CN110078873A - A kind of preparation method of magnetism carbon-based lithium ion imprinted material - Google Patents
A kind of preparation method of magnetism carbon-based lithium ion imprinted material Download PDFInfo
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- CN110078873A CN110078873A CN201910320710.5A CN201910320710A CN110078873A CN 110078873 A CN110078873 A CN 110078873A CN 201910320710 A CN201910320710 A CN 201910320710A CN 110078873 A CN110078873 A CN 110078873A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Abstract
The invention discloses a kind of preparation methods of magnetic carbon-based lithium ion imprinted material, it is using magnetic carbon sphere as carrier material, after carrying out surface silanization modification and the surface-functionalized processing of methacrylic acid, the lithium complex of 2- methylol -12- crown ether -4 in grafting, cross-linked polymeric is carried out by crosslinking agent of ethylene glycol dimethacrylate again, pickling is prepared after removing lithium ion.Magnetism carbon-based lithium ion imprinted material prepared by the present invention, which can be used as adsorbent, not only has good lithium ion absorption property for adsorbing lithium ion in water, and is easy to be separated from the water recycling.
Description
Technical field
The invention belongs to surface ion imprinted material preparation technical fields, and in particular to a kind of carbon-based lithium ion imprinted material
Preparation method.
Background technique
Lithium is the smallest metal of density, and silvery white, matter is soft, and there is many to be different from other metallic elements chemically and physically
Property, such as high electro-chemical activity, specific heat capacity, oxidation-reduction potential etc. are known as " promoting the energy gold of world's progress
Belong to ".In recent years, with the fast development of the industries such as nuclear power, aerospace, lithium electric car, demand of the whole world to lithium product by
Year increases.Lithium mainly exists in the form of solid mineral and two kinds of liquid mine in nature.It is explored the whole world lithium resource be about
39500000 tons, wherein 5,400,000 tons of China's proved reserves.According to statistics, China's salt lake bittern lithium resource reserves account for about lithium resource total amount
61.8%.Therefore, salt lake bittern has become the main path for obtaining lithium resource at present.
Conventional salt lake bittern mention lithium method specifically include that calcination leaching method mention lithium, absorption method mentions lithium, the precipitation method mention lithium,
Recovery by Solvent Extraction Methold lithium, carbonizatin method mention lithium etc..Wherein, absorption method due to having good selectivity, adsorption rate is high, extraction process
The advantages that simple will be the main method that lithium is extracted from low concentration seawater and salt lake bittern.
Ionic imprinting technique is received significant attention due to having height selection identity.Surface ion engram technology be
Material surface is by template ion and specific function monomer to be crosslinked in conjunction with the effects of electrostatic attraction, coordination chelating, non-covalent bond
Ion imprinted polymer is obtained under the cross-linked polymeric effect of agent, then there is spy either physically or chemically to remove template ion and be formed
The hole of different recognition reaction.Not only there is the absorption of conventional ion imprinted material using adsorbent prepared by surface ion engram technology
The feature that capacity is big, selectivity is high and reusing is good, and since its imprinted sites is located at surface, solve conventional ion
Imprinted material imprinted sites are easy the problem of being embedded, and mass transfer velocity is fast.
(the Synthesis of cauliflower-like ion imprinted polymers for such as Cui
selective adsorption and separation of lithium ion[J]. New Journal of Chemistry, 2018,42:14502-14509.) and it with phendioxin 2- crown ether -4 is function monomer, using the side of bulk polymerization
Method synthesizing lithium ion imprinted polymer, this method be easy to cause adsorption site to be embedded, influence mass transfer rate.
