CN106824048A - A kind of energy SEPARATION OF La, cerium, the preparation method of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium - Google Patents
A kind of energy SEPARATION OF La, cerium, the preparation method of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium Download PDFInfo
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Abstract
The present invention relates to it is a kind of can SEPARATION OF La, cerium, the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium preparation method, superparamagnetism Fe has been synthesized using hydro-thermal method3O4Nanocluster, with reference to hexadecane trimethyl ammonium bromide template, using lanthanum, cerium, praseodymium or neodymium ion as template ion, using the siloxanes of band functional group as function monomer, there is the molecular engram mesoporous material of high selectivity to lanthanum, cerium, praseodymium or neodymium ion using the synthesis of silicate class sol-gal process.The invention has the advantages that can SEPARATION OF La, cerium, the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium have specific recognition ability to lanthanum, cerium, praseodymium or neodymium, with magnetic responsiveness high, high-adsorption-capacity, the rate of adsorption high, strong anti acid alkali performance, and can realize simplifying solid-liquor separation flow to the efficiently concentrating of lanthanum, cerium, praseodymium or neodymium and while separation.
Description
Technical field
The present invention relates to it is a kind of can SEPARATION OF La, cerium, the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium preparation side
Method, belongs to technical field of material.
Background technology
The high efficiency extraction of low concentration lanthanum, cerium, praseodymium or neodymium is separated and typically uses extraction, but existing process to exist into solution
This height, pollution environment, technological process is long, labour intensity is big, poor continuity, be not easy to operate, separating effect and yield are also paid no attention to
Think.Metal ingredient should be allowed to separate in process of production thorough, allow it to be easy to reclaim again, and yield the higher the better.This is just needed
Improve or change original correlation technique.Adsorption technology has low, the simple to operate, good selective that consumes energy, and is capable of achieving low
Lanthanum, cerium, praseodymium or neodymium efficiently separates in concentration complex system.Therefore, it is necessary to study be suitable for adsorption of Low Concentration lanthanum, cerium, praseodymium
Or the imprinted material of neodymium.
The content of the invention
It is an object of the invention to provide a kind of energy SEPARATION OF La, cerium, the magnetic mesoporous trace material of the sandwich structure of praseodymium or neodymium
The preparation method of material.
To achieve these goals, the present invention by the following method realize by scheme：A kind of energy SEPARATION OF La, cerium, praseodymium or neodymium
The preparation method of the magnetic mesoporous imprinted material of sandwich structure, comprises the following steps：
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is（2.2~3.2）：
（6.5~7.8）：（1.5~2.5）, take FeCl3 .6H2O, sodium acetate and polyethylene glycol, then by above-mentioned three and the quality of ethylene glycol
Volume ratio g/mL is calculated as（10.2~13.5）：（5~500）, by FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol,
Magnetic agitation is allowed to dissolve, and the homogeneous yellow mixed solution that will be obtained is sealed in being transferred to polytetrafluoro hydrothermal reaction kettle, is heated to
6~72h is reacted at 160~250 DEG C, after naturally cool to room temperature, black particle thing is obtained, is washed for several times with ethanol, then carry out
Freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4Cluster；This step is with ethylene glycol as solvent, polyethylene glycol as stabilizer,
Iron chloride is source of iron, controllable using solvent-thermal method size（1~600nm）, the nanometer Fe that the intensity of magnetization is high and monodispersity is good3O4
Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster salt of 0.1mol/L
Ultrasonically treated 5~the 20min of acid solution, then alternately washed for several times, then by nanometer Fe with ethanol and deionized water3O4Cluster and water
The solid-to-liquid ratio g/mL for solving liquid is calculated as（0.05~0.15）:（90~100）, by the nanometer Fe after washing3O4Cluster is distributed to hydrolyzate
In, then 1~100mmol/L containing silicon ion in silicon source to system is slowly added dropwise, and 1~72h is stirred, it is scrubbed, obtain nucleocapsid knot
Structure Fe3O4@nSiO2Carrier；Add generation silicone hydroxyl (Si-OH) and Fe in the hydrolytic process of silicon source3O4The hydroxyl on surface there occurs
