CN105670635A - Preparation method of nano Ni/Fe-biochar composite material and application of nano Ni/Fe-biochar composite material in in-situ restoration of polybrominated diphenyl ether polluted soil - Google Patents
Preparation method of nano Ni/Fe-biochar composite material and application of nano Ni/Fe-biochar composite material in in-situ restoration of polybrominated diphenyl ether polluted soil Download PDFInfo
- Publication number
- CN105670635A CN105670635A CN201610131446.7A CN201610131446A CN105670635A CN 105670635 A CN105670635 A CN 105670635A CN 201610131446 A CN201610131446 A CN 201610131446A CN 105670635 A CN105670635 A CN 105670635A
- Authority
- CN
- China
- Prior art keywords
- charcoal
- solution
- preparation
- nano
- nanoparticle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Soil Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a preparation method of a nano Ni/Fe-biochar composite material and application of the nano Ni/Fe-biochar composite material in in-situ restoration of polybrominated diphenyl ether polluted soil. The preparation method comprises the following steps: dissolving iron salt or ferrous salt and polyvinylpyrrolidone in an ethanol water solution, uniformly mixing, adding biochar particles, and uniformly mixing to obtain a solution A; adding a reducer-containing ethanol water solution into the solution A, stirring to react completely, separating out the reaction product, washing, and adding into an ethanol water solution to obtain a solution B; and dropwisely adding a nickel-salt-containing ethanol water solution into the solution B, stirring to react completely, separating out the product material, washing, and drying to obtain the nano Ni/Fe-biochar composite material. The nano Ni/Fe bimetal particles are carried on the biochar, thereby further enhancing the flowability of the nanoparticles. The nano Ni/Fe-biochar composite material is beneficial to soil in-situ restoration due to the stability and dispersity. The nano Ni/Fe-biochar composite material can be used for restoring high-concentration PBDEs polluted soil, and has high restoration efficiency.
Description
Technical field
The invention belongs to environmental pollution improvement and recovery technique field, particularly to a kind of preparation method and application thereof repairing Biphenyl Ether contaminated soil in-situ remediation material more.
Background technology
PBDE (Polybrominateddiphenylethers, PBDEs) it is the bromide fire retardant of a quasi-representative, owing to it has the fire resistance of excellence, it is widely used in the various industrial products such as textile, electronics, electrical equipment, circuit board, oil, mining, building materials, paint and daily product. Different from the brominated flame retardant that other are combined with product by chemical bond, PBDEs simply adulterates in the product in the way of simply mixing, therefore it is easier to be discharged in environment from product in the process producing, use and disposing, and along with the migration of air and water body causes extensive pollution. PBDE (Polybrominateddiphenylethers, PBDEs) as the one of brominated flame retardant, it is taken as POPs in May, 2009 and adds into " Convention of Stockholm ", be the class global environment organic pollution with ecological risk. Owing to the octanol-water partition coefficient (Kow) of this pollutant is high, hydrophobicity is strong, is easily combined with suspended particulate substance and soil particle and transfers in soil, and therefore soil is the PBDEs important medium remained in the environment. It is reported, in past more than 30 year, the content of the PBDE in environment exponentially increased, and is often only the PBDE that about can be produced 67000 tonnes by electronic waste and is discharged in environment. The electronic waste that China is maximum in the world processes ground, and the electronic waste in the whole world 50%～80% enters Asia by legally or illegally approach, wherein 90% enters China. Detect research according to Leung et al. to show, your small island electronics disassemble plastics a little burn ground and stack PBDEs in soil at concentrations up to 1155ng/g. A large amount of toxicological studies show, mammal, Fish even human body is had multiple genotoxic potential by PBDEs, such as hepatotoxicity, genotoxicity, neurotoxicity etc.Therefore effective, the feasible technology repairing PBDEs contaminated soil how is developed extremely urgent.