(the An efficient lithium ion imprinted adsorbent using multi-wall such as Huang
carbon nanotubes as support to recover lithium from water[J]. Journal of Cleaner Production, 2018,205:201-209.) and using multi-walled carbon nanotube as carbon matrix, 2- phendioxin 4- hat
Ether -4 is function monomer, lithium ion imprinted polymer is formed in multi-walled carbon nanotube surface grafting polymerization, for adsorbing in water
Lithium ion.But it adsorbs the imprinted material after lithium ion to be not easy to be separated from the water recycling.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of magnetic carbon-based lithium ion imprinted material, make in the process of the present invention
Standby lithium ion imprinted material mass transfer is fast, absorption property is good, and is easily isolated and recycled.
The preparation method of magnetism carbon-based lithium ion imprinted material of the present invention be using magnetic carbon sphere as carrier material, it is right
Its progress surface silanization is modified, carries out surface-functionalized processing with methacrylic acid and obtains surface-functionalized magnetic carbon sphere,
In the lithium complex of the surface-functionalized magnetic carbon sphere surface grafting 2- methylol -12- crown ether -4, then with dimethacrylate
Glycol ester is that crosslinking agent progress cross-linked polymeric obtains magnetic lithium ion polymer, carries out acid to the magnetic lithium ion polymer
After washing processing removing lithium ion, the magnetic carbon-based lithium ion imprinted material is prepared.
Wherein, the magnetic carbon sphere is a kind of to possess Fe 3 O 4 magnetic kernel, the magnetic carbon material of tool.Text
Offering report, there are many preparation methods of magnetic carbon sphere.The magnetic carbon sphere of these methods preparation is adapted to the present invention, can be used as
Carrier material of the invention uses.
Specifically, The present invention gives the more detailed preparation methods of the magnetic carbon-based lithium ion imprinted material.
1) γ-methacryloxypropyl trimethoxy silane, is added in the ethanol water of magnetic carbon sphere, in ice
In the presence of acetic acid, 60~70 DEG C of reactions prepare silanization magnetic carbon sphere.
2), in 60~70 DEG C of acetonitrile reaction system, with methacrylic acid, azodiisobutyronitrile and the silanization magnetic
Property carbon ball reaction, prepare methacrylic acid modification surface-functionalized magnetic carbon sphere.
3) it, is reacted in solvent DMF with anhydrous lithium chloride and 2- methylol -12- crown ether -4, preparation 2- methylol -12- hat
The lithium complex of ether -4.
4) the surface-functionalized magnetic carbon sphere, is added in the lithium complex of Xiang Suoshu 2- methylol -12- crown ether -4,
115~125 DEG C of progress graft reactions, are grafted on the function of surface for the lithium complex under the catalytic action of p-methyl benzenesulfonic acid
Change magnetic carbon sphere surface.
5), addition azodiisobutyronitrile and ethylene glycol dimethacrylate in above-mentioned graft reaction product, 65~75
Cross-linking reaction is carried out at DEG C, prepares magnetic lithium ion polymer.
6), with the acid solution washing magnetic lithium ion polymer, after lithium ion is fallen in removing, drying is washed, is prepared into
To magnetic carbon-based lithium ion imprinted material.
Magnetism carbon-based lithium ion imprinted material prepared by the present invention using magnetic carbon sphere due to, as carrier material, ensure that
Prepared imprinted material has superparamagnetism, is convenient for subsequent separation and recovery.
Specifically, in the preparation of silanization magnetic carbon sphere of the present invention, the γ-methacryloxypropyl front three
The mass ratio of oxysilane and magnetic carbon sphere is 3~7: 1.
In turn, it is 13~16: 1 that the dosage of the glacial acetic acid, which meets glacial acetic acid and the mass ratio of magnetic carbon sphere,.
Preferably, the ethanol water for dispersing the magnetic carbon sphere is by dehydrated alcohol and distilled water with 2: 1 body
Product is obtained than preparation.
More specifically, in the preparation of surface-functionalized magnetic carbon sphere of the present invention, the silanization magnetic carbon sphere, first
The mass ratio of base acrylic acid and azodiisobutyronitrile is 1: 6~7: 0.03~0.04.
