CN105170113B - A kind of light-initiated method for preparing ionic composite magnetic particle adsorbent - Google Patents
A kind of light-initiated method for preparing ionic composite magnetic particle adsorbent Download PDFInfo
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Abstract
The invention belongs to inorganic-organic composite material technical field.A kind of light-initiated method for preparing ionic composite magnetic particle adsorbent, it is characterised in that comprise the following steps：1）Fe is prepared using coprecipitation first3O4Magnetic 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, prepares the Fe of surface organic modification3O4；3) the acrylic monomers aqueous solution is configured in quartz glass tube, light trigger is added, 30 min is preheated, adds step 2）The Fe of middle surface organic modification3O4, after mechanical dispersion, polymerization inhibitor is added, nitrogen is passed through and seal after 10 minutes, ultraviolet light carries out graft reaction under conditions of mechanical agitation, washing Magneto separate obtains polyacrylic acid grafted magnetic particle；4）Add in HCl solution and vibrate, stirring carries out sodium transition in NaOH solution, obtains ionic composite magnetic particle adsorbent.This method preparation is simple, be easily recycled, adsorption capacity is high, can be used for multiple times.
Description
Technical field
The invention belongs to inorganic-organic composite material technical field, and in particular to a kind of magnetic ion crossover particle is inhaled
Attached dose of preparation method.
Background technology
Number of polymers contains abundant functional group because of it, has evolved into excellent sorbing material, in Water warfare, enzyme
The fields such as immobilized, blood purification, medicament transport are all widely used.Wherein, ion-exchange polymer such as resin/fiber etc. is changed
Chemical product has as the most common sorbing material of in the market in terms of the Industrial Wastewater Treatments such as effluent containing heavy metal ions, dyeing waste water
Tremendous development.Although Polymer adsorption excellent performance, its in application process there is also intrinsic bottleneck, for example, its machine
Tool intensity is not enough, skeleton easily avalanche in use；Contaminant molecule/ion is difficult to close to the absorption inside polymer beads
Site；The problems such as soluble in the adsorbent solution (such as acid solution) of some polymer (such as chitosan) under given conditions.Cause
This, recent domestic researcher is considered Polymer-supported in solid particles surface：Polymer can not only be given full play to
Characterization of adsorption, and be conducive to pollutant mass transfer (because functional group is distributed in adsorbent top layer).But it is now widely used
Solid support materials (including silica gel, CNT, mineral etc.) all there is the problem of cost is higher, and resulting compound suction
Particle of the enclosure material generally by sub-micron to hundreds of microns is constituted, and typically can not directly fill post operation (post presses through height), and is used
Matrix decentralized model is adsorbed, and it is separated and recovered bothers very much again.Magnetic adsorbent is the new technology of rising in recent years, it
Outstanding advantages are that powder adsorption material is completed after absorption, flow through magnetic field with working solution and are quickly and easily collected.Therefore, such as
Fruit can be by polymer supported on magnetic-particle surface, the problem of obtained composite adsorbing material had not only solved separation and recovery but also simultaneously
Possesses the high-adsorption-capacity of polymer absorbant, it is clear that have broad application prospects in water treatment field.
At present, preparing the method for such organic-inorganic composite material mainly has two kinds of cladding and grafting, the former preparation process
Simply, but without firm chemical bonding is formed between base material and surface polymer, loaded article is easy to fall off, and material lifetime has
Limit, and cause secondary pollution.And Graft Method realizes the connection of inorganic organic matter by way of bonding, structure is steady
It is fixed, it can repeatedly use, be a kind of preferable preparation method.The method for the graft modification reported both at home and abroad has a lot, mainly
There are chemical graft, high-energy radiation grafting, plasma grafting and Graft copolymerization etc..Though chemical graft equipment is simple, reaction one
Denier is carried out, and easily occurs homopolymerization and reaction condition is whard to control.High-energy radiation and plasma grafting reaction are relatively rapider, grafting
Scope can be controlled, but higher to the condition and equipment requirement of grafting, and have injury to material main body.Though above grafting method energy
Realize grafting purpose, but have grafting rate it is low, grafting high cost, the utilization rate of monomer is low, be difficult to realize what is produced on a large scale
Common fault.Comparatively, Graft copolymerization is more easy to realize grafting purpose, and its principle is by ultraviolet light technology, in sensitising agent
In the presence of trigger base material Adsorption point, the macromolecular containing functional group is fixed by way of chemical bonding and (connect
Branch) the modification performance of material can be realized for a long time in substrate surface.
