CN110164642A - A kind of the hypergravity preparation method and device of graphene oxide modified magnetic nano material - Google Patents
A kind of the hypergravity preparation method and device of graphene oxide modified magnetic nano material Download PDFInfo
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- CN110164642A CN110164642A CN201910327272.5A CN201910327272A CN110164642A CN 110164642 A CN110164642 A CN 110164642A CN 201910327272 A CN201910327272 A CN 201910327272A CN 110164642 A CN110164642 A CN 110164642A
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- H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
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- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
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- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/026—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets protecting methods against environmental influences, e.g. oxygen, by surface treatment
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Abstract
The invention discloses a kind of hypergravity preparation method of graphene oxide modified magnetic nano material and devices, the mixed solution of graphene oxide and metal salt is prepared first, the mixed solution and lye are sent into supergravity reactor simultaneously and reacted, the degree of supersaturation for making reaction system moment reach higher and being evenly distributed, and the microcosmic mixing time of system is less than nucleation induction time；Magneto separate reaction product after reaction, deionized water and dehydrated alcohol are cleaned repeatedly to neutrality, and freeze-drying obtains the magnetic Nano material of graphene oxide modification.Invention introduces the Two-dimensional Carbon material oxidation graphene with honeycomb structure, the magnetic Nano material partial size of the graphene oxide modification of preparation is small, is uniformly dispersed, and has industrial applications prospect；This method is expected to be widely used in the fields such as environmental protection, biological medicine, chemical industry.
Description
Technical field
The present invention relates to a kind of hypergravity preparation method of graphene oxide modified magnetic nano material and devices, belong to and receive
Rice technical field of material.
Background technique
Graphene is a kind of two-dimentional carbon material with honeycomb structure, due to its big specific surface area and significant machine
Tool, electricity and hot property become a dazzling nova in Material Field.Graphene oxide (Graphene Oxide, GO) is
A kind of derivative of graphene, there are a large amount of oxygen-containing functional group, including hydroxyl, carboxyl, epoxy group and carbonyl in surface, wherein being located at
The group of the upper and lower surfaces of GO lamella mainly has hydroxyl, epoxy group and carbonyl, and the group positioned at lamella edge is usually carboxyl.
These oxygen-containing functional groups on the surface GO, make it have hydrophily, bear in addition its surface is presented in the ionization of carboxyl and hydroxyl itself
Electrical property makes GO be uniformly dispersed in aqueous solution, and assigns GO and can be used as due to the electrostatic repulsion between electronegative GO
The characteristics of good adsorption agent, applied to metal, biomolecule, fluorescent molecule, drug and inorganic nanoparticles Adsorption with
And carrier field, and then improve adsorption effect.These excellent physicochemical properties of graphene oxide and big specific surface area
So that its superior substrate for becoming carried magnetic nano particle.The surface that magnetic nanoparticle is loaded to graphene oxide, makes
Composite material had not only had the convenience of magnetic nanoparticle Magneto separate but also had had the high absorption capacity of graphene oxide.Widely grind
Study carefully it has been proved that graphene oxide shows better performance in terms of waste water removes pollutant, wherein to adsorb heavy metal
The adsorbent of ion is the most significant, not only solves harm of the heavy metal ion to human health and ecological environment in this way, also solves
The high problem of processing cost of having determined.Although graphite oxide alkenes adsorbent has many good qualities, it is applied to sewage treatment, it is difficult to real
Now it is separated by solid-liquid separation.
Magnetic Nano material not only has the fundamental characteristics of conventional nano material, such as a kind of special nano material
Dimensional effect, skin effect, quantum effect and macro quanta tunnel effect etc., while also having special magnetic property, magnetism is received
Rice material physics, in terms of show the property different from conventional material, magnetic Nano material is at sewage
Reason field is able to solve separation problem present in water process.By graphene oxide in conjunction with magnetic Nano material, on the one hand have
It is magnetic, the separation and recovery of magnetic composite can be quickly realized under externally-applied magnetic field, on the other hand, graphene oxide
Dispersibility, the biocompatibility of magnetic Nano material can be improved, improve magnetic Nano material to the adsorptivity of heavy metal ion
Energy.
