CN108262489A - A kind of hypergravity preparation method of chitosan loaded nano zero valence iron and its double metallic composite material - Google Patents
A kind of hypergravity preparation method of chitosan loaded nano zero valence iron and its double metallic composite material Download PDFInfo
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Abstract
The invention discloses the hypergravity preparation methods of a kind of chitosan loaded nano zero valence iron and its double metallic composite material, belong to technical field of nano material.It is an object of the present invention to provide a kind of methods for continuously preparing chitosan loaded nano zero valence iron and its double metallic composite material.Chitosan is sent into supergravity reactor by this method simultaneously with the mixed solution and reducing agent of metal salt to react, Magneto separate reaction product after reaction, deionized water and absolute ethyl alcohol are cleaned repeatedly to neutrality, and vacuum drying obtains chitosan loaded nano zero valence iron and nanometer iron double metal compound particle.One step of this method prepares chitosan loaded Zero-valent Iron nanometer or nanometer iron double metal composite particles; it is simple for process, the reaction time is short, it is at low cost, be produced on a large scale; the chitosan loaded nano zero-valence abrasive grit or nanometer iron double metal compound particle diameter of preparation are small simultaneously, favorable dispersibility, have good stability, reactivity height, have industrial applications prospect.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of chitosan loaded nano zero valence iron and its bimetallic
The hypergravity preparation method of composite material.
Background technology
With the fast development of social economy, heavy metal ion pollution is increasingly severe in water, since heavy metal cannot give birth to
Object is degraded, and serious harm is generated to human body by long-term ecological accumulation, and heavy metal pollution has become global pass extensively
The problem of environmental pollution of note.Therefore the method for exploitation Cheap highly effective go the heavy metal ion in water removal to the healthy and safe of the mankind and
Ecological environment is of crucial importance, is following a period of time to be badly in need of the important topic solved.Nano zero valence iron (NZVI) because its have than
The features such as surface area is big, reactivity is high, reproducibility is strong can promote the absorbing and reducing of pollutant, it has also become one receives pass
The research field of note.Although NZVI is directly used in environment has significant advantage to the reparation of heavy metal pollution, by
In its grain size is small, active height, easily occur to reunite in practical applications and by Oxidative inactivation, so as to reduce Zero-valent Iron to a huge sum of money
The removal efficiency of category, these make NZVI be restricted in practical heavy metal pollution reparation application.The study found that by nanometer
Another metal is adulterated in Zero-valent Iron system（Such as Cu, Ag, Ni, Pd）After Zero-valent Iron surface electronic can be promoted to shift, accelerate anti-
Rate is answered, further improves the reactivity of nano zero valence iron, the formation of passivation layer can be prevented to a certain extent.Hu etc.
[Water Research, 2010, 44(10):3101-3108] surface of Ni metal load and nano zero valence iron is formed and is received
Rice iron-copper bi-metal particle, for removing pollutant Cr (VI), research is found after nano zero valence iron area load Ni metal can be with
Improve oxidation state of the iron in film, so as to improve removal efficiency of the material to Cr (VI).
Although nano zero-valence Fe Bimetallic System presents huge compared to independent Zero-valent Iron in heavy metal contaminants reparation
Advantage, but in actual application, nano zero-valence iron double metal is due to the skin effect and magnetic dipole of nano-particle
Interaction so that duplex metal nano granule is easily reunited and is passivated, and influences nano zero valence iron double metallic composite material and is answering
With stability and activity in the process.The study found that the study found that by introduce certain carrier material be used as stabilizer can
Significantly improve the activity of nano zero valence iron.Studies have reported that bentonite, sodium carboxymethylcellulose, activated carbon, multi-wall carbon nano-tube
The material loads such as pipe nano zero valence iron or nano zero-valence iron double metal compound particle can effectively improve Zero-valent Iron and its bimetallic is answered
Close the reactivity of particle.Chitosan (Chitosan, CS, chemical name：β -1,4-2- amino-2-deoxy-D-glucoses)
It is a kind of basic amine group polysaccharide, is to be obtained by the natural polymer de-acetyl chitin being widely present in nature, has
The characteristics such as cheap, widely distributed, storage is enriched, biocompatibility is good, nontoxic, biodegradable, are a kind of excellent
Load matrix.In addition, hydroxyl and amino abundant on its strand makes it have good affinity to metal ion, it is existing to grind
Study carefully amino above chitosan and hydroxyl can be with Fe3+Form chitosan/Fe (III) complex compound.Therefore, by chitosan with
NZVI is combined, and one side chitosan has a large amount of active group, can improve the dispersibility and reactivity of NZVI, is improved
On the other hand NZVI can cause two to avoid iron ion is discharged in NZVI oxidation process to heavy metal ion removal efficiency to environment
Secondary pollution.
Although chitosan can effectively improve the reactivity of nano zero valence iron as stabilizer, chitosan loaded
Nano zero valence iron or nano zero-valence iron double metal compound particle lack method prepared by continuous batch.Usually there are two class preparation sides
Method：(1) later stage load method first prepares nano zero valence iron, then restores second of metal in aqueous solution with nano zero valence iron,
Finally nano zero valence iron or Zero-valent Iron double metallic composite material are loaded with chitosan.The method preparation process is complicated, no
Conducive to large-scale industrial production；(2) coprecipitation in situ, i.e., pass through chemical coprecipitation under the conditions of existing for chitosan
With strong reductant (NaBH4Or KBH4) while restore containing there are two types of the aqueous solution of metallic, a step prepares chitosan loaded receive
Rice double metallic composite material.Although the method preparation process is simple, its reaction unit is usually stirring reactor, is profit
Make reaction mass Strong dispersion hybrid reaction with the shearing force of agitating paddle, belong to intermittently operated, microcosmic uniformly mixed time
About 0.01 ~ 0.2 s.It it is one quick due to borohydride reduction iron or other metal ions generation zero-valent metal simple substance
Precipitation process is reacted, the characteristic time of nucleation is about 1ms, therefore the biography in traditional stirring reactor on molecular scale
The nucleation rate that liquid-phase reduction precipitation is much smaller than with mixing rate is passed, is on molecular scale so as to cause nucleation and growth course
Uneven environment, the Zero-valent Iron thus prepared using traditional stirring reactor or the distribution of zeroth order iron double metal particle diameter are not
Uniformly and the industrialness problems such as batch production poor reproducibility, Product management model effect is big.Therefore, exploitation can be prepared with continuous batch and be received
The new process and new method of rice zero-valent iron composite material are to solve the limited critical problem of nano zero valence iron application.
Invention content
The present invention is intended to provide prepared by the hypergravity of a kind of chitosan loaded nano zero valence iron and its double metallic composite material
Method, a step prepare chitosan loaded nano zero valence iron and its double metallic composite material, when this method has simple for process, reaction
Between short, at low cost, the characteristics of being produced on a large scale, while the chitosan loaded nano zero valence iron and its bimetallic composite wood prepared
Expect that good dispersion, stability is good, reactivity is high, grain size is small, has industrial applications prospect.
The characteristics of high-gravity technology is because of the microcosmic mixing of its reinforcing and mass transport process, can make reaction system moment reach higher
And the degree of supersaturation that is evenly distributed and the Determining Micromixing Characteristic Time less than nucleation induction time, it is therefore widely used in a nanometer material
In the preparation of material.High-gravity technology prepares nano material with the reaction time is short, the nano particle diameter of formation is small, particle diameter distribution
Uniformly, manufacturing cost is low, is easy to industrial amplification production（4-20 times can be improved compared with conventional method）The advantages that.Therefore, it is sharp
It is combined with high-gravity technology with reaction precipitation method, one-step synthesis good dispersion, stability is good, reactivity is high, particle diameter distribution is equal
Even chitosan loaded nano zero valence iron and its double metallic composite material can realize the continuous of nano zero valence iron based composites
It prepares, efficient utilize for nano zero valence iron provides new approaches.
The present invention provides the hypergravity preparation sides of a kind of chitosan loaded nano zero valence iron and its double metallic composite material
Method, it is characterised in that：Chitosan with the mixed solution and reducing agent of metal salt is sent into supergravity reactor simultaneously and is reacted, instead
Magneto separate reaction product after answering is cleaned with deionized water repeatedly to neutrality, and vacuum drying obtains chitosan loaded nanometer zero
Valency iron and its bimetallic compound particle.It is as follows：
(1) chitosan and metal mixed salt solution are prepared：Chitosan is dissolved in a concentration of 0.05mol/L aqueous solution of nitric acid and is matched
The solution that chitosan concentration is 0.1% ~ 2% is made.Then add in metal salt thereto, be configured to concentration of metal ions for 0.05 ~
The chitosan of 1.0 mol/L and the mixed solution of metal salt；
(2) reducing agent solution is prepared：Sodium borohydride or potassium borohydride are used as reducing agent, by BH4 -With mole of metal ion
Than being 2:1~3:1 prepares the aqueous solution that reductant concentration is 0.1 ~ 3.0 mol/L；
(3) chitosan loaded nano zero valence iron and its bimetal nano compound particle are synthesized：Respectively by chitosan and metal salt
Mixed solution, reducing agent aqueous solution are placed in reservoir, and two strands of isometric reaction masses are delivered to super by liquid distribution trough
Reacted in gravity reactor, any one moment chitosan and metal mixed salt solution and reducing agent aqueous solution be all by
According to setting ratio mixed after reaction generate chitosan loaded nano zero valence iron and its bimetal nano composite particles, control
The volume flow of two strands of material liquids is 20 ~ 100 L/h, and the rotating speed of supergravity reactor is in 100 ~ 2500 rpm；
(4) after reaction, reaction product is collected using magnetic separation technique, is cleaned repeatedly with deionized water to neutrality, vacuum
It is dried to obtain chitosan loaded nano zero valence iron and its bimetal nano compound particle..
In above-mentioned preparation method, the metal salt is ferrous salt, ferrous salt and nickel salt admixture, ferrous salt and mantoquita mix
The molar fraction that object, wherein nickel salt, mantoquita account for metal salt is 0 ~ 99%.Ferrous salt is ferrous sulfate, ferrous nitrate, frerrous chloride
Any one of；Nickel salt is any one of nickel sulfate, nickel nitrate, nickel chloride；Mantoquita is copper sulphate, in copper nitrate, copper chloride
It is any.
In above-mentioned preparation method, the supergravity reactor is Impinging Stream-Rotating Packed Bed, rotary packed bed or spiral is led to
Channel type revolving bed.
The nano zero valence iron and its compound grain of bimetallic that the present invention is loaded by supergravity reactor one-step synthesis of chitosan
Son acutely shears fluid process using high-speed rotating filler and broken, generates huge and quick newer boundary so that
Microcosmic mixing and mass transport process have obtained great reinforcing, and the microcosmic uniformly mixed characteristic time is 10- in supergravity reactor
100 μ s, much smaller than the induction Nucleation characteristics time of Traditional liquid phase precipitation reaction.That is, by hypergravity reaction technology, Zero-valent Iron
Or Zero-valent Iron bimetal nano particles have reached uniform degree of supersaturation before crystallization nucleation, in reactor, therefore made
Standby Zero-valent Iron or the nucleation of zeroth order iron double metal compound particle and growth carry out under conditions of a uniform degree of supersaturation,
Meet desired homogeneous into nuclear environment, control nucleation process, particle is made to show the relatively narrow nano material being distributed prepared by event
Grain size is smaller, particle diameter distribution is uniform；In addition, by high-gravity technology, chitosan loaded nano zero valence iron and its bimetallic are answered
Continuous preparation can be realized by closing particle, and preparation efficiency can reach 0.168 ~ 3.36 kg/h, this is that common stirred tank method is difficult
With realization, industrial applications prospect outclass traditional reaction kettle paddling process.
Beneficial effects of the present invention：
（1）Hypergravity of the present invention reaction coprecipitation be by control Zero-valent Iron or Zero-valent Iron duplex metal nano granule into
The crystalline nucleation time controls the forming process of nano material；
（2）The present invention reacts the supergravity reactor with powerful microcosmic composite character applied to quick chemical precipitation, together
Dispersant and surface modifier of the chitosan of Shi Liyong biomass as zeroth order iron nano-particle, the nano zero valence iron tool of preparation
Have good dispersion, stability are good, reactivity is high, preparation method is simple, manufacturing cost is low, can continuous batch prepare the advantages of；
（3）Method provided by the invention has prominent industrial applications prospect, it is expected to be widely used in environment remediation, magnetic is urged
The fields such as change, magnetic recording, magnetorheological, magnetic resonance imaging.
Description of the drawings
Fig. 1 is embodiment 1, preparation facilities figure used by embodiment 3 and embodiment 6.
Fig. 2 is that the TEM of the obtained chitosan loaded nano zero valence iron of embodiment 1 schemes.
Fig. 3 is the X-ray diffractogram of the obtained chitosan loaded nano zero valence iron of embodiment 1.
Fig. 4 is the infrared spectrogram of the obtained chitosan loaded nano zero valence iron of embodiment 1.
Fig. 5 is that the TEM of the obtained chitosan loaded Nanoscale Iron nickel bimetal compound particle of embodiment 3 schemes.
In figure, 1- molysite storage tanks;2- valves;3- spinner flowmeters;4- reducing agent storage tanks;5- percussion flows-rotation filler
Bed;6- product storage tanks.
Specific embodiment
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.
Embodiment 1：
The hypergravity preparation method of a kind of chitosan loaded nano zero valence iron and its double metallic composite material, by chitosan and metal
The miscible fluid and reducing agent of salt are sent into supergravity reactor simultaneously to react, after reaction Magneto separate reaction product, deionization
Water is cleaned repeatedly to neutrality, and vacuum drying obtains chitosan loaded nano zero valence iron and its bimetallic compound particle, specifically includes
Following steps：
Fig. 1 is that chitosan loaded nano zero-valence iron particle is prepared by reactor of Impinging Stream-Rotating Packed Bed shown in the embodiment
Experiment flow figure, the specific steps are：The chitosan for weighing 5 g is dissolved in the aqueous solution of nitric acid of 1L 0.05mol/L and prepares shelling
Glycan concentration is 0.5% aqueous solution, adds in FeCl thereto2•4H2(0.2 mol, 39.76 g) to be configured to ferrous ion dense by O
Spend the iron salt solutions for 0.2 mol/L；In addition, by BH4 -Molar ratio with ferrous ion is 2.5:1, weigh NaBH4 (0.5
Mol, 18.92 g) are dissolved in 1L water and are configured to NaBH4The aqueous solution of a concentration of 0.5 mol/L；By above-mentioned chitosan and molysite
Mixed solution and NaBH4Aqueous solution is added separately in molysite storage tank 1 and reducing agent storage tank 4, starts centrifugal pump by liquid through turning
Subflow gauge 3 is conveyed into Impinging Stream-Rotating Packed Bed 5, the nozzle that two strands of isometric reaction masses pass through liquid distribution trough
Constant speed is ejected into after hitting on rotary packed bed inner edge, is flowed under the influence of centrifugal force along the outside edge of filler hole, and
Reaction is mutually mixed in packing layer.Finally, reaction product is thrown to from the outer rim of filler on shell under the influence of centrifugal force, in weight
Exit is pooled under the action of power, is discharged through outlet.The volume flow for adjusting two kinds of material liquids in the process is 60 L/
H, the rotating speed for controlling Impinging Stream-Rotating Packed Bed are 1000 rpm；After reaction, reaction production is collected using magnetic separation technique
Object is cleaned with deionized water repeatedly to neutrality, and vacuum drying obtains chitosan loaded nano zero-valence iron particle.
Fig. 2 shows the TEM figures of the chitosan loaded nano zero valence iron of embodiment synthesis, and as can be seen from the figure shell gathers
Sugar load nano zero valence iron grain size is about 11 nm, and particle size is uniform, favorable dispersibility.Fig. 3 is that the shell that the embodiment obtains gathers
The X-ray diffractogram of sugar load nano zero valence iron.It can be seen from the figure that chitosan loaded nano zero valence iron is in 2 θ=44.76 °,
65.06 ° there are α-Fe0Characteristic diffraction peak, and the XRD diagram of unmodified nano zero valence iron have at 2 θ=35.56 ° it is one apparent
Peak, which is the oxidation peak of iron, and in corresponding place, chitosan loaded nano zero valence iron does not occur oxidation peak, illustrates not
Modified nano zero valence iron easily aoxidizes, while the introducing for also demonstrating chitosan is effectively protected nano zero valence iron and presses down
Zero-valent Iron has been made to be aoxidized.Fig. 4 shows the infrared spectrogram of the chitosan loaded nano zero valence iron of embodiment synthesis, from figure
In as can be seen that chitosan loaded nano zero valence iron infrared spectrum in 1059 cm-1It shakes corresponding to the flexible of C-OH of chitosan
Dynamic peak, in 3436 cm-1- the NH of corresponding chitosan2With the characteristic peak of-N-H, in 1640 cm-1It is that shell gathers corresponding to amide I band
The characteristic peak of sugar.Illustrate that chitosan is successfully modified in Zero-valent Iron nano grain surface.
Embodiment 2：
A kind of hypergravity preparation method of chitosan loaded nanometer iron-copper bi-metal compound particle, it includes the following steps：
Weigh 1 g chitosan be dissolved in be configured in the aqueous solution of nitric acid of 1L 0.05mol/L chitosan concentration be 0.1% it is water-soluble
Liquid adds in FeSO thereto4•7H2(0.04 mol, 11.12 g) and CuCl by O2•2H2(0.01 mol, 1.70 g) match O
It is set to the solution that concentration of metal ions is 0.05 mol/L, wherein Cu2+The molar fraction for accounting for metal salt is 20%；In addition, by BH4 -
Molar ratio with metal ion is 3:1, weigh KBH4 (0.15 mol, 8.09 g) are dissolved in 1L water and are configured to KBH4It is a concentration of
The aqueous solution of 0.15 mol/L；By above-mentioned chitosan and metal mixed salt solution and KBH4Aqueous solution is added separately in storage tank,
Start centrifugal pump and two kinds of material liquids are delivered to rotary packed bed middle hybrid reaction by liquid distribution trough respectively, adjust in the process
The volume flow for saving two kinds of material liquids is 20 L/h, and it is 100 rpm to control rotary packed bed rotating speed；After reaction, it adopts
With magnetic separation technique collecting reaction product, cleaned repeatedly with deionized water to neutrality, vacuum drying obtains chitosan loaded nanometer
Iron-copper bi-metal compound particle.
Embodiment 3：
A kind of hypergravity preparation method of chitosan loaded Nanoscale Iron nickel bimetal compound particle, it includes the following steps：
Weigh 5 g chitosan be dissolved in be configured in the aqueous solution of nitric acid of 1L 0.05mol/L chitosan concentration be 0.5% it is water-soluble
Liquid adds in Fe (NO thereto3)2(0.08 mol, 14.39 g) and NiCl2•6H2(0.12 mol, 28.52 g) prepare O
Into the solution that concentration of metal ions is 0.2 mol/L, wherein Ni2+The molar fraction for accounting for metal salt is 60%；In addition, by BH4 -With
The molar ratio of ferrous ion is 2.5:1, weigh NaBH4 (0.5 mol, 18.92 g) are dissolved in 1L water and are configured to NaBH4Concentration
Aqueous solution for 0.5 mol/L；By above-mentioned chitosan and metal mixed salt solution and NaBH4Aqueous solution is added separately to storage tank
In, start centrifugal pump and be conveyed into liquid in Impinging Stream-Rotating Packed Bed agent set through spinner, isometric two strands are anti-
Material is answered to be ejected on rotary packed bed inner edge after being 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 rotating speed for controlling Impinging Stream-Rotating Packed Bed is 1000 rpm；After reaction,
Using magnetic separation technique collecting reaction product, cleaned repeatedly with deionized water to neutrality, vacuum drying obtains chitosan loaded receive
Rice iron nickel bimetal compound particle.
Fig. 5 shows the TEM figures of the chitosan loaded Nanoscale Iron nickel bimetal compound particle of embodiment synthesis, from figure
It can be seen that the grain size of chitosan loaded Nanoscale Iron nickel bimetal compound particle is about 12 nm, particle size is uniform, and dispersibility is good
It is good
Embodiment 4：
A kind of hypergravity preparation method of chitosan loaded nanometer iron-copper bi-metal compound particle, it includes the following steps：
The chitosan for weighing 20 g is dissolved in the water for being configured to that chitosan concentration is 2.0% in the aqueous solution of nitric acid of 1L 0.05mol/L
Solution adds in FeCl thereto2•4H2(0.01 mol, 1.99 g) and CuSO by O4•5H2O (0.99 mol, 247.5 g )
It is configured to the solution that concentration of metal ions is 1.0 mol/L, wherein Cu2+The molar fraction for accounting for metal salt is 99%；In addition, it presses
BH4 -Molar ratio with metal ion is 2:1, weigh KBH4 (2.0 mol, 107.88 g) are dissolved in 1L water and are configured to KBH4It is dense
Spend the aqueous solution for 2.0 mol/L；By above-mentioned chitosan and metal mixed salt solution and KBH4Aqueous solution is added separately to storage tank
In, start centrifugal pump and two kinds of material liquids are delivered to hybrid reaction in rotating bed with helix channel by liquid distribution trough respectively,
The volume flow that two kinds of material liquids are adjusted during this is 100 L/h, and the rotating speed of adults power reactor is 2500 rpm；
After reaction, it using magnetic separation technique collecting reaction product, is cleaned repeatedly with deionized water to neutrality, vacuum drying obtains shell
Glycan loads nanometer iron-copper bi-metal compound particle.
Embodiment 5：
A kind of hypergravity preparation method of chitosan loaded Nanoscale Iron nickel bimetal compound particle, it includes the following steps：
The chitosan for weighing 10 g is dissolved in the water for being configured to that chitosan concentration is 1.0% in the aqueous solution of nitric acid of 1L 0.05mol/L
Solution adds in FeSO thereto4•7H2(0.0025 mol, 0.695 g) and NiSO by O4•6H2O (0.2475 mol,
65.05 g) are configured to the solution that concentration of metal ions is 0.25 mol/L, wherein Ni2+The molar fraction for accounting for metal salt is 99%；
In addition, by BH4 -Molar ratio with metal ion is 3:1, weigh NaBH4 (0.75 mol, 28.37 g) are dissolved in 1L water and preparing
Into NaBH4The aqueous solution of a concentration of 0.75 mol/L；By above-mentioned chitosan and metal mixed salt solution and NaBH4Aqueous solution is distinguished
It is added in storage tank, starts centrifugal pump and two kinds of material liquids are delivered to rotary packed bed middle mixing instead by liquid distribution trough respectively
Should, the volume flow for adjusting two kinds of material liquids in the process is 40 L/h, and it is 800 to control rotary packed bed rotating speed
rpm；After reaction, it using magnetic separation technique collecting reaction product, is cleaned repeatedly to neutrality, is dried in vacuo with deionized water
To chitosan loaded Nanoscale Iron nickel bimetal compound particle.
Embodiment 6：
A kind of hypergravity preparation method of chitosan loaded nanometer iron-copper bi-metal compound particle, it includes the following steps：
The chitosan for weighing 15 g is dissolved in the water for being configured to that chitosan concentration is 1.5% in the aqueous solution of nitric acid of 1L 0.05mol/L
Solution adds in Fe (NO thereto3)2(0.15 mol, 26.98 g) and Cu (NO3)2•3H2O (0.60 mol, 144.96 g
) it is configured to the solution that concentration of metal ions is 0.75 mol/L, wherein Cu2+The molar fraction for accounting for metal salt is 80%；In addition, it presses
BH4 -Molar ratio with metal ion is 2.5:1, weigh NaBH4 (1.875 mol, 70.93 g) are dissolved in 1L water and being configured to
NaBH4The aqueous solution of a concentration of 1.875 mol/L；By above-mentioned chitosan and metal mixed salt solution and NaBH4Aqueous solution adds respectively
Enter into storage tank 1 and 4, start centrifugal pump and be conveyed into liquid in Impinging Stream-Rotating Packed Bed agent set 5 through spinner 3,
Two strands of isometric reaction masses are ejected into after being hit by the nozzle constant speed of liquid distribution trough on rotary packed bed inner edge,
It is flowed, and reaction is mutually mixed in packing layer along the outside edge of filler hole under the action of centrifugal force.Finally, reaction product from
It is thrown on shell from the outer rim of filler under the action of mental and physical efforts, is pooled to exit under gravity, discharged through outlet.Herein
The volume flow for adjusting two kinds of material liquids in the process is 80 L/h, and the rotating speed for controlling Impinging Stream-Rotating Packed Bed is 1500
rpm；After reaction, it using magnetic separation technique collecting reaction product, is cleaned repeatedly to neutrality, is dried in vacuo with deionized water
To chitosan loaded nanometer iron-copper bi-metal compound particle.
Embodiment 7：
A kind of hypergravity preparation method of chitosan loaded Nanoscale Iron nickel bimetal compound particle, it includes the following steps：
The chitosan for weighing 20 g is dissolved in the water for being configured to that chitosan concentration is 2.0% in the aqueous solution of nitric acid of 1L 0.05mol/L
Solution adds in Fe (NO thereto3)2(0.6 mol, 107.92 g) and Ni (NO3)2•6H2O (0.40 mol, 116.32 g
) it is configured to the solution that concentration of metal ions is 1.0 mol/L, wherein Ni2+The molar fraction for accounting for metal salt is 40%；In addition, it presses
BH4 -Molar ratio with metal ion is 2:1, weigh KBH4 (2.0 mol, 107.88 g) are dissolved in 1L water and are configured to KBH4It is dense
Spend the aqueous solution for 2.0 mol/L；By above-mentioned chitosan and metal mixed salt solution and KBH4Aqueous solution is added separately to storage tank
In, start centrifugal pump and two kinds of material liquids are delivered to hybrid reaction in rotating bed with helix channel by liquid distribution trough respectively,
The volume flow that two kinds of material liquids are adjusted during this is 70 L/h, and the rotating speed for controlling revolving bed is 1200 rpm；Reaction knot
Shu Hou using magnetic separation technique collecting reaction product, is cleaned with deionized water to neutrality, vacuum drying obtains chitosan and bears repeatedly
Carry Nanoscale Iron nickel bimetal compound particle.
Claims (5)
1. a kind of hypergravity preparation method of chitosan loaded nano zero valence iron and its double metallic composite material, it is characterised in that：
Chitosan with the mixed solution and reducing agent of metal salt is sent into supergravity reactor simultaneously and is reacted, after reaction Magneto separate
Reaction product is cleaned with deionized water repeatedly to neutrality, and vacuum drying obtains chitosan loaded nano zero valence iron and its bimetallic
Compound particle.
2. the hypergravity preparation side of chitosan loaded nano zero valence iron according to claim 1 and its double metallic composite material
Method, it is characterised in that：Include the following steps：
(1) chitosan and metal mixed salt solution are prepared：Chitosan is dissolved in a concentration of 0.05mol/L aqueous solution of nitric acid and is matched
The solution that chitosan concentration is 0.1% ~ 2% is made；Then metal salt is added in thereto, and it is 0.05 ~ 1.0 to be configured to cation concn
The chitosan of mol/L and the mixed solution of metal salt；
（2）Prepare reducing agent solution：Sodium borohydride or potassium borohydride are used as reducing agent, by BH4 -With the molar ratio of metal ion
It is 2:1~3:1 prepares the aqueous solution that reductant concentration is 0.1 ~ 3.0 mol/L；
（3）Synthesize chitosan loaded nano zero valence iron and its bimetal nano compound particle：Respectively by chitosan and metal salt
Mixed solution, reducing agent aqueous solution are placed in reservoir, and two strands of isometric reaction masses are delivered to super by liquid distribution trough
It is reacted in gravity reactor, chitosan and metal mixed salt solution and reducing agent aqueous solution are all according to setting at any time
Reaction generates chitosan loaded nano zero valence iron and its bimetal nano composite particles after fixed ratio is mixed, and controls two strands
The volume flow of material liquid is 20 ~ 100 L/h, and the rotating speed of supergravity reactor is in 100 ~ 2500 rpm；
（4）After reaction, reaction product is collected using magnetic separation technique, is cleaned repeatedly with deionized water to neutrality, vacuum
It is dried to obtain chitosan loaded nano zero valence iron and its bimetal nano compound particle.
3. the hypergravity preparation side of chitosan loaded nano zero valence iron according to claim 2 and its double metallic composite material
Method, it is characterised in that：The metal salt is ferrous salt, ferrous salt and nickel salt admixture, ferrous salt and mantoquita mixture, the Central Asia
The molar fraction that nickel salt in molysite and nickel salt admixture accounts for metal salt is 0 ~ 99%；Mantoquita accounts in ferrous salt and mantoquita mixture
The molar fraction of metal salt total amount is 0 ~ 99%.
4. the hypergravity preparation side of chitosan loaded nano zero valence iron according to claim 2 and its double metallic composite material
Method, it is characterised in that：Ferrous salt is ferrous sulfate, one kind in ferrous nitrate, frerrous chloride；Nickel salt for nickel sulfate, nickel nitrate,
One kind in nickel chloride；Mantoquita is copper sulphate, one kind in copper nitrate, copper chloride.
5. the hypergravity preparation side of chitosan loaded nano zero valence iron according to claim 1 and its double metallic composite material
Method, it is characterised in that：The supergravity reactor is Impinging Stream-Rotating Packed Bed, the rotation of rotary packed bed or helical duct type
One kind in bed.
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