The content of the invention
Present invention aims at provide a kind of light-initiated method for preparing ionic composite magnetic particle adsorbent, this method
Preparation is simple, be easily recycled, adsorption capacity is high, can be used for multiple times.
To reach above-mentioned purpose, the present invention is as follows using technical scheme：Fe is prepared with coprecipitation3O4Magnetic Nano
Particle, then connects organic chain, introducing-CH using catalytic esterification in inorganic particle surfaces2- grafting avtive spot, profit
With hydrogen sensitising agent is taken by force, hydrogen abstraction reaction is induced in the case where absorbing ultraviolet luminous energy, selection PAA is as reaction monomers, anti-
Monomer free end can realize that chain increases by continuous addition polymerization during answering, and it is excellent to be bonded substantial amounts of absorption property in material surface
Weak acid ion exchange functional group (COO-), while the characteristics of realizing high-performance and be easily isolated.
A kind of a kind of light-initiated method (or magnetic bead ion crossover for preparing ionic composite magnetic particle adsorbent
The preparation method of compound adsorbent), it is characterised in that comprise the following steps：
1) Fe is prepared using coprecipitation first3O4(nanometer) magnetic particle：By FeCl3Middle Fe3+And FeSO4Middle Fe2+Mole
Than (Fe3+:Fe2+)=2:1, weigh FeCl3And FeSO4It is dissolved in deionized water, forms Fe3+Concentration be (8-16) mmol/
(10-30) mL solution；By FeCl3：NH3·H2The proportioning of O solution is (8-16) mmol：(40-80) mL, mechanical agitation
Under concentration is progressively slowly added dropwise for 5~10wt%NH3·H28~24h is reacted under O solution, normal temperature, with deionized water, ethanol repeatedly
Repeatedly (repeatedly to be each 2-4 times), magnetic separation is dried (being placed in 60 DEG C of vacuum drying chambers), obtains magnetic particle (Fe for ultrasound washing3O4
Magnetic particle)；
2) magnetic particle is pressed：Deionized water：Esterification catalyst：Organically-modified agent solution：Emulsifying agent (emulsifier op-10) matches somebody with somebody
Than for 1g：10-20mL：(0.05~0.1) g：20-40mL：0.1-0.2g, weighs step 1) in prepare magnetic particle be scattered in
In ionized water, organically-modified agent solution (concentration of organically-modified agent solution is 1~3wt%, is the aqueous solution) is added, emulsification is instilled
Agent OP-10, adds under esterification catalyst, mechanical agitation and reacts 12-24h, repeatedly rinsed with acetone, ethanol, deionized water respectively
(repeatedly to be each 2-4 times), removes after surface attachments, Magneto separate, dries and (is dried at 30 DEG C), obtains surface organic modification
Fe3O4；
3) configure the acrylic monomers aqueous solution in quartz glass tube, the volume of the acrylic monomers aqueous solution for 20~
40mL, the concentration of the acrylic monomers aqueous solution is 5~30wt%；By the acrylic monomers aqueous solution：Light trigger：Step 2) in table
The organically-modified Fe in face3O4Proportioning be 20~40mL：0.03g-0.125g：0.15g-0.3g, polymerization inhibitor and light trigger (or
Sensitising agent) mass ratio be called (0.5~1):1, light trigger is added in the acrylic monomers aqueous solution, 30min is preheated, adds
Step 2) in surface organic modification Fe3O4, after mechanical dispersion, polymerization inhibitor is added, nitrogen is passed through and is sealed after 10 minutes, in machinery
Ultraviolet light carries out graft reaction under conditions of stirring, and reaction completion boiling water, ethanol, acetone cyclic washing Magneto separate are (anti-
It is each 2-4 times again), obtain polyacrylic acid grafted magnetic particle (Fe3O4-g-PAA)；
4) by the polyacrylic acid grafted magnetic particle (Fe prepared3O4- g-PAA) add in HCl solution and vibrate, it is washed to
Neutrality, stirring carries out sodium transition in NaOH solution, then through being washed to neutrality, is repeated several times (being repeated several times repeating 2-4
Secondary, that is, add in HCl solution and vibrate, stirring carries out sodium transition in NaOH solution), dry obtained after (65 DEG C of dryings) from
Subtype composite magnetic particle adsorbent【Or composite magnetic particle adsorbent, or the magnetic particle that Sodium Polyacrylate is grafted
(Fe3O4-g-PAANa)】。
According to such scheme, the organic modifiers can be selected as oleic acid, stearic acid, palmitic acid, myristic acid, laurate
One kind in.
