CN106512943A - Nano composite material as well as preparation method and application thereof to water treatment - Google Patents
Nano composite material as well as preparation method and application thereof to water treatment Download PDFInfo
- Publication number
- CN106512943A CN106512943A CN201611096791.8A CN201611096791A CN106512943A CN 106512943 A CN106512943 A CN 106512943A CN 201611096791 A CN201611096791 A CN 201611096791A CN 106512943 A CN106512943 A CN 106512943A
- Authority
- CN
- China
- Prior art keywords
- composite material
- nano composite
- nano
- present
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a nano composite material as well as a preparation method and application thereof to water treatment. The nano composite material provided by the invention comprises a matrix and nanoparticles loaded on the surface of the matrix, wherein the matrix comprises one or more of graphene and graphene derivatives; and the nanoparticles comprise Fe3O4 and Mg(OH)2. According to the nano composite material provided by the invention, a matrix material is used as the matrix, and the nanoparticle composite material has magnetism through loaded Fe3O4 magnetic nanoparticles and is easy to separate; and meanwhile, the saturation adsorbing capacity of the nano composite material is enlarged, and heavy metal ions are efficiently adsorbed through loaded Mg(OH)2 nanoparticles. According to the nano composite material provided by the invention, the removal rates of Pb<2+>, Cu<2+>, Ag<+> and Zn<2+> with the initial concentration of 50ppm within 90min can reach 99.9%, 99.9%, 88% and 85% respectively.
Description
Technical field
The present invention relates to technical field of function materials, more particularly to a kind of nano composite material and preparation method thereof and in water
Application in process.
Background technology
Graphene be by monolayer carbon atom packing into a kind of carbonaceous new material with bi-dimensional cellular shape crystal structure, tool
There are good specific surface area height, high mechanical strength, good conductivity, thermal conductivity, room-temperature quantum Hall effect, be easy to the superiority such as modification
Energy.Based on any of the above excellent properties of Graphene, Graphene is in high sensor, ultracapacitor, memory cell, electric power storage
Pond, electromechanical resonator and solar cell etc. are multi-field to be widely applied.
Water is Source of life, and with the development of industrial society, increasing pollutant is unprocessed and is directly discharged
Into ground water regime.Traditional method for treating water includes desalinating, filters, counter-infiltration, disinfection and chemical settling etc., absorption
Method is widely used in water pollution control because of the low advantage of easy to operate, high treating effect, no coupling product and expense.Graphite
Alkene and its derivative (such as graphene oxide, hydroxylating Graphene and carboxylated Graphene) huge specific surface area make it excellent
The water treatment absorbent of matter.
At present, Graphene and its derivative are mainly used in adsorbing two pollutants as water treatment absorbent：Organic matter and
Inorganic anion.Macromolecular organic pollution in water easily occurs to interact with the group on Graphene and its derivative surface,
Stable compound is formed, Graphene and its derivative are higher to its adsorption capacity, such as：Liu T H.etal.Colloid
Surface B,2012,90:The Graphene under different pH value, time of contact and concentration is disclosed in 197-203 to methylene blue
Absorption；Also there is scholar that the inorganic pollution in water is processed using the friendly functionalization graphene derivative of environment, such as：Li Y
H,etal.Colloid Interface Sei.,2011,363:Disclose in 348-354 functionalization graphene different pH value,
Temperature and the absorption property under the reaction time to fluoride.
But, the property being not readily separated of Graphene and its derivative itself limits its application in water process；And
And, heavy metal ion present in sewage, such as lead, copper, zinc and silver etc., its intake also can serious harm human health.
The content of the invention
It is an object of the invention to provide a kind of nano composite material and preparation method thereof and the application in water process.This
The nano composite material that invention is provided is easily isolated, and can efficiently remove lead in eliminating water, copper, zinc and silver ion.
The invention provides a kind of nano composite material, including matrix and the nano-particle for being carried on described matrix surface,
Described matrix includes one or more in Graphene and Graphene derivative, and the nano-particle includes Fe3O4With Mg (OH)2。
Preferably, the load capacity of the nano-particle for nano composite material quality 90～99%.
Preferably, the particle diameter of the nano-particle is 3～100nm.
Preferably, the Fe3O4With Mg (OH)2Mol ratio be 0.1～10:1.
Preferably, the thickness of described matrix is 1～10nm.
The invention provides a kind of preparation method of nano composite material described in above-mentioned technical proposal, comprises the following steps：
(1) matrix material is mixed with watersoluble divalent molysite, water-soluble trivalent ferric salt, water-soluble magnesium salt and water, is obtained
Mixed solution；
(2) the mixed solution and dripping alkali lye obtained to the step (1), precipitation reaction obtain nano composite material.
Preferably, Fe in the mixed solution of the step (1)2+And Fe3+Mol ratio be 1:2.
Preferably, in the step (2), the temperature of precipitation reaction is 50～100 DEG C, and the time of precipitation reaction is 2～24h.