Currently, the preparation method of graphene oxide modified magnetic nano material the most commonly used is coprecipitation, hydro-thermal method and
Sol-gal process.Wherein, coprecipitation be by soluble graphene oxide and dissolving metal salts in a solvent, then will precipitating
Agent is added dropwise with certain speed, is precipitated until each component of the metal salt in precipitating reagent and solution uniformly mix generation, then into
Row water-bath reflux keeps precipitating complete.Since the advantages that its preparation process is simple, operating cost is low, experiment condition is mild, has become
The most commonly used preparation method for preparing graphene oxide modified magnetic nano material, but prepared graphene oxide modification
The particle diameter distribution of magnetic nano-particle is uneven, and is not easy to accomplish scale production.This is because the reaction that coprecipitation uses
Device is usually stirring reactor, is to make reaction mass Strong dispersion hybrid reaction using the shearing force of agitating paddle, between belonging to
It has a rest operation, the microcosmic uniformly mixed time is about 0.01 ~ 0.2 s.Since precipitating reagent and reacting metal salt generate magnetic Nano
Particle is a quickly reaction precipitation process, and the characteristic time of nucleation is about 1 ms, therefore is reacted in traditional stirring-type
Transmitting and mixing rate in device on molecular scale are much smaller than the nucleation rate of liquid-phase precipitation, so as to cause nucleation and growth course
Uneven environment on molecular scale, thus using the magnetism of the graphene oxide modification of traditional stirring reactor preparation
The industrialness problems such as nanoparticle is uneven there are particle diameter distribution and batch production poor reproducibility, Product management model effect are big.Therefore,
It develops the new process that can prepare graphene oxide modified magnetic nano material with continuous batch and new method is graphite oxide alkenes
Adsorbent applies critical problem to be solved.
Summary of the invention
The present invention is intended to provide the hypergravity preparation method and device of a kind of graphene oxide modified magnetic nano material, one
Footwork prepares graphene oxide modified magnetic nano material, this method have simple process, reaction time it is short, it is at low cost, can advise
The characteristics of modelling produces, and the magnetic Nano material partial size for the graphene oxide modification prepared is small, is uniformly dispersed, and has industry
Change application prospect.
High-gravity technology is applied in the preparation process of graphene oxide modified magnetic nano material by the present invention, realizes
The optimization of properties of product.The characteristics of high-gravity technology strengthens microcosmic mixing and mass transport process because of it, can make reaction system moment
The degree of supersaturation for reaching higher and being evenly distributed, and the microcosmic mixing time of system is less than nucleation induction time.Hypergravity
The nano particle diameter that technology preparation nano material is short with the reaction time, is formed is small, particle diameter distribution is uniform, preparation cost is low,
The advantages that being easy to industrial amplification production (4-20 times can be improved compared with conventional method).Therefore, using high-gravity technology and instead
The precipitation method are answered to combine, the magnetic Nano material of the uniform graphene oxide modification of one-step synthesis good dispersion, particle diameter distribution is expected to
To accelerate the sizable application for promoting graphite oxide alkenes adsorbent to provide important channel.
The present invention provides a kind of hypergravity preparation methods of graphene oxide modified magnetic nano material, including following step
It is rapid: to prepare the mixed solution of graphene oxide and metal salt first, the mixed solution and lye are sent into hypergravity reaction simultaneously
It is reacted in device, the degree of supersaturation for making reaction system moment reach higher and being evenly distributed, and the microcosmic mixing time of system
Less than nucleation induction time；Magneto separate reaction product after reaction, deionized water and dehydrated alcohol are cleaned repeatedly to neutrality, cold
Freeze the magnetic Nano material for being dried to obtain graphene oxide modification.
Above-mentioned hypergravity preparation method, specifically includes the following steps:
(1) it prepares the mixed solution of graphene oxide and metal salt: by graphene oxide ultrasonic disperse in deionized water, preparing
At the aqueous solution for the graphene oxide that concentration is 0.1 ~ 2.0 mg/mL, metal M is then added thereto2+Salt and Fe3+Salt is prepared
At the mixed solution of graphene oxide and metal salt that cation concn is 0.05 ~ 1.0 mol/L, wherein Fe3+Salt and metal M2+
The molar ratio of salt is 2:1 ~ 3:2, metal M2+Salt is one of nitrate, sulfate or chlorate；
(2) it prepares lye: using sodium hydroxide or ammonium hydroxide for alkali source, by cation and OH-Molar ratio be 1:2.4 ~ 1:5 prepare
Concentration of lye is the aqueous solution of 0.12 ~ 5.0 mol/L；
(3) magnetic Nano material of synthesis graphene oxide modification: respectively by the mixed solution of graphene oxide and metal salt, alkali
Liquid is placed in reservoir, is preheating to 25 ~ 100 DEG C, and then setting mixed solution is equal with the flow of lye, and isometric two strands anti-
It answers material to be delivered in supergravity reactor by liquid distribution trough to be reacted, in any one moment graphene oxide and gold
The mixed solution and lye for belonging to salt are all isometric hybrid reactions according to set proportion；
Fluid is acutely sheared and is crushed using high-speed rotating filler, phase interface that is huge and quickly updating is generated, makes
It obtains microcosmic mixing and mass transport process is strengthened, after the isometric repeated collision contact of two kinds of materials, conducive to particle diameter distribution is formed
Uniform nano particle；The microcosmic uniformly mixed characteristic time is 10-100 μ s in supergravity reactor；
(4) after reaction, Magneto separate reaction product is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, freeze-drying
Obtain the magnetic Nano material of graphene oxide modification.