Have many currently, with respect to the report of the degradation technique of PBDEs in liquid phase, including the aerobe method of oxidizing process, wet oxidation method, hydro-thermal method; The anaerobic biological process of reducing process, electrolysis, metal deoxidization, nano-TiO2Photocatalytic method etc. And very few about the report repairing degradation technique of PBDE in soil, it is mainly microbial degradation metabolism and Plant Transformation, electric repairing technique, and electromagnetism coupling recovery technique. But these restorative procedures have the limitation of its application, long including repair time, efficiency is low, cost is high, reaction condition requirement is harsher. Have the characteristics such as big specific surface area, good reactivity, powerful reducing power and low cost due to nano zero valence iron, it has become the focus of domestic and international in-situ immobilization research. Although nano zero valence iron oneself be successfully applied to the removal of the pollutant such as multiple difficult degradation organohalogen compounds, antibiotic, nitrate nitrogen and heavy metal, but it is due to interfacial effect and small-size effect, very easily reunite and oxidized, and then cause the reduction of specific surface area and degradation efficiency. The iron ion that Zero-valent Iron discharges in repair process simultaneously, it is possible to cause that Iron in Soil too high levels etc. can affect soil fertility. Therefore, for these problems, we adopt in early stage and propose on the basis that in Ni nanoparticle/Fe granule rehabilitating soil, PBDE pollutes to use charcoal that it is carried out effective modification, to improve the process performance to PBBs, widen its range of application. Dispersibility stability and the mobility of nano-particle can be effectively improved on the one hand, increase soil fertility on the other hand, provide advantage for the recovery of the productivity after contaminated soil remediation. Simultaneously, due to charcoal have that cation exchange capacity (CEC) is big, surface is with features such as negative charge and abundant oxygen-containing functional groups, the catabolite of Ni, Fe ion precipitated out in nano material course of reaction and BDE209 absorption can be carried out fixing, secondary pollution can be effectively slowed down. Additionally, due to the content of organic matter of charcoal is significantly high, there is again loose structure, add charcoal and also help the nutrition and moisture that keep soil, increase the yield of crop.
The electronic waste being maximum in the world in view of China processes ground, and PBDEs contaminated soil area is relatively big, needs exploitation a kind of economy, efficient, practical Treatment process badly.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of Ni nanoparticle/Fe-charcoal composite and repair the application in PBDE contaminated soil in position.
The technical solution used in the present invention is:
A kind of preparation method of Ni nanoparticle/Fe-charcoal composite, including following preparation method:
1) iron salt or ferrous salt and polyvinylpyrrolidone are dissolved in ethanol water, mixing, add charcoal granule, stirring and evenly mixing, obtain solution A;
2) ethanol water containing reducing agent is joined in solution A, after stirring reaction is complete, isolate product, add in ethanol water after washes clean, obtain solution B;
3) ethanol water containing nickel salt is added drop-wise in solution B, after stirring reaction is complete, isolates resulting material, wash, namely obtain Ni nanoparticle/Fe-charcoal composite after drying.
Further, in described ethanol water, the concentration of ethanol is 20～50%v/v.
Further, ferrum element in described iron salt or ferrous salt, polyvinylpyrrolidone, charcoal mass ratio be 1:(0.5～2): (0.5～5).
Further, step 1) in add charcoal granule after, with 300～600rpm stirring and evenly mixing 40～80min, obtain solution A.
Further, in step 2) in, when protective atmosphere, the ethanol water containing reducing agent is joined in solution A, add the stirring of fashionable limit.
Further, step 3) nickel element is (0.5～1.5) with the mol ratio of Fe element in described nickel salt: 1.
Further; the preparation method of described charcoal is: after broken for agricultural wastes; dry, put in crucible, be placed in the Muffle furnace of protective atmosphere; it is warming up to 600～800 DEG C with 15～25 DEG C/min; continue pyrolysis 1～3h at such a temperature, be cooled to room temperature, take out black solid; grind, sieve.
Further, described agricultural wastes are bagasse.
Ni nanoparticle described in one/Fe-charcoal composite application in PBDE contaminated soil in-situ immobilization.
A kind of method of in-situ immobilization PBDE contaminated soil, is added to the Ni nanoparticle of above-mentioned preparation/Fe-charcoal composite in PBDE contaminated soil, and add water mixing; Wherein, Ni nanoparticle/Fe-charcoal composite quality is more than 0.02 times of contaminated soil.