Wherein, the present invention is that 2- methylol -12- crown ether -4 and anhydrous lithium chloride is anti-with 1: 0.2~0.25 mass ratio
It should be to prepare the lithium complex of 2- methylol -12- crown ether -4.
Further, in graft reaction of the present invention, the surface-functionalized magnetic carbon sphere and 2- methylol -12- are preced with
The mass ratio of the lithium complex of ether -4 is 1: 0.6~0.65.
Further, the dosage of the catalyst p-methyl benzenesulfonic acid be surface-functionalized magnetic carbon sphere quality 75~
85%。
In turn, in the cross-linking reaction, two isobutyl of the graft reaction product, ethylene glycol dimethacrylate and azo
The mass ratio of nitrile is 1: 6~10: 0.02~0.04.
The acid solution that the present invention is used to wash the magnetic lithium ion polymer can be the aqueous solution of hydrochloric acid or nitric acid.
Preferably, the present invention washs the magnetic lithium ion polymer using nitric acid solution.It is highly preferred that described
The concentration of nitric acid solution is 0.5~1mol/L.
Magnetism carbon-based lithium ion imprinted material appearance prepared by the present invention is black powder, and having internal is Fe3O4Nanoparticle
The nucleocapsid structure of son, powder granule diameter≤100nm.
It is prepared by the present invention magnetism carbon-based lithium ion imprinted material can be used as adsorbent, for adsorb the lithium in water from
Son.
The present invention is using magnetic carbon sphere as trace carrier, and lithium ion is template ion, 2- methylol -12- crown ether -4 is function
Energy monomer carries out modification for magnetic carbon sphere surface, is graft-polymerized, after crosslinking trace, elution processing, in magnetic carbon sphere table
Face synthesis ion imprinted polymer has obtained magnetic carbon-based lithium ion imprinted material.Imprinted material prepared by the present invention both has four
The superparamagnetism of Fe 3 O is conducive to separation and recovery, and has good adsorption effect to the lithium ion in water.
On the one hand magnetism carbon-based lithium ion imprinted material prepared by the present invention solves adsorbent material adsorption site and is easily wrapped
The problem of burying possesses preferable absorption property so that the mass transfer of material prepared is fast.On the other hand, dusty material is also solved
The problem of hardly possible recycling.It is used for the separation and Extraction of Lithium from Salt Lake Brine ion, solves and obtains lithium resource hardly possible in salt lake bittern
Situation.
Detailed description of the invention
Fig. 1 is the transmission electron microscope shape appearance figure of magnetic carbon-based lithium ion imprinted material.
Fig. 2 is the X ray diffracting spectrum of magnetic carbon-based lithium ion imprinted material.
Fig. 3 is the infrared spectrogram of magnetic carbon-based lithium ion imprinted material.
Fig. 4 is discrete state figure of the magnetic carbon-based lithium ion imprinted material water slurry under magnetic fields.
Fig. 5 is magnetic carbon-based lithium ion imprinted material compared with the curve of adsorption kinetics of magnetic carbon-based non-imprinted material
Figure.
Specific embodiment
Following embodiments are only the preferred technical solution of the present invention, are not used to carry out any restrictions to the present invention.For
For those skilled in the art, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made
Any modification, equivalent substitution, improvement and etc., should all be included in the protection scope of the present invention.
Magnetic carbon sphere used in the embodiment of the present invention is to make using ferrocene and acetone as raw material in the oxidation of hydrogen peroxide
Under, it is prepared by hydro-thermal method high temperature and pressure.
But above-mentioned preparation method does not constitute any restriction to magnetic carbon sphere used herein.It is existing using other
The magnetic carbon sphere for having document report preparation method to be prepared can be used as the present invention and prepare magnetic carbon-based lithium ion trace material
The raw material of material uses.
Embodiment 1.
40mL dehydrated alcohol, 20mL deionized water are added in three-necked flask, sequentially adds magnetic carbon sphere 300mg, γ-first
Base acryloyloxypropyltrimethoxysilane 2mL, glacial acetic acid 4mL, ultrasonic disperse 10min obtain suspension.