Preferably, the aqueous solution of the alkali lye in the step (2) for inorganic base.
Present invention also offers nano composite material described in above-mentioned technical proposal or according to described in above-mentioned technical proposal prepare
The application of nano composite material prepared by method in water process.
The nano composite material that the present invention is provided includes matrix and is carried on the nano-particle on described matrix surface, the base
Body includes one or more in Graphene and Graphene derivative, and the nano-particle includes Fe3O4With Mg (OH)2.The present invention
Based on Graphene and/or Graphene derivative, by the Fe for loading3O4Magnetic nano-particle has nano composite material
Magnetic, it is easy to separate, while increasing the saturated adsorption capacity of nano composite material；By loading Mg (OH)2Nano-particle is efficient
Adsorption of Heavy Metal Ions.Test result indicate that, the nano composite material that the present invention is provided is the Pb of 50ppm for initial concentration2+,
Cu2+, Ag+And Zn2+Clearance in 90min can respectively reach 99.9%, 99.9%, 88% and 85%, saturated adsorption capacity
619,441,144 and 121mg/g can be respectively reached.
Present invention also offers the preparation method of above-mentioned nano composite material.The preparation method that the present invention is provided is simply fast
Speed, and it is workable, it is adaptable to large-scale industrial production.
Description of the drawings
TEM photos of the Fig. 1 for the graphene oxide in the embodiment of the present invention 1；
Fig. 2 is the TEM photos of the nano composite material that the embodiment of the present invention 1 is prepared；
Fig. 3 is the SEM photograph of Graphene in the embodiment of the present invention 3；
Fig. 4 is the SEM photograph of the nano composite material that the embodiment of the present invention 3 is prepared；
Fig. 5 is that removal effect of the nano composite material for preparing of the embodiment of the present invention 6 under additional magnetic fields shines
Piece.
Specific embodiment
The invention provides a kind of nano composite material, including matrix and the nano-particle for being carried on described matrix surface,
Described matrix includes one or more in Graphene and Graphene derivative, and the nano-particle includes Fe3O4With Mg (OH)2。
During the nano composite material that the present invention is provided includes that matrix, described matrix include Graphene and Graphene derivative
One or more.In the present invention, the Graphene derivative preferably includes graphene oxide, hydroxylating Graphene and carboxylated
One or more in Graphene.In the present invention, the thickness of described matrix is preferably 1～10nm, more preferably 3～8nm, most
Preferably 5～6nm.In the present invention, described matrix has great specific surface area, Graphene and Graphene derivative surface rich
Containing the pi-pi bond between substantial amounts of hydroxyl, carboxyl and carbon carbon, these functional groups are to the metal ion (Fe in solution2+,
Fe3+, Mg2+) there is stronger sucking action, site can as the ideal of nano-particle.
The present invention does not have special restriction to the source of the Graphene and Graphene derivative, using people in the art
Commercially available prod known to member is prepared using customary preparation methods.
The nano composite material that the present invention is provided also includes the nano-particle for being carried on described matrix surface, the nanoparticle
Attached bag includes Fe3O4With Mg (OH)2.In the present invention, the Fe3O4With Mg (OH)2It is preferred that compound by Fe-O-Mg metallic bonds.
In the present invention, the load capacity of the nano-particle be preferably nano composite material quality 90～99%, more preferably 92～
96%.In the present invention, the particle diameter of the nano-particle is preferably 3～100nm, more preferably 10～80nm, most preferably 30
～50nm.
The present invention does not have special restriction to the pattern and distribution mode of the nano-particle, using those skilled in the art
Well known nano particle pattern and the mode of distribution.In the present invention, the nano-particle is preferably irregular shape.
In the present invention, the nano-particle is preferably laid in matrix surface.
In the present invention, the Fe3O4With Mg (OH)2Mol ratio be preferably 0.1～10:1, more preferably 0.2～5:1,
Most preferably 0.5～2:1.In the present invention, the Fe3O4Nano-particle makes described nano composite material have magnetic, it is easy to
Separate, while increasing the saturated adsorption capacity of nano composite material, the Mg (OH)2Nano-particle can be with the heavy metal in water
There is the effect of the physical and chemical adsorptions such as chelating, efficient absorption heavy metal ion in ion.In the present invention, the Fe3O4And Mg
(OH)2It is preferred that compound by Fe-O-Mg metallic bonds, the Fe-O-Mg metallic bonds make nano composite material for heavy metal ion
With higher adsorption capacity.
In the present invention, the specific surface area of the nano composite material is preferably 100m2/ more than g, more preferably 120～
200m2/g.In the present invention, the nano-particle is by being carried on matrix surface, it is to avoid mutual aggregation is so which compares table
Area declines and caused adsorption efficiency is reduced.
