CN105032375B - Preparation method of magnetic graphite-based heavy metal adsorbing material - Google Patents
Preparation method of magnetic graphite-based heavy metal adsorbing material Download PDFInfo
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Abstract
The invention discloses a preparation method of a magnetic graphite-based heavy metal adsorbing material. The method comprises the following steps: first, preparing a ZnFe2O4/rGO composite material modified by PAA according to a solvothermal method; then, grafting PAM onto the ZnFe2O4/rGO composite material according to a dehydration-condensation method. The preparation method has the advantages that the selected raw materials are low in toxicity, and relatively high in biocompatibility, so as not to cause secondary pollution; the efficient environment-friendly magnetic graphite-based heavy metal adsorbing material can be prepared only by adjusting the adding proportion of PAA and the concentration of PAM; the adsorbing material is excellent in dispersity, and relatively high in Pb(II) adsorption effect, and can be recycled.
Description
Technical field
The present invention relates to a kind of preparation method of magnetic graphite base heavy-metal adsorption material, particularly a kind of magnetic of Adsorption of Lead
The preparation method of property graphite adsorbing material, belongs to field of material preparation.
Background technology
China's heavy metal pollution of water body faces various problems, and the heavy metal concentration in many basins is exceeded.Harmful heavy metal is dirty
Dye waste water is one of important environmental problem that current China is faced.The processing method of heavy metal wastewater thereby mainly has chemistry heavy
Shallow lake, new adsorbent absorption, membrance separation, electrochemical process, photocatalysis, bio-flocculation process etc..Wherein, absorption method because it is easy to operate,
Treatment effeciency is high, becomes the most-often used method of removal of heavy metal ions in actual waste water.
Heavy metal absorbent can be largely classified into inorganic adsorbent and organic (macromolecule) adsorbent.Although natural material into
This is low, but adsorption effect is poor；Organic (macromolecule) adsorbent advantages of good adsorption effect, but regeneration is detrimental to, it is also easy to produce secondary pollution.
So the nano material that inorganic-organic hybrid is formed becomes one of focus of Recent study personnel research.Magnetic nano-particle
Because its surface area easy separation unique greatly and under external magnetic field is to remove the very promising absorption of heavy metal in aqueous solution
Agent.Graphene itself is containing some to adsorbing favourable functional group, and SP in graphene sheet layer2Carbon atom is easily by other functions
Group is combined by covalent bonding forces so as to can reach the effect to different metal ions selective absorption.In addition, graphite
Alkene can also improve its adsorption effect by compound with other materials physics.Therefore Graphene has in terms of heavy metal containing wastewater treatment
There is wide application.In order to further enhance its absorbability, surface modification, including Surface coating and function are generally carried out to it
Change so that it is more selective to complexing of metal ion.
2012, Xin Yang etc. were by magnetic Fe3O4Nanoparticle is decorated on reduction graphite, and studies it to Pb
(II), the adsorption efficiency of naphthylamines, although the adsorption efficiency of Pb (II) is high, but due to Fe3O4Nanoparticle is unstable in acid condition
It is fixed, easily it is decomposed, this is unfavorable for the Adsorption of Heavy Metal Ions under sour environment.
2014, the method that Qingchun Zhao etc. pass through emulsion polymerization synthesized Al (OH)3/ (PAA-co-PAM) surpasses
Trickle ball, and its adsorption efficiency to Pb (II) is have studied, research shows, the adsorbent has higher absorption to hold to Pb (II)
Amount.But, the adsorbent is not suitable for large-scale production, on the one hand, the conventional separation process that its separation process is adopted, meeting
Cause substantial amounts of loss；On the other hand, the adsorbent is unfavorable for its recycling because not possessing magnetic responsiveness.
The content of the invention
It is an object of the invention to provide a kind of preparation method of magnetic graphite base heavy-metal adsorption material.