Under stirring, above-mentioned suspension is heated to 65 DEG C of reaction 4h, stops heating, is cooled to room temperature, with Buchner funnel mistake
Filter, washs filter cake with 200mL dehydrated alcohol.Filter cake is collected, silanization magnetic carbon sphere is prepared in 60 DEG C of dry 12h.
Silanization magnetic carbon sphere 100mg, azodiisobutyronitrile 3.6mg are weighed, three-necked flask is added in methacrylic acid 693mg
In, add 30mL acetonitrile, ultrasonic disperse 10min.Under stirring, 65 DEG C of reaction 5h are heated to, stops reaction, is cooled to room temperature.
40mL dehydrated alcohol, ultrasonic agitation washing 5min are added into reaction product, centrifugation washes repeatedly 5 times, and 60 DEG C dry
It is dry for 24 hours, surface-functionalized magnetic carbon sphere is prepared.
10.6mg anhydrous lithium chloride, 51.5mg 2- methylol -12- are added in the three-necked flask added with 20mL solvent DMF
Crown ether -4 controls reaction temperature at 25 DEG C and is stirred to react 2h.
Surface-functionalized magnetic carbon sphere 100mg, catalyst p-methyl benzenesulfonic acid 80mg are added into above-mentioned reaction system, heats up
6h is stirred to react to 120 DEG C.Stop heating, is cooled to room temperature.
Continue that azodiisobutyronitrile 2.5mg, ethylene glycol dimethacrylate 1mL are added into cooling reaction system,
70 DEG C are warming up to, 12h is stirred to react.Stop reaction, is cooled to room temperature.
40mL dehydrated alcohol, ultrasonic agitation washing 5min are added into reaction product, centrifugation washes repeatedly 5 times.
0.5mol/L nitric acid solution 40mL, ultrasonic agitation washing 5min, centrifugation, with nitric acid is added into product after washing again
Solution washes repeatedly 5 times.
The product of abundant removing lithium ion is placed in 40mL centrifuge tube, deionized water 40mL, ultrasonic agitation washing is added
5min, centrifugation wash repeatedly 5 times, and for 24 hours, magnetic carbon-based lithium ion imprinted material is prepared in 60 DEG C of dryings.
Fig. 1 gives the TEM shape appearance figure of magnetic carbon-based lithium ion imprinted material.It can be seen that the imprinted material has ball
Shape pattern, particle diameter≤100nm are nucleocapsid structure.The rough surface of material, it was demonstrated that formd on the surface of magnetic carbon sphere
Hole is adsorbed, provides guarantee for its good absorption property.
Fig. 2 show the XRD spectrum of magnetic carbon-based lithium ion imprinted material.At 30,36,43,53,57 and 63
Occur (220), (311), (400), (422), (511), (440) diffraction maximum of ferroso-ferric oxide structure respectively, shows made
Standby imprinted material is coated with ferroso-ferric oxide kernel, it is ensured that the subsequent separation and recovery of material solves dusty material and is difficult to
The problem of recycling.
Fig. 3 is the infrared spectrogram of magnetic carbon-based lithium ion imprinted material.In figure, 586cm-1Place is the flexible vibration of Fe-O-Fe
Dynamic peak, the presence at the peak show that the graft modification on magnetic carbon sphere does not influence the presence of ferroso-ferric oxide, prepared trace material
Material has good magnetic property；1050cm-1The C-O-Si stretching vibration peak at place shows the success of silylating reagent；1624cm-1Place
It is C=C stretching vibration peak, 2974cm-1Place is C-H stretching vibration peak, thus proves that methacrylic acid has successfully been grafted to magnetic carbon
Ball surface；And 1280cm-1The C-O-C stretching vibration peak at place then demonstrates the successful grafting of 2- methylol -12- crown ether -4.