In the above method, the source of the magnetic Nano material are as follows: Fe3O4、MnFe2O4、NiFe2O4、CoFe2O4、
ZnFe2O4、MgFe2O4One of ferrite.Final products are GO-Fe3O4、GO-MnFe2O4、GO-NiFe2O4、GO-
CoFe2O4、GO-ZnFe2O4、GO-MgFe2O4Etc. a variety of composite materials.
In the above method, the M2+For Mn2+、Fe2+、Ni2+、Co2+、Zn2+、Mg2+One of.
In the above method, in step (3), the volume flow for controlling two strands of material liquids is 10 ~ 100 L/h, hypergravity reaction
The revolving speed of device is in 100 ~ 2500 rpm.
In the above method, by the continuous preparation method of hypergravity, the production efficiency of magnetic Nano material reaches 0.022-2.2
kg/h。
The present invention provides a kind of hypergravity preparation facilities of graphene oxide modified magnetic nano material, for above-mentioned super
Gravity preparation method, the device include supergravity reactor, graphene oxide and metal mixed salt solution storage tank, lye storage tank,
Mixed solution storage tank, lye storage tank are separately connected supergravity reactor, are respectively equipped with pump and spinner flowmeter on connecting line, lead to
The flow for crossing pump control mixed solution and lye is equal；Be equipped with liquid distribution trough in supergravity reactor, control mixed solution and
Lye is mixed；Connection product storage tank below supergravity reactor.
The supergravity reactor is Impinging Stream-Rotating Packed Bed, in rotary packed bed or rotating bed with helix channel
It is any.
When supergravity reactor is Impinging Stream-Rotating Packed Bed, two strands of reaction masses are opposite by two on liquid distribution trough
Nozzle spray to form jet stream, and the circle perpendicular to jet direction or fan-shaped misty pellicular front are formed after hitting, herein
Two strands of reaction masses realize mixing for the first time, reaction in the process；The weaker shock cloudy surface edge of mixing enters rotary packed bed
Inner cavity, under the influence of centrifugal force along the outside edge flowing of filler hole, and during this period liquid repeatedly cut by filler, coalescence and
Second of mixing, reaction are completed in dispersion；Finally, reaction product is thrown on shell from the outer rim of filler under the influence of centrifugal force,
It is pooled to outlet discharge under gravity.
When supergravity reactor be it is rotary packed bed, two strands of reaction masses are sprayed by the nozzle of aperture on liquid distribution trough to be filled out
On material, liquid is flowed along filler hole from rotor inner edge to rotor periphery under the influence of centrifugal force；During this period, material liquid quilt
Filler repeatedly cuts, coalescence and dispersion, and reaction is mutually mixed in packing layer；Finally, reaction product is under the influence of centrifugal force
It is thrown on shell from filler outer rim, is pooled to outlet discharge under the effect of gravity.
When supergravity reactor is rotating bed with helix channel, two strands of reaction masses enter helical duct by liquid distribution trough
Interior, liquid is flowed out along the rotor with spiral of Archimedes shape channel from inside to outside in the effect of centrifugal force；In this phase
Between, material liquid is mutually mixed in helical duct, reacts；Finally, reaction product is got rid of from rotor periphery under the influence of centrifugal force
Onto shell, it is pooled to outlet discharge under gravity.
The magnetic Nano material that the present invention is modified by supergravity reactor one-step synthesis graphene oxide is revolved using high speed
The filler turned is acutely sheared and is crushed to fluid, phase interface that is huge and quickly updating is generated, so that microcosmic mixing and biography
Matter process has obtained great reinforcing, and the microcosmic uniformly mixed characteristic time is 10-100 μ s in supergravity reactor, is much smaller than
The induction Nucleation characteristics time of Traditional liquid phase precipitation reaction.That is, by hypergravity reaction technology, magnetic Nano material exists
Uniform degree of supersaturation, therefore the nucleation and life of prepared magnetic Nano material are had reached before crystallization nucleation, in reactor
Length carries out under conditions of a uniform degree of supersaturation, meets desired homogeneous into nuclear environment, controls nucleation process, make particle
Show relatively narrow distribution thus prepared by nano material partial size is smaller, particle diameter distribution is uniform；In addition, continuous by hypergravity
Preparation method, magnetic Nano material production efficiency can achieve 0.022-2.2 kg/h, this is that common stirred tank method is difficult to reality
Existing, industrial applications prospect outclass traditional reaction kettle paddling process.Hypergravity of the present invention reacts coprecipitation
The forming process of nano material is controlled by the control magnetic nano-particle nucleation and crystallization time.
