CN107175086A - The preparation method of ion blotting magnetite gathering material - Google Patents
The preparation method of ion blotting magnetite gathering material Download PDFInfo
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- CN107175086A CN107175086A CN201710492377.7A CN201710492377A CN107175086A CN 107175086 A CN107175086 A CN 107175086A CN 201710492377 A CN201710492377 A CN 201710492377A CN 107175086 A CN107175086 A CN 107175086A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention discloses a kind of preparation method of ion blotting magnetite gathering material, and this method includes：(1) nanometer Fe is prepared using solvent-thermal method first3O4Magnetic core；(2) functionalization monomer and then by template ion of metal ion is prepared；(3) suspension polymerization is assisted in nanometer Fe using ultrasound again3O4Magnetic core surface aggregate prepares the ion blotting magnetic composite with core shell structure；(4) last eluted template ion obtains object ion trace magnetic composite.With simple to operate, efficiency high, heavy metals effectively can be adsorbed and reclaimed, and have the advantages that to can be used for the SPE of matrix dispersed magnetic to detect heavy metals.
Description
Technical field
The present invention relates to a kind of ion blotting magnetic with metal ion in nucleocapsid structure energy efficiently concentrating and recovery waste water
The system of the preparation method and application technology, specially ion blotting Fe 3 O 4 magnetic polymer composite of property enrichment material
Preparation Method.Ion blotting magnetic high-molecular composite prepared by the present invention, can efficiently, high-selectivity adsorption and reclaim waste water in
Metallic nickel, copper, chromium heavy metal etc., can also set up on this basis matrix it is scattered-that Magnetic solid phases abstraction technique carries out sample is pre-
Processing, enrichment and detection for heavy metal ions in wastewater.
Background technology
With further speeding up for global industry process, the industry such as steel, plating, process hides and paint pigment chemistry is obtained
Significant progress.In the development of these industries, the effect of heavy metal can not be ignored, but at the same time, thing followed weight
Environmental pollution caused by metal also result in the extensive concern of people.For example, chromium is in aqueous with Cr (VI) and Cr (III)
Two kinds of valence states are present, and Cr (VI) has good water solubility, strong oxidizing property, and toxicity is 100 times of Cr (III), is the United Nations's ring
The typical environment persistent pollutant that border administration (U.S.EPA) announces.Although nickel be one of micro elements needed by human, but the world is defended
Raw tissue points out that adult's nickel intake can meet physiological requirements in 0.4mg/ days；Excessive nickel can produce certain to human body
Poison, pharynx cancer, lung cancer, cutaneum carcinoma etc. can be caused when serious.In the production waste water of the pretreatment of metal plating piece, plating, hair dye etc.
In contain substantial amounts of nickel (II), it can be carried out effectively to remove and reclaim to be not only the study hotspot of field of environment protection,
It is the focus of attention of resource regeneration.
The conventional method of processing heavy metal wastewater thereby has：Electroosmose process, reverse osmosis method, precipitation-reducing process and absorption method etc..
Wherein though electroosmose process, reverse osmosis method can effectively reclaim the heavy metals such as Cr (VI), Ni (II), the Cu (II) in waste water, without
Method makes the concentration meet the requirement of environmental protection of heavy metal in waste discharge.Comparatively, absorption method is to remove heavy metal in waste water extremely
Effective method.Some adsorbents are such as：γ-Fe2O3Nano particle, it is developed by polymer microsphere of function base etc. of quaternary amine
Out and for removing the heavy metal in waste water.Zhu Yan side et al. is combined with oil-in-water microemulsion template and rear grafting, system
Obtain the mesoporous SiO of amino functional2Material, the Cr (VI) that can effectively remove in waste water, its clearance are up to 97.2% (C0=
0.1mmol/L).Zhou Limin et al. prepares Fe using ethylene glycol dimethacrylate as crosslinking agent using suspension polymerization3O4/ poly-
Hydroxyethyl methacrylate magnetic microsphere (mPHEMA), is made a kind of new adsorbent (M-mPHEMA), and investigate after modified
It is to Al3+Absorption property, as a result show, 45~70 μm of the Magnetic Spherical adsorbent particle diameter of preparation, to Al3+Saturation inhale
Attached capacity is 428 μm of ol/g；Adsorption capacity is maximum during pH 5~7；Test result to drinking water shows that M-mPHEMA is to Al3+
Clearance up to 98%, higher than other ions.Use 1mol/L HNO3Desorption, Al3+Desorption rate is up to 98.5%.But existing one
A little methods still suffer from poor selectivity, are not readily separated and wait deficiency.
Ion imprinted polymer is the new material that a class heavy metal ion has selective absorption and separation, is generally adopted
Used after combining to form chelate, polymerization with function monomer or coordination monomer by electrostatic interaction, coordination etc. with template ion
Acid reagent etc. elutes template ion, final that the trace with the three-dimensional cavity structure corresponding with target metal ions is made
Material, so as to realize the enrichment to metal ion with separating.However, this kind of kind of material need to could be realized by high speed centrifugation
Separation of solid and liquid, its application is restricted to a certain extent, thus research and develop a kind of new composite overcome its sample with
The difficulty of matrix separation, it appears very necessary.In consideration of it, magnetic ion trace composite because of its own there is good magnetic to ring
Answering property can realize under external magnetic field fast and effectively separation of solid and liquid and gradually cause the concern of domestic and international researcher.
Matrix can be set up on the basis of this and disperses-Magnetic solid phases abstraction technique progress sample pretreatment.The technology is with magnetic or can magnetic
The material of change makees a kind of solid phase extraction techniques of adsorbent matrix, during magnetic solid phase extraction, and magnetic adsorbent need not be filled out
It is charged in adsorption column, and is added in the solution of sample or suspension, target analytes is adsorbed onto scattered magnetic and inhale
Attached dose of surface, is separated under outside magnetic fields；Cross column operation, the adsorption column that common solid phase extraction techniques can be avoided cumbersome hold
The problems such as easy blocking, poor repeatability, thus have a good application prospect.
The content of the invention
The present invention for prior art it is above-mentioned it is not enough there is provided a kind of simple to operate, efficiency high, effectively can adsorb and reclaim
Heavy metals, and with can be used for matrix it is scattered-the ion blotting magnetite gatherings of Magnetic solid phases extraction detection heavy metals
The preparation method of material.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of ion blotting magnetite gathering material
Preparation method, this method includes：(1) nanometer Fe is prepared using solvent-thermal method first3O4Magnetic core；(2) then using metal ion as
Template ion prepares functionalization monomer；(3) suspension polymerization is assisted in nanometer Fe using ultrasound again3O4It is prepared by magnetic core surface aggregate
Ion blotting magnetic composite with nucleocapsid structure；(4) last eluted template ion obtains object ion trace magnetic coupling
Material.
The preparation method of the above-mentioned ion blotting magnetite gathering material of the present invention, wherein step (1) solvent-thermal method are prepared and received
Rice Fe3O4Magnetic core, is specifically included：Nanometer Fe3O4The preparation of magnetic core：Ferric iron is weighed respectively and acetate is dissolved in ethylene glycol and stirred
Mix；Then polyethylene glycol is added to stir to the crocus reaction solution for forming stabilization；Reaction solution is transferred in reactor, 100
~240 DEG C of 2~24h of reaction；Magneto separate after cooling, wash, be drying to obtain nanometer Fe3O4Magnetic core (nFe3O4)；
The mass concentration of ferric iron and acetate of the present invention in ethylene glycol be respectively 0.01~5g/mL and
0.01~10g/mL, is preferably respectively 0.03~2g/mL and 0.1~5g/mL；Described stirring at room temperature stirring 5~
30min, preferably 8~15min；Mass fraction after described polyethylene glycol addition in the reaction solution of formation for 0.01~
5g/mL；Described washing is to use ionized water and ethanol respectively to wash 2-5 times to pH value for 7；Described drying is at 40~80 DEG C
Vacuum drying 4~24 hours.
Ferric iron described in step (1) of the present invention is one kind in ferric trichloride or ferric sulfate, and acetate is sodium acetate, vinegar
One kind in sour potassium or ammonium acetate, the molecular weight distribution of polyethylene glycol is 400-8000.
Reaction temperature in step (1) of the present invention is preferably 150~200 DEG C, reaction time preferably 10~20h.