Fig. 4 gives discrete state figure of the magnetic carbon-based lithium ion imprinted material water slurry under magnetic fields.According to
As shown in the figure, under the action of an external magnetic field, imprinted material can with solution quick separating in absorption system, so as to subsequent separation
Recycling.
Embodiment 2.
20mL dehydrated alcohol, 10mL deionized water are added in three-necked flask, sequentially adds magnetic carbon sphere 300mg, γ-first
Base acryloyloxypropyltrimethoxysilane 2mL, glacial acetic acid 4mL, ultrasonic disperse 10min obtain suspension.
Under stirring, above-mentioned suspension is heated to 70 DEG C of reaction 2h, stops heating, is cooled to room temperature, with Buchner funnel mistake
Filter, washs filter cake with 200mL dehydrated alcohol.Filter cake is collected, for 24 hours, silanization magnetic carbon sphere is prepared in 50 DEG C of dryings.
Silanization magnetic carbon sphere 100mg, azodiisobutyronitrile 4mg are weighed, three-necked flask is added in methacrylic acid 716mg
In, add 30mL acetonitrile, ultrasonic disperse 10min.Under stirring, 65 DEG C of reaction 4h are heated to, stops reaction, is cooled to room temperature.
40mL dehydrated alcohol, ultrasonic agitation washing 5min are added into reaction product, centrifugation washes repeatedly 5 times, and 50 DEG C dry
It is dry for 24 hours, surface-functionalized magnetic carbon sphere is prepared.
11mg anhydrous lithium chloride, 52mg 2- methylol -12- hat are added in the three-necked flask added with 20mL solvent DMF
Ether -4 controls reaction temperature at 25 DEG C and is stirred to react 2h.
Surface-functionalized magnetic carbon sphere 100mg, catalyst p-methyl benzenesulfonic acid 85mg are added into above-mentioned reaction system, heats up
6h is stirred to react to 115 DEG C.Stop heating, is cooled to room temperature.
Continue that azodiisobutyronitrile 2.5mg, ethylene glycol dimethacrylate are added into cooling reaction system
1.2mL is warming up to 65 DEG C, is stirred to react 16h.Stop reaction, is cooled to room temperature.
40mL dehydrated alcohol, ultrasonic agitation washing 5min are added into reaction product, centrifugation washes repeatedly 5 times.
0.5mol/L nitric acid solution 40mL, ultrasonic agitation washing 5min, centrifugation, with nitric acid is added into product after washing again
Solution washes repeatedly 5 times.
The product of abundant removing lithium ion is placed in 40mL centrifuge tube, deionized water 40mL, ultrasonic agitation washing is added
5min, centrifugation wash repeatedly 5 times, and for 24 hours, magnetic carbon-based lithium ion imprinted material is prepared in 60 DEG C of dryings.
Embodiment 3.
40mL dehydrated alcohol, 20mL deionized water are added in three-necked flask, sequentially adds magnetic carbon sphere 300mg, γ-first
Base acryloyloxypropyltrimethoxysilane 2mL, glacial acetic acid 5mL, ultrasonic disperse 10min obtain suspension.
Under stirring, above-mentioned suspension is heated to 60 DEG C of reaction 4h, stops heating, is cooled to room temperature, with Buchner funnel mistake
Filter, washs filter cake with 200mL dehydrated alcohol.Filter cake is collected, for 24 hours, silanization magnetic carbon sphere is prepared in 60 DEG C of dryings.
Silanization magnetic carbon sphere 100mg, azodiisobutyronitrile 3.8mg are weighed, three-necked flask is added in methacrylic acid 700mg
In, add 30mL acetonitrile, ultrasonic disperse 10min.Under stirring, 60 DEG C of reaction 5h are heated to, stops reaction, is cooled to room temperature.
40mL dehydrated alcohol, ultrasonic agitation washing 5min are added into reaction product, centrifugation washes repeatedly 5 times, and 60 DEG C dry
Surface-functionalized magnetic carbon sphere is prepared in dry 12h.