Present invention also offers a kind of preparation method of nano composite material described in above-mentioned technical proposal, including following step
Suddenly：
(1) matrix material is mixed with watersoluble divalent molysite, water-soluble trivalent ferric salt, water-soluble magnesium salt and water, is obtained
Mixed solution；
(2) the mixed solution and dripping alkali lye obtained to the step (1), precipitation reaction obtain nano composite material.
Matrix material is mixed by the present invention with watersoluble divalent molysite, water-soluble trivalent ferric salt, water-soluble magnesium salt and water, is obtained
To mixed solution.In the present invention, in the mixed solution, the mass concentration of matrix material is preferably 0.1～5%, more preferably
0.5～4%, most preferably 1～3%.In the present invention, Fe in the mixed solution2+With Fe3+Total concentration be preferably 0.05
～5mol/L, more preferably 0.1～4mol/L, most preferably 1～3mol/L.In the present invention, the Fe2+With Fe3+Mole
Than being preferably 1:2.In the present invention, Mg in the mixed solution2+Concentration be preferably 0.05～5mol/L, more preferably 0.1
～4mol/L, most preferably 1～3mol/L.
The present invention does not have special to the species of the watersoluble divalent molysite, water-soluble trivalent ferric salt and water-soluble magnesium salt
Limit, using water-soluble molysite well known to those skilled in the art and water-soluble magnesium salt.In the present invention, the water solubility
Divalent iron salt preferably includes FeSO4、FeCl2With Fe (NO3)2In one or more.In the present invention, the water-soluble trivalent
Molysite preferably includes Fe2(SO4)3、FeCl3With Fe (NO3)3In one or more.In the present invention, the water-soluble magnesium salt is excellent
Choosing includes MgSO4、MgCl2With Mg (NO3)2In one or more.
In the present invention, the mixing is preferably ultrasonic mixing.In the present invention, it is described ultrasound frequency be preferably 15～
40KHz, more preferably 20～35KHz；The time of the ultrasound is preferably 10～120min, more preferably 30～100min, most
Preferably 50～70min.In the present invention, the ultrasonic mixing makes Graphene and/or Graphene derivative be stably dispersed in gold
In category solion.
After obtaining mixed solution, to the mixed solution and dripping alkali lye, precipitation reaction obtains nano combined material to the present invention
Material.In the present invention, the speed of the dropwise addition is preferably 0.5～1mL/min, more preferably 0.6～0.8mL/min.At this
In bright, the mass concentration of the alkali lye is preferably 10～25%, more preferably 15～20%.In the present invention, the alkali lye with
The volume ratio of mixed solution is preferably 1～25:75～99, more preferably 5～20:80～95, most preferably 10～15:85～
90。
The present invention does not have special restriction to the species of the alkali lye, using alkali lye well known to those skilled in the art is
Can.In the present invention, the alkali lye is preferably the aqueous solution of inorganic base, more preferably one kind in ammoniacal liquor and inorganic strong alkali or many
Kind.In the present invention, the inorganic strong alkali is preferably alkali-metal hydroxide, more preferably NaOH and/or KOH.
In the present invention, the mode of heating of the precipitation reaction is preferably oil bath heating.In the present invention, the precipitation is anti-
The temperature answered is preferably 50～100 DEG C, more preferably 60～90 DEG C, most preferably 70～80 DEG C；The time of the precipitation reaction
Preferably 2～24h, more preferably 5～20h, most preferably 10～15h.In the present invention, the precipitation reaction is preferably included：
After reacting at the first temperature, second temperature reaction is heated to.In the present invention, first temperature is preferably 50～80 DEG C,
More preferably 60～75 DEG C；The time being incubated at a temperature of described first is preferably 1～2h.In the present invention, the second temperature
Preferably 80～100 DEG C, more preferably 85～95 DEG C；The time being incubated under the second temperature is preferably 1～22h.The present invention
There is no special restriction to the speed that first temperature is heated to second temperature, using intensification well known to those skilled in the art
Speed.
In the present invention, the precipitation reaction is preferably carried out under inert gas shielding.In the present invention, the indifferent gas
Body is preferably nitrogen or argon gas.The present invention preferably by control precipitation reaction temperature and time control nano-particle species and
Particle diameter.In the present invention, when reaction temperature is 50～100 DEG C, metal ion reacts in situ heavy in substrate material surface with alkali
Reaction of forming sediment generates Fe3O4With Mg (OH)2Nano-particle.In the present invention, the time of the precipitation reaction is longer, nano-particle
Particle diameter is less.
After the completion of precipitation reaction, the product of the precipitation reaction is preferably post-processed by the present invention, obtains nano combined
Material.Operation of the present invention to the post processing does not have special restriction, using post processing well known to those skilled in the art
Technical scheme.In the present invention, the post processing preferably includes following steps：By the product Magneto separate of precipitation reaction, obtain
To solid product；Dialyse after the solid product is washed, be then dried, obtain nano composite material.
