CN107349916B - A kind of preparation method of magnetic polymer adsorbent for heavy metal - Google Patents
A kind of preparation method of magnetic polymer adsorbent for heavy metal Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of magnetic polymer adsorbent for heavy metal, magnetic nano-particle is prepared using improvement chemical coprecipitation, then surface is carried out to it with γ-r-chloropropyl trimethoxyl silane and polyethyleneimine respectively to be modified, obtain polyethyleneimine-modified magnetic nano-particle, finally polyethyleneimine-modified magnetic nano-particle and functional monomer are copolymerized, prepare the magnetic polymer adsorbent for heavy metal with multi-layer cross-linked structure and a variety of adsorption groups, saturation magnetization is 3.5~15.5 emu/g, remanent magnetism and coercivity go to zero, with paramagnetism and magnetic responsiveness, it is 100~1000mg/L heavy metal ion aqueous solution for initial concentration, heavy metal ion adsorbed capacity reaches 35~450mg/g, 50~100min reaches To adsorption equilibrium, the heavy metal ion adsorbed capacity after recycling utilization 5 times is more than the 85% of first time adsorption capacity, can be widely applied to heavy metal ion adsorbed separation and heavy metal ion pollution control etc..
Description
One, technical field
It is prepared by the present invention magnetic poly- the present invention relates to a kind of preparation method of magnetic polymer adsorbent for heavy metal
The adsorbing separation that object adsorbent for heavy metal is suitable for heavy metal ion is closed, can be widely applied to heavy metal ion adsorbed, again
Separation of metal ions purification and heavy metal ion environmental pollution improvement etc..
Two, background technique
With the raising of global industry degree, environmental pollution is on the rise, and wherein water pollution has seriously affected people's
Production and living, industrial wastewater are the main source of heavy metal pollution of water body, many industrial process, such as plating, process hides, mining, steel-making,
Dyeing etc., can generate waste water largely containing heavy metal ion, such as Cd2+、Cu2+、Pb2+、Ni2+、As3+、Hg2+、Cr3+、Co2+And Co3+
Deng, by heavy metal cannot by biology degrade, after the industrial wastewater of heavy metal ion enters water body environment, aquatic life can be caused
Object poisoning, and be enriched in human body by food chain, the health of human body is threatened, therefore heavy metal is excessive rich in food chain
Rally causes very big harm to natural environment and human health.The improvement of heavy metal ion-containing waste water is always concerned by people
Key points and difficulties, there are many method for handling effluent containing heavy metal ions, and advantage and disadvantage are individually present, and wherein chemical Treatment plating contains zinc
Waste water has the advantages that small investment, processing technique are easily grasped, the disadvantage is that consumption chemical materials, the sludge of generation are not easy to discharge；From
Sub- exchange process treating capacity is big, but resin vulnerable to pollution, and operating cost is high；Though absorption method adsorption capacity is big, adsorbent material is used
Service life is short, must regenerate, operating cost is high.Therefore, domestic and foreign scholars are exploring and are studying a kind of efficient heavy ion removing
Method.Result of study in recent years shows the exploitation and use of cost effective chemical treatment medicament, is to solve heavy metal wastewater thereby dirt
The good approach of dye problem.
Traditional adsorbent such as ion exchange resin, absorption resin, carbonaceous class adsorbent and natural mesoporous mineral material
Deng, it can only be separated by conventional methods such as centrifugation, filtering, precipitatings after these adsorbent materials absorption heavy metal ion, it is not only time-consuming
Laborious and not energy-efficient and environmental protection, the structure of destructible adsorbent material affect the regeneration of adsorbent material.In recent years
Come, the appearance of nano material and nanotechnology has been greatly facilitated the progress and development of heavy mental treatment technology, magnetic Nano
The advantages that material is because of its own distinctive bigger serface, active site abundant and high magnetism is shown in heavy metals removal field
Huge application potential.Magnetic nanometer adsorbent can be with the heavy metal contaminants in adsorbed water body, after the completion of absorption, in external magnetic
By Magnetic Isolation under the action of, the fast and effective separation of adsorbent and mother liquor is realized, and at low cost, it is easy to operate, compared with
It is difficult to solve the problems, such as that common adsorbents are separated by solid-liquid separation difficult and recycling separation well.