According to such scheme, the esterification catalyst can use inorganic salts titanium sulfate, ferric trichloride, butter of tin or acid
One kind in type catalyst phosphoric acid, boric acid, organic sulfonic acid, hydrochloride and sulfate etc..
According to such scheme, light trigger can select benzoin ethyl ether, benzoin dimethylether, benzophenone, isopropyl sulphur
One kind in the hydrogen-abstraction sensitising agent such as miscellaneous anthrone.
According to such scheme, acrylic monomers can be replaced one kind in methacrylic acid, sodium p styrene sulfonate etc..
According to such scheme, the polymerization inhibitor is ferrous sulfate or iron ammonium sulfate.
According to such scheme, the ultraviolet light power is 100W~500W.
According to such scheme, the ultraviolet light lower reaction time is 0.5~2h.
According to such scheme, the step 5) in the concentration of NaOH solution be 2~5wt%, the concentration of HCl solution for 2~
5wt%.
The present invention is applied to the surface graft modification of various inorganic material.
Beneficial effect of the present invention is：
(1) present invention is realized under conditions of normal temperature in magnetic particle table using a small amount of molysite as catalyst for esterification reaction
Palmitic acid chain, introducing-CH have been connected on face2- grafting avtive spot；
(2) present invention is liquefied sensitising agent using pre-warmed mode, because its lipophile will more closely be attached to base material table
Face, it is more to trigger from substrate surface, reduce the autohemagglutination of monomer in aqueous phase.
(3) present invention adds product after the completion of a small amount of polymerization inhibitor makes reaction in polymerization system and keeps scattered, is grafted magnetic
Grain is easier to separation.
(4) polyacrylic acid is connected to substrate surface by the product that the present invention is obtained in the method being chemically bonded, and stability is strong, no
It is easily peelable, while graft polymer layer is fine to protect magnetic particle, improve its resistance to acids and bases in application；
(5) to there is cost higher with being difficult to for common solid support materials (including silica gel, CNT, molecular sieve etc.)
The problem of recovery.It is of the invention direct by using Fe2+With Fe3+Molysite coprecipitation prepares magnetic-particle, is then used as base using it
Material, raw material cheap products are easily recycled, can repeatedly regeneration
Brief description of the drawings
Fig. 1 is the magnetic particle (a) of the embodiment of the present invention 1, modified magnetic particle (b), grafting magnetic particle (c) apparent form feature with
Magnetic particle (a) and grafting magnetic particle (c) TEM figures.
Fig. 2 is the magnetic particle (a) of the embodiment of the present invention 1, modified magnetic particle (b), is grafted magnetic particle (c) infrared figure.
Fig. 3 is repeat performance figure of the magnetic particle base ion exchange absorbent of the present invention to cerium ion.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not
For limiting the present invention.
In following examples, unless specific instructions, the reagent of use is commercially available chemical reagent.