Condensation reaction, constantly hydrolytic condensation, finally in nanometer Fe3O4Cluster surface forms the nSiO of densification2Clad；According to waiting to locate
The acidity of solution is managed, the consumption and reaction time for changing silicon source regulate and control nSiO2The thickness of clad, if the acid of pending solution
Spend bigger, required nSiO2The thickness of clad is thicker, then the corresponding amount for adding silicon source is bigger, and the reaction time is more long；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By functional polyorganosiloxane monomer and the lanthanum of band functional group, cerium,
The mol ratio of praseodymium or neodymium ion is 1：（1.2~1.5）, by the functional polyorganosiloxane monomer of band functional group and target lanthanum, cerium, praseodymium or neodymium
Solion mixes, and obtains function monomer-template molecule host-guest coordination compound；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as（0.05~
0.15）:（0.15~0.25）, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core
Shell structure Fe3O4@nSiO2Support dispersion is in condensation liquid, then the silicon source of 0.3~0.5 mass parts to system is added dropwise in stirring
In, and 1~72h is stirred, it is scrubbed to obtain polymer matrix；In slow hydrolytic condensation, progressively aggregate into containing CTAB certainly
The polymer matrix of assembling micella and lanthanum, cerium, praseodymium or neodymium ion dual mould plate；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, leaves orderly on polymer matrix
It is mesoporous, back extraction is carried out as the eluant, eluent of target lanthanum, cerium, praseodymium or neodymium ion using complexing agent or acid solution and removes lanthanum, cerium, praseodymium or neodymium
Ion, leaves the micropore mutually matched with target lanthanum, cerium, praseodymium or neodymium ion space structure and action site, that is, obtain dividing
From the magnetic mesoporous imprinted material IIP-Fe of the sandwich structure of lanthanum, cerium, praseodymium or neodymium3O4@nSiO2@mSiO2。
The step（1）Polyethylene glycol and ethylene glycol be it is purchased in market analysis it is pure.
The step（2）With（4）Silicon source for tetraethyl orthosilicate, methyl silicate, butyl silicate, positive silicic acid propyl ester or
Other silicate class, are analysis purchased in market pure.
The step（2）Hydrolyzate be made up of the component of following parts by volume：75~85 parts of ethanol, deionized water 15~25
Part, concentration are 0.5~1.5 part of the ammoniacal liquor of 28wt%.
The step（2）Ethanol for it is purchased in market analysis it is pure.
The step（3）Functional polyorganosiloxane monomer with functional group is F-CH2CH2-NHCH2CH2CH2Si(OMe)3。
The F is-COOH ,-NH2,-POOH or-SH.
The step（3）Target lanthanum, cerium, praseodymium or neodymium ion solution be to contain target lanthanum, cerium, praseodymium or neodymium ion 0.1~2
The solution of mol/L, target lanthanum, cerium, praseodymium or neodymium ion are provided by its simple substance, oxide, nitric acid thing or chloride etc., by can dissolve
Solvent（Such as water or inorganic acid）Target lanthanum, cerium, praseodymium or neodymium ion solution are obtained after dissolving.
The step（4）Condensation liquid including following parts by volume component：55~65 parts of ethanol, deionized water 75~85
Part, concentration are 0.5~1.5 part of the ammoniacal liquor of 28wt%, and the CTAB of 0.1~0.4 mass parts is added in liquid mixed above.
The step（5）Complexing agent be P204Extractant.
The step（5）Acid solution be hydrochloric acid solution or sulfuric acid solution that concentration is 0.1~2mol/L.
The magnetic mesoporous imprinted material of gained energy SEPARATION OF La, cerium, the sandwich structure of praseodymium or neodymium can realize target metal ions
Efficiently separated from liquid to be adsorbed, specifically imprinted material is added to as adsorbent and contains target lanthanum, cerium, praseodymium or neodymium ion
Liquid to be adsorbed in（Target lanthanum, cerium, praseodymium or neodymium ion in liquid to be adsorbed are low concentration, 0.1~100mmol/L）, absorption
10min or so, the concentration of metal ion in liquid to be adsorbed before and after absorption is measured with ICP-OES, calculates adsorption rate, up to 90% with
On.
The adsorbent for terminating is adsorbed to be reclaimed using Magneto separate, and the washing that adds water is subsequently adding complexing agent or acid to weakly acidic pH
Solution carries out desorption lanthanum, cerium, praseodymium or neodymium as stripping liquid（Stripping liquid is consistent with the eluant, eluent used when synthesizing the adsorbent）, in
Different time is sampled, with concentration of metal ions, adsorption rate, up to more than 90% in ICP-OES measurement stripping liquids.After desorption terminates,
Adsorbent is reclaimed using Magneto separate, is dried after being washed to weakly acidic pH, you can recycle.