He etc. is by the way that using hollow cenosphere as core, magnetic material is the magnetic composite that shell preparation has core-shell structure, right
The removal rate of heavy metals lead ion can be up to 99.7%.Guan Xiaohui etc. uses self-control semi-permeable membrane Hydrolyze method preparation with regular spherical
Magnetic Fe_3O_4 nanoparticle based on structure, to heavy metal ion Pb2+、Cu2+And Cr6+It is adsorbed, has been obtained preferable
Adsorption effect.Chai Duoli etc. reaches the removal rate of pentavalent arsenic ion in water using the magnetic Fe_3O_4 nanoparticle of hydro-thermal method preparation
90%.Behzad has synthesized magnetic Fe_3O_4@SiO2 grafting schiff's base type adsorbent material, heavy metal ion Cu2+、Zn2+And Ni2+'s
Adsorption capacity reaches 97.2mg/g, 87mg/g and 81.6mg/g respectively.Souda etc. passes through 2- amino 2- methyl 1- propane sulfonic acid and magnetism
The reaction of Fe3O4 nanoparticle prepares magnetic hydrogel, counterweight configuration metal ions Zn2+And Cd2+Adsorption capacity be above it is common non-
Magnetic hydrogel.Feng etc. is prepared for magnetic hydroxylapatite adsorbent, counterweight Metal Ions Cd2+And Zn2+Theoretical maximum inhale
Attached capacity is respectively 1.964mmol/g and 2.151mmol/g.Zheng Genwu uses emulsion-crosslinking method by chitosan and Fe3O4 nanometers
Matrix is compound to obtain chitosan/Fe3O4 magnetic microsphere, aqueous solution Cu2+Adsorption capacity reach 78.15mg/g.The preparation such as Zhu is magnetic
Fe3O4/ cellulose is simultaneously used for aqueous solution heavy metal ion Mn2+、Pb2+And Cr3+Absorption finds magnetic Fe3O4/ cellulose
Heavy metal ion adsorbed performance and recycling better performances.Cheng Changjing etc. is using monoxone to chitosan with high deacetylation degree
Carboxy methylation processing is carried out, it is then subjected to surface graft copolymerization with magnetic Fe_3O_4 nanoparticle and obtains the magnetic of core-shell structure
Property chitosan absorbent, heavy metal ion Cu2+Adsorption capacity be 71.43mg/g.
Although magnetic polymer adsorbent for heavy metal gets more and more extensive concerning of people and is increasingly becoming the country
Outer research hotspot, but it how to be effectively improved the compatibility of magnetic nano-particle and polymeric matrix, avoid magnetic nano-particle
Reunion and inhibit the macroface separation of magnetic nano-particle and polymeric matrix, be still to influence magnetic polymer adsorbent
The key science and Pinch technology problem of magnetic property and heavy metal ion adsorbed performance.
Three, summary of the invention
In view of this, the object of the invention is to provide a kind of preparation side of magnetic polymer adsorbent for heavy metal
Method.Magnetic nano-particle is prepared using improvement chemical coprecipitation first, then respectively with γ-r-chloropropyl trimethoxyl silane and
Polyethyleneimine carries out surface to it and is modified, and obtains polyethyleneimine-modified magnetic nano-particle, finally changes polyethyleneimine
Property magnetic nano-particle and functional monomer be copolymerized, there is multi-layer cross-linked structure and contents of many kinds of heavy metal ion to adsorb for preparation
The magnetic polymer adsorbent for heavy metal of group improves magnetic Nano by polyethyleneimine-modified magnetic nano-particle
The compatibility of particle and polymeric matrix passes through the polyethyleneimine macromolecular chain and polymer of magnetic nano-particle surface grafting
The physical entanglement of matrix and hydrogen bond action avoid the reunion of magnetic nano-particle, inhibit magnetic nano-particle and polymeric matrix
Macroface separation, realize the heavy metal ion adsorbed magnetism intelligence separation of magnetic polymer, it is solid preferably to solve common adsorbents
Liquid separation is difficult, is also easy to produce the shortcomings that secondary pollution.