Operation of the present invention to the Magneto separate does not have special restriction, using Magneto separate well known to those skilled in the art
Technical scheme.In the present invention, the detergent of the washing is preferably water；The number of times of the washing is preferably 3～7
It is secondary.In the present invention, the dialysis is carried out preferably in bag filter；The molecular cut off of the bag filter is preferably 8000-
12000.In the present invention, the drying is preferably freeze-drying；The cryodesiccated temperature is preferably -90～-70 DEG C, more
Preferably -85～-75 DEG C；The cryodesiccated time preferably 48～96h, more preferably 55～85h, most preferably 65～
75h。
Present invention also offers nano composite material described in above-mentioned technical proposal or according to described in above-mentioned technical proposal prepare
The application of nano composite material prepared by method in water process.In the present invention, the nano composite material is preferably as suction
Attached dose is used for sewage disposal.In the present invention, application of the nano composite material in water process preferably includes following steps：
Nano composite material is mixed with treatment sewage, stirring and adsorbing；After the completion of the absorption, Magneto separate obtains nano combined material
Material.In the present invention, the treatment sewage is preferably the sewage containing heavy metal ion.
In the present invention, the quality of the nano composite material is preferably 0.01～2g/ with the volume ratio for the treatment of sewage
L, more preferably 0.1～1.5g/L, most preferably 0.5～1g/L.In the present invention, the speed of the stirring be preferably 200～
500rpm, more preferably 300～400rpm；The time of the stirring is preferably 0.5～24h, more preferably 5～20h, most preferably
For 10～15h.In the present invention, in the adsorption process, nano composite material is sent out with the heavy metal ion in treatment sewage
The physics chemical actions such as raw chelating, heavy-metal ion removal.
After the completion of absorption, the present invention preferably carries out Magneto separate to the nano composite material after absorption by externally-applied magnetic field.
In the present invention, the intensity of the externally-applied magnetic field is preferably ± more than 100G.
In order to further illustrate the present invention, with reference to nano composite material and its preparation of the embodiment to present invention offer
Method and the application in water process are described in detail, but they can not be interpreted as the limit to the scope of the present invention
It is fixed.
Embodiment 1:
In 250mL beakers, 90mL distilled water, 3.2gMg (NO are added3)2·6H2O, 1.2gFeSO4·7H2O,
2.2gFeCl3·6H2O and 0.05g graphene oxide powders, using the common 15KHz ultrasonic disperses 30min of biomixer, afterwards
Mixed dispersion liquid is transferred in 250mL flasks, nitrogen is passed through before reaction 5 minutes, system is under nitrogen guard mode,
Start afterwards ammoniacal liquor to be slowly added dropwise with 0.5mL/min speed, ammoniacal liquor (25wt%) 10mL is added dropwise, continue logical nitrogen 5 minutes.Closing
After system, it is placed in 70 DEG C of oil baths and reacts 2h, is warming up to 90 DEG C afterwards and continues reaction 10h.After reaction terminates, Magnetic Isolation reaction
Product, is cleaned 3 times repeatedly using deionized water, until solution ph is neutrality, product is used -90 DEG C of freeze drier afterwards
48h is dried, nano composite material is obtained.
The present embodiment using graphene oxide and the TEM photos of nano composite material that prepare respectively such as Fig. 1 and
Shown in Fig. 2, it will be seen from figure 1 that graphene oxide is the very smooth laminated structure in surface；Nanoparticle as can be seen from Figure 2
Son is evenly laid out in surface of graphene oxide in granular form.
Embodiment 2:
The nano composite material prepared in taking 0.1g embodiments 1 respectively, is respectively placed in the pb of 100mL2+Solution, Cu2+It is molten
Liquid, Ag+Solution, Zn2+In solution, using magnetic agitation 12 hours, with inductance coupled plasma optical emission spectrometer measurement, due to
There is chelation with above-mentioned heavy metal ion in the inorganic particulate for being loaded, make pb2+Concentration can be dropped by the 98.74ppm before adsorbing
The low 0.0075ppm to after absorption, Cu2+Concentration can be reduced to 0.0052ppm, Ag after absorption by the 60.78ppm before adsorbing+
Concentration can be reduced to 0.001ppm, Zn after absorption by the 32.93ppm before adsorbing2+Concentration can be dropped by the 42.92ppm before adsorbing
The low 0.044ppm to after absorption.
Embodiment 3:
In 250mL beakers, 90mL distilled water, 3.2gMg (NO are added3)2·6H2O, 1.2gFeSO4·7H2O,
2.2gFeCl3·6H2O and 0.1g graphene powders, using the common 40KHz ultrasonic disperses 30min of biomixer, afterwards will be mixed
Close dispersion liquid to be transferred in 250mL flasks, nitrogen is passed through before reaction 5 minutes, make system under nitrogen guard mode, afterwards
Start ammoniacal liquor to be slowly added dropwise with 0.5mL/min speed, ammoniacal liquor (25wt%) 10mL is added dropwise, continue logical nitrogen 5 minutes.Closed system
Afterwards, it is placed in 60 DEG C of oil baths and reacts 4h, is warming up to 90 DEG C afterwards and continues reaction 6h.After reaction terminates, Magnetic Isolation product,
Cleaned using deionized water repeatedly, until solution ph is neutrality, product be dried into 48h for -90 DEG C using freeze drier afterwards,
Obtain nano composite material.