Preferred 50-70 DEG C of drying temperature in step (1) of the present invention, drying time is preferably (drying in 10~15 hours
Condition is equally applicable to step (3) and (4)).
The corresponding reaction equation of above-mentioned steps (1) of the present invention is：
The preparation method of the above-mentioned ion blotting magnetite gathering material of the present invention, wherein step (2) template ion functionalization
The preparation (preparation of template ion functionalization monomer) of monomer：By the methyl-prop of the alcoholic solution of organic amine and grade substance withdrawl syndrome
The alcoholic solution of olefin(e) acid ethylene oxidic ester is mixed, stirred in equal volume, and organic amine is connected into methacrylic acid by ring-opening reaction contracts
On water glyceride, the alcoholic solution of amino functional monomer is obtained；Then by with the body such as the alcoholic solution of above-mentioned amino functional monomer
Product, etc. the target metal ions of substance withdrawl syndrome alcoholic solution mixing, stirring so that the amino on amino functional monomer enters
One step is coordinated with target heavy metal ion, forms the functionalization monomer of the template containing ion.
The substance withdrawl syndrome of organic amine is 0.1~1mol/L in the alcoholic solution of the above-mentioned organic amine of the present invention；The present invention
The substance withdrawl syndrome of metal ion in the alcoholic solution of above-mentioned target metal ions is 0.1~1mol/L；The present invention is above-mentioned
The alcoholic solution of organic amine and the alcoholic solution stirring condition of GMA be：10- is stirred at 20~50 DEG C
60min；The above-mentioned alcoholic solution of amino functional monomer of the present invention and the alcoholic solution stirring condition of target metal ions are：20~
30min-4hrs (0.5-4h) is stirred at 50 DEG C.
Organic amine is one kind in ethylenediamine, Diethylenetriamine, three second tetramines, tetren in above-mentioned steps (2) of the present invention；Have
The concentration of the substance withdrawl syndrome of organic amine is preferably 0.2~0.5mol/L in the alcoholic solution of machine amine.
Target metal ions are one kind in Ni (II), Cu (II), Cd (II) and Cr (VI) in above-mentioned steps (2) of the present invention
Or the mixture of 2-4 kinds；The substance withdrawl syndrome of metal ion in the alcoholic solution of target metal ions is 0.2~0.5mol/
L。
Above-mentioned steps (2) of the present invention are (exemplified by ethylenediamine) by corresponding reaction equation：
The preparation method of the above-mentioned ion blotting magnetite gathering material of the present invention, wherein step (3) have nucleocapsid structure
The preparation of ion blotting magnetic composite (the amino functional composite for being bonded with template ion)：Weigh step (1) institute
Obtain nanometer Fe3O4Magnetic core, by its ultrasonic disperse into alcoholic solution；The lower function list that the template containing ion obtained by step (2) is added dropwise of stirring
Body；Again by alkyl acrylic or its ester and/or styrene or its substituent, glycidyl esters compound and crosslinking agent successively
It is added drop-wise in reaction system；Then initiator is added, heating response 0.5~5 hour at 50~100 DEG C；It is cold after reaction terminates
But Magneto separate is carried out to room temperature, the amino functional magnetic composite for being bonded with template ion is made.
Above-mentioned steps (3) nanometer Fe of the present invention3O4Magnetic core (nFe3O4) alcoholic solution solid-to-liquid ratio for 10~200g/L (i.e.
The nFe of 10~200g of alcoholic solution correspondence per 1L3O4)。
Alkyl acrylic or its ester are methacrylic acid, methyl methacrylate or methyl in above-mentioned steps (3) of the present invention
One kind in ethyl acrylate.
The substituent (derivative) of styrene described in above-mentioned steps (3) of the present invention is methyl styrene, ethylo benzene second
One kind in alkene etc..
Crosslinking agent described in above-mentioned steps (3) of the present invention is divinylbenzene, bisacrylamide or its substituent, alkyl third
At least one of olefin(e) acid ethylene glycol or the serial silane crosslinker of alkyl acrylic glycol ester, KH.
Initiator described in above-mentioned steps (3) of the present invention is peroxidating two acyl, persulfate, the different nitrile compounds of azo two
At least one of.