Beneficial effects of the present invention:
The present invention will be reacted with the supergravity reactor of powerful microcosmic composite character applied to quick chemical precipitation, while benefit
Use carbon material graphene oxide as the dispersing agent and surface modifier of magnetic Nano material, the magnetic Nano material of preparation has
Partial size is small, particle diameter distribution is uniform, preparation method is simple, preparation cost is low, can continuous batch preparation, therefore have industry outstanding
Change application prospect；It can be widely applied to the fields such as sewage treatment, heavy metal analysis, magnetic catalysis, magnetic recording, biomedicine.
Detailed description of the invention
Fig. 1 is the hypergravity preparation facilities schematic diagram of graphene oxide modified magnetic nano material.
Fig. 2 is the Fe of the obtained graphene oxide of embodiment 1 modification3O4The TEM of magnetic nano-particle schemes.
Fig. 3 is the Fe of the obtained graphene oxide of embodiment 1 modification3O4Magnetic nano-particle and unmodified Fe3O4Magnetic
The X-ray diffractogram of property nanoparticle.
Fig. 4 is the Fe of the obtained graphene oxide of embodiment 1 modification3O4Magnetic nano-particle and unmodified Fe3O4Magnetic
The infrared spectrogram of property nanoparticle.
Fig. 5 is the Fe of the obtained graphene oxide of embodiment 1 modification3O4The Raman spectrogram of magnetic nano-particle.
In figure: 1- mixed solution storage tank；2- centrifugal pump；3- valve；4- flowmeter；5- supergravity reactor；The storage of 6- product
Slot；7- lye storage tank.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Fig. 1 is the flow chart of the hypergravity preparation facilities of graphene oxide modified magnetic nano material, which includes super
Gravity reactor 5, graphene oxide and metal mixed salt solution storage tank 1, lye storage tank 7, graphene oxide is mixed with metal salt
Solution storage trough 1, lye storage tank 7 are separately connected supergravity reactor, and pump 2 and spinner flowmeter 4 are respectively equipped on connecting line, lead to
It is equal with the flow of metal mixed salt solution and lye to cross pump control graphene oxide；Liquid distribution is equipped in supergravity reactor
Device, control graphene oxide are mixed with metal mixed salt solution and lye；Connection product storage tank below supergravity reactor
6。
Specific experiment step are as follows: the mixed solution and lye of graphene oxide and metal salt are added separately to mixed solution
In storage tank 1 and lye storage tank 7,25 ~ 100 °C are preheating to, starts centrifugal pump for material liquid and is conveyed into hypergravity through spinner flowmeter 4
In reactor 5, two strands of material liquids of constant speed enter the rotor of rotation by liquid distribution trough, liquid under the influence of centrifugal force from
The rotor of rotation, and the hybrid reaction in rotor are flowed through from inside to outside.Final reaction product is thrown to shell under the influence of centrifugal force
On, it is pooled to outlet discharge under gravity, into the product storage tank 6 of 5 bottom of supergravity reactor.