The present embodiment using Graphene and the SEM photograph of nano composite material for preparing respectively such as Fig. 3 and Fig. 4 institutes
Show, from figure 3, it can be seen that laminated structure of the Graphene for surfacing；Nano-particle is uniformly distributed in stone as can be seen from Figure 4
Black alkene surface.
Embodiment 4:
The nano composite material of the preparation of 0.1g embodiments 3 is taken respectively, is respectively placed in the pb of 100mL2+Solution, Cu2+Solution,
Ag+Solution, Zn2+In solution, using magnetic agitation 12 hours, with inductance coupled plasma optical emission spectrometer measurement, due to institute
There is chelation with above-mentioned heavy metal ion in the inorganic particulate of load, make pb2+Concentration can be reduced by the 102.99ppm before adsorbing
0.0087ppm to after absorption, Cu2+Concentration can be reduced to 0.0065ppm, Ag after absorption by the 70.66ppm before adsorbing+It is dense
Degree can be reduced to 0.005ppm, Zn after absorption by the 40.09ppm before adsorbing2+Concentration can be reduced by the 53.45ppm before adsorbing
0.078ppm to after absorption.
Embodiment 5:
The nano composite material prepared in taking 0.1g embodiments 3, is placed in containing Pb2+,Cu2+,Ag+And Zn2+Mixed solution
In, using magnetic agitation 12 hours, with inductance coupled plasma optical emission spectrometer measurement, due to the inorganic particulate that loaded with
There is chelation in above-mentioned heavy metal ion, make pb2+Concentration can be reduced to after absorption by the 20.78ppm before adsorbing
0.011ppm, Cu2+Concentration can be reduced to 058ppm, Ag after absorption by the 21.70ppm before adsorbing+Before concentration can be by adsorbing
19.99ppm is reduced to 2.17ppm, Zn after absorption2+Concentration can be reduced to after absorption by the 21.67ppm before adsorbing
13.45ppm。
Embodiment 6:
In 250mL beakers, 90mL distilled water, 1.3gMg (NO are added3)2·6H2O, 1.9gFeSO4·7H2O,
3.6gFeCl3·6H2O and 0.2g hydroxylating graphene powders, using the common 30KHz ultrasonic disperses 30min of biomixer, it
Afterwards mixed dispersion liquid is transferred in 250mL flasks, nitrogen is passed through before reaction 5 minutes, make system be in nitrogen guard mode
Under, start afterwards ammoniacal liquor to be slowly added dropwise with 0.8mL/min speed, ammoniacal liquor (25wt%) 10mL is added dropwise, continue logical nitrogen 5 minutes.
After closed system, it is placed in 60 DEG C of oil baths and reacts 2h, is warming up to 90 DEG C afterwards and continues reaction 6h.After reaction terminates, Magnetic Isolation
Product, is cleaned repeatedly using deionized water, until solution ph is neutrality, product is done using freeze drier afterwards
It is dry, obtain nano composite material.
Embodiment 7:
The nano composite material of the preparation of 0.1g embodiments 6 is taken respectively, is respectively placed in the pb of 100mL2+Solution, Cu2+Solution,
Ag+Solution, Zn2+In solution, using magnetic agitation 12 hours, with inductance coupled plasma optical emission spectrometer measurement, due to institute
There is chelation with above-mentioned heavy metal ion in the inorganic particulate of load, make pb2+Concentration can be reduced by the 100.13ppm before adsorbing
0.009ppm to after absorption, Cu2+Concentration can be reduced to 0.0123ppm, Ag after absorption by the 100.36ppm before adsorbing+It is dense
Degree can be reduced to 0.012ppm, Zn after absorption by the 50.89ppm before adsorbing2+Concentration can be reduced by the 63.54ppm before adsorbing
0.064ppm to after absorption.
Removal effect photo of the nano composite material that the present embodiment is used under additional magnetic fields as shown in figure 5, from
Fig. 5 can be seen that the nano composite material and can remove easily under additional magnetic fields.
Embodiment 8:
In 250mL beakers, 90mL distilled water, 2.6gMg (NO are added3)2·6H2O, 1.4gFeSO4·7H2O,
2.7gFeCl3·6H2O and 0.1g carboxylated graphene powders, using the common 25KHz ultrasonic disperses 30min of biomixer, it
Afterwards mixed dispersion liquid is transferred in 250mL flasks, nitrogen is passed through before reaction 5 minutes, make system be in nitrogen guard mode
Under, start afterwards ammoniacal liquor to be slowly added dropwise with 0.9mL/min speed, ammoniacal liquor (25wt%) 10mL is added dropwise, continue logical nitrogen 5 minutes.