Purpose according to the present invention proposes a kind of preparation method of magnetic polymer adsorbent for heavy metal, special
Sign has following processing step:
A) FeCl36H2O, FeCl24H2O and deionized water are added in three-necked flask, are stirred evenly, nitrogen is protected
50~80 DEG C are warming up to after shield 30min, the ammonia spirit that mass concentration is 25~30% is then added dropwise, ammonia spirit is added dropwise
3~6h of nitrogen protection isothermal reaction afterwards is cooled to room temperature, and deionized water is washed 3~5 times, and magnet separation obtains magnetic nano particle
Son；The mass ratio of ammonia spirit and deionized water that FeCl36H2O, FeCl24H2O, mass concentration are 25~30% is 10
~30:5~10:25~60:100~200；
B) magnetic nano-particle, γ-r-chloropropyl trimethoxyl silane and deionized water are added in three-necked flask and are stirred
Uniformly, 50~80 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that mass concentration is 25~30%, nitrogen is then added dropwise
Room temperature is cooled to after protection 3~6h of isothermal reaction, deionized water is washed 3~5 times, and magnet separation obtains chloropropyl modified Nano
Magnetic particle；Magnetic nano-particle, γ-r-chloropropyl trimethoxyl silane, mass concentration be 25~30% ammonia spirit and go
The mass ratio of ionized water is 1~5:2~15:2~15:100~200；
C) chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water are added in three-necked flask and are stirred
It is even, 40~70 DEG C are warming up to, room temperature is cooled to after 2~5h of nitrogen protection isothermal reaction, deionized water is washed 3~5 times, magnet point
From obtaining polyethyleneimine-modified magnetic nanoparticle；Chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water
Mass ratio be 1~5:1~5:100~200；
D) NaOH is dissolved in 200mL deionized water, acrylic acid is slowly dropped to NaOH aqueous solution in ice bath, stirring is anti-
0.5~2h is answered, part is obtained and neutralizes acrylic acid aqueous solution；By polyethyleneimine-modified magnetic nano-particle, acrylamide and friendship
Connection agent is added to part and neutralizes acrylic acid aqueous solution, stirs evenly, and is warming up to 50~60 DEG C, and redox initiator is added, draws
Hair polymerization reaction 3~5 hours, finally washs product 3~5 times with dehydrated alcohol, Magnetic Isolation, and 80 DEG C of drying are crushed, obtained
Magnetic polymer adsorbent for heavy metal；The molar ratio of acrylic acid and NaOH are 1:0.5~0.8；Acrylic acid and acrylamide
Mass ratio be 1~5:1~5；Crosslinking agent accounts for the 0.1~0.8% of acrylic acid and acrylamide monomer quality total amount；Redox
Initiator accounts for the 0.1%~2.0% of acrylic acid and acrylamide monomer quality total amount, redox initiator include oxidant and
Reducing agent, oxidant are selected from ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate, and reducing agent is selected from sodium hydrogensulfite, sodium sulfite, sulphur
Sodium thiosulfate and ferrous sulfate, the molar ratio of Oxidizing and Reducing Agents are 1~2:1；Polyethyleneimine-modified magnetic nano-particle
Account for the 5~30% of acrylic acid and acrylamide monomer quality total amount；
E) magnetic polymer adsorbent for heavy metal saturation magnetization is 10~30emu/g, and remanent magnetism and coercivity are equal
It goes to zero, there is paramagnetism and magnetic responsiveness, be 100~1000mg/L heavy metal ion aqueous solution, a huge sum of money for initial concentration
Belong to ionic adsorption capacity and reach 35~450mg/g, 50~100min reaches adsorption equilibrium, the huge sum of money after recycling utilization 5 times
Belong to ionic adsorption capacity is more than first time adsorption capacity 85%.
Crosslinking agent used in the present invention is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, a contracting second
Diol acrylate, tirethylene glycol double methacrylate, 1,3- propylene glycol double methacrylate, trimethylolpropane tris acrylic acid
Ester, pentaerythritol triacrylate, glycidyl methacrylate and polyethyleneglycol diacrylate.
Heavy metal ion used in the present invention is selected from Cd2+、Cu2+、Pb2+、Ni2+、Cr3+And Cr6+。
Advantages of the present invention and effect are:
1) polymerization reaction directly carries out in aqueous solution, and non-environmental-pollution, method is simple, is not necessarily to nitrogen protection, because
This eliminates nitrogen device, reduces the Meteorological of equipment.