The corresponding reaction equation of above-mentioned steps (3) of the present invention is (by taking methyl methacrylate as an example, crosslinking agent is comonomer
Exemplified by divinylbenzene)：
The preparation method of the above-mentioned ion blotting magnetite gathering material of the present invention, wherein step (4) ion blotting magnetic are answered
The preparation of condensation material, with including:Take prepared by step (3) to be bonded with template ion magnetic composite ultrasonic disperse molten to alcohol
In liquid, it is uniformly dispersed in reaction system；Acid/alcohol mixed liquor is slowly added dropwise to adjust to pH2~5 of reaction system, to elute height
Template ion on molecular composite material, until not measuring object ion, products therefrom ethanol with Atomic Absorption Spectrometer inspection
With deionized water washing, Magneto separate, drying, object ion trace magnetic composite.
It is 10~200g/L that step (4) of the present invention, which is bonded with template ion magnetic composite and the solid-to-liquid ratio of alcoholic solution,；
The concentration of acid/alcohol mixed liquor is 0.1~5mol/L (i.e. concentration of the acid in alcohol is 0.1~0.5mol/L)；Be dried in vacuo for
Dried 2~24 hours at 30~80 DEG C
Acid/alcohol mixed liquor described in above-mentioned steps (4) of the present invention, be hydrochloric acid or acetic acid/methanol and hydrochloric acid or acetic acid/
The mixed solution of ethanol, concentration is preferably 0.2~2mol/L.
In step (2), (3) and (4) of the present invention alcohol used be methanol, ethanol, isopropanol, n-butanol, ethylene glycol, the third two
One kind in alcohol, glycerine.
Proportion relation in the above-mentioned preparation process of the present invention between each material can expand according to said ratio equal proportion or
Reduce, will not be influenceed by material amounts unit-sized.
The corresponding reaction equation of above-mentioned steps (4) of the present invention is (acetic acid/methanol solution be eluant, eluent exemplified by)：
The advantages of the present invention：
1. the present invention uses solvent hot preparation nanometer Fe3O4Magnetic core, then by suspension polymerization, using coordination with
Surface ion engram technology obtains ion blotting magnetic composite；With good dispersion, that technique is simple, be easily achieved etc. is excellent
Point, can avoid that the nano magnetic nuclear particle of ferroso-ferric oxide in conventional preparation techniques is uneven, is difficult to nanoscale, is easy to
The drawbacks such as reunion, the low, bad dispersibility of magnetic content；And nanometer Fe prepared by prior art3O4Outside be often also wrapped on SiO2、
The non-magnetic material such as SBA, chitosan, can reduce the magnetic content of resulting materials, be unfavorable for Magneto separate, and thing is based on absorption principle more
Reason absorption, its specificity adsorbed can be reduced, and be unfavorable for high-selectivity adsorption and identification, and resulting materials unit volume is effective
Active adsorption sites can be reduced so that adsorbance declines；In addition, the preparation of prior art nanometer Fe_3O_4 will also add γ-chlorine third
Base trimethoxy silane, the reagent such as solvent toluene, acid anhydrides, these reagents can stimulate eyes, respiratory system, skin, and long
Phase, wherein acid anhydrides belonged to precursor chemicals using there is certain risk to hematopoiesis function, be national regulation control can be used for make
The precursor, raw material and chemical assistant class material of drugs are made, there is the purchasing of raw materials, production and management equivalent risk；And the present invention is exactly
Nanometer Fe is directly prepared using heat of solution method3O4Any other material need not be coated, prepares that particle is uniform, easy Magneto separate；This
Outside, between polyamines of the invention and template ion reaction condition is gentle, will not cause the autohemagglutination of function monomer, be conducive to material to enter
One step carries out suspension polymerisation；Use acid/alcohol system for extractant in step (4), can be adjusted merely by pH can just elute mould
Plate ion, the pattern for not only contributing to preserve ion blotting magnetic composite also saves process and cost.