Realizing the technical scheme of the object of the invention is：A kind of preparation method of magnetic graphite base heavy-metal adsorption material, it is first
First, using solvent-thermal method, the modified ZnFe of Jing polyacrylic acid (PAA) is prepared2O4The composite of/rGO；Then, using dehydration contracting
The method of conjunction, by poly- propionic acid amide. (PAM) ZnFe that Jing PAA were modified is grafted to2O4On/rGO composites, prepare described
Heavy-metal adsorption material, specifically includes following steps：
1. a certain amount of Graphene, PAA are added in ethylene glycol, ultrasound makes system be uniformly dispersed；
2. by FeCl3.6H2O、ZnCl2, anhydrous Na Ac above-mentioned solution is dissolved under ultrasound condition, ultrasound, make system abundant
Mixing, it is dispersed；
3. this system is subsequently carried out at a temperature of 195-205 DEG C hydro-thermal reaction；
4. after cooling Magnet is separated, washing, is dried, by products therefrom ZnFe2O4/ rGO-PAA is dispersed in dimethyl sulfoxide
In, form magnetic fluid；
5. by N, N- Dicyclohexylcarbodiimides (DCC), PAM solution are added in above-mentioned magnetic fluid, after ultrasonic disperse,
Reaction is stirred under room temperature；
6. reaction terminates rear Magnet separation, is obtained using the mixed solution washing of ethanol and deionized water, after being dried described
Adsorbing material.
Step 1. in, described ultrasonic time is 20~30min, and concentration of the Graphene in ethylene glycol is 1.5~2g/L,
Graphene is 1 with the mass ratio of PAA:5~1:6.
Step 2. in, described ultrasonic time is more than 30min, FeCl3·6H2O、ZnCl2, anhydrous Na Ac mol ratio
For 2:1:11, FeCl3·6H2The mass ratio of O and step 1. middle Graphene is 5.4:1.
Step 3. in, the time of described hydro-thermal reaction is 10~16h.
Step 4. in, described ZnFe2O4The concentration of/rGO-PAA magnetic fluids is 5~10g/L.
Step 5. in, the mass ratio of described DCC and PAM is 25:1~5:The concentration of 1, PAM solution is 1~5g/L, DCC
With step 1. middle FeCl3·6H2The mass ratio of O is 2.5:5.4~5:5.4, ultrasonic time is 15~30min, and mixing time is 10
~12h.
Step 6. in, described ethanol and the volume ratio of deionized water are 1:1, baking temperature at 40~50 DEG C, when being dried
Between be 12~14h.
Compared with prior art, it is an advantage of the invention that：
1st, the present invention prepares a kind of environmentally friendly, efficient magnetic graphite base heavy-metal adsorption material by ease of Use.Should
Adsorbing material has preferable stability, though in the state of temperature is higher also can stable existence, need not draw in experimentation
Meet requirement of experiment by entering the special operational of such as gamma-radiation radiation, conventional baking oven for heating, convention stir device.
2nd, the raw material selected by the present invention is almost non-toxic, and biocompatibility preferably, will not produce secondary pollution；
3rd, the addition concentration for adding ratio and PAM that the present invention passes through regulation PAA, prepare a kind of magnetic efficiently, environmentally friendly
Property graphite-based heavy-metal adsorption material, with fine dispersibility, preferable adsorption effect is adsorbed with to Pb (II), capable of circulation to make
With.
Description of the drawings
Fig. 1 is ZnFe obtained in present example 52O4The transmission electron microscope picture of/rGO-PAA-PAM adsorbing materials.
Fig. 2 is ZnFe obtained in present example 52O4The infrared spectrum of/rGO-PAA-PAM adsorbing materials.
Fig. 3 is Pb (II) absorption property of obtained product in 7 cases in the present invention.
Specific embodiment
Comparative example 1：ZnFe2O4The preparation of/rGO adsorbing materials
Weigh 100mg Graphenes to be added in 50ml ethylene glycol, ultrasonic 30min makes system be uniformly dispersed；Again by 2mmol
FeCl3.6H2O、1mmol ZnCl2, 1.5g NaAc be dissolved in above-mentioned solution successively under ultrasound condition, ultrasonic 30min makes system
It is sufficiently mixed, it is dispersed；Subsequently this solution is proceeded in the high-pressure sealed reactor of 150ml rustless steel politef, in perseverance
200 DEG C of constant temperature 12h in warm baking oven；Deionized water and ethanol are repeatedly washed, and are dried under conditions of 323K with vacuum drying oven
12h, draws product.