Embodiment 1:
A kind of hypergravity preparation method of graphene oxide modified magnetic nano material, by the miscible of graphene oxide and metal salt
Liquid and lye are sent into supergravity reactor simultaneously to react, after reaction Magneto separate reaction product, deionized water and anhydrous second
Alcohol is cleaned repeatedly to neutrality, and freeze-drying obtains the magnetic Nano material of graphene oxide modification, the specific steps are as follows:
The graphene oxide for weighing 0.25 g is scattered in the deionized water of 500 mL that be configured to graphene oxide concentration be 0.5
The aqueous solution of mg/mL, is added FeCl thereto2•4H2O (23.85 g, 0.12 mol) and FeCl3•6H2O (54.06 g, 0.2
Mol the iron salt solutions that cation concn is 0.32 mol/L) are configured to, wherein Fe3+Salt and Fe2+The molar ratio of salt is 5:3；Separately
Outside, according to cation and OH-Molar ratio be 2:5, weigh 16 g sodium hydroxides be configured to naoh concentration be 0.8 mol/L
Aqueous solution；Above-mentioned graphene oxide and molysite mixed solution and NaOH aqueous solution are added separately in storage tank, are preheating to 80
DEG C, liquid is conveyed into Impinging Stream-Rotating Packed Bed agent set by starting centrifugal pump through spinner, and isometric two strands are anti-
It is ejected on rotary packed bed inner edge after answering material to hit by the nozzle constant speed of liquid distribution trough, under the influence of centrifugal force
Along the outside edge flowing of filler hole, and reaction is mutually mixed in packing layer.Finally, reaction product under the influence of centrifugal force from
The outer rim of filler is thrown on shell, is pooled to exit under gravity, is discharged through outlet.Two kinds are adjusted in the process
The volume flow of material liquid is 60 L/h, and the revolving speed for controlling Impinging Stream-Rotating Packed Bed is 900 rpm；After reaction, it adopts
With magnetic separation technique collecting reaction product, cleaned repeatedly with deionized water to neutrality, freeze-drying obtains graphene oxide modification
Fe3O4Magnetic nano-particle.
Fig. 2 shows the Fe of the graphene oxide modification of embodiment synthesis3O4The TEM of magnetic nano-particle schemes, Cong Tuzhong
It can be seen that the Fe of graphene oxide modification3O4The partial size of magnetic nano-particle is about 11 nm, and particle size is uniform, and dispersibility is good
It is good.
Fig. 3 is the Fe for the graphene oxide modification that the embodiment obtains3O4The X-ray diffractogram of magnetic nano-particle.From figure
In as can be seen that graphene oxide modification Fe3O4Magnetic nano-particle at 30.1 °, 35.4 °, 43.1 °, 53.2 °, 57.0 °,
62.6 ° and 74.0 ° there is Fe3O4The characteristic diffraction peak of magnetic nano-particle, respectively correspond (220), (311), (400), (422),
(511), (440) and (533) crystal face, and diffraction peak intensity is high, almost without other miscellaneous peaks, illustrates prepared graphene oxide
The Fe of modification3O4Nanoparticle is cubic phase, and graphene oxide modification does not influence Fe3O4The crystal phase of magnetic nano-particle, and crystallize
Property preferably, partial size is smaller, purity is higher.
Fig. 4 shows the Fe of the graphene oxide modification of embodiment synthesis3O4The infrared spectroscopy of magnetic nano-particle, from
It can be seen that the Fe of graphene oxide modification in figure3O4The infrared spectrum of magnetic nano-particle is in 570 cm-1The spy of corresponding Fe-O
Peak is levied, in 1629 cm-1Corresponding to-C=O characteristic peak peak of graphene oxide, in 33438 cm-1Locate corresponding H2O molecule is stretched
Contracting vibration peak.Illustrate that graphene oxide is successfully modified in Fe3O4Magnetic nano-particle surface.
Fig. 5 shows the embodiment and obtains graphene oxide modification Fe3O4The Raman spectrogram of magnetic nano-particle.From figure
In as can be seen that the D spectral peak of composite material is offset, illustrate that the defect level of surface of graphene oxide increases, reflect nanometer
Ferroso-ferric oxide has been supported on the surface of graphene oxide.
Embodiment 2:
A kind of hypergravity preparation method of graphene oxide modified magnetic nano material, includes the following steps:
The graphene oxide for weighing 1.5 g is scattered in the deionized water of 1 L that be configured to graphene oxide concentration be 1.5 mg/mL
Aqueous solution, thereto be added Mn (NO3)2(7.16 g, 0.04 mol), Fe2(SO4)3(12.0 g, 0.03 mol), is configured to
Cation concn is the metal salt solution of 0.07 mol/L, wherein Fe3+Salt and Mn2+The molar ratio of salt is 3:2；In addition, according to sun
Ion and OH-Molar ratio be 1:5, weigh 12.95 g ammonium hydroxide be configured to ammonia concn be 0.35 mol/L aqueous solution；It will be upper
It states graphene oxide and metal mixed salt solution and ammonia aqueous solution is added separately in storage tank, be preheating to 25 DEG C, starting centrifugation
Two kinds of material liquids are delivered in rotary packed bed by liquid distribution trough by pump respectively, and material liquid is sprayed by the aperture on liquid distribution trough
Onto the filler of rotation, the hole of filler is flowed through from inside to outside under the influence of centrifugal force, and be mutually mixed instead in packing layer
It answers.Finally, reaction product is thrown on shell from the outer rim of filler under the influence of centrifugal force, is pooled to out under gravity
At mouthful, it is discharged through outlet.Adjusting the volume flow of two kinds of material liquids in the process is 20 L/h, is controlled rotary packed bed
Revolving speed is 100 rpm；After reaction, it using magnetic separation technique collecting reaction product, is cleaned repeatedly with dehydrated alcohol to neutrality,
Freeze-drying obtains the MnFe of graphene oxide modification2O4Magnetic nano-particle.