The invention has the beneficial effects as follows:
Repair materials prepared by the present invention can be used for the in-situ immobilization of PBDEs contaminated soil, and remediation efficiency is high. There are following several respects specifically:
(1) what prepared by the present invention is carried on charcoal by Ni nanoparticle/Fe bimetal granule, further increases the mobility of nano-particle. Stability and dispersibility, be conducive to soil in-situ reparation.
(2) to have specific surface area big for charcoal prepared by the present invention, rich in oxygen-containing functional groups such as carboxyl, carbonyl and hydroxyls, cation exchange capacity (CEC) is big, surface is with features such as negative charges, the catabolite of Ni, Fe ion precipitated out in nano material course of reaction and BDE209 absorption can be carried out fixing, secondary pollution can be effectively slowed down. Simultaneously as the content of organic matter of charcoal is significantly high, there is again loose structure, add charcoal and also help the nutrition and moisture that keep soil, increase the yield of crop.
(3) charcoal of the present invention is to utilize discarded bagasse to be prepared from, and this material preparation cost is low, is conducive to the recycling of resource, turns waste into wealth, and has great economic results in society.
(4) preparation method of restoration materials of the present invention is simple, repair time is short, easy and simple to handle, it is simple to implement.
(5) repair materials of the present invention is applicable to in-situ immobilization, may use the reparation of the PBDEs contaminated soil of higher concentration, and remediation efficiency is high.
Accompanying drawing explanation
Fig. 1 is the SEM image of the bimetallic nano ferronickel solid particle of embodiment 1 preparation;
Fig. 2 is the SEM image of the charcoal of embodiment 2 preparation;
Fig. 3 is the SEM image of the composite of embodiment 3 preparation;
Fig. 4 is the TEM image of the composite of embodiment 3 preparation;
Fig. 5 is that the different ferrum element material with the mass ratio of charcoal is to the remediation efficiency of PBDEs in soil;
Fig. 6 is that the Ni nanoparticle/Fe-charcoal composite of different dosage is to the remediation efficiency of PBDEs in soil;
Fig. 7 is that Ni nanoparticle of the present invention/Fe-charcoal composite is to the remediation efficiency of PBDEs in different water cut soil;
Fig. 8 is that three kinds of different materials are to the comparison of the remediation efficiency of PBDEs in soil.
Detailed description of the invention
A kind of preparation method of Ni nanoparticle/Fe-charcoal composite, including following preparation method:
1) iron salt or ferrous salt and polyvinylpyrrolidone are dissolved in ethanol water, mixing, add charcoal granule, stirring and evenly mixing, obtain solution A;
2) ethanol water containing reducing agent is joined in solution A, after stirring reaction is complete, isolate product, add in ethanol water after washes clean, obtain solution B;
3) ethanol water containing nickel salt is added drop-wise in solution B, after stirring reaction is complete, isolates resulting material, wash, namely obtain Ni nanoparticle/Fe-charcoal composite after drying.
Preferably, described ethanol water is the ethanol water through deoxidation treatment.
Preferably, in described ethanol water, the concentration of ethanol is 20～50%v/v.
Preferably, ferrum element in described iron salt or ferrous salt, polyvinylpyrrolidone, charcoal mass ratio be 1:(0.5～2): (0.5～5).
Preferably, described ferrous salt is ferrous sulfate.
Preferably, described polyvinylpyrrolidone is at least one in polyvinylpyrrolidone K25, K30, K60.
Preferably, step 1) in add charcoal granule after, with 300～600rpm stirring and evenly mixing 40～80min, obtain solution A.
Preferably, step 2) described in reducing agent be negative hydrogen reduction agent.
It is furthermore preferred that described reducing agent is sodium borohydride.
It is furthermore preferred that the mol ratio of described sodium borohydride and Fe element is (1～3): 1.
Preferably, in step 2) in, when protective atmosphere, the ethanol water containing reducing agent is joined in solution A, add the stirring of fashionable limit.
Preferably, step 3) described nickel salt is Nickel dichloride..
Preferably, step 3) nickel element is (0.5～1.5) with the mol ratio of Fe element in described nickel salt: 1.
Preferably, step 2) and step 3) time of described stirring reaction is 20～40min, mixing speed is 300～600rpm.
Preferably, step 3) described dry as vacuum drying, drying time is 6～10h.
Preferably, described charcoal is the charcoal that can cross 60～180 mesh sieves.