After closed system, it is placed in 80 DEG C of oil baths and reacts 2h, is warming up to 90 DEG C afterwards and continues reaction 10h.After reaction terminates, Magnetic Isolation
Product, is cleaned repeatedly using deionized water, until solution ph is neutrality, product is done using freeze drier afterwards
It is dry, obtain nano composite material.
Embodiment 9:
The nano composite material of the preparation of 0.1g embodiments 8 is taken respectively, is respectively placed in the pb of 100mL2+Solution, Cu2+Solution,
Ag+Solution, Zn2+In solution, using magnetic agitation 24 hours, with inductance coupled plasma optical emission spectrometer measurement, due to institute
There is chelation with above-mentioned heavy metal ion in the inorganic particulate of load, make pb2+Concentration can be reduced by the 220.34ppm before adsorbing
0.23ppm to after absorption, Cu2+Concentration can be reduced to 0.33ppm, Ag after absorption by the 120.24ppm before adsorbing+Concentration can
0.89ppm, Zn after absorption are reduced to by the 100.69ppm before adsorbing2+Concentration can be reduced to suction by the 112.33ppm before adsorbing
Attached 10.87ppm.
Embodiment 10:
In 250mL beakers, 90mL distilled water, 6.4gMg (NO are added3)2·6H2O, 1.2gFeSO4·7H2O,
2.2gFeCl3·6H2O and 0.2g graphene powders, using the common 20KHz ultrasonic disperses 30min of biomixer, afterwards will be mixed
Close dispersion liquid to be transferred in 250mL flasks, nitrogen is passed through before reaction 5 minutes, make system under nitrogen guard mode, afterwards
Start ammoniacal liquor to be slowly added dropwise with 0.7mL/min speed, ammoniacal liquor (25wt%) 10mL is added dropwise, continue logical nitrogen 5 minutes.Closed system
Afterwards, it is placed in 60 DEG C of oil baths and reacts 5h, is warming up to 90 DEG C afterwards and continues reaction 7h.After reaction terminates, Magnetic Isolation product,
Cleaned using deionized water repeatedly, until solution ph is neutrality, afterwards product is dried using freeze drier, nanometer is obtained
Composite.
Embodiment 11:
The nano composite material of the preparation of 0.1g embodiments 10 is taken respectively, is respectively placed in the pb of 100mL2+Solution, Cu2+Solution,
Ag+Solution, Zn2+In solution, using magnetic agitation 12 hours, with inductance coupled plasma optical emission spectrometer measurement, due to institute
There is chelation with above-mentioned heavy metal ion in the inorganic particulate of load, make pb2+Concentration can be reduced by the 600.93ppm before adsorbing
0.18ppm to after absorption, Cu2+Concentration can be reduced to 0.56ppm, Ag after absorption by the 400.32ppm before adsorbing+Concentration can
50.56ppm, Zn after absorption are reduced to by the 203.53ppm before adsorbing2+Concentration can be reduced to by the 156.70ppm before adsorbing
34.34ppm after absorption.
As can be seen from the above embodiments, the nano composite material that the present invention is provided can efficient adsorbing heavy metal in water
Ion, in making water, content of beary metal is far below national standard, and the adsorption capacity with wider array of adsorption range and Geng Gao, while
Quick under additional magnetic fields can remove from water.
The above is only the preferred embodiment of the present invention, not makees any pro forma restriction to the present invention.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of nano composite material, including matrix and the nano-particle for being carried on described matrix surface, described matrix include stone
One or more in black alkene and Graphene derivative, the nano-particle include Fe3O4With Mg (OH)2。
2. nano composite material according to claim 1, it is characterised in that the load capacity of the nano-particle is multiple for nanometer
The 90～99% of condensation material quality.
3. nano composite material according to claim 1 and 2, it is characterised in that the particle diameter of the nano-particle is 3～
100nm。
4. nano composite material according to claim 1 and 2, it is characterised in that the Fe3O4With Mg (OH)2Mol ratio
For 0.1～10:1.
5. nano composite material according to claim 1, it is characterised in that the thickness of described matrix is 1～10nm.
6. the preparation method of nano composite material described in Claims 1 to 5 any one, comprises the following steps：
(1) matrix material is mixed with watersoluble divalent molysite, water-soluble trivalent ferric salt, water-soluble magnesium salt and water, is mixed
Solution；
(2) the mixed solution and dripping alkali lye obtained to the step (1), precipitation reaction obtain nano composite material.
7. preparation method according to claim 6, it is characterised in that Fe in the mixed solution of the step (1)2+And Fe3+
Mol ratio be 1:2.