Embodiment 3:
A kind of hypergravity preparation method of graphene oxide modified magnetic nano material, includes the following steps:
The graphene oxide for weighing 2.0 g is scattered in the deionized water of 1 L that be configured to graphene oxide concentration be 2 mg/mL's
NiSO is added in aqueous solution thereto4•6H2O (78.85 g, 0.3 mol), Fe (NO3)3•9H2O (242.4 g, 0.6 mol), matches
It is set to the metal salt solution that cation concn is 0.9 mol/L, wherein Fe3+Salt and Ni2+The molar ratio of salt is 2:1；In addition, pressing
According to cation and OH-Molar ratio be 1:2.4, weigh 86.4 g sodium hydroxides be configured to naoh concentration be 2.16 mol/L
Aqueous solution；Above-mentioned graphene oxide and metal mixed salt solution and lye are added in storage tank, are preheating to 60 DEG C, start from
Two kinds of material liquids are delivered in rotating bed with helix channel by liquid distribution trough by heart pump respectively, and liquid is entered by liquid distribution trough
It is flowed out from inside to outside along the rotor with spiral of Archimedes shape channel in helical duct in the effect of centrifugal force.Herein
Period, material liquid are mutually mixed in helical duct, react.Finally, reaction product is under the influence of centrifugal force from rotor periphery
It is thrown on shell, is pooled to outlet discharge under gravity.The volume flow for adjusting two kinds of material liquids in the process is equal
For 100 L/h, the revolving speed for controlling rotating bed with helix channel is 2500 rpm；After reaction, Magneto separate reaction product is spent
Ionized water is cleaned repeatedly to neutrality, and freeze-drying obtains the NiFe of graphene oxide modification2O4Magnetic nano-particle.
Embodiment 4:
A kind of hypergravity preparation method of graphene oxide modified magnetic nano material, includes the following steps:
The graphene oxide for weighing 1.0 g is scattered in the aqueous solution for being configured to that graphene oxide concentration is 1 mg/mL in 1 L water,
Co (NO is added thereto3)2•6H2O (29.2 g, 0.10 mol), Fe (NO3)3•9H2O (60.6 g, 0.15 mol), is configured to
Cation concn is the metal salt solution of 0.25 mol/L, wherein Fe3+Salt and Co2+The molar ratio of salt is 3:2；In addition, according to sun
Ion and OH-Molar ratio be 1:5, weigh 43.81 g ammonium hydroxide be configured to ammonia concn be 1.25 mol/L aqueous solution；It will be upper
It states graphene oxide and metal mixed salt solution and ammonia aqueous solution is added separately in storage tank, be preheating to 40 DEG C, starting centrifugation
Two kinds of material liquids are delivered in rotary packed bed by liquid distribution trough by pump respectively, and material liquid is sprayed by the aperture on liquid distribution trough
Onto the filler of rotation, the hole of filler is flowed through from inside to outside under the influence of centrifugal force, and be mutually mixed instead in packing layer
It answers.Finally, reaction product is thrown on shell from the outer rim of filler under the influence of centrifugal force, is pooled to out under gravity
At mouthful, it is discharged through outlet.Adjusting the volume flow of two kinds of material liquids in the process is 80 L/h, is controlled rotary packed bed
Revolving speed is 1500 rpm；After reaction, it using magnetic separation technique collecting reaction product, is cleaned repeatedly into dehydrated alcohol
Property, freeze-drying obtains the CoFe of graphene oxide modification2O4Magnetic nano-particle.