10.6mg anhydrous lithium chloride, 53mg 2- methylol -12- hat are added in the three-necked flask added with 20mL solvent DMF
Ether -4 controls reaction temperature at 25 DEG C and is stirred to react 2h.
Surface-functionalized magnetic carbon sphere 100mg, catalyst p-methyl benzenesulfonic acid 75mg are added into above-mentioned reaction system, heats up
6h is stirred to react to 125 DEG C.Stop heating, is cooled to room temperature.
Continue that azodiisobutyronitrile 2.5mg, ethylene glycol dimethacrylate are added into cooling reaction system
1.5mL is warming up to 65 DEG C, is stirred to react for 24 hours.Stop reaction, is cooled to room temperature.
40mL dehydrated alcohol, ultrasonic agitation washing 5min are added into reaction product, centrifugation washes repeatedly 5 times.
1mol/L nitric acid solution 30mL is added into product after washing again, ultrasonic agitation washing 5min is centrifuged, molten with nitric acid
Liquid washes repeatedly 5 times.
The product of abundant removing lithium ion is placed in 40mL centrifuge tube, deionized water 40mL, ultrasonic agitation washing is added
5min, centrifugation wash repeatedly 5 times, and for 24 hours, magnetic carbon-based lithium ion imprinted material is prepared in 60 DEG C of dryings.
Application examples.
In addition to being added without anhydrous lithium chloride, remaining preparation process is the same as embodiment 1, the magnetic carbon-based non-imprinted material of preparation.
The aqueous solution for preparing lithium concentration 10ppm, is divided into 20 parts of samples, every part of sample 10mL.
Wherein 10 parts of samples are taken at random, and magnetic carbon-based lithium ion trace prepared by 10mg embodiment 1 is added in every part of sample
Material carries out adsorption treatment at 25 DEG C.An examination is taken at 5,10,20,40,60,90,120,150,180,210min respectively
Sample filters out imprinted material with filter, using in sample after inductive coupling plasma emission spectrograph test adsorption treatment
The adsorbance of the time magnetic carbon-based lithium ion imprinted material is calculated in lithium concentration.
In remaining 10 parts of samples, the magnetic carbon-based non-imprinted material of 10mg is added in every part of sample, is carried out according to the method described above
Lithium concentration in sample, is calculated the carbon-based non-imprinted material of time magnetic after adsorption treatment and test adsorption treatment
Adsorbance.
Fig. 5 gives the curve of adsorption kinetics ratio of magnetic carbon-based lithium ion imprinted material and magnetic carbon-based non-imprinted material
Compared with figure.It can be seen from the figure that magnetic carbon-based lithium ion imprinted material reaches adsorption equilibrium in 150min, when adsorption equilibrium
Maximal absorptive capacity is 5.84mg/g.And the maximal absorptive capacity of magnetic carbon-based non-imprinted material only has 2.19mg/g, and needs
175min can be only achieved adsorption equilibrium.Magnetic carbon-based lithium ion imprinted material is magnetic carbon-based non-trace to the adsorbance of lithium ion
2.7 times of material.
Claims (10)
1. a kind of preparation method of magnetism carbon-based lithium ion imprinted material, is to be carried out using magnetic carbon sphere as carrier material to it
Surface silanization is modified, carries out surface-functionalized processing with methacrylic acid and obtains surface-functionalized magnetic carbon sphere, described
The lithium complex of surface-functionalized magnetic carbon sphere surface grafting 2- methylol -12- crown ether -4, then with ethylene glycol dimethacrylate
Ester is that crosslinking agent progress cross-linked polymeric obtains magnetic lithium ion polymer, carries out pickling processes to the magnetic lithium ion polymer
After removing lithium ion, the magnetic carbon-based lithium ion imprinted material is prepared.
