CN105670635B - Application in Ni nanoparticle/Fe- biology carbon composite preparation method and its in situ reparation polybrominated diphenyl ethers contaminated soil - Google Patents
Application in Ni nanoparticle/Fe- biology carbon composite preparation method and its in situ reparation polybrominated diphenyl ethers contaminated soil Download PDFInfo
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Abstract
The application in polybrominated diphenyl ethers contaminated soil is repaired the invention discloses Ni nanoparticle/Fe- biology carbon composite preparation method and its in situ.Molysite or ferrous salt and polyvinylpyrrolidone are dissolved in ethanol water by the present invention, are mixed, are added charcoal particle, stir and evenly mix, obtain solution A；Ethanol water containing reducing agent is added in solution A, after being stirred to react completely, reaction product is isolated, is added in ethanol water after washes clean, obtains solution B；Ethanol water containing nickel salt is added drop-wise in solution B, after being stirred to react completely, resulting material is isolated, obtains Ni nanoparticle/Fe- biology carbon composite after washing, drying.It is prepared by the present invention that Ni nanoparticle/Fe bimetal granule is carried on charcoal, further improve the mobility of nano particle.Stability and dispersibility are conducive to soil in-situ reparation；It can be used in the reparation of the PBDEs contaminated soil of higher concentration, remediation efficiency is high.
Description
Technical field
The invention belongs to environmental pollution improvements and recovery technique field, in particular to a kind of to repair Biphenyl Ether contaminated soil original more
The preparation method and applications of position repair materials.
Background technique
Polybrominated diphenyl ethers (Polybrominated diphenyl ethers, PBDEs) is that a kind of typical bromine system is fire-retardant
Agent is widely used in textile, electronics, electric appliance, circuit board, petroleum, digs up mine, builds since it is with excellent flame retardant property
In the various industrial products such as material, paint and daily product.It is different by brominated flame retardant of the chemical bond in conjunction with product from other,
PBDEs is only adulterated in the product in a manner of being simply mixed, therefore is easier during producing, using and disposing from production
It can be discharged into environment in product, and as the migration of atmosphere and water body causes to pollute extensively.Polybrominated diphenyl ethers (Polybrominated
Diphenyl ethers, PBDEs) one kind as brominated flame retardant, it is added as POPs into " Si Degeer in May, 2009
Rub pact ", it is a kind of global environment organic pollutant with ecological risk.Due to the octanol-water disposition of the pollutant
Number (Kow) is high, and hydrophobicity is strong, is easily transferred in soil in conjunction with suspended particulate substance and soil particle, therefore soil is PBDEs
Remaining important medium in the environment.It is reported that the content of the polybrominated diphenyl ethers in more than 30 years of past in environment is with index side
Formula increases, and 67000 tonnes of polybrominated diphenyl ethers can about be generated by electronic waste by, which being often only, can be discharged into environment.China is generation
Maximum electronic waste processing ground, the electronic waste in the whole world 50%~80% enter Asia by legally or illegally approach in boundary,
Wherein 90% enters China.It is detected according to Leung et al. studies have shown that the plastics in your small island electronics dismantling point burn ground and stack
PBDEs in ground soil is at concentrations up to arriving 1155ng/g.A large amount of toxicological studies show PBDEs to mammal, fish even people
Body has a variety of genotoxic potentials, such as hepatotoxicity, genotoxicity, neurotoxicity.Therefore effective, feasible reparation how is developed
The technology of PBDEs contaminated soil is extremely urgent.