Embodiment 5:
A kind of hypergravity preparation method of graphene oxide modified magnetic nano material, includes the following steps:
The graphene oxide for weighing 0.7 g, which is scattered in, is configured to graphene oxide concentration as the water-soluble of 0.7 mg/mL in 1 L water
ZnCl is added in liquid thereto2(2.6 g, 0.017 mol), FeCl3•6H2O (8.92 g, 0.033 mol) is configured to cation
Concentration is the metal salt solution of 0.05 mol/L, wherein Fe3+Salt and Zn2+The molar ratio of salt is 2:1；In addition, according to cation and
OH-Molar ratio be 1:2.4, weigh 4.8 g sodium hydroxides be configured to naoh concentration be 0.12 mol/L aqueous solution；It will
Above-mentioned graphene oxide and metal mixed salt solution and NaOH aqueous solution are added separately in storage tank, are preheating to 50 DEG C, start from
Liquid is conveyed into Impinging Stream-Rotating Packed Bed agent set by heart pump through spinner, and two strands of isometric reaction masses are logical
It is ejected on rotary packed bed inner edge after crossing the nozzle constant speed shock of liquid distribution trough, under the influence of centrifugal force along stuffing hole
Gap is flowed to outer rim, and reaction is mutually mixed in packing layer.Finally, reaction product is under the influence of centrifugal force from the outer of filler
Edge is thrown on shell, is pooled to exit under gravity, is discharged through outlet.Two kinds of material liquids are adjusted in the process
Volume flow is 70 L/h, and the revolving speed for controlling Impinging Stream-Rotating Packed Bed is 1200 rpm；After reaction, using magnetic point
From technology collecting reaction product, cleaned repeatedly with deionized water to neutrality, freeze-drying obtains graphene oxide modification
ZnFe2O4Magnetic nano-particle.
Embodiment 6:
A kind of hypergravity preparation method of graphene oxide modified magnetic nano material, includes the following steps:
The graphene oxide for weighing 0.9 g, which is scattered in, is configured to graphene oxide concentration as the water-soluble of 0.9 mg/mL in 1 L water
MgSO is added in liquid thereto4(36.12 g, 0.3 mol), Fe2(SO4)3 (90g, 0.225 mol), is configured to cation concn
For the metal salt solution of 0.75 mol/L, wherein Fe3+Salt and Mg2+The molar ratio of salt is 3:2；In addition, according to cation and OH-'s
Molar ratio is 1:4, weighs 105.15 g ammonium hydroxide and is configured to the aqueous solution that ammonia concn is 3.0 mol/L；By above-mentioned graphite oxide
Alkene and metal mixed salt solution and lye are added in storage tank, are preheating to 70 DEG C, starting centrifugal pump by two kinds of material liquids respectively by
Liquid distribution trough is delivered in rotating bed with helix channel, and liquid is entered the work in helical duct in centrifugal force by liquid distribution trough
With from inside to outside along the rotor outflow with spiral of Archimedes shape channel.During this period, material liquid is in helical duct
It is inside mutually mixed, reacts.Finally, reaction product is thrown on shell from rotor periphery under the influence of centrifugal force, in the work of gravity
Outlet discharge is pooled under.Adjusting the volume flow of two kinds of material liquids in the process is 40 L/h, controls helical duct
The revolving speed of type revolving bed is 800 rpm；After reaction, Magneto separate reaction product is cleaned with deionized water repeatedly to neutrality, cold
Freeze the MgFe for being dried to obtain graphene oxide modification2O4Magnetic nano-particle.
Claims (10)
1. a kind of hypergravity preparation method of graphene oxide modified magnetic nano material, it is characterised in that the following steps are included:
The mixed solution and lye are sent into supergravity reactor by the mixed solution for preparing graphene oxide and metal salt first simultaneously
Reaction, the degree of supersaturation for making reaction system moment reach higher and being evenly distributed, and the microcosmic mixing time of system is less than
It is nucleated induction time；Magneto separate reaction product after reaction, deionized water and dehydrated alcohol are cleaned repeatedly to neutrality, and freezing is dry
The dry magnetic Nano material for obtaining graphene oxide modification.
2. the hypergravity preparation method of graphene oxide modified magnetic nano material according to claim 1, feature exist
In the following steps are included:
(1) it prepares the mixed solution of graphene oxide and metal salt: by graphene oxide ultrasonic disperse in deionized water, preparing
At the aqueous solution for the graphene oxide that concentration is 0.1 ~ 2.0 mg/mL, metal M is then added thereto2+Salt and Fe3+Salt is prepared
At the mixed solution of graphene oxide and metal salt that cation concn is 0.05 ~ 1.0 mol/L, wherein Fe3+Salt and metal M2+
The molar ratio of salt is 2:1 ~ 3:2, metal M2+Salt is one of nitrate, sulfate or chlorate；
(2) it prepares lye: using sodium hydroxide or ammonium hydroxide for alkali source, by cation and OH-Molar ratio be 1:2.4 ~ 1:5 prepare
Concentration of lye is the aqueous solution of 0.12 ~ 5.0 mol/L；
(3) magnetic Nano material of synthesis graphene oxide modification: respectively by the mixed solution of graphene oxide and metal salt, alkali
Liquid is placed in reservoir, is preheating to 25 ~ 100 DEG C, and then setting mixed solution is equal with the flow of lye, and isometric two strands anti-
It answers material to be delivered in supergravity reactor by liquid distribution trough to be reacted, in any one moment graphene oxide and gold
The mixed solution and lye for belonging to salt are all isometric hybrid reactions according to set proportion；
Fluid is acutely sheared and is crushed using high-speed rotating filler, phase interface that is huge and quickly updating is generated, makes
It obtains microcosmic mixing and mass transport process is strengthened, after the isometric repeated collision contact of two kinds of materials, conducive to particle diameter distribution is formed
Uniform nano particle；The microcosmic uniformly mixed time is 10-100 μ s in supergravity reactor；
(4) after reaction, Magneto separate reaction product is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, freeze-drying
Obtain the magnetic Nano material of graphene oxide modification.