2) by polyethyleneimine-modified magnetic nano-particle, improve the compatible of magnetic nano-particle and polymeric matrix
Property, made by the physical entanglement of the polyethyleneimine macromolecular chain and polymeric matrix of magnetic nano-particle surface grafting and hydrogen bond
With avoiding the reunion of magnetic nano-particle, inhibit the separation of the macroface of magnetic nano-particle and polymeric matrix, realize magnetic poly-
The intelligent separation of the heavy metal ion adsorbed magnetism of object is closed, common adsorbents is preferably solved and is separated by solid-liquid separation hardly possible, is also easy to produce secondary pollution
The shortcomings that.
3) polyethyleneimine-modified magnetic nano-particle and functional monomer are copolymerized, preparation has multi-layer crosslinking
The magnetic polymer adsorbent for heavy metal of structure and contents of many kinds of heavy metal ion adsorption group, passes through the association of a variety of adsorption groups
Same effect further increases the absorption property of magnetic polymer adsorbent heavy metal ion；
The hysteresis property of magnetic polymer adsorbent for heavy metal of the present invention, heavy metal ion adsorbed rate,
Adsorption capacity, recycling utilization performance measurement method are as follows.
Using the hysteresis of LDJ-9600 type vibration magnetometer (VSM) measurement magnetic polymer adsorbent for heavy metal
Energy.
It is heavy metal ion aqueous solution and the 0.2g drying of 100~1000mg/L, finely ground magnetic polymer weight by concentration
Metal ion adsorbent is put into 250mL conical flask, is subsequently placed in oscillator and is vibrated absorption, and oscillation samples after a certain period of time,
Using the absorbance of atomic absorption spectrometry sample, each sample is measured 3 times and is averaged, heavy metal ion adsorbed amount qt
With adsorption capacity qeIt is calculated as follows respectively:
qt(mg/g)={ (C0-Ct)V}/m (1)
qe(mg/g)={ (C0-Ce)V}/m (2)
Wherein C0、CtAnd CeRespectively heavy metal ion initial concentration, oscillation absorption certain time concentration of heavy metal ion,
Heavy metal ion adsorbed equilibrium concentration (mg.L-1), V are liquor capacity (L), and m is magnetic polymer adsorbent for heavy metal
Quality (g).
The magnetic polymer adsorbent hydrochloric acid solution of 50mL 0.5mol/L of saturation absorption heavy metal ion is shaken into solution
It inhales, desorption uses atomic absorption spectrometry heavy metal ions concentration in solution after a certain period of time, flat until reaching desorption
Weighing apparatus.Magnetic polymer adsorbent after desorption is dried and crushed, then heavy metal ion is inhaled again under the same conditions
It is attached, using the heavy metal ion adsorbed capacity of atomic absorption spectrometry magnetic polymer adsorbent, and with much money with first time
The adsorption capacity for belonging to ion compares, and characterizes the recycling utilization performance of magnetic polymer adsorbent for heavy metal, repeatedly
Regeneration cycle adsorbs 5 recycling utilization performances to assess magnetic polymer adsorbent for heavy metal.
Four, specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is further explained, but it is of the invention
Content be not limited solely to the following examples.
Embodiment 1:
19.6g FeCl36H2O and 7.2g FeCl24H2O and 150mL deionized water is added in three-necked flask,
It stirs evenly, 60 DEG C is warming up to after nitrogen protection 30min, the ammonia spirit that 50g mass concentration is 25~30%, ammonia is then added dropwise
Rear nitrogen protection isothermal reaction 5h is added dropwise in aqueous solution, is cooled to room temperature, and deionized water is washed 3 times, and magnet separation obtains magnetic
Property nanoparticle；1g magnetic nano-particle, 2g γ-r-chloropropyl trimethoxyl silane and 100mL deionized water are added to three mouthfuls
It is stirred evenly in flask, 60 DEG C is warming up to after nitrogen protection 30min, it is molten that the ammonium hydroxide that 2g mass concentration is 25~30% is then added dropwise
Liquid is cooled to room temperature after nitrogen protection isothermal reaction 5h, and deionized water is washed 5 times, and magnet separation obtains chloropropyl modified Nano
Magnetic particle.1g chloropropyl modified Nano magnetic particle, 1g polyethyleneimine and 100mL deionized water are added to three-necked flask
In stir evenly, be warming up to 40 DEG C, be cooled to room temperature after nitrogen protection isothermal reaction 5h, deionized water is washed 3 times, magnet point
From obtaining polyethyleneimine-modified magnetic nanoparticle.
9g NaOH is dissolved in 200mL deionized water, 24g acrylic acid is slowly dropped to NaOH aqueous solution in ice bath,
It is stirred to react 2h, part is obtained and neutralizes acrylic acid aqueous solution；By 12g polyethyleneimine-modified magnetic nanoparticle, 16g acryloyl
Amine and 0.12g ethylene glycol diacrylate are added to part and neutralize acrylic acid aqueous solution, stir evenly, and are warming up to 60 DEG C, are added
0.48g ammonium persulfate and 0.16g sodium hydrogensulfite initiated polymerization 3 hours, finally wash product 3 times with dehydrated alcohol,
Magnetic Isolation, 80 DEG C of drying, crushes, obtains magnetic polymer adsorbent for heavy metal, saturation magnetization 15.5emu/
G, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；The Cd for being 100mg/L for initial concentration2+、Ni2+、
Pb2+And Cu2+Aqueous solution, magnetic polymer adsorbent for heavy metal Cd2+、Ni2+、Pb2+And Cu2+Adsorption capacity respectively reaches
41mg/g, 35mg/g, 54mg/g and 45mg/g, 100min reach adsorption equilibrium, the heavy metal ion after recycling utilization 5 times
Cd2+、Ni2+、Pb2+And Cu2+Adsorption capacity is more than the 85% of first time adsorption capacity.
Embodiment 2:
30gFeCl36H2O and 10gFeCl24H2O and 200mL deionized water are added in three-necked flask, stirred
Uniformly, 70 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that 60g mass concentration is 25~30% is then added dropwise, ammonium hydroxide is molten
Rear nitrogen protection isothermal reaction 4h is added dropwise in liquid, is cooled to room temperature, and deionized water is washed 5 times, and magnet separation obtains magnetism and receives
Rice corpuscles；5g magnetic nano-particle, 15g γ-r-chloropropyl trimethoxyl silane and 200mL deionized water are added to three-necked flask
In stir evenly, 70 DEG C are warming up to after nitrogen protection 30min, then be added dropwise 15g mass concentration be 25~30% ammonia spirit,
Room temperature is cooled to after nitrogen protection isothermal reaction 4h, deionization is washed 5 times or so, and magnet separation obtains chloropropyl modified Nano
Magnetic particle.2.5g chloropropyl modified Nano magnetic particle, 3g polyethyleneimine and 150mL deionized water are added to three mouthfuls of burnings
It is stirred evenly in bottle, is warming up to 70 DEG C, room temperature is cooled to after nitrogen protection isothermal reaction 2h, deionized water is washed 5 times, magnet point
From obtaining polyethyleneimine-modified magnetic nanoparticle.
7.2g NaOH is dissolved in 200mL deionized water, it is water-soluble that 20g acrylic acid is slowly dropped to NaOH in ice bath
Liquid is stirred to react 0.5h, obtains part and neutralizes acrylic acid aqueous solution；By 6g polyethyleneimine-modified magnetic nanoparticle, 20g third
Acrylamide and 0.08g diethylene glycol double methacrylate are added to part and neutralize acrylic acid aqueous solution, stir evenly, are warming up to 60
DEG C, addition 0.36g sodium peroxydisulfate and 0.12g sodium hydrogensulfite, initiated polymerization 3 hours, finally by product dehydrated alcohol
Washing 5 times, Magnetic Isolation, 80 DEG C of drying crush, obtain magnetic polymer adsorbent for heavy metal, saturation magnetization is
8.6emu/g, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；The Cu for being 300mg/L for initial concentration2 +、Ni2+、Cr3+And Cr6+Aqueous solution, magnetic polymer adsorbent for heavy metal Cu2+、Ni2+、Cr3+And Cr6+Adsorption capacity difference
Reach 105mg/g, 83mg/g, 76mg/g and 62mg/g, 85min reaches adsorption equilibrium, the heavy metal after recycling utilization 5 times
Ion Cu2+、Ni2+、Cr3+And Cr6+Adsorption capacity is more than the 85% of first time adsorption capacity.
Embodiment 3:
10gFeCl36H2O and 5gFeCl24H2O and 100mL deionized water are added in three-necked flask, stirring is equal
It is even, it is warming up to 80 DEG C after nitrogen protection 30min, the ammonia spirit that 25g mass concentration is 25~30%, ammonia spirit is then added dropwise
Rear nitrogen protection isothermal reaction 3h is added dropwise, is cooled to room temperature, deionized water is washed 4 times, and magnet separation obtains magnetic Nano
Particle；3g magnetic nano-particle, 8g γ-r-chloropropyl trimethoxyl silane and 150mL deionized water are added in three-necked flask
It stirs evenly, 80 DEG C is warming up to after nitrogen protection 30min, the ammonia spirit that 10g mass concentration is 25~30%, nitrogen is then added dropwise
Room temperature is cooled to after gas shielded isothermal reaction 3h, deionized water is washed 3 times, and it is magnetic to obtain chloropropyl modified Nano for magnet separation
Particle.5g chloropropyl modified Nano magnetic particle, 5g polyethyleneimine and 200mL deionized water are added in three-necked flask and are stirred
It mixes uniformly, is warming up to 60 DEG C, room temperature is cooled to after nitrogen protection isothermal reaction 3h, deionized water is washed 5 times, and magnet separation obtains
To polyethyleneimine-modified magnetic nanoparticle.
5.4g NaOH is dissolved in 200mL deionized water, it is water-soluble that 16g acrylic acid is slowly dropped to NaOH in ice bath
Liquid is stirred to react 1h, obtains part and neutralizes acrylic acid aqueous solution；By 8g polyethyleneimine-modified magnetic nanoparticle, 24g propylene
Amide and 0.10g tirethylene glycol double methacrylate are added to part and neutralize acrylic acid aqueous solution, stir evenly, are warming up to 50
DEG C, addition 0.54g potassium peroxydisulfate and 0.18g sodium thiosulfate, initiated polymerization 5 hours, finally by product dehydrated alcohol
Washing 3 times, Magnetic Isolation, 80 DEG C of drying crush, obtain magnetic polymer adsorbent for heavy metal, saturation magnetization is
11.2emu/g, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；It is 600mg/L's for initial concentration
Pb2+、Cu2+、Cd2+And Ni2+Aqueous solution, magnetic polymer adsorbent for heavy metal Pb2+、Cu2+、Cd2+And Ni2+Adsorption capacity
Respectively reach 214mg/g, 166mg/g, 148mg/g and 115mg/g, 70min reaches adsorption equilibrium, after recycling utilization 5 times
Heavy metal ion Pb2+、Cu2+、Cd2+And Ni2+Adsorption capacity is more than the 85% of first time adsorption capacity.
Embodiment 4:
15gFeCl36H2O and 6gFeCl24H2O and 150mL deionized water are added in three-necked flask, stirring is equal
It is even, it is warming up to 50 DEG C after nitrogen protection 30min, the ammonia spirit that 35g mass concentration is 25~30%, ammonia spirit is then added dropwise
Rear nitrogen protection isothermal reaction 6h is added dropwise, is cooled to room temperature, deionized water is washed 5 times, and magnet separation obtains magnetic Nano
Particle；2.5g magnetic nano-particle, 5g γ-r-chloropropyl trimethoxyl silane and 100mL deionized water are added to three-necked flask
In stir evenly, 50 DEG C are warming up to after nitrogen protection 30min, then be added dropwise 6g mass concentration be 25~30% ammonia spirit,
Room temperature is cooled to after nitrogen protection isothermal reaction 6h, deionized water is washed 5 times, and magnet separation obtains chloropropyl modified Nano magnetic
Property particle.Chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water are added in three-necked flask and are stirred evenly,
50 DEG C are warming up to, room temperature is cooled to after nitrogen protection isothermal reaction 4h, deionized water is washed 3 times, and magnet separation obtains polyethylene
Imine modified magnetic nanoparticle.
9g NaOH is dissolved in 200mL deionized water, 24g acrylic acid is slowly dropped to NaOH aqueous solution in ice bath,
It is stirred to react 2h, part is obtained and neutralizes acrylic acid aqueous solution；By 2g polyethyleneimine-modified magnetic nanoparticle, 16g acryloyl
Amine and 0.16g 1,3-PD double methacrylate are added to part and neutralize acrylic acid aqueous solution, stir evenly, are warming up to 50 DEG C,
0.60g potassium peroxydisulfate and 0.20g sodium sulfite is added, initiated polymerization 5 hours, product is finally washed 5 with dehydrated alcohol
Secondary, Magnetic Isolation, 80 DEG C of drying crush, obtain magnetic polymer adsorbent for heavy metal, saturation magnetization is
3.5emu/g, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；The Pb for being 800mg/L for initial concentration2 +、Cu2+、Cd2+And Cr3+Aqueous solution, magnetic polymer adsorbent for heavy metal Pb2+、Cu2+、Cd2+And Cr3+Adsorption capacity difference
Reach 324mg/g, 186mg/g, 153mg/g and 98mg/g, 60min reaches adsorption equilibrium, the huge sum of money after recycling utilization 5 times
Belong to ion Pb2+、Cu2+、Cd2+And Cr3+Adsorption capacity is more than the 85% of first time adsorption capacity.
Embodiment 5:
20gFeCl36H2O and 8gFeCl24H2O and 200mL deionized water are added in three-necked flask, stirring is equal
It is even, it is warming up to 70 DEG C after nitrogen protection 30min, the ammonia spirit that 50g mass concentration is 25~30%, ammonia spirit is then added dropwise
Rear nitrogen protection isothermal reaction 4h is added dropwise, is cooled to room temperature, deionized water is washed 4 times, and magnet separation obtains magnetic Nano
Particle；4g magnetic nano-particle, 12g γ-r-chloropropyl trimethoxyl silane and 200mL deionized water are added in three-necked flask
It stirs evenly, 80 DEG C is warming up to after nitrogen protection 30min, the ammonia spirit that 12g mass concentration is 25~30%, nitrogen is then added dropwise
Room temperature is cooled to after gas shielded isothermal reaction 3h, deionized water is washed 3 times, and it is magnetic to obtain chloropropyl modified Nano for magnet separation
Particle.3g chloropropyl modified Nano magnetic particle, 2g polyethyleneimine and 150mL deionized water are added in three-necked flask and are stirred
It mixes uniformly, is warming up to 40 DEG C, room temperature is cooled to after nitrogen protection isothermal reaction 5h, deionized water is washed 5 times, and magnet separation obtains
To polyethyleneimine-modified magnetic nanoparticle.
8g NaOH is dissolved in 200mL deionized water, 24g acrylic acid is slowly dropped to NaOH aqueous solution in ice bath,
It is stirred to react 2h, part is obtained and neutralizes acrylic acid aqueous solution；By 4g polyethyleneimine-modified magnetic nanoparticle, 18g acryloyl
Amine and 0.10g N, N '-methylene-bisacrylamide are added to part and neutralize acrylic acid aqueous solution, stir evenly, are warming up to 50
DEG C, addition 0.62g ammonium persulfate and 0.21g sodium hydrogensulfite, initiated polymerization 5 hours, finally by product dehydrated alcohol
Washing 3 times, Magnetic Isolation, 80 DEG C of drying crush, obtain magnetic polymer adsorbent for heavy metal, saturation magnetization is
5.9emu/g, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；It is 1000mg/L's for initial concentration
Pb2+、Cu2+、Cd2+And Ni2+Aqueous solution, magnetic polymer adsorbent for heavy metal Pb2+、Cu2+、Cd2+And Ni2+Adsorption capacity
Respectively reach 450mg/g, 236mg/g, 190mg/g and 132mg/g, 50min reaches adsorption equilibrium, after recycling utilization 5 times
Heavy metal ion Pb2+、Cu2+、Cd2+And Ni2+Adsorption capacity is more than the 85% of first time adsorption capacity.
Claims (3)
1. a kind of preparation method of magnetic polymer adsorbent for heavy metal, it is characterised in that there is following processing step:
A) FeCl36H2O, FeCl24H2O and deionized water are added in three-necked flask, are stirred evenly, nitrogen protection
It is warming up to 50~80 DEG C after 30min, the ammonia spirit that mass concentration is 25~30% is then added dropwise, after ammonia spirit is added dropwise
Nitrogen protection 3~6h of isothermal reaction is cooled to room temperature, and deionized water is washed 3~5 times, and magnet separation obtains magnetic nano particle
Son；The mass ratio of ammonia spirit and deionized water that FeCl36H2O, FeCl24H2O, mass concentration are 25~30% is 10
~30:5~10:25~60:100~200；
B) magnetic nano-particle, γ-r-chloropropyl trimethoxyl silane and deionized water are added in three-necked flask and are stirred evenly,
It is warming up to 50~80 DEG C after nitrogen protection 30min, the ammonia spirit that mass concentration is 25~30% is then added dropwise, nitrogen protection is permanent
It is cooled to room temperature after 3~6h of temperature reaction, deionized water is washed 3~5 times, and magnet separation obtains chloropropyl modified Nano magnetic particles
Son；Magnetic nano-particle, γ-r-chloropropyl trimethoxyl silane, the ammonia spirit that mass concentration is 25~30% and deionized water
Mass ratio be 1~5:2~15:2~15:100~200；
C) chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water are added in three-necked flask and are stirred evenly,
40~70 DEG C are warming up to, room temperature is cooled to after 2~5h of nitrogen protection isothermal reaction, deionized water is washed 3~5 times, magnet separation,
Obtain polyethyleneimine-modified magnetic nanoparticle；Chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water
Mass ratio is 1~5:1~5:100~200；
D) NaOH is dissolved in 200mL deionized water, acrylic acid is slowly dropped to NaOH aqueous solution in ice bath, is stirred to react
0.5~2h obtains part and neutralizes acrylic acid aqueous solution；By polyethyleneimine-modified magnetic nano-particle, acrylamide and crosslinking
Agent is added to part and neutralizes acrylic acid aqueous solution, stirs evenly, and is warming up to 50~60 DEG C, and redox initiator is added, and causes
Polymerization reaction 3~5 hours, finally product is washed 3~5 times with dehydrated alcohol, Magnetic Isolation, 80 DEG C of drying crush, obtain magnetic
Property polymer adsorbent for heavy metal；The molar ratio of acrylic acid and NaOH are 1:0.5~0.8；Acrylic acid and acrylamide
Mass ratio is 1~5:1~5；Crosslinking agent accounts for the 0.1~0.8% of acrylic acid and acrylamide monomer quality total amount；Redox is drawn
Hair agent accounts for the 0.1%~2.0% of acrylic acid and acrylamide monomer quality total amount, and the redox initiator includes oxidation
Agent and reducing agent, oxidant are selected from ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate, and reducing agent is selected from sodium hydrogensulfite, sulfurous acid
Sodium, sodium thiosulfate and ferrous sulfate, the molar ratio of Oxidizing and Reducing Agents are 1~2:1；Polyethyleneimine-modified magnetic Nano
Particle accounts for the 5~30% of acrylic acid and acrylamide monomer quality total amount；
E) magnetic polymer adsorbent for heavy metal saturation magnetization is 3.5~15.5emu/g, and remanent magnetism and coercivity become
In zero, there is paramagnetism and magnetic responsiveness, be 100~1000mg/L heavy metal ion aqueous solution, heavy metal for initial concentration
Ionic adsorption capacity reaches 35~450mg/g, and 50~100min reaches adsorption equilibrium, the heavy metal after recycling utilization 5 times
Ionic adsorption capacity is more than the 85% of first time adsorption capacity.
2. a kind of preparation method of magnetic polymer adsorbent for heavy metal according to claim 1, it is characterised in that:
The crosslinking agent be selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, diethylene glycol double methacrylate,
Tirethylene glycol double methacrylate, 1,3- propylene glycol double methacrylate, trimethylolpropane trimethacrylate, pentaerythrite 3 third
Olefin(e) acid ester, glycidyl methacrylate and polyethyleneglycol diacrylate.
3. a kind of preparation method of magnetic polymer adsorbent for heavy metal according to claim 1, it is characterised in that:
The heavy metal ion is selected from Cd2+、Cu2+、Pb2+、Ni2+、Cr3+And Cr6+。
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