2. prepared by the ion blotting magnetic composite of the present invention, with simple to operate, efficiency high, magnetic content be controllable, official
The controllable advantage of ratio can be rolled into a ball, high-selectivity adsorption and heavy metal ions in wastewater can be removed, and available for heavy metal in waste water
The enrichment and detection of ion；Why the material of gained efficiently high-selectivity adsorption heavy metal ion can be mainly：(1) use
Ionic imprinting technique, using its can be predetermined selectivity and high identity carry out " lock-spoon " performance characteristic of ion identification
To realize that the high selectivity of material heavy metal ion is recognized；(2) material surface is rich in amino and hydroxyl, can pass through coordination etc.
Interaction is combined with heavy metal ion, reaches the effect of efficiently concentrating.
Brief description of the drawings
Fig. 1 is according to embodiments of the present invention, the transmission electron microscope photo of obtained ion blotting magnetic composite；
Fig. 2 is according to embodiments of the present invention, the x-ray diffraction pattern of obtained ion blotting magnetic composite；
Fig. 3 is according to embodiments of the present invention, the weight-loss curve of obtained ion blotting magnetic composite；
Fig. 4 is according to embodiments of the present invention, the hysteresis curve of obtained ion blotting magnetic composite.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described further to present disclosure, the purpose of the present invention and effect are made
It is really more obvious, but the present invention is not limited solely to following examples.
Embodiment 1
(1) 4g FeCl are weighed respectively3·6H2O and 12g anhydrous Nas Ac is dissolved in 120mL ethylene glycol, is stirred at room temperature
10min, adds 2g polyethylene glycol.Reaction solution is transferred in reactor, 180 DEG C of reaction 6h.Magneto separate after cooling, spend from
Sub- water and ethanol are washed each 3 times, and being 7,60 DEG C to pH value is dried in vacuo 12 hours, produces nanometer Fe3O4。
(2) ethanol of 5mL 0.2mol/L ethylenediamine and 5mL 0.2mol/L GMAs (GMA)
Solution is mixed, and stirs 30min at room temperature, then by 10mL 0.2mol/L Cu (Ac)2Ethanol solution be added dropwise in reaction system
Continue to stir 2h, obtain function monomer (Cu (II)-NH containing Cu (II) ion template2- HPMA) ethanol solution (with concentration C u
(II) it is calculated as：0.1mol/L).
(3) by nanometer Fe obtained by 1g3O4In ultrasonic disperse 2min to 25mL ethanol, it is added dropwise successively under agitation above-mentioned
0.1mol/L Cu (II)-NH2- HPMA ethanol solutions 20mL and 0.2mol/L methyl methacrylate (MMA) ethanol solution
10mL and 0.5g divinylbenzenes (DVB).1g is crossed into methoxybenzoyl (BPO) to be dissolved in 20mL hot ethanol solution, stirred
Mix down and be added drop-wise in reaction system.Under 80 DEG C, 700r/min rotating speed, 3h, Magneto separate are reacted.Obtain being bonded with template Cu
(II) the amino functional magnetic composite of ion.
(4) with the 2mol/L repeated multiple times immersions of HAc, until not measuring Cu with atomic absorption spectrum (AAS) inspection2+, then
Washed with ionized water and ethanol each 3 times, 60 DEG C of vacuum drying 12h obtain Ni (II) ion blotting magnetic composite.
The operating procedure be the same as Example 1 of embodiment 2~6, raw material, composition of raw materials and preparation condition parameter are shown in Table 1 institute
Show.
The raw material components of 1 embodiment of the present invention of table 1~6 and preparation parameter
Ion blotting magnetic composite prepared by the embodiment of the present invention passes through transmission electron microscope (TEM), vibrating example magnetic
The means such as strong meter (VSM), X-ray diffraction (XRD) are characterized to it, and applied to absorption and reclaim heavy metal in waste water, and
Available for matrix it is scattered-Magnetic solid phases extraction is enriched with and detected to trace heavy metal in waste water.
Fig. 1-4 be respectively according to embodiments of the present invention 1 obtained ion blotting magnetic composite transmission electron microscope photo,
X-ray diffraction pattern, weight-loss curve and hysteresis curve；
Fig. 1 is the transmission electron microscope photo of ion blotting magnetic composite.Understand, ion blotting magnetic composite it is flat
Equal particle diameter is about 100nm；
Fig. 2 is the x-ray diffraction pattern of ion blotting magnetic composite.As can be seen that occurring in that Fe3O46 typical cases
, 2 θ angles be located at 30.1 ° (220), 35.5 ° (311), 43.1 ° (400), 53.4 ° (422), 57.0 ° (511) and 62.6 ° (440)
Diffraction maximum.It can be seen that the crystalline phase of ion blotting magnetic composite does not change, Fe is maintained3O4Spinel structure.From
The purer Fe of the diffraction maximum of sub- trace magnetic composite3O4There is wider peak width to show that it has less yardstick.Material is received
Metrical scale makes the increase of its specific surface area, is conducive to the quick progress and the raising of adsorbance of absorption.
Fig. 3 is the weight-loss curve of ion blotting magnetic composite；Understand, the differential curve (DTG) of pyrolysis weight loss is 385
~420 DEG C and~290 DEG C nearby show two peaks；Show that ion blotting magnetic composite has well within 250 DEG C
Heat endurance.42.8% thermal weight loss can be attributed to the pyrolysis weight loss of copolymerized macromolecule layer at 385~415 DEG C；At~290 DEG C
Weightlessness can be attributed to ion blotting magnetic composite surface functional groups (- NH2) pyrolysis weight loss.
Fig. 4 is the Curve of Magnetic Hysteresis Loop of ion blotting magnetic composite；It is 43.8emu/g to understand its intensity of magnetization.Say
Bright ion blotting magnetic composite magnetic response is good, and good separation can be realized under magnetic field.
Above-mentioned sign illustrates that the invention operating procedure is simple, with low cost, obtained ion blotting magnetic composite grain
Degree is evenly distributed, and property is stable.
Present invention application ion blotting magnetic composite is to the adsorption recovery of heavy metal in waste water, and applied to waste water
Middle trace heavy metal pollutant carry out matrix it is scattered-Magnetic solid phases extracting and enriching and detection.Here is embodiment 1 in waste water
The absorption and recovery of heavy metal Cu (II), and embodiment 5 is to Ni in waste water (II), Cu (II), Cd (II), the seed scars of Cr (VI) four
The matrix of measuring heavy metal is scattered-Magnetic solid phases extracting and enriching and the application examples of detection.
Application examples 1：
The gained ion blotting magnetic composite of embodiment 1 is applied to the absorption and recovery of the Cu (II) in waste water.Take
Cu (II) solution of 25.00mL 10,100,500mg/L a series of, is separately added into 0.02g ion blotting magnetic composites, inhales
Constant temperature oscillation under enclosure temperature 308K, 150r/min, adsorption time 3h, pH span 2.0~10.0 determines absorption Optimal pH；
0~1000mg/L Cu (II) solution 25mL is taken, 0.02g ion blotting magnetic composites, adsorption temp difference is separately added into
For 308K, adsorption time is 3h, determines its saturated extent of adsorption.100mg/L Cu (II) solution 25mL is taken, 0.02g is separately added into
Ion blotting magnetic composite, adsorption temp is respectively 303K, 308K, 313K, and 1~180min of adsorption time studies it and moved
Mechanical and thermal properties.The residual concentration of Cu (II) in solution after absorption is determined using AAS.As a result gained ion blotting is shown
Magnetic composite has higher absorption property to Cu (II), and optimal pH is 4.0, and absorption isotherm substantially conforms to Langmuir
Pattern, saturated extent of adsorption is 500mg/g, is 3.1~397 times of document report.Adsorption dynamics adsorption kinetics research shows that adsorption process can
Balance is reached in 5min, meets pseudo-second order kinetic model.The HAc solution for selecting 2mol/L is desorbing agent, has investigated desorption
Closed matereial cycle effect afterwards.As a result show that material C u (II) adsorption efficiency is remained to keep 90% left side after circulating through 10 times
The right side, material can be recycled for multiple times；To Cu in waste water (II) rate of recovery up to more than 95%, obtained copper acetate purity reaches
More than 90%.
Application examples 2：
The wastewater sample solution for pipetting 400mL is placed in 150mL boiling flasks, regulation solution ph to 3.0, adds 20mg
The gained ion blotting magnetic composite of embodiment 5, the lower 150 revs/min of constant temperature oscillation 5min of 308K, Magneto separate goes to upper strata
Solution.Then add 1mL 2mol/L HAc methanol solution vortex oscillations 4min to be desorbed, Magneto separate draws supernatant liquor,
Nitrogen is blown to dry, with 200 μ L deionized water dissolvings, carries out atomic absorption analysis, enrichment times reach 500-2000 times.Heavy metal ion
Detection limit be respectively 0.45~5.8 μ g/L, be quantitatively limited to 1.8~18 μ g/L.
Determine with the Ni (II) in wastewater sample, Cu (II), Cd (II), Cr (VI) content, and be separately added into 4 kinds of huge sum of moneys
Category carries out the recovery testu (table 2) of basic, normal, high three concentration levels.4 heavy metal species ions are returned in the mark-on of three levels
Yield is 88.4%~99.9%, and withinday precision is 0.8%~6.8%, and day to day precision is 1.2%~8.0%.
The accuracy and precision of the heavy metal species ion measurement of table 24
Waste water intermediate ion trace magnetite gathering material of the present invention, is experimentally confirmed：The invention preparation method is simple,
With low cost, obtained target product even particle size distribution, property is stable；Absorption and recovery and trace to heavy metal in waste water
Measure heavy metal ion have efficiently, high selectivity and high-adsorption-capacity, absorption available for such environmental contaminants, reclaim and go
Remove, and available for matrix it is scattered-Magnetic solid phases extraction detection waste water in trace heavy metal pollutant.
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, any modifications and changes made to the present invention both fall within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of ion blotting magnetite gathering material, it is characterised in that：This method includes：(1) first using molten
The hot method of agent prepares nanometer Fe3O4Magnetic core；(2) functionalization monomer and then by template ion of metal ion is prepared；(3) again using super
Sound assists suspension polymerization in nanometer Fe3O4Magnetic core surface aggregate prepares the ion blotting magnetic coupling material with nucleocapsid structure
Material；(4) last eluted template ion obtains object ion trace magnetic composite.
2. the preparation method of ion blotting magnetite gathering material according to claim 1, it is characterised in that：Step (1) is molten
The hot method of agent prepares nanometer Fe3O4Magnetic core, is specifically included：Ferric iron is weighed respectively and acetate is dissolved in ethylene glycol and stirred, Ran Houjia
Enter polyethylene glycol to stir to the crocus reaction solution for forming stabilization；Reaction solution is transferred in reactor, 100~240 DEG C of reactions 2
~24h；Magneto separate after cooling, wash, be drying to obtain nanometer Fe3O4。
3. the preparation method of ion blotting magnetite gathering material according to claim 2, it is characterised in that：In step (1)
The ferric iron is one kind in ferric trichloride or ferric sulfate, and acetate is one kind in sodium acetate, potassium acetate or ammonium acetate, is gathered
The molecular weight distribution of ethylene glycol is 400-8000；The mass concentration of described ferric iron and acetate in ethylene glycol is respectively
0.01~5g/mL and 0.01~10g/mL；Described stirring is stirs 5~30min at room temperature, after described polyethylene glycol addition
Mass fraction in the reaction solution of formation is 0.01~5g/mL；Described washing is respectively to wash 2-5 using ionized water and ethanol
It is secondary to pH value be 7；Described drying is to be dried in vacuo 4~24 hours at 40~80 DEG C；Reaction temperature is 150~200 DEG C, reaction
Time is 10~20h.
4. the preparation method of ion blotting magnetite gathering material according to claim 3, it is characterised in that：Described trivalent
The mass concentration of iron and acetate in ethylene glycol is respectively 0.03~2g/mL and 0.1~5g/mL；Described stirring is room
8~15min of the lower stirring of temperature；Drying temperature in step (1) is 50-70 DEG C, drying time is 10~15 hours.
5. the preparation method of ion blotting magnetite gathering material according to claim 1, it is characterised in that：Step (2) mould
The preparation of plate ion functionalization monomer：By the GMA of the alcoholic solution of organic amine and grade substance withdrawl syndrome
Alcoholic solution mix, stir in equal volume, organic amine is connected on GMA by ring-opening reaction, obtained
The alcoholic solution of amino functional monomer；Then by with the alcoholic solution of above-mentioned amino functional monomer it is isometric, etc. material amount it is dense
Alcoholic solution mixing, the stirring of the target metal ions of degree so that amino on amino functional monomer further with a target huge sum of money
Belong to ion coordination, form the functionalization monomer of the template containing ion.