8. preparation method according to claim 6, it is characterised in that the temperature of precipitation reaction is 50 in the step (2)
～100 DEG C, the time of precipitation reaction is 2～24h.
9. preparation method according to claim 6, it is characterised in that water of the alkali lye in the step (2) for inorganic base
Solution.
10. nano composite material described in Claims 1 to 5 any one or preparation method described in claim 6～9 any one
Application of the nano composite material of preparation in water process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611096791.8A CN106512943B (en) | 2016-12-02 | 2016-12-02 | A kind of nanocomposite and preparation method thereof and the application in water process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611096791.8A CN106512943B (en) | 2016-12-02 | 2016-12-02 | A kind of nanocomposite and preparation method thereof and the application in water process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106512943A true CN106512943A (en) | 2017-03-22 |
| CN106512943B CN106512943B (en) | 2019-09-17 |
Family
ID=58354770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611096791.8A Active CN106512943B (en) | 2016-12-02 | 2016-12-02 | A kind of nanocomposite and preparation method thereof and the application in water process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106512943B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008230A (en) * | 2017-05-26 | 2017-08-04 | 湖南农业大学 | Magnetic composite adsorbent and preparation method thereof |
| CN107081123A (en) * | 2017-05-26 | 2017-08-22 | 湖南农业大学 | Magnetic magnesium hydroxide adsorbent and preparation method thereof |
| CN107159112A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | The method that magnetic composite adsorbent removes tetracycline in waste water |
| CN107159094A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | The method that magnetic magnesium hydroxide adsorbent removes tetracycline in waste water |
| CN107473319A (en) * | 2017-08-28 | 2017-12-15 | 华南理工大学 | A kind of method of phase transformation regulation and control recycle-water cationic heavy metal |
| CN108714423A (en) * | 2018-05-08 | 2018-10-30 | 中国科学院烟台海岸带研究所 | A kind of water process composite magnetic nano catalytic material and its preparation and application |
| CN109585959A (en) * | 2018-11-05 | 2019-04-05 | 天齐锂业资源循环技术研发(江苏)有限公司 | Utilize the method for old and useless battery negative electrode active material synthesizing new carbon material adsorbent |
| CN110395790A (en) * | 2019-07-30 | 2019-11-01 | 中国科学院青海盐湖研究所 | A kind of magnetism magnesium hydroxide composite material and preparation method |
| CN114160090A (en) * | 2021-11-30 | 2022-03-11 | 中国科学技术大学 | Magnetic magnesium hydroxide composite material and preparation method and application thereof |
| CN114958058A (en) * | 2022-06-20 | 2022-08-30 | 东莞市万科建筑技术研究有限公司 | Mildew-proof antibacterial coating and preparation method thereof |
| CN116143110A (en) * | 2021-11-23 | 2023-05-23 | 北京工业大学 | Preparation and purification method of nanoparticle with plasma ammoniated graphene@magnetic core structure |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258810A (en) * | 2014-09-29 | 2015-01-07 | 扬州大学 | Adsorbing agent based on ferroferric oxide and graphene and preparation method of adsorbing agent |
-
2016
- 2016-12-02 CN CN201611096791.8A patent/CN106512943B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258810A (en) * | 2014-09-29 | 2015-01-07 | 扬州大学 | Adsorbing agent based on ferroferric oxide and graphene and preparation method of adsorbing agent |
Non-Patent Citations (1)
| Title |
|---|
| PANPAN WANG等: "Layered mesoporous Mg(OH)2/GO nanosheet composite for efficient removal of water contaminants", 《RSC ADV》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159112B (en) * | 2017-05-26 | 2019-11-01 | 湖南农业大学 | The method that magnetic composite adsorbent removes tetracycline in waste water |
| CN107081123A (en) * | 2017-05-26 | 2017-08-22 | 湖南农业大学 | Magnetic magnesium hydroxide adsorbent and preparation method thereof |
| CN107159112A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | The method that magnetic composite adsorbent removes tetracycline in waste water |
| CN107159094A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | The method that magnetic magnesium hydroxide adsorbent removes tetracycline in waste water |
| CN107008230A (en) * | 2017-05-26 | 2017-08-04 | 湖南农业大学 | Magnetic composite adsorbent and preparation method thereof |
| CN107081123B (en) * | 2017-05-26 | 2020-09-18 | 湖南农业大学 | Magnetic magnesium hydroxide adsorbent and preparation method thereof |
| CN107159094B (en) * | 2017-05-26 | 2019-11-01 | 湖南农业大学 | The method of tetracycline in magnetic magnesium hydroxide adsorbent removal waste water |
| CN107473319A (en) * | 2017-08-28 | 2017-12-15 | 华南理工大学 | A kind of method of phase transformation regulation and control recycle-water cationic heavy metal |
