CN105170113A - Method for preparing ionic composite magnetic particle adsorbent through photo-initiation - Google Patents
Method for preparing ionic composite magnetic particle adsorbent through photo-initiation Download PDFInfo
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Abstract
The invention belongs to the inorganic-organic composite material technology field. Provided is a method for preparing an ionic composite magnetic particle adsorbent through photo-initiation. The method is characterized in that the method comprises the following steps: firstly, Fe3O4 magnetic particles are prepared through a coprecipitation method; secondly, surface organic modified Fe3O4 is prepared from the magnetic particles, deionized water, esterification catalysts, an organic modifier solution and an emulsifier according to ratios of 1g:10-20mL:0.05-0.1g:20-40mL:0.1-0.2g; thirdly, an acrylic monomer aqueous solution is prepared in a quartz glass tube, photoinitiators are added, preheating is carried out for 30min, then surface organic modified Fe3O4 obtained in the second step is added, mechanical dispersion is carried out, then polymerization inhibitors are added, after nitrogen is inputted for 10min, sealing is carried out, a grafting reaction is carried out under ultraviolet irradiation with mechanical stirring, washing magnetic separation is carried out, and polyacrylic acid grafting magnetic particles are obtained; fourthly, the polyacrylic acid grafting magnetic particles are added in a HCl solution, shaking is carried out, then the polyacrylic acid grafting magnetic particles are stirred in a NaOH solution, sodium modification transition is carried out, and an ionic composite magnetic particle adsorbent is obtained. The method is advantageous in that preparation is simple, recovery is easy, the adsorption capacity is high, and the prepared adsorbent can be used repeatedly.
Description
Technical field
The invention belongs to inorganic-organic composite material technical field, be specifically related to a kind of preparation method of magnetic ion crossover granule adsorbent.
Background technology
Number of polymers contains abundant functional group because of it, has developed into excellent sorbing material, and the fields such as, blood purification, medicament transport immobilized at Water warfare, enzyme are all widely used.Wherein, ion-exchange polymer such as the chemical products such as resin/fiber there has been tremendous development as sorbing material the most common on market in the Industrial Wastewater Treatment such as effluent containing heavy metal ions, dyeing waste water.Although Polymer adsorption excellent performance, also there is intrinsic bottleneck in it in application process, and such as, its mechanical strength is not enough, and skeleton is in use avalanche easily; Contaminant molecule/ion is difficult to the adsorption site close to polymer beads inside; The problem such as soluble in some polymer (as shitosan) adsorbent solution under given conditions (as acid solution).Therefore, recent domestic researcher to consider Polymer-supported in solid particles surface: the characterization of adsorption that not only can give full play to polymer, and is conducive to pollutant mass transfer (because functional group be distributed in adsorbent top layer).But all there is the higher problem of cost in now widely used solid support materials (comprising silica gel, CNT, mineral etc.), and the composite adsorbing material obtained is made up of the particle of sub-micron to hundreds of micron usually, generally directly can not fill post and run (post presses through height), and adopting matrix decentralized model to adsorb, its separation and recovery bothers again very much.Magnetic adsorbent is the new technology of rising in recent years, and its outstanding advantages, after powder adsorption material completes absorption, flows through magnetic field and collected quickly and easily with working solution.Therefore, if can by polymer supported on magnetic-particle surface, obtained composite adsorbing material not only solves the problem of separation and recovery but also possesses the high-adsorption-capacity of polymer absorbant simultaneously, obviously has broad application prospects in water treatment field.
At present, the method preparing this type of organic-inorganic composite material mainly contains coated with grafting two kinds, and the former preparation process is simple, but do not form firmly chemical bonding between base material and surface aggregate thing, loaded article easily comes off, and material lifetime is limited, and has the shortcoming causing secondary pollution.And Graft Method realizes inorganic organic connection by the mode of bonding, Stability Analysis of Structures, can repeatedly use, and is a kind of desirable preparation method.The method of the graft modification of domestic and international report has a lot, mainly contains chemical graft, high-energy radiation grafting, plasma grafting and Graft copolymerization etc.Though chemical graft equipment is simple, once carry out, very easily there is homopolymerization and reaction condition is wayward in reaction.High-energy radiation and plasma grafting reaction relatively rapid, grafting scope can control, but to the condition of grafting and equipment requirement higher, and have injury to material main body.Though above grafting method can realize grafting object, there is the common fault that percent grafting is low, grafting cost is high, utilization rate that is monomer is low, not easily realize large-scale production.Comparatively speaking, Graft copolymerization more easily realizes grafting object, its principle is by UV-irradiation technology, under the effect of sensitising agent, cause base material Adsorption point, the large molecule containing functional group is fixed by the mode of chemical bonding (grafting) can to realize material for a long time modification performance at substrate surface.
Summary of the invention
The object of the invention is to provide a kind of light-initiated method preparing ionic composite magnetic particle adsorbent, and the method preparation is simple, be easy to reclaim, adsorption capacity is high, can repeatedly use.
For achieving the above object, the present invention adopts technical scheme as follows: prepare Fe with coprecipitation
3o
4magnetic nanoparticle, then adopts catalytic esterification to connect organic chain at inorganic particle surfaces, introducing-CH
2-grafting avtive spot, hydrogen sensitising agent is taken in utilization by force, hydrogen abstraction reaction is brought out when absorbing ultraviolet luminous energy, select PAA as reaction monomers, in course of reaction, monomer free end realizes chain growth by continuous addition polymerization, exchanges functional group (COO at the weak acid ion of a large amount of absorption property excellence of material surface bonding
-), achieve high-performance simultaneously and be easy to be separated feature.
A kind of light-initiated a kind of method (or claiming preparation method of magnetic bead ion crossover compound adsorbent) preparing ionic composite magnetic particle adsorbent, is characterized in that comprising the steps:
1) coprecipitation is first adopted to prepare Fe
3o
4(nanometer) magnetic particle: by FeCl
3middle Fe
3+and FeSO
4middle Fe
2+mol ratio (Fe
3+: Fe
2+)=2:1, takes FeCl
3and FeSO
4be dissolved in deionized water, form Fe
3+concentration be the solution of (8-16) mmol/ (10-30) mL; By FeCl
3: NH
3h
2the proportioning of O solution is (8-16) mmol:(40-80) mL, progressively slowly dripping concentration under mechanical agitation is 5 ~ 10wt%NH
3h
2o solution, under normal temperature react 8 ~ 24h, with deionized water, ethanol repeatedly ultrasonic washing repeatedly (be repeatedly each 2-4 time), magnetic separation, drying (being placed in 60 DEG C of vacuum drying chambers), obtain magnetic particle (Fe
3o
4magnetic particle);
2) by magnetic particle: deionized water: esterification catalyst: organically-modified agent solution: the proportioning of emulsifying agent (emulsifier op-10) is 1g:10-20mL:(0.05 ~ 0.1) g:20-40mL:0.1-0.2g, take step 1) in preparation magnetic Granular composite in deionized water, (concentration of organically-modified agent solution is 1 ~ 3wt% to add organically-modified agent solution, for the aqueous solution), instillation emulsifier op-10, add esterification catalyst, 12-24h is reacted under mechanical agitation, use acetone respectively, ethanol, deionized water is repeatedly rinsed (being repeatedly each 2-4 time), remove surface attachments, after Magneto separate, dry (dry at 30 DEG C), obtain the Fe of surface organic modification
3o
4,
3) in quartz glass tube, configure the acrylic monomers aqueous solution, the volume of the described acrylic monomers aqueous solution is 20 ~ 40mL, and the concentration of the acrylic monomers aqueous solution is 5 ~ 30wt%; By the acrylic monomers aqueous solution: light trigger: step 2) in the Fe of surface organic modification
3o
4proportioning be 20 ~ 40mL:0.03g-0.125g:0.15g-0.3g, the mass ratio of polymerization inhibitor and light trigger (or claiming sensitising agent) is (0.5 ~ 1): 1, light trigger is added in the acrylic monomers aqueous solution, preheating 30min, then add step 2) in the Fe of surface organic modification
3o
4after mechanical dispersion, add polymerization inhibitor, pass into nitrogen to seal after 10 minutes, under churned mechanically condition, UV-irradiation carries out graft reaction, react with boiling water, ethanol, acetone cyclic washing Magneto separate (repeatedly for each 2-4 time), obtained polyacrylic acid grafted magnetic particle (Fe
3o
4-g-PAA);
4) the polyacrylic acid grafted magnetic particle (Fe will prepared
3o
4-g-PAA) add in HCl solution and vibrate, be washed to neutrality, stir in NaOH solution again and carry out sodium transition, again through being washed to neutrality, repeat (to repeat, several times for repeating 2-4 time, namely add in HCl solution and vibrate, then sodium transition to be carried out in stirring in NaOH solution) several times, obtain ionic composite magnetic particle adsorbent after dry (65 DEG C of dryings) [or to claim composite magnetic particle adsorbent, or claim the magnetic particle (Fe of Sodium Polyacrylate grafting
3o
4-g-PAANa)].
According to such scheme, described organic modifiers can be chosen as the one in oleic acid, stearic acid, palmitic acid, myristic acid, laurate etc.
According to such scheme, described esterification catalyst can adopt the one in inorganic salts titanium sulfate, ferric trichloride, butter of tin or acid type catalyst phosphoric acid, boric acid, organic sulfonic acid, hydrochloride and sulfate etc.
According to such scheme, light trigger can select the one in the hydrogen-abstraction sensitising agents such as benzoin ethyl ether, benzoin dimethylether, benzophenone, isopropyl thioxanthone.
According to such scheme, acrylic monomers can be replaced the one in methacrylic acid, sodium p styrene sulfonate etc.
According to such scheme, described polymerization inhibitor is ferrous sulfate or iron ammonium sulfate.
According to such scheme, described UV-irradiation power is 100W ~ 500W.
According to such scheme, the UV-irradiation lower reaction time is 0.5 ~ 2h.
According to such scheme, described step 5) in the concentration of NaOH solution be the concentration of 2 ~ 5wt%, HCl solution be 2 ~ 5wt%.
The present invention is applicable to the surface graft modification of various inorganic material.
Beneficial effect of the present invention is:
(1) the present invention is using a small amount of molysite as catalyst for esterification reaction, achieves and on magnetic particle surface, connected palmitic acid chain under the condition of normal temperature, introducing-CH
2-grafting avtive spot;
(2) the present invention adopts pre-warmed mode to liquefy sensitising agent, because its lipophile will be attached to substrate surface more closely, manyly to cause from substrate surface, reduces the autohemagglutination of monomer in aqueous phase.
(3) the present invention add in polymerization system a small amount of polymerization inhibitor make reaction complete afterproduct keep dispersion, grafting magnetic particle be easier to be separated.
(4) polyacrylic acid is received substrate surface with the method for chemical bonding by the product that the present invention obtains, and stability is strong, not easily peels off, and graft polymer layer is fine simultaneously protects magnetic particle, improves its resistance to acids and bases when applying;
(5) common solid support materials (comprising silica gel, CNT, molecular sieve etc.) also exists the higher problem with being difficult to reclaim of cost.The present invention is directly by using Fe
2+with Fe
3+molysite coprecipitation prepares magnetic-particle, then using as base material, cheaper starting materials product be easy to reclaim, can repeatedly regeneration
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 magnetic particle (a), modification magnetic particle (b), and grafting magnetic particle (c) apparent form feature and magnetic particle (a) are schemed with grafting magnetic particle (c) TEM.
Fig. 2 is the embodiment of the present invention 1 magnetic particle (a), modification magnetic particle (b), the infrared figure of grafting magnetic particle (c).
Fig. 3 is that magnetic particle base ion exchange absorbent of the present invention is to the repeat performance figure of cerium ion.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
In following examples, as no specific instructions, the reagent of employing is commercially available chemical reagent.
Embodiment 1
A preparation method for magnetic bead ion crossover compound adsorbent, comprises the steps:
1) coprecipitation is first adopted to prepare Fe
3o
4(nanometer) magnetic particle: take 6mmolFeSO
4and 12mmolFeCl
3be dissolved in (mol ratio Fe in 20mL deionized water
3+: Fe
2+=2:1), progressively slowly drip 80mLNH under mechanical agitation
3h
2o (concentration is 5wt%) solution, continues reaction 8h under normal temperature, by deionized water, ethanol repeated ultrasonic washing (being repeatedly each 2-4 time), magnetic separation, is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe
3o
4magnetic particle);
2) take 1g step 1) in preparation magnetic Granular composite in 20mL deionized water, drip the modifier solution (2.5wt%, oleic acid) of 40mL, add 0.1g molysite as catalyst for esterification reaction (ferric trichloride), instill an OP-10 (0.2g), mechanical dispersion, 12h is reacted under normal temperature, repeatedly rinse (being repeatedly each 2-4 time) by acetone, ethanol, deionized water, remove surface attachments, after Magneto separate, dry at 30 DEG C, obtain the Fe of surface organic modification
3o
4;
3) in quartz glass tube, configure the acrylic monomers aqueous solution of 30mL, 20wt%, add 0.1g light trigger (benzoin ethyl ether), preheating 30min, then add 0.25g step 2) in the Fe of surface organic modification
3o
4(or claim the Fe of surface modification
3o
4following examples are identical), after mechanical dispersion, add 0.1g polymerization inhibitor (ferrous sulfate), seal after passing into nitrogen 10min, under churned mechanically condition, 500W UV-irradiation 1h carries out graft reaction, has reacted with boiling water, ethanol, acetone cyclic washing Magneto separate (repeatedly for each 2-4 time), has obtained polyacrylic acid grafted magnetic particle (Fe
3o
4-g-PAA).
4) the polyacrylic acid grafted magnetic particle (Fe will prepared
3o
4-g-PAA) to add concentration be vibrate in the HCl solution of the 2wt% proportioning of the polyacrylic acid grafted magnetic particle of 0.5h[and HCl solution is 1g:40ml, following examples are identical], be washed to neutrality, be stir 0.5h in the NaOH solution of 2wt% to carry out sodium [polyacrylic acid grafted magnetic particle and the proportioning of NaOH solution are 1g:40ml transition again in concentration, following examples are identical], be washed to neutrality again, repeat (2-4 time) several times, after 65 DEG C of dryings, obtain the magnetic particle (Fe of Sodium Polyacrylate grafting
3o
4-g-PAANa).
Transmission electron microscope TEM before and after grafting materials and magnetic particle, modification magnetic particle, grafting magnetic apparent particle feature is shown in Fig. 1.Can obviously find out from Fig. 1, magnetic particle is through modified, because the introducing of organic chain, surface becomes hydrophobic; And the compound magnetic particle after grafting is unfolded through alkali rear surface polymer chain transition, there is significant swellability (volume is that multiple increases), contraction can be become in acid condition, smaller volume after dry.
Magnetic particle (a), modification magnetic particle (b), grafting magnetic particle (c) infrared spectrum is shown in Fig. 2.Can find out, at 2926cm in figure (b)
-1and 2850cm
-1occur proving that palmitic acid successfully anchors to modification magnetic particle surface by the stretching vibration peak that C-H is strong, 1380cm in Fig. 2 (c)
-1and 1532cm
-1cOO
-group symmetry and asymmetrical stretching vibration peak, illustrate that polyacrylic acid has been grafted to magnetic particulate substrate surface.
Embodiment 2
A preparation method for magnetic bead ion crossover compound adsorbent, comprises the steps:
1) coprecipitation is first adopted to prepare Fe
3o
4(nanometer) magnetic particle: take 8mmolFeSO
4and 16mmolFeCl
3be dissolved in (mol ratio Fe in 20mL deionized water
3+: Fe
2+=2:1), progressively slowly drip 40mLNH under mechanical agitation
3h
2o (concentration is 10wt%) solution, continues reaction 24h under normal temperature, by deionized water, ethanol repeated ultrasonic washing (being repeatedly each 2-4 time), magnetic separation, is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe
3o
4magnetic particle);
2) take 1g step 1) in the magnetic Granular composite of preparation in 20mL deionized water, drip modifier solution (1.25wt%, the stearic acid of 20mL.I.e. organically-modified agent solution, identical below), add 0.05gFeCl
3molysite is as catalyst for esterification reaction, instill an emulsifier op-10 (0.1-0.2g), mechanical dispersion, 24h is reacted under normal temperature, repeatedly rinse (being repeatedly each 2-4 time) by acetone, ethanol, deionized water, remove surface attachments, after Magneto separate, dry at 30 DEG C, obtain the Fe of surface organic modification
3o
4;
3) in quartz glass tube, configure the acrylic monomers aqueous solution of 20mL, 5wt%, add 0.03g light trigger (benzoin dimethylether), preheating 30min, then add 0.15g step 2) in the Fe of surface modification
3o
4after mechanical dispersion, add 0.015g polymerization inhibitor (ferrous sulfate), seal after passing into nitrogen 10min, under churned mechanically condition, 500W UV-irradiation 2h carries out graft reaction, react with boiling water, ethanol, acetone cyclic washing Magneto separate (repeatedly for each 2-4 time), obtained polyacrylic acid grafted magnetic particle (Fe
3o
4-g-PAA);
4) the polyacrylic acid grafted magnetic particle (Fe will prepared
3o
4-g-PAA) to add concentration be the 0.5h that vibrates in the HCl solution of 5wt%, be washed to neutrality, be stir 0.5h in the NaOH solution of 5wt% to carry out sodium transition again in concentration, be washed to neutrality again, repeat (2-4 time) several times, after 65 DEG C of dryings, obtain the magnetic particle (Fe of Sodium Polyacrylate grafting
3o
4-g-PAANa).
Embodiment 3
A preparation method for magnetic bead ion crossover compound adsorbent, comprises the steps:
1) coprecipitation is first adopted to prepare Fe
3o
4(nanometer) magnetic particle: take 4mmolFeSO
4and 8mmolFeCl
3be dissolved in (mol ratio Fe in 10mL deionized water
3+: Fe
2+=2:1), progressively slowly drip 40mLNH under mechanical agitation
3h
2o (concentration is 5wt%) solution, continues reaction 24h under normal temperature, by deionized water, ethanol repeated ultrasonic washing (being repeatedly each 2-4 time), magnetic separation, is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe
3o
4magnetic particle);
2) 1g step 1 is taken) the middle magnetic Granular composite prepared is in 10mL deionized water, and dropping 20mL modifier solution (2.0wt%, palmitic acid), adds 0.075g molysite as catalyst for esterification reaction (ferric trichloride), instillation emulsifier op-10 (0.1g), mechanical dispersion, reacts 18h under normal temperature, with acetone, ethanol, deionized water is repeatedly rinsed, and removes surface attachments, after Magneto separate, dry at 30 DEG C, obtain the Fe of surface organic modification
3o
4;
3) in quartz glass tube, configure the acrylic monomers aqueous solution of 40mL, 15wt%, add 0.1g light trigger, preheating 30min, then add 0.3g step 2) in the Fe of surface modification
3o
4after mechanical dispersion, add 0.075g polymerization inhibitor, seal after passing into nitrogen 10min, under churned mechanically condition, 500W UV-irradiation 1h carries out graft reaction, react with boiling water, ethanol, acetone cyclic washing Magneto separate (repeatedly for each 2-4 time), obtained polyacrylic acid grafted magnetic particle (Fe
3o
4-g-PAA);
4) the polyacrylic acid grafted magnetic particle (Fe will prepared
3o
4-g-PAA) to add concentration be the 1h that vibrates in the HCl solution of 2.5wt%, be washed to neutrality, be stir 1h in the NaOH solution of 2.5wt% to carry out sodium transition again in concentration, be washed to neutrality again, repeat (2-4 time) several times, after 65 DEG C of dryings, obtain the magnetic particle (Fe of Sodium Polyacrylate grafting
3o
4-g-PAANa).
Embodiment 4
A preparation method for magnetic bead ion crossover compound adsorbent, comprises the steps:
1) coprecipitation is first adopted to prepare Fe
3o
4(nanometer) magnetic particle: take 8mmolFeSO
4and 16mmolFeCl
3be dissolved in (mol ratio Fe in 20mL deionized water
3+: Fe
2+=2:1), progressively slowly drip 80mLNH under mechanical agitation
3h
2o (5wt%) solution, continues reaction 12h under normal temperature, by deionized water, ethanol repeated ultrasonic washing (being repeatedly each 2-4 time), magnetic separation, is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe
3o
4magnetic particle);
2) take 1g step 1) in preparation magnetic Granular composite in 20mL deionized water, drip 40mL modifier solution (1.25wt%, myristic acid), add 0.05g molysite as catalyst for esterification reaction (ferric trichloride), instillation emulsifier op-10 (0.2g), mechanical dispersion, 12h is reacted under normal temperature, repeatedly rinse (being repeatedly each 2-4 time) by acetone, ethanol, deionized water, remove surface attachments, after Magneto separate, dry at 30 DEG C, obtain the Fe of surface organic modification
3o
4;
3) in quartz glass tube, configure 30mL, 30wt% acrylic monomers aqueous solution, add 0.125g light trigger (benzophenone), preheating 30min, then add 0.25g step 2) in the Fe of surface organic modification
3o
4(the i.e. Fe of palmitic acid modification
3o
4), after mechanical dispersion, add 0.125g polymerization inhibitor (iron ammonium sulfate), seal after passing into nitrogen 10min, under churned mechanically condition, 500W UV-irradiation 0.5h carries out graft reaction, react with boiling water, ethanol, acetone cyclic washing Magneto separate (repeatedly for each 2-4 time), obtained polyacrylic acid grafted magnetic particle (Fe
3o
4-g-PAA).
4) the polyacrylic acid grafted magnetic particle (Fe will prepared
3o
4-g-PAA) to add concentration be the 0.5h that vibrates in the HCl solution of 2wt%, be washed to neutrality, be stir 0.5h in the NaOH solution of 2wt% to carry out sodium transition again in concentration, be washed to neutrality again, repeat (2-4 time) several times, after 65 DEG C of dryings, obtain the magnetic particle (Fe of Sodium Polyacrylate grafting
3o
4-g-PAANa).
Embodiment 5
A preparation method for magnetic bead ion crossover compound adsorbent, comprises the steps:
1) coprecipitation is first adopted to prepare Fe
3o
4(nanometer) magnetic particle: take 8mmolFeSO
4and 16mmolFeCl
3be dissolved in (mol ratio Fe in 20mL deionized water
3+: Fe
2+=2:1), progressively slowly drip 80mLNH under mechanical agitation
3h
2o (5wt%) solution, continues reaction 12h under normal temperature, by deionized water, ethanol repeated ultrasonic washing (being repeatedly each 2-4 time), magnetic separation, is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe
3o
4magnetic particle);
2) take 1g step 1) in preparation magnetic Granular composite in 20mL deionized water, drip 40mL modifier solution (2.5wt%, laurate), add 0.1g molysite as catalyst for esterification reaction (ferric trichloride), instillation emulsifier op-10 (0.2g), mechanical dispersion, 12h is reacted under normal temperature, repeatedly rinse (being repeatedly each 2-4 time) by acetone, ethanol, deionized water, remove surface attachments, after Magneto separate, dry at 30 DEG C, obtain the Fe of surface organic modification
3o
4;
3) in quartz glass tube, configure the acrylic monomers aqueous solution of 30mL, 10wt%, add 0.1g light trigger (isopropyl thioxanthone), preheating 30min, then add 0.2g step 2) in the Fe of surface organic modification
3o
4(the i.e. Fe of palmitic acid modification
3o
4), after mechanical dispersion, add 0.1g polymerization inhibitor (ferrous sulfate), seal after passing into nitrogen 10min, under churned mechanically condition, 500W UV-irradiation 2h carries out graft reaction, react with boiling water, ethanol, acetone cyclic washing Magneto separate (repeatedly for each 2-4 time), obtained polyacrylic acid grafted magnetic particle (Fe
3o
4-g-PAA).
4) the polyacrylic acid grafted magnetic particle (Fe will prepared
3o
4-g-PAA) to add concentration be the 0.5h that vibrates in the HCl solution of 2wt%, be washed to neutrality, be stir 0.5h in the NaOH solution of 2wt% to carry out sodium transition again in concentration, be washed to neutrality again, repeat (2-4 time) several times, after 65 DEG C of dryings, obtain the magnetic particle (Fe of Sodium Polyacrylate grafting
3o
4-g-PAANa).
The performance test results:
Ion-exchange type compound magnetic granule adsorbent obtained for embodiment 1 ~ 5 is applied to the absorption and enrichment of carrying out rare earth ion, specifically comprise the following steps: be that the ion-exchange type compound magnetic granule adsorbent of M puts into conical flask by quality, then in this conical flask, add concentration C
0for the Ce (NO) of 200mg/L
3solution, the addition making ion-exchange type compound magnetic granule adsorbent is 0.5g/L, and vibrate 24h in constant temperature oscillator at 30 DEG C, after absorption terminates, measures Ce in solution
3+the ultimate density Ce of ion.Adopt ICP measuring method, calculate Ce
3+the adsorbance Q of ion
0=V* (C
0-Ce)/M, the results are shown in Table 1.
The ion exchange capacity of the magnetic coupling ion-exchange type sorbing material that table 1 embodiment 1 ~ 5 is obtained
| Magnetic composite adsorbent | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Adsorbance Q 0(mg/g) | 314.58 | 178.90 | 237.92 | 289.53 | 257.62 |
In order to verify De contamination ability and the power of regeneration of the magnetic coupling ion-exchange type sorbing material that the present invention obtains, the ion-exchange type compound magnetic particle that Example 1 obtains is added to solid-to-liquid ratio 0.5g/L the Ce that 40ml concentration is 200mg/L
3+in solion, at 30 DEG C of vibration 12h in constant temperature oscillator, analyze and detect it to Ce
3+after the adsorbance of ion, be that the HCl solution of 0.2mol/L carries out De contamination experiment to adsorbing saturated sample by 40ml concentration, De contamination step is: vibrate 12h in 30 DEG C of constant temperature oscillators.After distilled water washing, put into the NaOH solution activation 1h that 20ml concentration is 5.0%, then extremely neutral with deionized water rinsing.Repeat absorption and De contamination experiment, testing result is shown in Fig. 3.As can be seen from the figure, the absorption property of obtained ion-exchange type compound magnetic granule adsorbent is stablized, to Ce after regenerating 8 times
3+the absorption of ion still can maintain higher level.
Testing result shows, the ion-exchange type compound magnetic granule adsorbent that the present invention obtains has excellent absorption and regeneration performance.
Embodiment 6
Substantially identical with the one in embodiment 1-5, difference is: esterification catalyst adopts the one in inorganic salts titanium sulfate, butter of tin or acid type catalyst phosphoric acid, boric acid, organic sulfonic acid, hydrochloride and sulfate.The performance test results shows: absorption property is stablized, to Ce after regenerating 8 times
3+the absorption of ion still can maintain higher level.Testing result shows, the ion-exchange type compound magnetic granule adsorbent that the present invention obtains has excellent absorption and regeneration performance.
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of technological parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
The foregoing is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, make some improvement and conversion, these all belong to protection scope of the present invention.
Claims (10)
1. the light-initiated method preparing ionic composite magnetic particle adsorbent, is characterized in that comprising the steps:
1) coprecipitation is first adopted to prepare Fe
3o
4magnetic particle: by FeCl
3middle Fe
3+and FeSO
4middle Fe
2+mol ratio=2:1, take FeCl
3and FeSO
4be dissolved in deionized water, form Fe
3+concentration be the solution of (8-16) mmol/ (10-30) mL; By FeCl
3: NH
3h
2the proportioning of O solution is (8-16) mmol:(40-80) mL, dripping concentration under mechanical agitation is 5 ~ 10wt%NH
3h
2o solution, reacts 8 ~ 24h under normal temperature, washing, and magnetic separation is dry, obtains magnetic particle;
2) by magnetic particle: deionized water: esterification catalyst: organically-modified agent solution: the proportioning of emulsifying agent is 1g:10-20mL:(0.05 ~ 0.1) g:20-40mL:0.1-0.2g, take step 1) in preparation magnetic Granular composite in deionized water, add organically-modified agent solution, instillation emulsifying agent, adds esterification catalyst, 12-24h is reacted under mechanical agitation, rinse, remove surface attachments, after Magneto separate, drying, obtains the Fe of surface organic modification
3o
4;
3) in quartz glass tube, configure the acrylic monomers aqueous solution, the volume of the described acrylic monomers aqueous solution is 20 ~ 40mL, and the concentration of the acrylic monomers aqueous solution is 5 ~ 30wt%; By the acrylic monomers aqueous solution: light trigger: step 2) in the Fe of surface organic modification
3o
4proportioning be 20 ~ 40mL:0.03g-0.125g:0.15g-0.3g, the mass ratio of polymerization inhibitor and light trigger is (0.5 ~ 1): 1, add light trigger in the acrylic monomers aqueous solution, preheating 30min, then add step 2) in the Fe of surface organic modification
3o
4, after mechanical dispersion, add polymerization inhibitor, pass into nitrogen and seal after 10 minutes, under churned mechanically condition, UV-irradiation carries out graft reaction, and washing Magneto separate, obtains polyacrylic acid grafted magnetic particle;
4) the polyacrylic acid grafted magnetic particle prepared is added in HCl solution vibrate, be washed to neutrality, then stir in NaOH solution and carry out sodium transition, then through being washed to neutrality, after drying, obtain ionic composite magnetic particle adsorbent.
2. a kind of light-initiated method preparing ionic composite magnetic particle adsorbent according to claim 1, it is characterized in that, described organic modifiers can be chosen as the one in oleic acid, stearic acid, palmitic acid, myristic acid, laurate etc.
3. a kind of light-initiated method preparing ionic composite magnetic particle adsorbent according to claim 1, it is characterized in that, described esterification catalyst adopts the one in inorganic salts titanium sulfate, ferric trichloride, butter of tin or acid type catalyst phosphoric acid, boric acid, organic sulfonic acid, hydrochloride, sulfate.
4. a kind of light-initiated method preparing ionic composite magnetic particle adsorbent according to claim 1, it is characterized in that, light trigger can select the one in benzoin ethyl ether, benzoin dimethylether, benzophenone, isopropyl thioxanthone.
5. a kind of light-initiated method preparing ionic composite magnetic particle adsorbent according to claim 1, it is characterized in that, acrylic monomers can be replaced the one in methacrylic acid, sodium p styrene sulfonate.
6. a kind of light-initiated method preparing ionic composite magnetic particle adsorbent according to claim 1, it is characterized in that, described polymerization inhibitor is ferrous sulfate or iron ammonium sulfate.
7. a kind of light-initiated method preparing ionic composite magnetic particle adsorbent according to claim 1, it is characterized in that, described UV-irradiation power is 100W ~ 500W.
8. a kind of light-initiated method preparing ionic composite magnetic particle adsorbent according to claim 1, it is characterized in that, the UV-irradiation lower reaction time is 0.5 ~ 2h.
9. a kind of light-initiated method preparing ionic composite magnetic particle adsorbent according to claim 1, is characterized in that, described step 5) in the concentration of NaOH solution be the concentration of 2 ~ 5wt%, HCl solution be 2 ~ 5wt%.
10. a kind of light-initiated method preparing ionic composite magnetic particle adsorbent according to claim 1, is characterized in that, described step 2) in emulsifying agent be emulsifier op-10.
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| CN113351184A (en) * | 2021-06-16 | 2021-09-07 | 西安理工大学 | Nylon ferroferric oxide adsorbing material containing carboxyl and preparation method thereof |
| CN113441117A (en) * | 2021-07-30 | 2021-09-28 | 西安理工大学 | Starch-based polyacrylic acid magnetic adsorption material and preparation method and application thereof |
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Cited By (3)
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