It is aerobe method including oxidizing process, wet currently, about there are many reports of the degradation technique of PBDEs in liquid phase
Method oxidizing process, hydro-thermal method；The anaerobic biological process of reduction method, electrolysis method, metal deoxidization, nano-TiO2Photocatalytic method etc..And it closes
The report of the reparation degradation technique of polybrominated diphenyl ethers is very few in soil, predominantly microbial degradation metabolism and Plant Transformation, electricity
Dynamic recovery technique and electromagnetism are combined recovery technique.However the limitation that these restorative procedures have it to apply, including repair time
Too long, low efficiency spends high, reaction condition requirement is harsher etc..Since nano zero valence iron has big specific surface area, good
The characteristics such as reactive, powerful reducing power and low cost, have become the hot spot of domestic and international in-situ immobilization research.Although receiving
Rice Zero-valent Iron oneself be successfully applied to the pollutants such as a variety of organohalogen compounds difficult to degrade, antibiotic, nitrate nitrogen and heavy metal
Removal, but it is easily reunited and is oxidized due to interfacial effect and small-size effect, and then leads to specific surface area and degradation
The reduction of efficiency.The iron ion that Zero-valent Iron discharges in repair process simultaneously may cause the excessively high meeting shadow of iron content in soil
Ring soil fertility.Therefore, for these problems, we are in early period using polybrominated biphenyls in Ni nanoparticle/Fe particle rehabilitating soil
It proposes to carry out effective modification to it with charcoal on the basis of ether pollution, to improve the treatability to polybrominated biphenyls
Can, widen its application range.On the one hand the dispersed stability and mobility that can effectively improve nano particle, on the other hand mention
High soil fertility, the recovery for productivity after contaminated soil remediation provide advantage.Simultaneously as charcoal has cation
The features such as exchange capacity is big, surface has negative electrical charge and oxygen-containing functional group abundant, can be to being precipitated in nano material reaction process
Ni, Fe ion and the catabolite of BDE209 carry out absorption fixation, can effectively slow down secondary pollution.Further, since biological
The content of organic matter of charcoal is very high, and has porous structure, and charcoal is added and also helps the nutrition for keeping soil and moisture, increases
The yield of crop.
It is that maximum electronic waste handles ground in the world in view of China, PBDEs contaminated soil area is larger, needs exploitation one
Economic, efficient, the practical Treatment process of kind.
Summary of the invention
The purpose of the present invention is to provide a kind of Ni nanoparticle/Fe- biology carbon composite preparation method and its in situ
Repair the application in polybrominated diphenyl ethers contaminated soil.
The technical solution used in the present invention is:
A kind of preparation method of Ni nanoparticle/Fe- biology carbon composite, including following preparation method:
1) molysite or ferrous salt and polyvinylpyrrolidone are dissolved in ethanol water, mix, adds charcoal
Grain, stirs and evenly mixs, obtains solution A；
2) ethanol water containing reducing agent is added in solution A, after being stirred to react completely, isolates reaction product,
It is added in ethanol water after washes clean, obtains solution B；
3) ethanol water containing nickel salt is added drop-wise in solution B, after being stirred to react completely, isolates resulting material, wash
Ni nanoparticle/Fe- biology carbon composite is obtained after washing, drying.
Further, the concentration of ethyl alcohol is 20~50%v/v in the ethanol water.
Further, ferro element in the molysite or ferrous salt, polyvinylpyrrolidone, charcoal mass ratio be 1:
(0.5~2): (0.5~5).
Further, after charcoal particle being added in step 1), 40~80min is stirred and evenly mixed with 300~600rpm, is obtained
Solution A.
Further, in step 2), under the conditions of protective atmosphere, the ethanol water containing reducing agent is added to solution
In A, side is stirred when addition.
Further, the molar ratio of nickel element and Fe element is (0.5~1.5) in the step 3) nickel salt: 1.
Further, the charcoal the preparation method comprises the following steps: by agricultural wastes it is broken after, it is dry, be put into crucible, set
In the Muffle furnace for having protective atmosphere, be warming up to 600~800 DEG C with 15~25 DEG C/min, continue at such a temperature pyrolysis 1~
3h is cooled to room temperature, takes out black solid, grinding, sieving.
Further, the agricultural wastes are bagasse.
One Ni nanoparticle/application of the Fe- biology carbon composite in polybrominated diphenyl ethers contaminated soil in-situ immobilization.
A kind of method of in-situ immobilization polybrominated diphenyl ethers contaminated soil, the Ni nanoparticle of above-mentioned preparation/Fe- charcoal is compound
Material is added in polybrominated diphenyl ethers contaminated soil, and water is added to mix；Wherein, Ni nanoparticle/Fe- biology carbon composite
Quality is 0.02 times or more of contaminated soil.
The beneficial effects of the present invention are:
Repair materials prepared by the present invention can be used for the in-situ immobilization of PBDEs contaminated soil, and remediation efficiency is high.Specifically
There are following several respects:
(1) prepared by the present invention that Ni nanoparticle/Fe bimetal granule is carried on charcoal, further improve nanometer
The mobility of grain.Stability and dispersibility are conducive to soil in-situ reparation.
(2) charcoal prepared by the present invention has large specific surface area, is rich in the oxygen-containing functional groups such as carboxyl, carbonyl and hydroxyl,
The features such as cation exchange capacity (CEC) is big, surface has negative electrical charge, can to Ni, Fe ion being precipitated in nano material reaction process with
And the catabolite of BDE209 carries out absorption fixation, can effectively slow down secondary pollution.Simultaneously as the content of organic matter of charcoal
It is very high, and there is porous structure, charcoal is added and also helps the nutrition for keeping soil and moisture, increases the yield of crop.