Comparative example 2：ZnFe2O4The preparation of/rGO-PAA adsorbing materials
Weigh 100mg Graphenes, 500uL PAA to be added in 50ml ethylene glycol, ultrasonic 30min makes system be uniformly dispersed；
Again by 2mmol FeCl3.6H2O、1mmol ZnCl2, 1.5g NaAc be dissolved in above-mentioned solution successively under ultrasound condition, ultrasound
30min, is sufficiently mixed system, dispersed；Subsequently this solution is proceeded to into 150ml rustless steel politef high-pressure sealed anti-
In answering kettle, 200 DEG C of constant temperature 12h in constant temperature oven；Deionized water and ethanol are repeatedly washed, with vacuum drying oven 323K bar
12h is dried under part, product is drawn.
Embodiment 1：ZnFe2O4The preparation of/rGO-PAA-PAM adsorbing materials
Weigh 100mg Graphenes, 500uL PAA to be added in 50ml ethylene glycol, ultrasonic 30min makes system be uniformly dispersed；
Again by 2mmol FeCl3.6H2O、1mmol ZnCl2, 1.5g NaAc be dissolved in above-mentioned solution successively under ultrasound condition, ultrasound
30min, is sufficiently mixed system, dispersed；Subsequently this solution is proceeded to into 150ml rustless steel politef high-pressure sealed anti-
In answering kettle, 200 DEG C of constant temperature 12h in constant temperature oven；It is cooled to Magnet after room temperature to separate, it is first multiple with ethanol and deionized water
Wash, be dried, finally products therefrom is dispersed in 50ml dimethyl sulfoxides (formation magnetic fluid)；100ml 1g/L PAM are molten for configuration
Liquid, then weighs 500mg DCC, 20ml PAM solution and is added in above-mentioned magnetic fluid, after ultrasonic 15min, is stirred at room temperature
12h；Reaction terminates rear Magnet and separates, and the mixed liquor with ethanol and deionized water repeatedly washs (V:V=1:1)；Dried with vacuum
Case is dried 12h under conditions of 323K, draws product.
Embodiment 2：ZnFe2O4The preparation of/rGO-PAA-PAM adsorbing materials
Weigh 100mg Graphenes, 500uL PAA to be added in 50ml ethylene glycol, ultrasonic 30min makes system be uniformly dispersed；
Again by 2mmol FeCl3.6H2O、1mmol ZnCl2, 1.5g NaAc be dissolved in above-mentioned solution successively under ultrasound condition, ultrasound
30min, is sufficiently mixed system, dispersed；Subsequently this solution is proceeded to into 150ml rustless steel politef high-pressure sealed anti-
In answering kettle, 200 DEG C of constant temperature 12h in constant temperature oven；It is cooled to Magnet after room temperature to separate, it is first multiple with ethanol and deionized water
Wash, be dried, finally products therefrom is dispersed in 50ml dimethyl sulfoxides (formation magnetic fluid)；100ml 2g/L PAM are molten for configuration
Liquid, then weighs 500mg DCC, 20ml PAM solution and is added in above-mentioned magnetic fluid, after ultrasonic 15min, is stirred at room temperature
12h；Reaction terminates rear Magnet and separates, and the mixed liquor with ethanol and deionized water repeatedly washs (V:V=1:1)；Dried with vacuum
Case is dried 12h under conditions of 323K, draws product.
Embodiment 3：ZnFe2O4The preparation of/rGO-PAA-PAM adsorbing materials
Weigh 100mg Graphenes, 500uL PAA to be added in 50ml ethylene glycol, ultrasonic 30min makes system be uniformly dispersed；
Again by 2mmol FeCl3.6H2O、1mmol ZnCl2, 1.5g NaAc be dissolved in above-mentioned solution successively under ultrasound condition, ultrasound
30min, is sufficiently mixed system, dispersed；Subsequently this solution is proceeded to into 150ml rustless steel politef high-pressure sealed anti-
In answering kettle, 200 DEG C of constant temperature 12h in constant temperature oven；It is cooled to Magnet after room temperature to separate, it is first multiple with ethanol and deionized water
Wash, be dried, finally products therefrom is dispersed in 50ml dimethyl sulfoxides (formation magnetic fluid)；100ml 3g/L PAM are molten for configuration
Liquid, then weighs 500mg DCC, 20ml PAM solution and is added in above-mentioned magnetic fluid, after ultrasonic 15min, is stirred at room temperature
12h；Reaction terminates rear Magnet and separates, and the mixed liquor with ethanol and deionized water repeatedly washs (V:V=1:1)；Dried with vacuum
Case is dried 12h under conditions of 323K, draws product.
Embodiment 4：ZnFe2O4The preparation of/rGO-PAA-PAM adsorbing materials
Weigh 100mg Graphenes, 500uL PAA to be added in 50ml ethylene glycol, ultrasonic 30min makes system be uniformly dispersed；
Again by 2mmol FeCl3.6H2O、1mmol ZnCl2, 1.5g NaAc be dissolved in above-mentioned solution successively under ultrasound condition, ultrasound
30min, is sufficiently mixed system, dispersed；Subsequently this solution is proceeded to into 150ml rustless steel politef high-pressure sealed anti-
In answering kettle, 200 DEG C of constant temperature 12h in constant temperature oven；It is cooled to Magnet after room temperature to separate, it is first multiple with ethanol and deionized water
Wash, be dried, finally products therefrom is dispersed in 50ml dimethyl sulfoxides (formation magnetic fluid)；100ml 4g/L PAM are molten for configuration
Liquid, then weighs 500mg DCC, 20ml PAM solution and is added in above-mentioned magnetic fluid, after ultrasonic 15min, is stirred at room temperature
12h；Reaction terminates rear Magnet and separates, and the mixed liquor with ethanol and deionized water repeatedly washs (V:V=1:1)；Dried with vacuum
Case is dried 12h under conditions of 323K, draws product.
Embodiment 5：ZnFe2O4The preparation of/rGO-PAA-PAM adsorbing materials
Weigh 100mg Graphenes, 500uL PAA to be added in 50ml ethylene glycol, ultrasonic 30min makes system be uniformly dispersed；
Again by 2mmol FeCl3.6H2O、1mmol ZnCl2, 1.5g NaAc be dissolved in above-mentioned solution successively under ultrasound condition, ultrasound
30min, is sufficiently mixed system, dispersed；Subsequently this solution is proceeded to into 150ml rustless steel politef high-pressure sealed anti-
In answering kettle, 200 DEG C of constant temperature 12h in constant temperature oven；It is cooled to Magnet after room temperature to separate, it is first multiple with ethanol and deionized water
Wash, be dried, finally products therefrom is dispersed in 50ml dimethyl sulfoxides (formation magnetic fluid)；100ml 5g/L PAM are molten for configuration
Liquid, then weighs 500mg DCC, 20ml PAM solution and is added in above-mentioned magnetic fluid, after ultrasonic 15min, is stirred at room temperature
12h；Reaction terminates rear Magnet and separates, and the mixed liquor with ethanol and deionized water repeatedly washs (V:V=1:1)；Dried with vacuum
Case is dried 12h under conditions of 323K, draws product.
Transmissioning electric mirror test is carried out respectively (such as Fig. 1 institutes to the magnetic graphite base heavy-metal adsorption material prepared by embodiment 5
Show) and infrared test (as shown in Figure 2).
Magnetic graphite base heavy-metal adsorption material to preparing in above-mentioned 7 examples carries out the test of Pb (II) absorption property.
Specifically method of testing is：Pb (II) solution of 200mg/L is prepared, with pipet the taper that 50ml is respectively placed in 100ml is measured
Bottle, with the HCl or NaOH of 0.1mol/L PH is adjusted, and makes pH be 5.5, and into 7 conical flasks above-mentioned adsorbing material is separately added into, and is used
Constant temperature oscillator stirs 10h at 30 DEG C, and Magnet is separated and takes a small amount of supernatant, and with Atomic Absorption Pb (II) not to be adsorbed is detected
Concentration.Experimental data is as shown in Figure 3.At the beginning of adsorption efficiency=(residual concentration after heavy metal initial concentration-absorption)/heavy metal
Beginning concentration.
Claims (7)
1. a kind of preparation method of magnetic graphite base heavy-metal adsorption material, it is characterised in that comprise the steps：
1. step is added to Graphene, polyacrylic acid in ethylene glycol, ultrasound, makes system be uniformly dispersed, wherein, Graphene with it is poly-
Acrylic acid mass ratio is 1:5~1:6；
Step is 2. by FeCl3.6H2O、ZnCl2, anhydrous Na Ac above-mentioned solution is dissolved under ultrasound condition, ultrasound, make system abundant
Mixing, it is dispersed；
3. this system is subsequently carried out at a temperature of 195-205 DEG C step hydro-thermal reaction；
4. after cooling Magnet is separated, washing, is dried, by products therefrom ZnFe step2O4/ rGO- polyacrylic acid is dispersed in two
In first sulfoxide, magnetic fluid is formed；
5. by N, N- Dicyclohexylcarbodiimides, polyacrylamide solution are added in above-mentioned magnetic fluid step, after ultrasonic disperse,
Reaction is stirred at room temperature, wherein, the concentration of polyacrylamide solution is 1~5g/L；
6. step reacts and terminates rear Magnet separation, is obtained using the mixed solution washing of ethanol and deionized water, after being dried described
Adsorbing material.
2. the preparation method of magnetic graphite base heavy-metal adsorption material as claimed in claim 1, it is characterised in that step is 1.
In, described ultrasonic time is 20~30min, and concentration of the Graphene in ethylene glycol is 1.5~2g/L.
3. the preparation method of magnetic graphite base heavy-metal adsorption material as claimed in claim 1, it is characterised in that step is 2.
In, described ultrasonic time is more than 30min, FeCl3·6H2O、ZnCl2, anhydrous Na Ac mol ratio be 2:1:11,
FeCl3·6H2The mass ratio of O and step 1. middle Graphene is 5.4:1.
4. the preparation method of magnetic graphite base heavy-metal adsorption material as claimed in claim 1, it is characterised in that step is 3.
In, the time of described hydro-thermal reaction is 10~16h.
5. the preparation method of magnetic graphite base heavy-metal adsorption material as claimed in claim 1, it is characterised in that step is 4.
In, described ZnFe2O4The concentration of/rGO- polyacrylic acid magnetic fluids is 5~10g/L.
6. the preparation method of magnetic graphite base heavy-metal adsorption material as claimed in claim 1, it is characterised in that step is 5.
In, described N, N- Dicyclohexylcarbodiimides are 25 with the mass ratio of polyacrylamide:1~5:1, N, N- dicyclohexyl phosphinylidyne
Imines and step 1. middle FeCl3·6H2The mass ratio of O is 2.5:5.4~5:5.4, ultrasonic time be 15~30min, mixing time
For 10~12h.
7. the preparation method of magnetic graphite base heavy-metal adsorption material as claimed in claim 1, it is characterised in that step is 6.
In, described ethanol and the volume ratio of deionized water is 1:1, at 40~50 DEG C, drying time is 12~14h to baking temperature.
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| CN105618002B (en) * | 2016-02-18 | 2018-03-30 | 陕西科技大学 | modified starch/graphene oxide magnetic composite microsphere and preparation method thereof |
| CN110465266A (en) * | 2018-05-11 | 2019-11-19 | 南京理工大学 | Threonine is modified montmorillonite used, preparation method and applications |
| CN108832100B (en) * | 2018-06-15 | 2021-02-26 | 复旦大学 | Preparation method of carbon-coated zinc ferrite/graphene composite negative electrode material |
| CN109772274B (en) * | 2019-01-07 | 2021-12-07 | 中科京投环境科技江苏有限公司 | Mercury-containing wastewater treatment method |
| CN109772275B (en) * | 2019-01-07 | 2021-12-07 | 中科京投环境科技江苏有限公司 | Mercury adsorbent and preparation method thereof |
| CN109761331B (en) * | 2019-03-06 | 2021-07-06 | 青岛洛克环保科技有限公司 | Magnetic sewage treatment agent and preparation method thereof |
| CN111318255B (en) * | 2020-03-05 | 2021-03-02 | 国家地质实验测试中心 | Magnetic graphene oxide composite material and preparation method and application thereof |
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| CN104689798A (en) * | 2015-01-12 | 2015-06-10 | 冯云 | Method for preparing composite mesoporous material |
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