Embodiment 1
A kind of preparation method of magnetic bead ion crossover compound adsorbent, comprises the following steps：
1) Fe is prepared using coprecipitation first3O4(nanometer) magnetic particle：Weigh 6mmol FeSO4With 12mmol FeCl3
(mol ratio Fe is dissolved in 20mL deionized waters3+:Fe2+=2:1) 80mL NH, are progressively slowly added dropwise under mechanical agitation3·
H2Continue to react 8h under O (concentration is 5wt%) solution, normal temperature, (be repeatedly each 2-4 with deionized water, the washing of ethanol repeated ultrasonic
It is secondary), magnetic separation is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe3O4Magnetic particle)；
2) 1g steps 1 are weighed) in prepare magnetic particle be scattered in 20mL deionized waters, be added dropwise 40mL modifier solution
(2.5wt%, oleic acid), adds 0.1g molysite as catalyst for esterification reaction (ferric trichloride), instills one and drips OP-10 (0.2g),
12h is reacted under mechanical dispersion, normal temperature, is repeatedly rinsed with acetone, ethanol, deionized water (repeatedly to be each 2-4 times), surface is removed attached
After thing, Magneto separate, dried at 30 DEG C, obtain the Fe of surface organic modification3O4；
3) 30mL, 20wt% the acrylic monomers aqueous solution are configured in quartz glass tube, 0.1g light triggers (peace is added
The fragrant ether of breath), preheat 30min, add 0.25g steps 2) in surface organic modification Fe3O4(or surface modification
Fe3O4, following examples are identical), after mechanical dispersion, 0.1g polymerization inhibitors (ferrous sulfate) are added, is passed through after nitrogen 10min and seals,
500W ultraviolet lights 1h carries out graft reaction under conditions of mechanical agitation, and reaction completion is washed repeatedly with boiling water, ethanol, acetone
Magneto separate (repeatedly to be each 2-4 times) is washed, polyacrylic acid grafted magnetic particle (Fe is obtained3O4-g-PAA)。
4) by the polyacrylic acid grafted magnetic particle (Fe prepared3O4- g-PAA) add the HCl solution that concentration is 2wt%
Middle vibration 0.5h【Polyacrylic acid grafted magnetic particle and the proportioning of HCl solution are 1g：40ml, following examples are identical】, washing
To neutral, sodium transition is carried out for stirring 0.5h in 2wt% NaOH solution then at concentration【Polyacrylic acid grafted magnetic particle with
The proportioning of NaOH solution is 1g：40ml, following examples are identical】, then neutrality is washed to, it is repeated several times (2-4 times), 65 DEG C of dryings
Magnetic particle (the Fe of Sodium Polyacrylate grafting is obtained afterwards3O4-g-PAANa)。
Transmission electron microscope TEM and magnetic particle before and after grafting materials, modified magnetic particle, grafting magnetic apparent particle feature are shown in Fig. 1.
, it is apparent that magnetic particle is by modified, because the introducing of organic chain, surface becomes hydrophobic from Fig. 1；And after being grafted
Compound magnetic particle surface polymer chain after alkali makes the transition is unfolded, with significant swellability (volume increases in multiple), in acid
Property under the conditions of can become shrink, dry after volume diminish.
Magnetic particle (a), modified magnetic particle (b), grafting magnetic particle (c) infrared spectrum is shown in Fig. 2.Scheme to can be seen that in (b),
2926cm-1And 2850cm-1There are the strong stretching vibration peaks of C-H, it was demonstrated that palmitic acid successfully anchors to modified magnetic particle surface,
1380cm in Fig. 2 (c)-1And 1532cm-1It is COO-Group is symmetrical and asymmetrical stretching vibration peak, illustrates that polyacrylic acid is grafted
Magnetic particulate substrate surface is arrived.