3. the hypergravity preparation method of graphene oxide modified magnetic nano material according to claim 1, feature exist
In: the source of the magnetic Nano material are as follows: Fe3O4、MnFe2O4、NiFe2O4、CoFe2O4、ZnFe2O4、MgFe2O4Ferrite
One of.
4. the hypergravity preparation method of graphene oxide modified magnetic nano material according to claim 1, feature exist
In: the M2+For Mn2+、Fe2+、Ni2+、Co2+、Zn2+、Mg2+One of.
5. the hypergravity preparation method of graphene oxide modified magnetic nano material according to claim 1, feature exist
In: in step (3), the volume flow for controlling two strands of material liquids is 10 ~ 100 L/h, the revolving speed of supergravity reactor 100 ~
2500 rpm。
6. the hypergravity preparation method of graphene oxide modified magnetic nano material according to claim 1, feature exist
In: pass through the continuous preparation method of hypergravity, the production efficiency of magnetic Nano material reaches 0.022-2.2 kg/h.
7. a kind of hypergravity preparation facilities of graphene oxide modified magnetic nano material, for any one of claim 1 ~ 6 institute
The hypergravity preparation method stated, it is characterised in that: stored up including supergravity reactor, graphene oxide and metal mixed salt solution
Slot, lye storage tank, mixed solution storage tank, lye storage tank are separately connected supergravity reactor, be respectively equipped on connecting line pump and
Spinner flowmeter, the flow by pump control mixed solution and lye are equal；Liquid distribution trough, control are equipped in supergravity reactor
Mixed solution and lye processed are mixed；Connection product storage tank below supergravity reactor.
8. the hypergravity preparation facilities of graphene oxide modified magnetic nano material according to claim 7, feature exist
In: the supergravity reactor is Impinging Stream-Rotating Packed Bed, and two strands of reaction masses are by two opposite sprays on liquid distribution trough
Mouth sprays to form jet stream, and the circle perpendicular to jet direction or fan-shaped misty pellicular front are formed after hitting, in this process
In two strands of reaction masses realize mixing for the first time, reaction；It mixes weaker shock cloudy surface edge and enters rotary packed bed inner cavity,
Under the influence of centrifugal force along the outside edge flowing of filler hole, and during this period liquid repeatedly cut by filler, coalescence and dispersion,
Complete second of mixing, reaction；Finally, reaction product is thrown on shell from the outer rim of filler under the influence of centrifugal force, in weight
Outlet discharge is pooled under the action of power.
9. the hypergravity preparation facilities of graphene oxide modified magnetic nano material according to claim 7, feature exist
Be in: the supergravity reactor it is rotary packed bed, two strands of reaction masses are sprayed onto filler by the nozzle of aperture on liquid distribution trough
On, liquid is flowed along filler hole from rotor inner edge to rotor periphery under the influence of centrifugal force；During this period, material liquid is filled out
Material repeatedly cutting, coalescence and dispersion, is mutually mixed reaction in packing layer；Finally, reaction product under the influence of centrifugal force from
It is thrown on shell at filler outer rim, is pooled to outlet discharge under the effect of gravity.
10. the hypergravity preparation facilities of graphene oxide modified magnetic nano material according to claim 7, feature exist
In: the supergravity reactor is rotating bed with helix channel, and two strands of reaction masses are entered in helical duct by liquid distribution trough,
Liquid is flowed out along the rotor with spiral of Archimedes shape channel from inside to outside in the effect of centrifugal force；During this period,
Material liquid is mutually mixed in helical duct, reacts；Finally, reaction product is thrown to from rotor periphery outer under the influence of centrifugal force
On shell, it is pooled to outlet discharge under gravity.
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