The present invention is with superparamagnetic core-shell structure Fe3O4@SiO2It is core, with lanthanum, cerium, praseodymium or neodymium ion trace and with rule
Then meso-hole structure SiO2It is shell, the magnetic mesoporous imprinted material (IIP-Fe of the sandwich structure obtained by preparation3O4@nSiO2@mSiO2)
Solution efficiently separates after nanometer lanthanum, cerium, praseodymium or neodymium adsorbent being realized under magnetic force auxiliary and is adsorbed.
The invention has the advantages that：（1）The magnetic mesoporous imprinted material of sandwich structure of gained, not only material structure set
Meter is novel, and the technology of preparing of material functional has innovation, be capable of achieving to the efficiently concentrating of lanthanum, cerium, praseodymium or neodymium with separate
Simplify solid-liquor separation flow simultaneously.（2）The magnetic mesoporous imprinted material tool of sandwich structure of gained energy SEPARATION OF La, cerium, praseodymium or neodymium
There are magnetic responsiveness high, high-adsorption-capacity, the rate of adsorption high, strong anti acid alkali performance, and have specific recognition ability to lanthanum, cerium, praseodymium or neodymium.
Specific embodiment
The present invention is further specifically described below by specific embodiment, but is not to be construed as protecting the present invention
Protect the restriction of scope.
Embodiment 1
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is 2.2：6.5：1.5,
Take FeCl3 .6H2O, sodium acetate and polyethylene glycol, then it is calculated as 10.2 by the mass volume ratio g/mL of above-mentioned three and ethylene glycol：5,
By FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol, and magnetic agitation is allowed to dissolve, and the homogeneous yellow that will be obtained is mixed
Close during solution is transferred to polytetrafluoro hydrothermal reaction kettle and seal, 72h is reacted at being heated to 160 DEG C, after naturally cool to room temperature, obtain
Black particle thing, is washed 6 times with ethanol, then carries out freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster salt of 0.1mol/L
The ultrasonically treated 5min of acid solution, then with alternately washing 6 times of ethanol and deionized water, then by nanometer Fe3O4Cluster and hydrolyzate
Solid-to-liquid ratio g/mL is calculated as 0.05:90, by the nanometer Fe after washing3O4Cluster is distributed in hydrolyzate, then is slowly added dropwise positive silicic acid second
1mmol/L containing silicon ion in ester to system, and 1h is stirred, it is scrubbed, obtain core shell structure Fe3O4@nSiO2Carrier；The hydrolysis
Liquid is made up of the component of following parts by volume：75 parts of ethanol, 15 parts of deionized water, concentration are 0.5 part of the ammoniacal liquor of 28wt%；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By the functional polyorganosiloxane monomer and lanthanum ion of band functional group
Mol ratio be 1：1.2, by COOH-CH2CH2-NHCH2CH2CH2Si(OMe)3Mix with target lanthanum ion solution, obtain function
Monomer-template molecule host-guest coordination compound；Wherein, target lanthanum ion solution is the solution containing lanthanum ion 0.1mol/L；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as 0.05:
0.15, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core shell structure Fe3O4@
nSiO2Support dispersion is in condensation liquid, then is added dropwise in the tetraethyl orthosilicate of 0.3 mass parts to system in stirring, and stirs 1h,
It is scrubbed to obtain polymer matrix；The condensation liquid includes the component of following parts by volume：It is 55 parts of ethanol, 75 parts of deionized water, dense
0.5 part of the ammoniacal liquor for 28wt% is spent, and the CTAB of 0.1 mass parts is added in liquid mixed above；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, leaves orderly on polymer matrix
It is mesoporous, with weak acidity P204Extractant carries out back extraction and removes lanthanum ion as the eluant, eluent of lanthanum ion, leaves empty with target lanthanum ion
Between micropore that structurally and functionally site mutually matches, that is, obtain can SEPARATION OF La the magnetic mesoporous imprinted material of sandwich structure
IIP-Fe3O4@nSiO2@mSiO2。
The magnetic mesoporous imprinted material of sandwich structure of gained energy SEPARATION OF La can realize target metal ions from liquid to be adsorbed
In efficiently separate, be specifically added to imprinted material as adsorbent in the liquid to be adsorbed containing target lanthanum ion（It is to be adsorbed
Target lanthanum concentration in liquid is 0.1mmol/L）, absorption 10min or so, measure the front and rear liquid to be adsorbed of absorption with ICP-OES
The concentration of middle metal ion, calculates adsorption rate, up to 97%.