Embodiment 2
A kind of preparation method of magnetic bead ion crossover compound adsorbent, comprises the following steps：
1) Fe is prepared using coprecipitation first3O4(nanometer) magnetic particle：Weigh 8mmolFeSO4And 16mmolFeCl3It is molten
(the mol ratio Fe in 20mL deionized waters3+:Fe2+=2:1) 40mL NH, are progressively slowly added dropwise under mechanical agitation3·H2O
Continue to react 24h under (concentration is 10wt%) solution, normal temperature, (be repeatedly each 2-4 with deionized water, the washing of ethanol repeated ultrasonic
It is secondary), magnetic separation is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe3O4Magnetic particle)；
2) 1g steps 1 are weighed) in prepare magnetic particle be scattered in 20mL deionized waters, be added dropwise 20mL modifier solution
(1.25wt%, stearic acid.I.e. organically-modified agent solution, same as below), add 0.05gFeCl3Molysite is urged as esterification
Agent, instills one and drips and react 24h under emulsifier op-10 (0.1-0.2g), mechanical dispersion, normal temperature, with acetone, ethanol, deionization
Water is repeatedly rinsed (repeatedly to be each 2-4 times), is removed after surface attachments, Magneto separate, is dried at 30 DEG C, is obtained surface organic modification
Fe3O4；
3) 20mL, 5wt% the acrylic monomers aqueous solution are configured in quartz glass tube, 0.03g light triggers (peace is added
The fragrant double methyl ethers of breath), preheat 30min, add 0.15g steps 2) in the Fe that is modified of surface3O4, after mechanical dispersion, add 0.015g
Polymerization inhibitor (ferrous sulfate), is passed through after nitrogen 10min and seals, 500W ultraviolet lights 2h is connect under conditions of mechanical agitation
Branch reaction, reaction completion boiling water, ethanol, acetone cyclic washing Magneto separate (repeatedly to be each 2-4 times), obtains polyacrylic acid grafted
Magnetic particle (Fe3O4-g-PAA)；
4) by the polyacrylic acid grafted magnetic particle (Fe prepared3O4- g-PAA) add the HCl solution that concentration is 5wt%
Middle vibration 0.5h, is washed to neutrality, carries out sodium transition then at concentration for stirring 0.5h in 5wt% NaOH solution, then wash
To neutral, it is repeated several times (2-4 times), the magnetic particle (Fe of Sodium Polyacrylate grafting is obtained after 65 DEG C of dryings3O4-g-PAANa)。
Embodiment 3
A kind of preparation method of magnetic bead ion crossover compound adsorbent, comprises the following steps：
1) Fe is prepared using coprecipitation first3O4(nanometer) magnetic particle：Weigh 4mmolFeSO4And 8mmolFeCl3It is dissolved in
(mol ratio Fe in 10mL deionized waters3+:Fe2+=2:1) 40mL NH, are progressively slowly added dropwise under mechanical agitation3·H2O is (dense
Spend for 5wt%) solution, continue under normal temperature to react 24h, with deionized water, the washing of ethanol repeated ultrasonic (repeatedly to be each 2-4 times),
Magnetic separation, is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe3O4Magnetic particle)；
2) 1g steps 1 are weighed) in prepare magnetic particle be scattered in 10mL deionized waters, be added dropwise 20mL modifier solutions
(2.0wt%, palmitic acid), adds 0.075g molysite as catalyst for esterification reaction (ferric trichloride), instills emulsifier op-10
18h is reacted under (0.1g), mechanical dispersion, normal temperature, with acetone, ethanol, deionized water is repeatedly rinsed, remove surface attachments, magnetic
After separation, dried at 30 DEG C, obtain the Fe of surface organic modification3O4；
3) 40mL, 15wt% the acrylic monomers aqueous solution are configured in quartz glass tube, 0.1g light triggers are added, in advance
Hot 30min, adds 0.3g steps 2) in surface be modified Fe3O4, after mechanical dispersions, 0.075g polymerization inhibitors are added, nitrogen is passed through
Sealed after 10min, 500W ultraviolet lights 1h carries out graft reaction, reaction completion boiling water, second under conditions of mechanical agitation
Alcohol, acetone cyclic washing Magneto separate (repeatedly to be each 2-4 times), obtain polyacrylic acid grafted magnetic particle (Fe3O4-g-PAA)；
4) by the polyacrylic acid grafted magnetic particle (Fe prepared3O4- g-PAA) add concentration for 2.5wt% HCl it is molten
1h is vibrated in liquid, neutrality is washed to, sodium transition is carried out then at concentration for stirring 1h in 2.5wt% NaOH solution, then wash
To neutral, it is repeated several times (2-4 times), the magnetic particle (Fe of Sodium Polyacrylate grafting is obtained after 65 DEG C of dryings3O4-g-PAANa)。
Embodiment 4
A kind of preparation method of magnetic bead ion crossover compound adsorbent, comprises the following steps：
1) Fe is prepared using coprecipitation first3O4(nanometer) magnetic particle：Weigh 8mmolFeSO4And 16mmolFeCl3It is molten
(the mol ratio Fe in 20mL deionized waters3+:Fe2+=2:1) 80mL NH, are progressively slowly added dropwise under mechanical agitation3·H2O
Continue to react 12h under (5wt%) solution, normal temperature, with deionized water, the washing of ethanol repeated ultrasonic (repeatedly to be each 2-4 times), magnetic force
Separation, is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe3O4Magnetic particle)；
2) 1g steps 1 are weighed) in prepare magnetic particle be scattered in 20mL deionized waters, be added dropwise 40mL modifier solutions
(1.25wt%, myristic acid), adds 0.05g molysite as catalyst for esterification reaction (ferric trichloride), instills emulsifier op-10
12h is reacted under (0.2g), mechanical dispersion, normal temperature, (repeatedly to be each 2-4 times) is repeatedly rinsed with acetone, ethanol, deionized water, is gone
Except surface attachments, after Magneto separate, dried at 30 DEG C, obtain the Fe of surface organic modification3O4；
3) 30mL, 30wt% acrylic monomers aqueous solution are configured in quartz glass tube, 0.125g light triggers (two are added
Benzophenone), preheat 30min, add 0.25g steps 2) in surface organic modification Fe3O4(the Fe that i.e. palmitic acid is modified3O4),
After mechanical dispersion, 0.125g polymerization inhibitors (iron ammonium sulfate) are added, is passed through after nitrogen 10min and seals, in churned mechanically condition
Lower 500W ultraviolet lights 0.5h carries out graft reaction, and reaction completion boiling water, ethanol, acetone cyclic washing Magneto separate are (repeatedly
To be each 2-4 times), obtain polyacrylic acid grafted magnetic particle (Fe3O4-g-PAA)。
4) by the polyacrylic acid grafted magnetic particle (Fe prepared3O4- g-PAA) add the HCl solution that concentration is 2wt%
Middle vibration 0.5h, is washed to neutrality, carries out sodium transition then at concentration for stirring 0.5h in 2wt% NaOH solution, then wash
To neutral, it is repeated several times (2-4 times), the magnetic particle (Fe of Sodium Polyacrylate grafting is obtained after 65 DEG C of dryings3O4-g-PAANa)。
Embodiment 5
A kind of preparation method of magnetic bead ion crossover compound adsorbent, comprises the following steps：
1) Fe is prepared using coprecipitation first3O4(nanometer) magnetic particle：Weigh 8mmolFeSO4And 16mmolFeCl3It is molten
(the mol ratio Fe in 20mL deionized waters3+:Fe2+=2:1) 80mL NH, are progressively slowly added dropwise under mechanical agitation3·H2O
Continue to react 12h under (5wt%) solution, normal temperature, with deionized water, the washing of ethanol repeated ultrasonic (repeatedly to be each 2-4 times), magnetic force
Separation, is placed in 60 DEG C of vacuum drying chamber dryings, obtains magnetic particle (Fe3O4Magnetic particle)；
2) 1g steps 1 are weighed) in prepare magnetic particle be scattered in 20mL deionized waters, be added dropwise 40mL modifier solutions
(2.5wt%, laurate), adds 0.1g molysite as catalyst for esterification reaction (ferric trichloride), instills emulsifier op-10
12h is reacted under (0.2g), mechanical dispersion, normal temperature, (repeatedly to be each 2-4 times) is repeatedly rinsed with acetone, ethanol, deionized water, is gone
Except surface attachments, after Magneto separate, dried at 30 DEG C, obtain the Fe of surface organic modification3O4；
3) 30mL, 10wt% the acrylic monomers aqueous solution are configured in quartz glass tube, 0.1g light triggers are added (different
Propyl group thioxanthone), preheat 30min, add 0.2g steps 2) in surface organic modification Fe3O4(i.e. palmitic acid is modified
Fe3O4), after mechanical dispersion, 0.1g polymerization inhibitors (ferrous sulfate) are added, is passed through after nitrogen 10min and seals, in churned mechanically bar
500W ultraviolet lights 2h carries out graft reaction under part, and reaction completion boiling water, ethanol, acetone cyclic washing Magneto separate are (repeatedly
To be each 2-4 times), obtain polyacrylic acid grafted magnetic particle (Fe3O4-g-PAA)。
4) by the polyacrylic acid grafted magnetic particle (Fe prepared3O4- g-PAA) add the HCl solution that concentration is 2wt%
Middle vibration 0.5h, is washed to neutrality, carries out sodium transition then at concentration for stirring 0.5h in 2wt% NaOH solution, then wash
To neutral, it is repeated several times (2-4 times), the magnetic particle (Fe of Sodium Polyacrylate grafting is obtained after 65 DEG C of dryings3O4-g-PAANa)。
The performance test results：
Ion-exchange type made from embodiment 1~5 is combined the absorption that magnetic granule adsorbent is applied to carry out rare earth ion
With enrichment, following steps are specifically included：Quality is combined into magnetic granule adsorbent for M ion-exchange type to be put into conical flask, so
Concentration C is added in the backward conical flask0For 200mg/L Ce (NO)3Solution, makes ion-exchange type be combined magnetic granule adsorbent
Addition is 0.5g/L, vibrates 24h at 30 DEG C in constant temperature oscillator, after absorption terminates, Ce in measurement solution3+Ion is most
Final concentration Ce.Using ICP measuring methods, Ce is calculated3+The adsorbance Q of ion0=V* (C0- Ce)/M, it the results are shown in Table 1.
The ion exchange capacity of magnetic coupling ion-exchange type sorbing material made from the embodiment 1~5 of table 1
| Magnetic composite adsorbent | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Adsorbance Q0(mg/g) | 314.58 | 178.90 | 237.92 | 289.53 | 257.62 |
In order to verify the De contamination ability and power of regeneration of magnetic coupling ion-exchange type sorbing material produced by the present invention,
Ion-exchange type made from Example 1 is combined magnetic particle and is added to Ce of the 40ml concentration as 200mg/L using solid-to-liquid ratio 0.5g/L3+
In solion, 12h is vibrated at 30 DEG C in constant temperature oscillator, analysis detects it to Ce3+It is dense with 40ml after the adsorbance of ion
Spend and De contamination experiment is carried out to the sample of adsorption saturation for 0.2mol/L HCl solution, De contamination step is：In 30 DEG C of constant temperature
12h is vibrated in oscillator.With distillation water washing after, be put into 20ml concentration be 5.0% NaOH solution activation 1h, then spend from
Sub- water is rinsed to neutrality.Repeat absorption and De contamination experiment, testing result is shown in Fig. 3.It can be seen that it is obtained from
The absorption property that sub- crossover is combined magnetic granule adsorbent is stable, to Ce after regenerating 8 times3+The absorption of ion remain able to maintain compared with
High level.
Testing result shows, ion-exchange type produced by the present invention be combined magnetic granule adsorbent have excellent absorption with again
Natural disposition energy.
Embodiment 6
With it is a kind of essentially identical in embodiment 1-5, difference is：Esterification catalyst using inorganic salts titanium sulfate,
One kind in butter of tin or acid type catalyst phosphoric acid, boric acid, organic sulfonic acid, hydrochloride and sulfate.The performance test results
Display：Absorption property is stable, to Ce after regenerating 8 times3+The absorption of ion remains able to maintain higher level.Testing result table
Bright, ion-exchange type produced by the present invention, which is combined magnetic granule adsorbent, has excellent absorption and regenerability.
Each raw material cited by the present invention, and each raw material of the invention bound, interval value, and technological parameter
The bound of (such as temperature, time), interval value can realize the present invention, embodiment numerous to list herein.
It the foregoing is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, make some modifications and variations, these belong to the protection model of the present invention
Enclose.