2. the preparation method of magnetism carbon-based lithium ion imprinted material according to claim 1, it is characterized in that:
1) γ-methacryloxypropyl trimethoxy silane, is added in the ethanol water of magnetic carbon sphere, in glacial acetic acid
In the presence of, 60~70 DEG C of reactions prepare silanization magnetic carbon sphere；
2), in 60~70 DEG C of acetonitrile reaction system, with methacrylic acid, azodiisobutyronitrile and the silanization magnetic carbon
Ball reaction, prepares the surface-functionalized magnetic carbon sphere of methacrylic acid modification；
3) it, is reacted in solvent DMF with anhydrous lithium chloride and 2- methylol -12- crown ether -4, prepares 2- methylol -12- crown ether -4
Lithium complex；
4) the surface-functionalized magnetic carbon sphere, is added in the lithium complex of Xiang Suoshu 2- methylol -12- crown ether -4, to first
115~125 DEG C of progress graft reactions under the catalytic action of benzene sulfonic acid, are grafted on the surface-functionalized magnetic for the lithium complex
Property carbon ball surface；
5) azodiisobutyronitrile and ethylene glycol dimethacrylate, are added in above-mentioned graft reaction product, at 65~75 DEG C
Cross-linking reaction is carried out, magnetic lithium ion polymer is prepared；
6), with the acid solution washing magnetic lithium ion polymer, after lithium ion is fallen in removing, drying is washed, magnetic is prepared
Property carbon-based lithium ion imprinted material.
3. the preparation method of magnetism carbon-based lithium ion imprinted material according to claim 2 the, it is characterized in that γ-methyl
The mass ratio of acryloyloxypropyltrimethoxysilane and magnetic carbon sphere is 3~7: 1.
4. the preparation method of magnetism carbon-based lithium ion imprinted material according to claim 2, it is characterized in that the silanization
The mass ratio of magnetic carbon sphere, methacrylic acid and azodiisobutyronitrile is 1: 6~7: 0.03~0.04.
5. the preparation method of magnetism carbon-based lithium ion imprinted material according to claim 2, it is characterized in that the 2- hydroxyl first
The mass ratio of base -12- crown ether -4 and anhydrous lithium chloride is 1: 0.2~0.25.
6. the preparation method of magnetism carbon-based lithium ion imprinted material according to claim 2, it is characterized in that the surface work
The mass ratio that the lithium complex of magnetic carbon sphere and 2- methylol -12- crown ether -4 can be changed is 1: 0.6~0.65, and catalyst is to toluene
The dosage of sulfonic acid is the 75~85% of surface-functionalized magnetic carbon sphere quality.
7. the preparation method of magnetism carbon-based lithium ion imprinted material according to claim 2, it is characterized in that the grafting is anti-
The mass ratio for answering product, ethylene glycol dimethacrylate and azodiisobutyronitrile is 1: 6~10: 0.02~0.04.
8. the preparation method of magnetism carbon-based lithium ion imprinted material according to claim 2, it is characterized in that the acidity is molten
Liquid is the aqueous solution of nitric acid of 0.5~1mol/L.
9. the magnetic carbon-based lithium ion imprinted material that any preparation method of claim 1~8 is prepared.
10. application of the magnetism carbon-based lithium ion imprinted material described in claim 9 as lithium ion in adsorbent absorption water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113000035A (en) * | 2021-03-04 | 2021-06-22 | 南京大学 | Cerium ion imprinted magnetic nano material and preparation method and application thereof |
| CN114835211A (en) * | 2022-05-13 | 2022-08-02 | 中国矿业大学 | Imprinted capacitive deionization electrode tablet and preparation method and application thereof |
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| CN113000035B (en) * | 2021-03-04 | 2022-05-17 | 南京大学 | Cerium ion imprinted magnetic nano material and preparation method and application thereof |
| CN114835211A (en) * | 2022-05-13 | 2022-08-02 | 中国矿业大学 | Imprinted capacitive deionization electrode tablet and preparation method and application thereof |
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