(3) charcoal of the present invention is prepared using discarded bagasse, and the material preparation cost is low, favorably
In the recycling of resource, turn waste into wealth, there are great economic results in society.
(4) preparation method of restoration materials of the present invention is simple, repair time is short, easy to operate, convenient to carry out.
(5) repair materials of the present invention are suitable for in-situ immobilization, can be used in the PBDEs contaminated soil of higher concentration
Reparation, remediation efficiency is high.
Detailed description of the invention
Fig. 1 is the SEM image of bimetallic nano ferronickel solid particle prepared by embodiment 1；
Fig. 2 is the SEM image of charcoal prepared by embodiment 2；
Fig. 3 is the SEM image of composite material prepared by embodiment 3；
Fig. 4 is the TEM image of composite material prepared by embodiment 3；
Fig. 5 is remediation efficiency of the material to PBDEs in soil of the mass ratio of different ferro elements and charcoal；
Fig. 6 is remediation efficiency of the Ni nanoparticle/Fe- biology carbon composite to PBDEs in soil of different dosages；
Fig. 7 is remediation efficiency of the Ni nanoparticle of the present invention/Fe- biology carbon composite to PBDEs in different water cut soil；
Fig. 8 is comparison of three kinds of different materials to the remediation efficiency of PBDEs in soil.
Specific embodiment
A kind of preparation method of Ni nanoparticle/Fe- biology carbon composite, including following preparation method:
1) molysite or ferrous salt and polyvinylpyrrolidone are dissolved in ethanol water, mix, adds charcoal
Grain, stirs and evenly mixs, obtains solution A；
2) ethanol water containing reducing agent is added in solution A, after being stirred to react completely, isolates reaction product,
It is added in ethanol water after washes clean, obtains solution B；
3) ethanol water containing nickel salt is added drop-wise in solution B, after being stirred to react completely, isolates resulting material, wash
Ni nanoparticle/Fe- biology carbon composite is obtained after washing, drying.
Preferably, the ethanol water is the ethanol water through deoxidation treatment.
Preferably, the concentration of ethyl alcohol is 20~50%v/v in the ethanol water.
Preferably, ferro element in the molysite or ferrous salt, polyvinylpyrrolidone, charcoal mass ratio be 1:(0.5
~2): (0.5~5).
Preferably, the ferrous salt is ferrous sulfate.
Preferably, the polyvinylpyrrolidone is at least one of polyvinylpyrrolidone K25, K30, K60.
Preferably, after charcoal particle being added in step 1), 40~80min is stirred and evenly mixed with 300~600rpm, is obtained molten
Liquid A.
Preferably, reducing agent described in step 2) is negative hydrogen reduction agent.
It is furthermore preferred that the reducing agent is sodium borohydride.
It is furthermore preferred that the molar ratio of the sodium borohydride and Fe element is (1~3): 1.
Preferably, in step 2), under the conditions of protective atmosphere, the ethanol water containing reducing agent is added to solution A
In, side is stirred when addition.
Preferably, the step 3) nickel salt is nickel chloride.
Preferably, the molar ratio of nickel element and Fe element is (0.5~1.5) in the step 3) nickel salt: 1.
Preferably, step 2) and step 3) time being stirred to react are 20~40min, mixing speed is 300~
600rpm。
Preferably, the step 3) drying is vacuum drying, and drying time is 6~10h.
Preferably, the charcoal is the charcoal that can cross 60~180 meshes.
Preferably, the charcoal the preparation method comprises the following steps: by agricultural wastes it is broken after, it is dry, be put into crucible, be placed in
Have in the Muffle furnace of protective atmosphere, be warming up to 600~800 DEG C with 15~25 DEG C/min, continue 1~3h of pyrolysis at such a temperature,
It is cooled to room temperature, takes out black solid, grinding, sieving.
Preferably, the agricultural wastes are bagasse.
Preferably, the protective atmosphere is at least one of nitrogen, helium, neon, argon gas, xenon.
Application of the Ni nanoparticle described above/Fe- biology carbon composite in polybrominated diphenyl ethers contaminated soil in-situ immobilization.
A kind of method of in-situ immobilization polybrominated diphenyl ethers contaminated soil, by the Ni nanoparticle of any of the above-described preparation/Fe- charcoal
Composite material is added in polybrominated diphenyl ethers contaminated soil, and water is added to mix；Wherein, Ni nanoparticle/Fe- charcoal is compound
Quality of materials is 0.02 times or more of contaminated soil.
Preferably, the Ni nanoparticle/Fe- biology carbon composite quality is 0.06~0.1 times of contaminated soil.
Preferably, the dosage of the water is to make soil moisture content 50%~90%.
The present invention is further illustrated combined with specific embodiments below, and however, it is not limited to this.
The preparation method of 1 bimetallic nano ferronickel solid particle of embodiment
(1) ferrous salt and polyvinylpyrrolidone are dissolved in the ethanol water through deoxidation treatment, are stirred.
(2) sodium borohydride is added drop-wise under agitation in (1) described solution dropwise, nano zero-valence ferrous solution is made,
Washing.
(3) ethanol solution is added disperses nano zero valence iron.Meanwhile a certain amount of nickel salt ethanol water is added, it vibrates
30min.It allows Ni to deposit to iron surface, bimetallic nano Ni/Fe particle is made.
Fig. 1 is the SEM image of bimetallic nano Ni/Fe prepared by embodiment 1, as seen from Figure 1, individual nano nickel
Iron double metal particle, agglomeration are serious.
The preparation method of 2 charcoal of embodiment
(1) dry: dry at 105 DEG C after the bagasse of collection is shredded.
(2) it is pyrolyzed: the bagasse after weighing being put into crucible and is placed in Muffle furnace, under a nitrogen atmosphere, set final temperature
It is 600 DEG C, is warming up to after the temperature range with 20 DEG C/min and continues to carbonize 2h.It takes out, grinds after Muffle furnace is cooled to room temperature
Afterwards, 60~120 meshes are crossed to be sealed.
Fig. 2 is charcoal SEM image prepared by embodiment 2.As seen from Figure 2, charcoal manufactured in the present embodiment has
Pore structure abundant.
3 Ni nanoparticles of embodiment/Fe- biology carbon composite preparation method
1) 100ml 0.1mol/L FeSO is prepared with the ethanol solution of 20%v/v4·7H2The solution of O, adds polyethylene
Pyrrolidones K25 (mass ratio of polyvinylpyrrolidone K25 and Fe element is 1:1), stirs 5min with the speed of 300rpm, makes
Dissolution mix, then charcoal particle prepared by embodiment 2 (mass ratio of Fe element and charcoal is 1:1) is added thereto,
1h is stirred with the speed of 500rpm, dissolution is allowed to and mixes, obtain solution A；
2) sodium borohydride solution that 50ml 0.3mol/L is prepared with the ethanol solution of 20%v/v, at protective atmosphere (nitrogen)
Under, side stirring condition is added drop-wise in solution A dropwise, continues to be stirred to react 30min with the speed of 500rpm, then with magnetic method point
From the ethanol water of addition 50ml 20%, obtains solution B after washing.
3) NiCl of 50ml 0.2mol/L is prepared with the ethanol solution of 20%v/v2·6H2O solution, it is fast under agitation
Speed is added in solution B 500rpm and stirs 30min, 8h is dried in vacuo after washing to get Ni nanoparticle/Fe- biology carbon composite,
It can be used for the in-situ immobilization of PBDEs contaminated soil.
Fig. 3, Fig. 4 are respectively Ni nanoparticle/Fe- biology carbon composite SEM image and TEM image prepared by embodiment 3.
The phenomenon that nanoscale bimetallic particles can be observed by Fig. 3 and be attached to biological carbon surface, and significantly improve reunion.As shown in Figure 4,
Gained Ni nanoparticle/Fe- biology carbon composite partial size of the invention is 20~70nm.
4 Ni nanoparticles of embodiment/Fe- biology carbon composite preparation method
1) 100ml 0.1mol/L FeSO is prepared with the ethanol solution of 50%v/v4·7H2The solution of O, adds polyethylene
Pyrrolidones K30 (mass ratio of PVP K30 and Fe element is 0.5:1), stirs 5min with the speed of 300rpm,
It is allowed to dissolution to mix, then it is added in charcoal particle (mass ratio of Fe element and charcoal is 1:0.5) prepared by embodiment 2
In, 40min is stirred with the speed of 300rpm, dissolution is allowed to and mixes, obtain solution A；
2) sodium borohydride solution that 50ml 0.2mol/L is prepared with the ethanol solution of 50%v/v, at protective atmosphere (nitrogen)
Under, side stirring condition is added drop-wise in solution A dropwise, continues to be stirred to react 40min with the speed of 300rpm, then with magnetic method point
From the ethanol water of addition 50ml 50%, obtains solution B after washing.
3) NiCl of 50ml 0.1mol/L is prepared with the ethanol solution of 50%v/v2·6H2O solution, it is fast under agitation
Speed is added to 600rpm in solution B and stirs 20min, isolates resulting material, and 8h is dried in vacuo after washing to get Ni nanoparticle/Fe-
Biological carbon composite can be used for the in-situ immobilization of PBDEs contaminated soil.
5 Ni nanoparticles of embodiment/Fe- biology carbon composite preparation method
1) 100ml 0.1mol/L FeSO is prepared with the ethanol solution of 30%v/v4·7H2The solution of O, adds polyethylene
Pyrrolidones K60 (mass ratio of polyvinylpyrrolidone K60 and Fe element is 2:1), stirs 5min with the speed of 300rpm, makes
Dissolution mix, then it is added in charcoal particle prepared by embodiment 2 (mass ratio of Fe element and charcoal is 1:1.5)
In, 80min is stirred with the speed of 600rpm, dissolution is allowed to and mixes, obtain solution A；
2) sodium borohydride solution that 50ml 0.6mol/L is prepared with the ethanol solution of 30%v/v, at protective atmosphere (nitrogen)
Under, side stirring condition is added drop-wise in solution A dropwise, continues to be stirred to react 20min with the speed of 600rpm, then with magnetic method point
From the ethanol water of addition 50ml 40%, obtains solution B after washing.
3) NiCl of 50ml 0.3mol/L is prepared with the ethanol solution of 40%v/v2·6H2O solution, it is fast under agitation
Speed is added to 600rpm in solution B and stirs 20min, isolates resulting material, and 8h is dried in vacuo after washing to get Ni nanoparticle/Fe-
Biological carbon composite can be used for the in-situ immobilization of PBDEs contaminated soil.
6 Ni nanoparticles of embodiment/Fe- biology carbon composite preparation method
1) 100ml 0.1mol/L FeSO is prepared with the ethanol solution of 30%v/v4·7H2The solution of O, adds polyethylene
Pyrrolidones K60 (mass ratio of polyvinylpyrrolidone K60 and Fe element is 1:1), stirs 5min with the speed of 300rpm, makes
Dissolution mix, then charcoal particle prepared by embodiment 2 (mass ratio of Fe element and charcoal is 1:2) is added thereto,
60min is stirred with the speed of 400rpm, dissolution is allowed to and mixes, obtain solution A；
2) sodium borohydride solution that 50ml 0.4mol/L is prepared with the ethanol solution of 40%v/v, at protective atmosphere (nitrogen)
Under, side stirring condition is added drop-wise in solution A dropwise, continues to be stirred to react 20min with the speed of 600rpm, then with magnetic method point
From the ethanol water of addition 50ml 40%, obtains solution B after washing.
3) NiCl of 50ml 0.3mol/L is prepared with the ethanol solution of 40%v/v2·6H2O solution, it is fast under agitation
Speed is added to 500rpm in solution B and stirs 30min, isolates resulting material, and 6h is dried in vacuo after washing to get Ni nanoparticle/Fe-
Biological carbon composite can be used for the in-situ immobilization of PBDEs contaminated soil.
7 Ni nanoparticles of embodiment/Fe- biology carbon composite preparation method
1) 100ml 0.1mol/L FeSO is prepared with the ethanol solution of 30%v/v4·7H2The solution of O, adds polyethylene
Pyrrolidones K60 (mass ratio of polyvinylpyrrolidone K60 and Fe element is 1:1), stirs 5min with the speed of 300rpm, makes
Dissolution mix, then charcoal particle prepared by embodiment 2 (mass ratio of Fe element and charcoal is 1:3) is added thereto,
60min is stirred with the speed of 400rpm, dissolution is allowed to and mixes, obtain solution A；
2) sodium borohydride solution that 50ml 0.3mol/L is prepared with the ethanol solution of 40%v/v, at protective atmosphere (nitrogen)
Under, side stirring condition is added drop-wise in solution A dropwise, continues to be stirred to react 20min with the speed of 600rpm, then with magnetic method point
From the ethanol water of addition 50ml 40%, obtains solution B after washing.
3) NiCl of 50ml 0.2mol/L is prepared with the ethanol solution of 40%v/v2·6H2O solution, it is fast under agitation
Speed is added in solution B 500rpm and stirs 30min, isolates resulting material, be dried in vacuo after washing 10h to get Ni nanoparticle/
Fe- biology carbon composite, can be used for the in-situ immobilization of PBDEs contaminated soil.
8 Ni nanoparticles of embodiment/Fe- biology carbon composite preparation method
1) 100ml 0.1mol/L FeSO is prepared with the ethanol solution of 30%v/v4·7H2The solution of O, adds polyethylene
Pyrrolidones K60 (mass ratio of polyvinylpyrrolidone K60 and Fe element is 1:1), stirs 5min with the speed of 300rpm, makes
Dissolution mix, then charcoal particle prepared by embodiment 2 (mass ratio of Fe element and charcoal is 1:5) is added thereto,
60min is stirred with the speed of 400rpm, dissolution is allowed to and mixes, obtain solution A；
2) sodium borohydride solution that 50ml 0.3mol/L is prepared with the ethanol solution of 40%v/v, at protective atmosphere (nitrogen)
Under, side stirring condition is added drop-wise in solution A dropwise, continues to be stirred to react 20min with the speed of 600rpm, then with magnetic method point
From the ethanol water of addition 50ml 40%, obtains solution B after washing.
3) NiCl of 50ml 0.2mol/L is prepared with the ethanol solution of 40%v/v2·6H2O solution, it is fast under agitation
Speed is added to 500rpm in solution B and stirs 30min, isolates resulting material, and 8h is dried in vacuo after washing to get Ni nanoparticle/Fe-
Biological carbon composite can be used for the in-situ immobilization of PBDEs contaminated soil.
A kind of method of the in-situ immobilization polybrominated diphenyl ethers contaminated soil of embodiment 9
Ni nanoparticle/Fe- biology carbon composite prepared by embodiment 3 is added in polybrominated diphenyl ethers contaminated soil,
Water mixing is added to make soil moisture content 50%~90%；
Wherein, Ni nanoparticle/Fe- biology carbon composite quality is 0.02 times or more (preferably 0.06~0.1 of contaminated soil
Times).
Further effect detection is made to Ni nanoparticle prepared by the present invention/Fe- biology carbon composite below.
One, in-situ immobilization PBDEs contaminated soil is tested
The preparation of manual simulation's PBDEs contaminated soil:
1) laboratory test is used, is to pick up from the unpolluted soil of Guangzhou university city for examination soil, removes after acquisition withered
Plant residues and the soil animals such as branch fallen leaves root system, air-dry, cross 60 meshes, sealed storage is spare in drier.
2) BDE209 (decabromodiphenyl oxide) stock solution that 200mg/L is prepared with tetrahydrofuran, weighs above-mentioned soil 50g in burning
In cup, a certain amount of BDE209 stock solution is pipetted, required concentration is diluted to tetrahydrofuran, is added in above-mentioned soil；
3) it is stirred uniformly in draught cupboard using magnetic stirring apparatus, evaporates into antecedent soil moisture completely to tetrahydrofuran,
As pollute soil sample；
4) soil sample is ground, is placed in sealing in wide-mouth bottle and is kept in dark place；
5) after soil pollution is extracted using ultrasonic extraction method, supernatant is poured out in centrifugation, with 0.22 μm of membrane filtration,
With the content of BDE209 in high effective liquid chromatography for measuring extract liquor, the content of BDE209 is 8.6mg/kg in final soil, i.e.,
For PBDEs contaminated soil.
Experiment 1: Ni nanoparticle/Fe- charcoal composite repair contaminated soil ability of different embodiment preparations
The contaminated soil for weighing the above-mentioned preparation of 2g is added in reaction flask, deionized water is added by the solid-to-liquid ratio of 1:2, respectively again
Be added 0.12g embodiment 3~7 prepare Ni nanoparticle/Fe- biology carbon composite, embodiment 3~7 prepare composite material in
The mass ratio of Fe element (i.e. nano zero valence iron) and charcoal is followed successively by 1:1,1:0.5,1:1.5,1:2 and 1:3, covers polytetrafluoro
Ethylene lid, shakes on shaking table, and the speed of shaking table is 300r/min, and temperature is 25 DEG C, takes out sample bottle after reacting 72h, adds
Enter suitable acetonitrile solvent concussion 30min, then carry out ultrasonic extraction, the ultrasonic extraction time is 30min.It is repeated twice, then
Then centrifugation step, centrifugal rotational speed 2000r/min, centrifugal force 716g, time 8min are carried out.Merge extract liquor twice,
0.22 μm of filtering with microporous membrane of 2mL is taken, HPLC analyzes the concentration of BDE209.
Testing result is as shown in figure 5, wherein mFe 0:mBCIndicate the mass ratio of ferro element (i.e. nano zero valence iron) and charcoal,
There it can be seen that as the material (m of the preparation of example example 3Fe 0:mBCMass ratio is 1:1), the removal rate highest of BDE209 reaches
86.32%, compare 4 material (m of embodimentFe 0:mBCMass ratio be 1:0.5) when increase 6.67%；Work as mFe:mBCMass ratio
After reaching 1:1, with the increase of charcoal, composite material is in downward trend to the removal rate of BDE209, this may be due to
Excessive charcoal occupies the active site of bimetallic nano, hinders contact of the BDE209 with bimetallic nano, causes to repair
Multiple efficiency reduces, therefore best m in composite materialFe 0:mBCMass ratio be 1:1.
Test influence of the amount ratio of 2 Ni nanoparticles/Fe- biology carbon composite and contaminated soil to soil remediation
The contaminated soil for weighing the above-mentioned preparation of 2g is added in reaction flask, deionized water is added by the solid-to-liquid ratio of 1:2, then distinguish
Ni nanoparticle/Fe- biology carbon composite prepared by 0g, 0.04g, 0.08g, 0.12g, 0.16g, 0.2g embodiment 3 is added, covers
Polytetrafluoroethylene (PTFE) lid, shakes on shaking table, and the speed of shaking table is 300r/min, and temperature is 25 DEG C, takes out sample after reacting 72h
Suitable acetonitrile solvent concussion 30min is added in bottle, then carries out ultrasonic extraction, and the ultrasonic extraction time is 30min.It is repeated twice,
It is then followed by centrifugation step, centrifugal rotational speed 2000r/min, centrifugal force 716g, time 8min.Merging extracts twice
Liquid, takes 0.22 μm of filtering with microporous membrane of 2mL, and HPLC analyzes the concentration of BDE209.
Testing result is as shown in fig. 6, with the increase of composite material dosage, the removal of BDE209 it can be seen from
Rate is in increasing trend.When the dosage of composite material is 0.02g/g, the removal rate of BDE209 only has 43.81%, with adding
When amount increases to 0.06g/g, the removal rate of BDE209 has reached 86.21%, increases 42.4%；Continue growing composite material
When dosage is to 0.1g/g, BDE20 removal rate is 94.83%, when compared to dosage being 0.06g/g, merely adds 8.62%,
Increase unobvious, therefore selects optimum dosage for 0.06g/g.
Test influence of 3 different water cuts to repairing polluted soil
The removal effect of PBDEs, determines optimum moisture content in soil to study different water cut, 4 groups of this experimental setup
Experimental group, every group weighs 2.00g soil, and three Duplicate Samples, preparing soil moisture content respectively is 33%, 50%, 66.7%, 71%
Reaction system, respectively by 0.06g/g dosage be added embodiment 3 prepare Ni nanoparticle/Fe- biology carbon composite,
With speed for concussion reaction 72h on the shaking table of 300r/min after, take out sample bottle be added acetonitrile solution carry out ultrasonic extraction after, from
The heart, then takes 0.22 μm of filtering with microporous membrane of 2mL, and HPLC analyzes the concentration of BDE209.
Testing result is as shown in fig. 7, with the increase of moisture content it can be seen from, the removal rate of BDE209 in soil
Increase with the increase of soil moisture content.When soil moisture content is 33%, removal rate of the composite material to BDE209 in soil
Only 33.74%, when moisture content increases to 50%, removal rate 45.75%；Continue growing moisture content be 66.7% when, go
Except rate reaches 86.39%.When moisture content is 71%, removal rate continues to increase to 91.29%.Due to time of BDE209 in soil
Yield is influenced by soil moisture content, therefore selects optimum moisture content for 66.7%.
Test comparison of 4 three kinds of different materials to the remediation efficiency of PBDEs in soil
For the charcoal and prepared by the present invention for probing into Ni nanoparticle/Fe bimetallic of the preparation of embodiment 1, prepared by embodiment 2
Influence of the composite material to the remediation efficiency of PBDEs in soil selects three kinds of materials to repair PBDEs contaminated soil respectively.It is fixed
The Ni nanoparticle that the bimetallic dosage of Ni nanoparticle/Fe is 0.06g/g, the dosage of charcoal is 0.06g/g, prepared by embodiment 3/
The compound dosage of Fe- charcoal is 0.06g/g, and soil moisture content 66.7% carries out anti-according to above-mentioned 3 the method for experiment
It answers.
Experimental results are shown in figure 8, there it can be seen that no matter material all has certain reparation to the BDE209 in soil
Effect, and with the increase of repair time, material increases accordingly the remediation efficiency of BDE209 in soil.But to three kinds of materials
For, it is finally charcoal that composite repair effect is best, followed by Ni nanoparticle/Fe bimetallic.After repairing 72h, three kinds of materials
Material is 86.32%, 63.91%, 16.28% respectively to the removal effect of BDE209 in soil.Compare the reparation effect of three kinds of materials
Fruit, hence it is evident that find out that the repairing effect of composite material is best.Show that composite material has given full play to Ni nanoparticle/both Fe and charcoal
Advantage, enhance material to the repairing effect of PBDEs in soil.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. a kind of Ni nanoparticle/Fe- biology carbon composite preparation method, it is characterised in that: including following preparation method:
1) molysite or ferrous salt and polyvinylpyrrolidone are dissolved in ethanol water, mix, adds charcoal particle, stir
Mixing is mixed, solution A is obtained；
2) ethanol water containing reducing agent is added in solution A, after being stirred to react completely, isolates reaction product, washed
It is added in ethanol water after clean, obtains solution B；
3) ethanol water containing nickel salt is added drop-wise in solution B, after being stirred to react completely, isolates resulting material, washing is done
Ni nanoparticle/Fe- biology carbon composite is obtained after dry；
Wherein, the charcoal the preparation method comprises the following steps: by agricultural wastes it is broken after, it is dry, be put into crucible, be placed in protection
In the Muffle furnace of atmosphere, 600~800 DEG C are warming up to 15~25 DEG C/min, continues 1~3 h of pyrolysis at such a temperature, is cooled to
Room temperature takes out black solid, and grinding, sieving, the agricultural wastes are bagasse, and the ethanol water is through deoxidation
The ethanol water of processing, ferro element in the molysite or ferrous salt, polyvinylpyrrolidone, charcoal mass ratio be 1:
(0.5~2): (0.5~5), the molar ratio of nickel element and Fe element is (0.5~1.5) in nickel salt described in step 3): 1.
2. according to the method described in claim 1, it is characterized by: the concentration of ethyl alcohol is 20~50% in the ethanol water
v/v。
3. according to the method described in claim 1, it is characterized by: after charcoal particle is added in step 1), with 300~
600rpm stirs and evenly mixs 40~80min, obtains solution A.
4. according to the method described in claim 1, it is characterized by: under the conditions of protective atmosphere, reduction will be contained in step 2
The ethanol water of agent is added in solution A, and side is stirred when addition.
5. Ni nanoparticle/Fe- biology carbon composite of any method preparation of Claims 1 to 4 is in polybrominated diphenyl ethers dirt
Contaminate the application in soil in-situ reparation.
6. a kind of method of in-situ immobilization polybrominated diphenyl ethers contaminated soil, it is characterised in that: by any preparation of Claims 1 to 4
Ni nanoparticle/Fe- biology carbon composite be added in polybrominated diphenyl ethers contaminated soil, add water to mix；Wherein, it receives
Rice Ni/Fe- biology carbon composite quality is 0.02 times or more of contaminated soil.
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| CN106186163A (en) * | 2016-08-15 | 2016-12-07 | 华南师范大学 | A kind of preparation method and application of PBDE pollution waters restoration material |
| CN107243509A (en) * | 2017-07-04 | 2017-10-13 | 江苏东珠景观股份有限公司 | A kind of soil remediation method suitable for landscape ecosystem |
| CN107716942B (en) * | 2017-09-04 | 2019-08-30 | 绍兴文理学院 | The method that ferronickel bimetallic material is prepared in situ using nickel ion pollutant effluents is repaired |
| CN110003912B (en) * | 2019-04-18 | 2020-11-24 | 江西师范大学 | Modification method of biochar and application of biochar in soil remediation |
| CN110560470A (en) * | 2019-09-04 | 2019-12-13 | 四川大学 | Biochar for repairing vanadium-contaminated soil and preparation method and application thereof |
| CN111117643A (en) * | 2020-01-09 | 2020-05-08 | 江西省地质环境监测总站(鄱阳湖生态环境研究所) | Soil Cd and Pb repairing agent and preparation method thereof |
| US11702374B2 (en) * | 2020-06-17 | 2023-07-18 | Iowa State University Research Foundation, Inc. | Biochar product, its use in fertilizers, and methods of making the biochar |
| CN115960611B (en) * | 2022-12-29 | 2023-10-31 | 北京建工环境修复股份有限公司 | Contaminated soil restoration agent and preparation method and application thereof |
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