Claims (8)
1. a kind of light-initiated method for preparing ionic composite magnetic particle adsorbent, it is characterised in that comprise the following steps：
1) Fe is prepared using coprecipitation first3O4Magnetic particle：By FeCl3Middle Fe3+And FeSO4Middle Fe2+Mol ratio=2:1, claim
Take FeCl3And FeSO4It is dissolved in deionized water, forms Fe3+Concentration be (8-16) mmol/ (10-30) mL solution；Press
FeCl3：NH3·H2The proportioning of O solution is (8-16) mmol：Under (40-80) mL, mechanical agitation be added dropwise concentration be 5~
10wt%NH3·H28~24h is reacted under O solution, normal temperature, washing, magnetic separation is dried, obtains magnetic particle；
2) magnetic particle is pressed：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, weighs step 1) in prepare magnetic particle be scattered in deionized water, addition has
Machine modifier solution, instills emulsifying agent, adds under esterification catalyst, mechanical agitation and reacts 12-24h, rinse, removes surface attachment
After thing, Magneto separate, dry, obtain the Fe of surface organic modification3O4；
3) configure the acrylic monomers aqueous solution in quartz glass tube, the volume of the acrylic monomers aqueous solution for 20~
40mL, the concentration of the acrylic monomers aqueous solution is 5~30wt%；By the acrylic monomers aqueous solution：Light trigger：Step 2) in table
The organically-modified Fe in face3O4Proportioning be 20~40mL：0.03g-0.125g：The matter of 0.15g-0.3g, polymerization inhibitor and light trigger
Amount is than being (0.5~1):1, light trigger is added in the acrylic monomers aqueous solution, 30min is preheated, adds step 2) in surface
Organically-modified Fe3O4, after mechanical dispersion, polymerization inhibitor is added, nitrogen is passed through and is sealed after 10 minutes, under conditions of mechanical agitation
Ultraviolet light carries out graft reaction, washs Magneto separate, obtains polyacrylic acid grafted magnetic particle；
4) the polyacrylic acid grafted magnetic particle prepared is added in HCl solution and vibrated, neutrality is washed to, then at NaOH solution
Middle stirring carries out sodium transition, then through being washed to neutrality, ionic composite magnetic particle adsorbent is obtained after drying；
The organic modifiers selection is one kind in oleic acid, stearic acid, palmitic acid, myristic acid, laurate；
Described light trigger is from one in benzoin ethyl ether, benzoin dimethylether, benzophenone, isopropyl thioxanthone
Kind.
2. a kind of light-initiated method for preparing ionic composite magnetic particle adsorbent according to claim 1, its feature
Be, the esterification catalyst using inorganic salts titanium sulfate, ferric trichloride, butter of tin or acid type catalyst phosphoric acid, boric acid,
One kind in organic sulfonic acid, hydrochloride, sulfate.
3. a kind of light-initiated method for preparing ionic composite magnetic particle adsorbent according to claim 1, its feature
It is that acrylic monomers replaces with one kind in methacrylic acid, sodium p styrene sulfonate.
4. a kind of light-initiated method for preparing ionic composite magnetic particle adsorbent according to claim 1, its feature
It is that the polymerization inhibitor is ferrous sulfate or iron ammonium sulfate.
5. a kind of light-initiated method for preparing ionic composite magnetic particle adsorbent according to claim 1, its feature
It is that the ultraviolet light power is 100W~500W.
6. a kind of light-initiated method for preparing ionic composite magnetic particle adsorbent according to claim 1, its feature
It is that the ultraviolet light lower reaction time is 0.5~2h.
7. a kind of light-initiated method for preparing ionic composite magnetic particle adsorbent according to claim 1, its feature
Be, the step 4) in the concentration of NaOH solution be 2~5wt%, the concentration of HCl solution is 2~5wt%.
8. a kind of light-initiated method for preparing ionic composite magnetic particle adsorbent according to claim 1, its feature
Be, the step 2) in emulsifying agent be emulsifier op-10.
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| EP0687501A2 (en) * | 1994-06-15 | 1995-12-20 | Precision System Science Co., Ltd. | Magnetic material separating method making use of a pipette device and various types of clinical inspection apparatus using the method |
| CN101544730A (en) * | 2009-04-10 | 2009-09-30 | 华东理工大学 | Method for preparing nanometer spherical polyelectrolyte brush with magnetic kernel |
| CN102516562A (en) * | 2011-09-28 | 2012-06-27 | 东华大学 | Method for preparing gel by using magnetic hybrid microspheres as cross-link points |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0687501A2 (en) * | 1994-06-15 | 1995-12-20 | Precision System Science Co., Ltd. | Magnetic material separating method making use of a pipette device and various types of clinical inspection apparatus using the method |
| CN101544730A (en) * | 2009-04-10 | 2009-09-30 | 华东理工大学 | Method for preparing nanometer spherical polyelectrolyte brush with magnetic kernel |
| CN102516562A (en) * | 2011-09-28 | 2012-06-27 | 东华大学 | Method for preparing gel by using magnetic hybrid microspheres as cross-link points |
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