The adsorbent for terminating is adsorbed to be reclaimed using Magneto separate, and the washing that adds water is subsequently adding complexing agent or acid to weakly acidic pH
Solution carries out desorption lanthanum as stripping liquid（Stripping liquid is consistent with the eluant, eluent used when synthesizing the adsorbent）, taken in different time
Sample, with concentration of metal ions, adsorption rate, up to 96% in ICP-OES measurement stripping liquids.After desorption terminates, adsorbent uses Magneto separate
Reclaim, dried after being washed to weakly acidic pH, you can recycle.
Embodiment 2
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is 2.7：7.2：2, take
FeCl3 .6H2O, sodium acetate and polyethylene glycol, then it is calculated as 11.9 by the mass volume ratio g/mL of above-mentioned three and ethylene glycol：100,
By FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol, and magnetic agitation is allowed to dissolve, and the homogeneous yellow that will be obtained is mixed
Close during solution is transferred to polytetrafluoro hydrothermal reaction kettle and seal, 36h is reacted at being heated to 200 DEG C, after naturally cool to room temperature, obtain
Black particle thing, is washed 5 times with ethanol, then carries out freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster salt of 0.1mol/L
The ultrasonically treated 10min of acid solution, then with alternately washing 5 times of ethanol and deionized water, then by nanometer Fe3O4Cluster and hydrolyzate
Solid-to-liquid ratio g/mL be calculated as 0.1:95, by the nanometer Fe after washing3O4Cluster is distributed in hydrolyzate, then is slowly added dropwise positive silicic acid
10mmol/L containing silicon ion in methyl esters to system, and 36h is stirred, it is scrubbed, obtain core shell structure Fe3O4@nSiO2Carrier；It is described
Hydrolyzate is made up of the component of following parts by volume：80 parts of ethanol, 20 parts of deionized water, concentration are 1 part of the ammoniacal liquor of 28wt%；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By functional polyorganosiloxane monomer and the lanthanum of band functional group, cerium,
The mol ratio of praseodymium or neodymium ion is 1：1.3, by NH2-CH2CH2-NHCH2CH2CH2Si(OMe)3Mix with target cerium ion solution,
Obtain function monomer-template molecule host-guest coordination compound；Wherein, target cerium ion solution is to contain the molten of cerium ion 1mol/L
Liquid；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as 0.1:
0.2, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core shell structure Fe3O4@nSiO2
Support dispersion is in condensation liquid, then is added dropwise in the methyl silicate of 0.4 mass parts to system in stirring, and stirs 36h, through washing
Wash and obtain polymer matrix；The condensation liquid includes the component of following parts by volume：60 parts of ethanol, 80 parts of deionized water, concentration are
1 part of the ammoniacal liquor of 28wt%, and the CTAB of 0.3 mass parts is added in liquid mixed above；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, leaves orderly on polymer matrix
Mesoporous, the sulfuric acid solution using concentration as 1mol/L carries out back extraction and removes cerium ion as the eluant, eluent of cerium ion, leaves and target
The micropore that cerium ion space structure and action site are mutually matched, that is, obtain the magnetic mesoporous print of sandwich structure of energy separating cerium
Mark material IIP-Fe3O4@nSiO2@mSiO2。
The magnetic mesoporous imprinted material of sandwich structure of gained energy separating cerium can realize target metal ions from liquid to be adsorbed
In efficiently separate, be specifically added to imprinted material as adsorbent in the liquid to be adsorbed containing target cerium ion（It is to be adsorbed
Target cerium ion concentration in liquid is 10mmol/L）, absorption 10min or so, with the ICP-OES front and rear liquid to be adsorbed of measurement absorption
The concentration of metal ion, calculates adsorption rate, up to 98%.
The adsorbent for terminating is adsorbed to be reclaimed using Magneto separate, and the washing that adds water is subsequently adding complexing agent or acid to weakly acidic pH
Solution carries out desorption cerium as stripping liquid（Stripping liquid is consistent with the eluant, eluent used when synthesizing the adsorbent）, taken in different time
Sample, with concentration of metal ions, adsorption rate, up to 98% in ICP-OES measurement stripping liquids.After desorption terminates, adsorbent uses Magneto separate
Reclaim, dried after being washed to weakly acidic pH, you can recycle.
Embodiment 3
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is 3.2： 7.8：2.5,
Take FeCl3 .6H2O, sodium acetate and polyethylene glycol, then it is calculated as 13.5 by the mass volume ratio g/mL of above-mentioned three and ethylene glycol：
500, by FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol, and magnetic agitation is allowed to dissolve, the homogeneous Huang that will be obtained
Mixture of colours solution is sealed in being transferred to polytetrafluoro hydrothermal reaction kettle, and 1h is reacted at being heated to 250 DEG C, after naturally cool to room temperature,
Black particle thing is obtained, is washed for several times with ethanol, then carry out freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster salt of 0.1mol/L
The ultrasonically treated 20min of acid solution, then alternately washed for several times, then by nanometer Fe with ethanol and deionized water3O4Cluster and hydrolyzate
Solid-to-liquid ratio g/mL be calculated as 0.15:100, by the nanometer Fe after washing3O4Cluster is distributed in hydrolyzate, then is slowly added dropwise positive silicon
100mmol/L containing silicon ion in acid butyl ester to system, and 72h is stirred, it is scrubbed, obtain core shell structure Fe3O4@nSiO2Carrier；
The hydrolyzate is made up of the component of following parts by volume：85 parts of ethanol, 25 parts of deionized water, concentration are the ammoniacal liquor 1.5 of 28wt%
Part；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By functional polyorganosiloxane monomer and the lanthanum of band functional group, cerium,
The mol ratio of praseodymium or neodymium ion is 1：1.5, by POOH-CH2CH2-NHCH2CH2CH2Si(OMe)3It is mixed with target praseodymium ion solution
Close, obtain function monomer-template molecule host-guest coordination compound；Wherein, target praseodymium ion solution is to contain praseodymium ion 2mol/L
Solution；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as 0.15:
0.25, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core shell structure Fe3O4@
nSiO2Support dispersion is in condensation liquid, then is added dropwise in the butyl silicate of 0.5 mass parts to system in stirring, and stirs
72h, it is scrubbed to obtain polymer matrix；The condensation liquid includes the component of following parts by volume：65 parts of ethanol, deionized water 85
Part, concentration are 1.5 parts of the ammoniacal liquor of 28wt%, and the CTAB of 0.4 mass parts are added in liquid mixed above；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, leaves orderly on polymer matrix
It is mesoporous, with weak acidity P204Extractant as the eluant, eluent of target praseodymium ion carry out back extraction remove praseodymium ion, leave with target praseodymium from
The subspace micropore that structurally and functionally site mutually matches, that is, obtain separating the magnetic mesoporous trace material of sandwich structure of praseodymium
Material IIP-Fe3O4@nSiO2@mSiO2。
The magnetic mesoporous imprinted material of sandwich structure that gained can separate praseodymium can realize target metal ions from liquid to be adsorbed
In efficiently separate, be specifically added to imprinted material as adsorbent in the liquid to be adsorbed containing target praseodymium ion（It is to be adsorbed
Praseodymium ion concentration in liquid is 100mmol/L）, absorption 10min or so, measure golden in liquid to be adsorbed before and after adsorbing with ICP-OES
Belong to the concentration of ion, calculate adsorption rate, up to 96%.
The adsorbent for terminating is adsorbed to be reclaimed using Magneto separate, and the washing that adds water is subsequently adding complexing agent or acid to weakly acidic pH
Solution carries out desorption praseodymium as stripping liquid（Stripping liquid is consistent with the eluant, eluent used when synthesizing the adsorbent）, taken in different time
Sample, with concentration of metal ions, adsorption rate, up to 97% in ICP-OES measurement stripping liquids.After desorption terminates, adsorbent uses Magneto separate
Reclaim, dried after being washed to weakly acidic pH, you can recycle.
Claims (9)
1. it is a kind of can SEPARATION OF La, cerium, the preparation method of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium, it is characterised in that
Comprise the following steps：
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is（2.2~3.2）：
（6.5~7.8）：（1.5~2.5）, take FeCl3 .6H2O, sodium acetate and polyethylene glycol, then by above-mentioned three and the quality of ethylene glycol
Volume ratio g/mL is calculated as（10.2~13.5）：（5~500）, by FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol,
Magnetic agitation is allowed to dissolve, the mixed solution sealing that will be obtained, and 6~72h is reacted at being heated to 160~250 DEG C, treats natural cooling
To room temperature, black particle thing is obtained, washed for several times with ethanol, then carry out freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4
Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster hydrochloric acid of 0.1mol/L
Ultrasonically treated 5~the 20min of solution, then alternately washed for several times, then by nanometer Fe with ethanol and deionized water3O4Cluster and hydrolysis
The solid-to-liquid ratio g/mL of liquid is calculated as（0.05~0.15）:（90~100）, by the nanometer Fe after washing3O4Cluster is distributed to hydrolyzate
In, then 1~100mmol/L containing silicon ion in silicon source to system is slowly added dropwise, and 1~72h is stirred, it is scrubbed, obtain nucleocapsid knot
Structure Fe3O4@nSiO2Carrier；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By functional polyorganosiloxane monomer and the lanthanum of band functional group, cerium,
The mol ratio of praseodymium or neodymium ion is 1：（1.2~1.5）, by the functional polyorganosiloxane monomer of band functional group and target lanthanum, cerium, praseodymium or neodymium
Solion mixes, and obtains function monomer-template molecule host-guest coordination compound；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as（0.05~
0.15）:（0.15~0.25）, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core
Shell structure Fe3O4@nSiO2Support dispersion is in condensation liquid, then the silicon source of 0.3~0.5 mass parts to system is added dropwise in stirring
In, and 1~72h is stirred, it is scrubbed to obtain polymer matrix；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, with complexing agent P204Extractant or acid
Solution carries out back extraction and removes lanthanum, cerium, praseodymium or neodymium ion as eluant, eluent, that is, obtain the sandwich knot of energy SEPARATION OF La, cerium, praseodymium or neodymium
The magnetic mesoporous imprinted material of structure.
2. energy SEPARATION OF La according to claim 1, cerium, the preparation of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium
Method, it is characterised in that：It is pure that the polyethylene glycol, ethylene glycol and ethanol are analysis purchased in market.
3. energy SEPARATION OF La according to claim 1, cerium, the preparation of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium
Method, it is characterised in that：The step（2）With（4）Silicon source be tetraethyl orthosilicate, methyl silicate, butyl silicate, positive silicon
Propyl propionate or other silicate class, are analysis purchased in market pure.
4. energy SEPARATION OF La according to claim 1, cerium, the preparation of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium
Method, it is characterised in that：The step（2）Hydrolyzate be made up of the component of following parts by volume：75~85 parts of ethanol, deionization
15~25 parts of water, concentration are 0.5~1.5 part of the ammoniacal liquor of 28wt%.
5. energy SEPARATION OF La according to claim 1, cerium, the preparation of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium
Method, it is characterised in that：The step（3）Functional polyorganosiloxane monomer with functional group is F-CH2CH2-NHCH2CH2CH2Si
(OMe)3。
6. energy SEPARATION OF La according to claim 5, cerium, the preparation of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium
Method, it is characterised in that：The F is-COOH ,-NH2,-POOH or-SH.
7. energy SEPARATION OF La according to claim 1, cerium, the preparation of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium
Method, it is characterised in that：The step（3）Target lanthanum, cerium, praseodymium or neodymium ion solution be containing target lanthanum, cerium, praseodymium or neodymium from
The solution of 0.1~2 mol/L of son.
8. energy SEPARATION OF La according to claim 1, cerium, the preparation of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium
Method, it is characterised in that：The step（4）Condensation liquid including following parts by volume component：55~65 parts of ethanol, deionized water
75~85 parts, 0.5~1.5 part of the ammoniacal liquor that concentration is 28wt%, and 0.1~0.4 mass parts are added in liquid mixed above
CTAB。
9. energy SEPARATION OF La according to claim 1, cerium, the preparation of the magnetic mesoporous imprinted material of the sandwich structure of praseodymium or neodymium
Method, it is characterised in that：The step（5）Acid solution be hydrochloric acid solution or sulfuric acid solution that concentration is 0.1~2mol/L.
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| CN113332957A (en) * | 2021-06-09 | 2021-09-03 | 江西理工大学 | Preparation method of modified magnetic doping material and method for recovering rare earth elements from rare earth ore wastewater |
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| CN110961086A (en) * | 2019-12-15 | 2020-04-07 | 江西理工大学 | Extractant functionalized magnetic nano-adsorption material, preparation method and application |
| CN110961086B (en) * | 2019-12-15 | 2021-12-03 | 江西理工大学 | Extractant functionalized magnetic nano-adsorption material, preparation method and application |
| CN113332957A (en) * | 2021-06-09 | 2021-09-03 | 江西理工大学 | Preparation method of modified magnetic doping material and method for recovering rare earth elements from rare earth ore wastewater |
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Application publication date: 20170613 |