| CN107473319B (en) * | 2017-08-28 | 2020-04-28 | 华南理工大学 | Method for recovering cationic heavy metals in water through phase change regulation |
| CN108714423B (en) * | 2018-05-08 | 2020-10-30 | 中国科学院烟台海岸带研究所 | Composite magnetic nano catalytic material for water treatment and preparation and application thereof |
| CN108714423A (en) * | 2018-05-08 | 2018-10-30 | 中国科学院烟台海岸带研究所 | A kind of water process composite magnetic nano catalytic material and its preparation and application |
| CN109585959A (en) * | 2018-11-05 | 2019-04-05 | 天齐锂业资源循环技术研发(江苏)有限公司 | Utilize the method for old and useless battery negative electrode active material synthesizing new carbon material adsorbent |
| CN110395790A (en) * | 2019-07-30 | 2019-11-01 | 中国科学院青海盐湖研究所 | A kind of magnetism magnesium hydroxide composite material and preparation method |
| CN116143110A (en) * | 2021-11-23 | 2023-05-23 | 北京工业大学 | Preparation and purification method of nanoparticle with plasma ammoniated graphene@magnetic core structure |
| CN114160090A (en) * | 2021-11-30 | 2022-03-11 | 中国科学技术大学 | Magnetic magnesium hydroxide composite material and preparation method and application thereof |
| CN114958058A (en) * | 2022-06-20 | 2022-08-30 | 东莞市万科建筑技术研究有限公司 | Mildew-proof antibacterial coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106512943B (en) | 2019-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106512943B (en) | A kind of nanocomposite and preparation method thereof and the application in water process | |
| Venkateswarlu et al. | Core–shell ferromagnetic nanorod based on amine polymer composite (Fe3O4@ DAPF) for fast removal of Pb (II) from aqueous solutions | |
| CN108745396B (en) | Water treatment method by catalytic oxidation of nano-confined zero-valent iron @ spindle-type porous carbon | |
| CN108940335B (en) | Advanced redox water treatment method based on nitrogen-doped nuclear shell structure magnetic field recoverable iron-carbon material | |
| Zhang et al. | Polyacrylic acid-functionalized graphene oxide for high-performance adsorption of gallium from aqueous solution | |
| Lopez-Tejedor et al. | Iron nanostructured catalysts: design and applications | |
| CN103480333A (en) | Compound grapheme absorption agent, method for preparing compound grapheme absorption agent and application of compound grapheme absorption agent | |
| CN105032375B (en) | Preparation method of magnetic graphite-based heavy metal adsorbing material | |
| CN101574641A (en) | Environment-friendly carbon nanotube/sodium alginate heavy metal ion sorbing material and preparation method thereof | |
| CN110841654B (en) | Zero-valent iron-loaded iron-manganese oxide composite material, and preparation method and application thereof | |
| CN109876779B (en) | Nano mesoporous Fe 3 O 4 Preparation and application of-chitosan core-shell crosslinked microsphere material | |
| Liu et al. | Highly efficient peroxymonosulfate activation by MOFs-derived oxygen vacancy-rich Co3O4/ZnO pn heterojunction nanocomposites to degrade pefloxacin | |
| Jiang et al. | New and highly efficient Ultra-thin g-C3N4/FeOCl nanocomposites as photo-Fenton catalysts for pollutants degradation and antibacterial effect under visible light | |
| Aruljothi et al. | Magnetic recyclable CuFe2O4/rGO nanocomposite for the degradation of tetracycline under sunlight irradiation | |
| CN109607739A (en) | A kind of application of piezoelectric material barium titanate Ultrasound-activated persulfate in processing waste water | |
| CN110280308A (en) | A kind of sodium tartrate Modified Cu ferro-cobalt houghite load carbon quantum dot nanocomposite and its preparation method and application | |
| Zhong et al. | Enhanced photo-reduction of chromium (VI) from aqueous solution by nanosheet hybrids of covalent organic framework and graphene-phase carbon nitride | |
| Peng et al. | Electropositive carbon sites and sulfur vacancies in SnS2/g-C3N4 for achieving adsorption and photocatalytic degradation of As (III) in stages by pH regulation | |
| Yuan et al. | Construction of Fe3S4/g-C3N4 composites as photo-Fenton-like catalysts to realize high-efficiency degradation of pollutants | |
| CN103933937B (en) | The preparation method of graphene oxide compound and nickel oxide loaded graphene complex and application | |
| CN108355623A (en) | Magnetic oxygenated graphene-Chitosan Composites and its preparation method and application | |
| Guan et al. | Polyacrylic acid-grafted magnetite nanoparticles for remediation of Pb (II)-contained water | |
| Zhang et al. | Core@ Shell structured coal fly ash Magnetospheres@ C/g-C3N4 for degradation of Rh B via photo-Fenton catalysis | |
| CN108404850A (en) | A kind of mesoporous manganese oxide adsorbent and the method for preparing adsorbent using corona treatment | |
| CN114653376A (en) | Method for removing ofloxacin by activating persulfate through composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |