A kind of nanometer nulvalent iron particle of support type and preparation method thereof
Technical field
The present invention relates to a kind of nanometer nulvalent iron particle of support type and preparation method thereof, belong to nano material and prepare and ring
Border Environmental capacity new material technology field.
Background technology
It is the topic of recent domestic application study using the reproducibility removal environmental contaminants of nano zero valence iron.Than
Common iron powder, nano zero valence iron has a larger specific surface area, smaller particle diameter, and reactivity higher is being other materials
Activity higher is shown during reaction, treatment effect is more preferable, with preferable application prospect.Yet with the easy of nano zero valence iron
In agglomeration and oxidisability is easy to, its degradation efficiency is caused to decline.Therefore, develop and using nano zero valence iron support materials skill
Art, the reunion to suppressing even elimination nano zero-valence iron particle, improves its inoxidizability and enhancing nano zero valence iron is dirty to environment
Contaminating the aspects such as the removal effect of thing has important meaning.
Mainly there are solid phase method, liquid phase process and gas phase process currently used for the method for preparing nano zero-valence iron particle.With
Although it is simple that solid phase method prepares nano zero-valence iron particle method, workable, particle is susceptible in preparation engineering
Reunite, and particle diameter distribution is uneven etc.;The nano zero-valence iron particle prepared with gas phase process, although its particle diameter is small, and purity is high,
It is evenly distributed, but requirement to instrument and equipment is higher, while requiring to be operated under conditions of HTHP, costly and operation
It is dangerous.
Liquid-phase reduction method has reaction principle simple, and equipment requirement is not high, workable, and production cost is low excellent
Point, but it is uneven to there is the nano zero valence iron particle size distribution of preparation simultaneously, is susceptible to reunite, and reactivity is low to be lacked
Point, therefore solve this problem by adding certain dispersant.For many years in order to overcome nano zero-valence iron particle easily to occur
The problem of reunion, generally employs load method or cladding process and nano zero-valence iron particle is modified.
The loaded article of nanometer nulvalent iron particle generally can be inorganic materials, such as activated carbon, montmorillonite, bentonite, silicon
Glue, graphite etc.;And coating is typically organic material, such as starch, shitosan, sodium carboxymethylcellulose(CMC)Deng, but it is this kind of
Covering material can not completely prevent the reunion of nano zero-valence iron particle, and additive is relatively costly.
Sepiolite due to its adsorptivity higher, larger specific surface area, preferably dispersiveness, and it is cheap, point
Cloth is extensive, as a kind of important nano zero valence iron support materials.
There is no with the report of sepiolite supported nanometer nulvalent iron particle at present.
The content of the invention
An object of the present invention is uneven in order to solve above-mentioned nano zero valence iron particle size distribution, is susceptible to
Reunite, the low technical problem of reactivity provides a kind of nanometer nulvalent iron particle of support type and preparation method thereof.The support type
Nanometer nulvalent iron particle have nano zero valence iron particle size distribution uniform, be not susceptible to reunite, reactivity feature high.
The second object of the present invention is to provide a kind of preparation method of the nanometer nulvalent iron particle of above-mentioned support type, the preparation
Method with sepiolite as carrier, using liquid phase reduction by nano zero valence iron particulate load on sepiolite, its preparation method, work
Skill is easy, and easy to operate, required equipment is simple.
Know-why of the invention
Using NaBH4Or KBH4Strong reducing property by Fe3+Reduction obtains Fe0, its reaction equation is:
。
Technical scheme
A kind of nanometer nulvalent iron particle of support type, with modified meerschaum as carrier, on the surface of modified meerschaum carrier
And inside is loaded with nanometer nulvalent iron particle;
The area load of modified meerschaum carrier nanometer nulvalent iron particle particle diameter be 5-20nm, preferably 3-7nm, and
It is about 0.01-1nm, preferably 1nm in the diameter of the nanometer nulvalent iron particle of the internal load of modified meerschaum.
A kind of preparation method of the nanometer nulvalent iron particle of above-mentioned support type, specifically includes following steps:
(1), modified meerschaum preparation
To the aqueous hydrochloric acid solution that mass percent concentration is 15% is added in natural sepiolite powder, then at 25-30 DEG C
Stirring 48h is sufficiently mixed, it is neutral then to be washed with deionized deoxygenated water to efflux, it is 115-125 DEG C then to control temperature
It is dried, then controls temperature to be calcined for 310-330 DEG C, then grind, cross 160-200 mesh sieves, the powder of gained is
It is modified meerschaum;
Mass percent concentration is the consumption of 15% aqueous hydrochloric acid solution, is calculated in mass ratio, i.e. natural sepiolite powder:
Mass percent concentration be 15% aqueous hydrochloric acid solution be 1:5 ;
(2), the modified meerschaum solution containing iron ion preparation
By step(1)It is the FeCl of 0.1-0.3mol/L that the above-mentioned 6g modified meerschaums of gained add 100mL concentration3It is water-soluble
In liquid, after being sufficiently mixed 12h at room temperature, rotating speed is controlled to be centrifuged for 8000-10000r/min to remove unnecessary iron ion,
The precipitation for obtaining with the FeCl that concentration is 0.1-0.3mol/L3The isometric deionized deoxygenated water dissolving of the aqueous solution, Ran Houyong
It is 3.0 that concentration adjusts pH for the HCl/water solution and concentration of 0.5mol/L for the NaOH aqueous solution of 0.5mol/L, is obtained final product containing iron ion
Modified meerschaum solution;
Above-mentioned modified meerschaum and concentration are the FeCl of 0.1-0.3mol/L3The consumption of the aqueous solution, by modified meerschaum:It is dense
Spend the FeCl for 0.1-0.3mol/L3The aqueous solution is 3g:The ratio of 50ml is calculated;
(3), nano zero-valence ferrous solution preparation
With N2It is protection, under conditions of rotating speed is 300-340r/min, to step(2)Being modified containing iron ion of gained
After controlling drop rate to add reducing agent, addition to finish for 15-20ml/min in sepiolite solution, it is 300- that continuation controls rotating speed
340r/min stirs 30-60min, obtains final product the nano zero-valence ferrous solution of black;
The reducing agent is that concentration is the NaBH of 0.4-1.5mol/L4The aqueous solution or concentration are the KBH of 0.4-1.5mol/L4
The aqueous solution, the consumption of reducing agent, for calculation in the molar ratio, i.e., the boron hydracid radical ion in reducing agent:Modified Hai Pao containing iron ion
Iron ion in stone solution is 4-5:1;
(4), support type nanometer nulvalent iron particle preparation
Through step(3)The nano zero-valence ferrous solution of the black of gained control rotating speed for 8000-10000r/min carry out from
The heart, the precipitation of gained is washed 3-5 times with deionized deoxygenated water, straight alcohol successively, then controls temperature to carry out vacuum for 60-70 DEG C
Dry, obtain final product the nanometer nulvalent iron particle of support type.
The nanometer nulvalent iron particle of the support type of above-mentioned gained, by the nanometer nulvalent iron particle distribution for being loaded is more equal
Even, average grain diameter is smaller, and the particle size distribution range of the nanometer nulvalent iron particle that sepiolite surface is loaded is 5-20nm, and Hai Pao
The diameter of the nanometer nulvalent iron particle of stone internal load is about 0.01-1nm, than some other loaded nano Zero-valent Iron, its
With smaller particle size distribution range, bigger specific surface area has removal efficiency higher to pollutant, therefore it not only can be with
The removal of underground water pollutant is applied to, the pollutant in rehabilitating soil is can also be applied to, with more preferable reality
Meaning and engineering application value, in specific embodiment of the invention, only enter by taking the degraded of the decabromodiphenyl oxide in water as an example
Go explanation, but be not intended to limit the removal of its other pollutant in underground water, and be applied to other pollutions in rehabilitating soil
Thing.
Beneficial effects of the present invention
A kind of nanometer nulvalent iron particle of support type of the invention, because the loaded article for using is sepiolite, its distribution is wide
It is general, cheap, and with adsorptivity higher, larger specific surface area, preferably dispersiveness so that iron ion is easily inhaled
It is attached to its surface and enters in its internal gutter, and then more dispersivenesses preferably nano zero-valence iron particle can be formed, because
The distributing homogeneity of the nanometer nulvalent iron particle in the nanometer nulvalent iron particle of this support type, inoxidizability and anti-agglomeration are all
Great raising is arrived.
Further, the nanometer nulvalent iron particle of support type of the invention, the nanometer nulvalent iron particle distribution for being loaded is more equal
Even, average grain diameter is smaller, and the particle size distribution range of the nanometer nulvalent iron particle that sepiolite surface is loaded is 5-20nm, and Hai Pao
The diameter of the nanometer nulvalent iron particle of stone internal load is about 0.01-1nm, than some other loaded nano Zero-valent Iron, its
With smaller particle size distribution range, bigger specific surface area has removal efficiency higher to pollutant, therefore it not only can be with
The removal of underground water pollutant is applied to, the pollutant in rehabilitating soil is can also be applied to.
Further, the preparation method of the nanometer nulvalent iron particle of support type of the invention, required equipment is simple, operation
Convenient, reaction can be completed at normal temperatures and pressures, therefore low cost, high financial profit;And the support type for preparing gained is received
Rice nulvalent iron particle is solid, and reaction system is water phase, and both be can be easily separated after reaction terminates, and environmental pollution is not easily caused,
Therefore it is adapted to large-scale industrial production application.
Brief description of the drawings
The transmission electron microscope picture of Fig. 1, the nanometer nulvalent iron particle of the support type of the gained of embodiment 1.
The x-ray diffraction pattern of Fig. 2, the nanometer nulvalent iron particle of the support type of the gained of embodiment 1.
The nanometer nulvalent iron particle of the support type of the final gained of Fig. 3, embodiment 1, the nano zero-valence of the gained of comparative examples 1
Iron particle, the step of embodiment 1(1)The modified meerschaum and the step of embodiment 1 of gained(1)Natural sepiolite powder used is to water
In decabromodiphenyl oxide(BDE209)Clearance with the reaction time situation of change.
Specific embodiment
The present invention is expanded on further below by specific embodiment and with reference to accompanying drawing, but is not intended to limit the present invention.
Embodiment 1
A kind of nanometer nulvalent iron particle of support type, with modified meerschaum as carrier, on the surface of modified meerschaum carrier
And inside is loaded with nanometer nulvalent iron particle, its preparation process specifically includes following steps:
(1), modified meerschaum preparation
To the aqueous hydrochloric acid solution that mass percent concentration is 15% is added in natural sepiolite powder, then at 25-30 DEG C
Stirring 48h is sufficiently mixed, it is neutral then to be washed with deionized deoxygenated water to efflux, it is 115-125 DEG C then to control temperature
It is dried, then controls temperature to be calcined for 310-330 DEG C, then grind, cross 160-200 mesh sieves, the powder of gained is
It is modified meerschaum;
Mass percent concentration is the consumption of 15% aqueous hydrochloric acid solution, is calculated in mass ratio, i.e. natural sepiolite powder:
Mass percent concentration be 15% aqueous hydrochloric acid solution be 1:5;
(2), the modified meerschaum solution containing iron ion preparation
By 6g steps(1)The modified meerschaum of gained is added to the FeCl that 100mL concentration is 0.1mol/L3In the aqueous solution,
After being sufficiently mixed 12h at room temperature, control rotating speed to be centrifuged for 8000r/min to remove unnecessary iron ion, the precipitation for obtaining
Dissolved with 100ml deionized deoxygenated waters, then with the HCl/water solution that concentration is 0.5mol/L and the NaOH that concentration is 0.5mol/L
It is 3.0 that the aqueous solution adjusts pH, obtains final product the modified meerschaum solution containing iron ion;
Above-mentioned modified meerschaum and concentration are the FeCl of 0.1mol/l3The consumption of the aqueous solution, by modified meerschaum:Concentration is
The FeCl of 0.1mol/L3The aqueous solution is 3g:The ratio of 50ml is calculated;
(3), nano zero-valence ferrous solution preparation
With N2It is protection, under conditions of rotating speed is 300r/min, to step(2)The modified Hai Pao containing iron ion of gained
After controlling drop rate to add reducing agent, addition to finish for 15-20ml/min in stone solution, it is 300r/min that continuation controls rotating speed
Stirring 30-60min, obtains final product the nano zero-valence ferrous solution of black;
The reducing agent is that concentration is the NaBH of 0.4mol/L4The aqueous solution, the consumption of reducing agent, for calculation in the molar ratio, i.e.,
Boron hydracid radical ion in reducing agent:Iron ion in modified meerschaum solution containing iron ion is 4:1;
(4), support type nanometer nulvalent iron particle preparation
Through step(3)The nano zero-valence ferrous solution of the black of gained controls rotating speed to be centrifuged for 8000r/min, gained
Precipitation is washed 3 times with deionized deoxygenated water, straight alcohol successively, then controls temperature to be vacuum dried for 60 DEG C, obtains final product load
The nanometer nulvalent iron particle of type.
Using transmission electron microscope(JEM 2011, Jeol, Japan)To the nano zero-valence of the support type of above-mentioned gained
Iron particle is measured, and the projection electron microscope of gained is as shown in figure 1, the nanometer zero of the support type obtained by as can be seen from Figure 1
Valency iron particle, with modified meerschaum as carrier, nano zero-valence abrasive grit is loaded with the surface and inside of modified meerschaum carrier
Son, the particle size distribution range of the nano zero-valence iron ion that surface is loaded is 5-20nm, and the nanometer zero of sepiolite internal load
The diameter of valency iron particle is about 0.01nm.
Using x-ray diffractometer(X’Pert PW 3040/60, PANalytical, Netherlands)To above-mentioned institute
The nanometer nulvalent iron particle of the support type for obtaining is measured, and the XRD of gained is as shown in Fig. 2 from figure 2 it can be seen that scanning
When the θ of angle of diffraction 2 is 30 ° -90 °, in 2 θ=44.8 °, 65.1 °, at 82.4 °, there is obvious diffraction maximum, compare the mark of iron
Quasi- PDF cards are known that:Just correspond to corresponding 110 crystal face diffraction(Fe-110), 200 crystal face diffraction(Fe-200), 211 crystal faces
Diffraction(Fe-211), the particle for indicating preparation is the nanometer nulvalent iron particle of support type.
Comparative examples 1
A kind of nanometer nulvalent iron particle, is prepared by a method comprising the following steps and forms:
, except modified meerschaum is added without, other are with the step in embodiment 1 for preparation process(2)、(3)、(4), final
To nanometer nulvalent iron particle.
Application Example 1
Using the nanometer nulvalent iron particle of the support type of gained in embodiment 1 to the decabromodiphenyl oxide in water(BDE209)Enter
Row degraded, to remove decabromodiphenyl oxide(BDE209), while with step in embodiment 1(1)Natural sepiolite powder, reality used
Apply step in example 1(1)The nanometer nulvalent iron particle of gained is control in modified meerschaum, the comparative examples 1 of gained, and step is such as
Under:
To 5 parts of 100mL concentration for the BDE209 aqueous solution of 2mg/L is separately added into the negative of final gained in 0.8g embodiments 1
Step in nanometer nulvalent iron particle, the 0.8g embodiments 1 of load type(1)Walked in natural sepiolite powder, 0.8g embodiments 1 used
Suddenly(1)The nanometer nulvalent iron particle of gained in modified meerschaum, the 10.4mg comparative examples 1 of gained, to be not added with any material
It is to carry out reaction 24h under blank control group, normal temperature and pressure, the BDE209 remained in solution is determined using GC/MS in course of reaction,
Then with the reaction time as abscissa, mapped by ordinate of BDE209 residual rates, obtained the load of gained in embodiment 1
Step in nanometer nulvalent iron particle, the embodiment 1 of type(1)In step in natural sepiolite powder, embodiment 1 used(1)Institute
Modified meerschaum, comparative examples 1 in gained nanometer nulvalent iron particle with the reaction time change, to concentration be 2mg/
The removal situation of BDE209 in the BDE209 aqueous solution of L, as a result as shown in Figure 3, the sepiolite in Fig. 3 is walked in representing embodiment 1
Suddenly(1)In natural sepiolite powder used, modified meerschaum represents step in embodiment 1(1)The modified meerschaum of gained, sea
Afrodite loaded nano Zero-valent Iron represents the nanometer nulvalent iron particle of the support type of final gained in embodiment 1, nano zero valence iron
The nanometer nulvalent iron particle of gained in comparative examples 1 is represented, blank is represented and is not added with any material, from figure 3, it can be seen that instead
After answering 24h, the concentration for using the nanometer nulvalent iron particle processing procedure of the support type of final gained in embodiment 1 is 2mg/L's
The residual rate of BDE209 is only 0.05 in the BDE209 aqueous solution, and uses step in embodiment 1(1)Natural sepiolite powder used
Step in end, embodiment 1(1)The nanometer nulvalent iron particle processing procedure of gained in modified meerschaum, the comparative examples 1 of gained
Concentration for 2mg/L the BDE209 aqueous solution in BDE209 residual rate more than 0.6, be indicated above obtained by the present invention bearing
The nanometer nulvalent iron particle of load type is much better than natural sepiolite powder, modified meerschaum to the removal effect of BDE209 in water, receives
Rice nulvalent iron particle.
Embodiment 2
A kind of nanometer nulvalent iron particle of support type, with modified meerschaum as carrier, on the surface of modified meerschaum carrier
And inside is loaded with nanometer nulvalent iron particle, its preparation process removes step(3)In concentration for 0.4mol/L NaBH4It is water-soluble
Liquid concentration is the KBH of 0.4mol/L4The aqueous solution replaces, and other are same as embodiment 1.
Using transmission electron microscope instrument(JEM 2011, Jeol, Japan)To the nanometer of the support type of above-mentioned gained
Nulvalent iron particle is measured, it can be deduced that, in the particle diameter of the nanometer nulvalent iron particle of the area load of modified meerschaum carrier
It is 5-20nm, and the diameter of the nanometer nulvalent iron particle in the internal load of modified meerschaum is about 0.01-1nm.
Embodiment 3
A kind of nanometer nulvalent iron particle of support type, with modified meerschaum as carrier, on the surface of modified meerschaum carrier
And inside is loaded with nanometer nulvalent iron particle, its preparation process specifically includes following steps:
(1), modified meerschaum preparation
To the aqueous hydrochloric acid solution that mass percent concentration is 15% is added in natural sepiolite powder, then at 25-30 DEG C
Stirring 48h is sufficiently mixed, it is neutral then to be washed with deionized deoxygenated water to efflux, then controls temperature to be carried out for 115 DEG C
Dry, then control temperature to be calcined for 320 DEG C, then grind, cross 160 mesh sieves, the powder of gained is modified meerschaum;
Mass percent concentration is the consumption of 15% aqueous hydrochloric acid solution, is calculated in mass ratio, i.e. natural sepiolite powder:
Mass percent concentration be 15% aqueous hydrochloric acid solution be 1:5 ;
(2), the modified meerschaum solution containing iron ion preparation
By 6g steps(1)The modified meerschaum of gained is added to the FeCl that 100mL concentration is 0.2mol/L3In the aqueous solution,
After being sufficiently mixed 12h at room temperature, control rotating speed to be centrifuged for 9000r/min to remove unnecessary iron ion, the precipitation for obtaining
Dissolved with 100ml deionized deoxygenated waters, then with the HCl/water solution that concentration is 0.5mol/L and the NaOH that concentration is 0.5mol/L
It is 3.0 that the aqueous solution adjusts pH, obtains final product the modified meerschaum solution containing iron ion;
Above-mentioned modified meerschaum and concentration are the FeCl of 0.2mol/L3The consumption of the aqueous solution, by modified meerschaum:Concentration is
The FeCl of 0.2mol/L3The aqueous solution is 3g:The ratio of 50ml is calculated;
(3), nano zero-valence ferrous solution preparation
With N2It is protection, under conditions of rotating speed is 320r/min, to step(2)The modified Hai Pao containing iron ion of gained
After controlling drop rate to add reducing agent, addition to finish for 15ml/min in stone solution, continuation controls rotating speed to be stirred for 320r/min
30-60min is mixed, the nano zero-valence ferrous solution of black is obtained final product;
The reducing agent is that concentration is the NaBH of 0.9mol/L4The aqueous solution, the consumption of reducing agent, for calculation in the molar ratio, i.e.,
Boron hydracid radical ion in reducing agent:Iron ion in modified meerschaum solution containing iron ion is 4.5:1;
(4), support type nanometer nulvalent iron particle preparation
Through step(3)The nano zero-valence ferrous solution of the black of gained controls rotating speed to be centrifuged for 9000r/min, gained
Precipitation is washed 4 times with deionized deoxygenated water, straight alcohol successively, then controls temperature to be vacuum dried for 65 DEG C, obtains final product load
The nanometer nulvalent iron particle of type.
Using transmission electron microscope instrument(JEM 2011, Jeol, Japan)To the nanometer of the support type of above-mentioned gained
Nulvalent iron particle is measured, it can be deduced that, in the particle diameter of the nanometer nulvalent iron particle of the area load of modified meerschaum carrier
It is 5-20nm, and the diameter of the nanometer nulvalent iron particle in the internal load of modified meerschaum is about 0.01-1nm.
Embodiment 4
A kind of nanometer nulvalent iron particle of support type, with modified meerschaum as carrier, on the surface of modified meerschaum carrier
And inside is loaded with nanometer nulvalent iron particle, its preparation process removes step(3)In concentration for 0.9mol/L NaBH4It is water-soluble
Liquid concentration is the KBH of 0.9mol/L4The aqueous solution replaces, and other are same as embodiment 3.
Using transmission electron microscope instrument(JEM 2011, Jeol, Japan)To the nanometer of the support type of above-mentioned gained
Nulvalent iron particle is measured, it can be deduced that, in the particle diameter of the nanometer nulvalent iron particle of the area load of modified meerschaum carrier
It is 5-20nm, and the diameter of the nanometer nulvalent iron particle in the internal load of modified meerschaum is about 0.01-1nm.
Embodiment 5
A kind of nanometer nulvalent iron particle of support type, with modified meerschaum as carrier, on the surface of modified meerschaum carrier
And inside is loaded with nanometer nulvalent iron particle, its preparation process specifically includes following steps:
(1), modified meerschaum preparation
To the aqueous hydrochloric acid solution that mass percent concentration is 15% is added in natural sepiolite powder, then at 25-30 DEG C
Stirring 48h is sufficiently mixed, it is neutral then to be washed with deionized deoxygenated water to efflux, then controls temperature to be carried out for 125 DEG C
Dry, then control temperature to be calcined for 330 DEG C, then grind, cross 200 mesh sieves, the powder of gained is modified meerschaum;
Mass percent concentration is the consumption of 15% aqueous hydrochloric acid solution, is calculated in mass ratio, i.e. natural sepiolite powder:
Mass percent concentration be 15% aqueous hydrochloric acid solution be 1:5 ;
(2), the modified meerschaum solution containing iron ion preparation
By 6g steps(1)The modified meerschaum of gained is added to the FeCl that 100mL concentration is 0.3mol/L3In the aqueous solution,
After being sufficiently mixed 12h at room temperature, control rotating speed to be centrifuged for 10000r/min to remove unnecessary iron ion, the precipitation for obtaining
With with the FeCl that concentration is 0.3mol/L3The isometric deionized deoxygenated water dissolving of the aqueous solution, is then 0.5mol/L with concentration
HCl/water solution and concentration for 0.5mol/L the NaOH aqueous solution adjust pH be 3.0, obtain final product the modified meerschaum containing iron ion molten
Liquid;
Above-mentioned modified meerschaum and concentration are the FeCl of 0.3mol/L3The consumption of the aqueous solution, by modified meerschaum:Concentration is
The FeCl of 0.3mol/L3The aqueous solution is 3g:The ratio of 50ml is calculated;
(3), nano zero-valence ferrous solution preparation
With N2It is protection, under conditions of rotating speed is 340r/min, to step(2)The modified Hai Pao containing iron ion of gained
After controlling drop rate to add reducing agent, addition to finish for 20ml/min in stone solution, continuation controls rotating speed to be stirred for 340r/min
30-60min is mixed, the nano zero-valence ferrous solution of black is obtained final product;
The reducing agent is that concentration is the NaBH of 1.5mol/L4The aqueous solution, the consumption of reducing agent, for calculation in the molar ratio, i.e.,
Boron hydracid radical ion in reducing agent:Iron ion in modified meerschaum solution containing iron ion is 5:1;
(4), loaded nano nulvalent iron particle preparation
Through step(3)The nano zero-valence ferrous solution of the black of gained controls rotating speed to be centrifuged for 10000r/min, gained
Precipitation washed 5 times with deionized deoxygenated water, straight alcohol successively, then control temperature to be vacuum dried for 70 DEG C, obtain final product negative
The nanometer nulvalent iron particle of load type.
Using transmission electron microscope instrument(JEM 2011, Jeol, Japan)To the nanometer of the support type of above-mentioned gained
Nulvalent iron particle is measured, it can be deduced that, in the particle diameter of the nanometer nulvalent iron particle of the area load of modified meerschaum carrier
It is 5-20nm, and the diameter of the nanometer nulvalent iron particle in the internal load of modified meerschaum is about 0.01-1nm.
Embodiment 6
A kind of nanometer nulvalent iron particle of support type, with modified meerschaum as carrier, on the surface of modified meerschaum carrier
And inside is loaded with nanometer nulvalent iron particle, its preparation process removes step(3)In concentration for 1.5mol/L NaBH4It is water-soluble
Liquid concentration is the KBH of 1.5mol/L4The aqueous solution replaces, and other are same as embodiment 5.
Using transmission electron microscope instrument(JEM 2011, Jeol, Japan)To the nanometer of the support type of above-mentioned gained
Nulvalent iron particle is measured, it can be deduced that, in the particle diameter of the nanometer nulvalent iron particle of the area load of modified meerschaum carrier
It is 5-20nm, and the diameter of the nanometer nulvalent iron particle in the internal load of modified meerschaum is about 0.01-1nm.
In sum, the nanometer nulvalent iron particle of a kind of support type of the invention, with modified meerschaum as carrier, modified
The surface and inside of sepiolite carrier are loaded with nanometer nulvalent iron particle, the particle diameter of the nano zero-valence iron ion that surface is loaded
Distribution is 5-20nm, and the diameter of the nanometer nulvalent iron particle of sepiolite internal load is about 0.01-1nm;And going
Depollution thing decabromodiphenyl oxide aspect, the nanometer nulvalent iron particle of support type is much better than sepiolite to its removal effect, is modified
Sepiolite and unsupported nano zero valence iron.
The above is only the citing of embodiments of the present invention, it is noted that for the ordinary skill of the art
For personnel, on the premise of the technology of the present invention principle is not departed from, some improvement can also be made, these improvement also should be regarded as this
The protection domain of invention.