polyvinyl alcohol and Polyethylene Glycol are successively dissolved in deionized water, ultrasonic It is uniformly dispersed, after deaeration, obtains spinning liquid；Spinning liquid is injected in needle tubing, obtains Nanowire by high-voltage electrostatic spinning technology Dimension, controlling the thickness of chien shih nano fibrous membrane during spinning is 200 microns；
B) preparing metal mass of ion percentage ratio is the calcium dihydrogen phosphate aqueous solution of 10%, as ion crosslinking agent；
C) nano fibrous membrane that step a) obtains is dipped in the calcium dihydrogen phosphate aqueous solution that step b) obtains crosslinking 5h, It is washed with deionized water surface phosphoric acid calcium dihydrogen, obtains macroporous structure through lyophilization, then by the nanometer after lyophilization Fibrous membrane is dipped into 8h in deionized water again, washes away Polyethylene Glycol and obtains microcellular structure, thus obtains a kind of extracting and enriching The nanofiber of heavy metal ion；
D) nanofiber of the extracting and enriching heavy metal ion obtained by step c) is put in extracting tube, makes copper ion solution Flow through, the nanofiber after absorbing copper ion is put into stirring 8h in disodium EDTA, utilizes metal chelating agent relatively Strong adhesion makes alginate/carboxymethyl chitosan composite aquogel dissolve, and copper ion is dispersed in the solution；By test Before and after nanofiber absorption, the concentration change of copper ion calculates adsorbance, according to solution and disodium EDTA before absorption The volume ratio calculating nanofiber of solution is to measuring copper multiplying power, and result is 20 times to measuring copper multiplying power.
Embodiment 4.
A) sodium alginate, carboxymethyl chitosan, sericin and carbamide being successively dissolved in deionized water, ultrasonic disperse is equal Even, obtain spinning liquid after deaeration；Spinning liquid is injected in needle tubing, obtains nanofiber by high-voltage electrostatic spinning technology, control During spinning processed, the thickness of chien shih nano fibrous membrane is 100 microns；
B) preparing metal mass of ion percentage ratio is the calcium bicarbonate aqueous solution of 5%, as ion crosslinking agent；
C) nano fibrous membrane that step a) obtains is dipped in the calcium bicarbonate aqueous solution that step b) obtains crosslinking 4h, uses Deionized water washes away surface calcium bicarbonate, obtains macroporous structure through lyophilization, then by the nanofiber after lyophilization Film is dipped into 12h in deionized water again, washes away carbamide and obtains microcellular structure, thus obtain a kind of extracting and enriching heavy metal from The nanofiber of son；
D) nanofiber of the extracting and enriching heavy metal ion obtained by step c) is put in extracting tube, makes zinc ion solution Flow through, the nanofiber after absorption zinc ion is put into stirring 8h in thiourea, utilizes the stronger adhesion of metal chelating agent to make Sargassum Hydrochlorate/carboxymethyl chitosan composite aquogel dissolves, and zinc ion is dispersed in the solution；Before being adsorbed by test nanofiber The concentration change of rear zinc ion calculates adsorbance, calculates nanofiber to zinc according to the volume ratio of solution and thiourea solution before absorption Enrichment multiplying power, result is 5 times to the enrichment multiplying power of zinc.

Claims (7)

1. a nanofiber for extracting and enriching heavy metal ion, is characterized in that material component and weight/mass percentage composition are as follows:
2. the preparation of the nanofiber of extracting and enriching heavy metal ion and a heavy metal accumulation method, is characterized in that including following Step:
A) sodium alginate, carboxymethyl chitosan, the macromolecule of auxiliary spinning and porogen are successively dissolved in deionized water, super Sound is uniformly dispersed, and obtains spinning liquid after deaeration；Spinning liquid is injected in needle tubing, obtains nanometer by high-voltage electrostatic spinning technology Fiber, controlling the thickness of chien shih nano fibrous membrane during spinning is 50-300 micron；
B) preparing metal mass of ion percentage ratio is the aqueous metal salt of 2%-30%, as ion crosslinking agent；
C) nano fibrous membrane that step a) obtains is dipped in the aqueous metal salt that step b) obtains crosslinking 0.5-24h, uses Deionized water washes away surface metal salt, obtains macroporous structure through lyophilization, then by the nano fibrous membrane after lyophilization Again it is dipped into 2-24h in deionized water, washes away porogen and obtain microcellular structure, thus obtain a kind of extracting and enriching heavy metal The nanofiber of ion；
D) nanofiber of the extracting and enriching heavy metal ion obtained by step c) is put in extracting tube, makes heavy metal ion solution Flow through, the nanofiber after Adsorption of Heavy Metal Ions is put into stirring 1-24h in ionic complexing agent, utilizes metal chelating agent stronger Adhesion makes alginate/carboxymethyl chitosan composite aquogel dissolve, and heavy metal ion is dispersed in the solution；By surveying Before and after examination nanofiber absorption, the concentration change of heavy metal ion calculates adsorbance, molten according to solution and ionic complexing agent before absorption The volume ratio of liquid calculates the enrichment multiplying power of nanofiber heavy metal.
3. such as claim 1, the preparation of the nanofiber of a kind of extracting and enriching heavy metal ion described in 2 and heavy metal accumulation side Method, is characterized in that the macromolecule of described auxiliary spinning is in polyoxyethylene ether, polyvinyl alcohol, water-soluble cellulose, sericin Any one or two or more mixture.
4. such as claim 1, the preparation of the nanofiber of a kind of extracting and enriching heavy metal ion described in 2 and heavy metal accumulation side Method, is characterized in that described aqueous metal salt is appointing in calcium chloride, dalcium biphosphate, calcium nitrate, calcium bicarbonate aqueous solution Anticipate one or more mixture.
5. such as claim 1, the preparation of the nanofiber of a kind of extracting and enriching heavy metal ion described in 2 and heavy metal accumulation side Method, is characterized in that described porogen is any one in polyvinyl pyrrolidone, Polyethylene Glycol, polyacrylamide, carbamide Kind.
The preparation of the nanofiber of a kind of extracting and enriching heavy metal ion the most as claimed in claim 2 and heavy metal accumulation side Method, is characterized in that described ionic complexing agent is any in ethylenediamine, sodium citrate, disodium EDTA, thiourea A kind of.
The preparation of the nanofiber of a kind of extracting and enriching heavy metal ion the most as claimed in claim 2 and heavy metal accumulation side Method, it is characterized in that described heavy metal ion be in copper ion, cadmium ion, lead ion, zinc ion, nickel ion any one or Two or more mixture, its enrichment multiplying power is 5-50 times.
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