6. the preparation method of ion blotting magnetite gathering material according to claim 5, it is characterised in that：In step (2)
Organic amine is one kind in ethylenediamine, Diethylenetriamine, three second tetramines, tetren；Organic amine in the alcoholic solution of described organic amine
Substance withdrawl syndrome be 0.1~1mol/L, preferably 0.2~0.5mol/L；
Target metal ions are the mixing of Ni (II), Cu (II), Cd (II) and one kind or 2-4 kinds in Cr (VI) in step (2)
The substance withdrawl syndrome of metal ion in thing, the alcoholic solution of target metal ions be 0.1~1mol/L, preferably 0.2~
0.5mol/L；The alcoholic solution of organic amine and the alcoholic solution stirring condition of GMA are：At 20~50 DEG C
Stir 10-60min；The alcoholic solution of amino functional monomer and the alcoholic solution stirring condition of target metal ions are：20~50 DEG C
Lower stirring 30min-4hrs.
7. the preparation method of ion blotting magnetite gathering material according to claim 1, it is characterised in that：Step (3) has
There is the preparation of the ion blotting magnetic composite of nucleocapsid structure：Weigh nanometer Fe obtained by step (1)3O4Magnetic core, by its ultrasound
It is distributed in alcoholic solution；The lower function monomer that the template containing ion obtained by step (2) is added dropwise of stirring；Again by alkyl acrylic or its ester
And/or styrene or its substituent, glycidyl esters compound and crosslinking agent are added drop-wise in reaction system successively；Then plus
Enter initiator, heating response 0.5~5 hour at 50~100 DEG C；After reaction terminates, it is cooled to room temperature and carries out Magneto separate, be made
It is bonded with the amino functional magnetic composite of template ion.
8. the preparation method of ion blotting magnetite gathering material according to claim 7, it is characterised in that：Step (3) is received
Rice Fe3O4The solid-to-liquid ratio of magnetic core alcoholic solution is 10~200g/L；Alkyl acrylic or its ester are methacrylic acid, first in step (3)
One kind in base methyl acrylate or EMA；The substituent of styrene described in step (3) is methylbenzene second
One kind in alkene, ethyl styrene etc.；Crosslinking agent described in step (3) be divinylbenzene, bisacrylamide or its substituent,
At least one of alkyl acrylic ethylene glycol or the serial silane crosslinker of alkyl acrylic glycol ester, KH；Institute in step (3)
It is at least one of peroxidating two acyl, persulfate, the different nitrile compounds of azo two to state initiator.
9. the preparation method of ion blotting magnetite gathering material according to claim 1, it is characterised in that：Step (4) from
The preparation of sub- trace magnetic composite, with including:The template ion magnetic composite that is bonded with for taking step (3) to prepare surpasses
Sound is distributed in alcoholic solution, is uniformly dispersed in reaction system；Acid/alcohol mixed liquor is slowly added dropwise to adjust to the pH2 of reaction system
~5, to elute the template ion on polymer composite, until object ion is not measured with Atomic Absorption Spectrometer inspection, institute
Product wash with ethanol and deionized water, Magneto separate, drying, obtain object ion trace magnetic composite.
10. the preparation method of ion blotting magnetite gathering material according to claim 9, it is characterised in that：Step (4) key
The solid-to-liquid ratio that closing has template ion magnetic composite and alcoholic solution is 10~200g/L；Acid/alcohol mixing described in step (4)
Liquid, is the mixed solution of hydrochloric acid or acetic acid/methanol and hydrochloric acid or acetic acid/ethanol, the concentration of acid/alcohol mixed liquor for 0.1~
5mol/L, concentration is preferably 0.2~2mol/L；It is dried in vacuo to dry 2~24 hours at 30~80 DEG C；Institute in step (4)
Alcohol is one kind in methanol, ethanol, isopropanol, n-butanol, ethylene glycol, propane diols, glycerine.
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