Preferably; the preparation method of described charcoal is: after broken for agricultural wastes; dry, put in crucible, be placed in the Muffle furnace of protective atmosphere; it is warming up to 600～800 DEG C with 15～25 DEG C/min; continue pyrolysis 1～3h at such a temperature, be cooled to room temperature, take out black solid; grind, sieve.
Preferably, described agricultural wastes are bagasse.
Preferably, described protective atmosphere is at least one in nitrogen, helium, neon, argon, xenon.
Ni nanoparticle described above/Fe-charcoal composite application in PBDE contaminated soil in-situ immobilization.
A kind of method of in-situ immobilization PBDE contaminated soil, is added to the Ni nanoparticle of any of the above-described preparation/Fe-charcoal composite in PBDE contaminated soil, and add water mixing; Wherein, Ni nanoparticle/Fe-charcoal composite quality is more than 0.02 times of contaminated soil.
Preferably, described Ni nanoparticle/Fe-charcoal composite quality is 0.06～0.1 times of contaminated soil.
Preferably, the consumption of described water is 50%～90% for making soil moisture content.
Below in conjunction with specific embodiment, the present invention is further illustrated, but is not limited thereto.
The preparation method of embodiment 1 bimetallic nano ferronickel solid particle
(1) ferrous salt and polyvinylpyrrolidone are dissolved in the ethanol water of deoxidation treatment, stirring mixing.
(2) under agitation sodium borohydride is dropwise added drop-wise in (1) described solution, prepares nano zero-valence ferrous solution, washing.
(3) adding alcoholic solution makes nano zero valence iron disperse.Meanwhile, adding a certain amount of nickel salt ethanol water, vibrate 30min. Allow Ni deposit to iron surface, prepare bimetallic nano Ni/Fe granule.
Fig. 1 is the SEM image of the bimetallic nano Ni/Fe of embodiment 1 preparation, and as seen from Figure 1, independent nano nickel iron double metal granule, agglomeration is serious.
The preparation method of embodiment 2 charcoal
(1) dry: after the bagasse of collection is shredded, dry at 105 DEG C.
(2) pyrolysis: the bagasse after weighing is put into crucible and is placed in Muffle furnace, under a nitrogen atmosphere, set final temperature as 600 DEG C, continues carbonization 2h after being warming up to this temperature range with 20 DEG C/min. It is cooled to after room temperature until Muffle furnace to take out, after grinding, crosses 60～120 mesh sieves and seal preservation.
Fig. 2 is the charcoal SEM image of embodiment 2 preparation. As seen from Figure 2, the charcoal that prepared by the present embodiment has abundant pore structure.
The preparation method of embodiment 3 Ni nanoparticle/Fe-charcoal composite
1) with the alcoholic solution preparation 100ml0.1mol/LFeSO of 20%v/v4·7H2The solution of O, add polyvinylpyrrolidone K25 (mass ratio of polyvinylpyrrolidone K25 and Fe element is 1:1), 5min is stirred with the speed of 300rpm, so as to dissolve mixing, the charcoal granule (mass ratio of Fe element and charcoal is 1:1) embodiment 2 prepared again adds wherein, stir 1h with the speed of 500rpm, so as to dissolve mixing, obtain solution A;
2) with the sodium borohydride solution of the alcoholic solution preparation 50ml0.3mol/L of 20%v/v; under protective atmosphere (nitrogen); limit stirring condition is dropwise added drop-wise in solution A; continue the speed stirring reaction 30min with 500rpm; then separate by magnetic method; add the ethanol water of 50ml20% after washing, obtain solution B.
3) with the NiCl of the alcoholic solution preparation 50ml0.2mol/L of 20%v/v2·6H2O solution, is quickly adding in solution B 500rpm under agitation and stirs 30min, the dry 8h of washing final vacuum, obtains Ni nanoparticle/Fe-charcoal composite, can be used for the in-situ immobilization of PBDEs contaminated soil.
The SEM image of the Ni nanoparticle/Fe-charcoal composite of Fig. 3, Fig. 4 respectively embodiment 3 preparation and TEM image. Nanoscale bimetallic particles be can be observed by Fig. 3 and be attached to charcoal surface, and significantly improve the phenomenon of reunion. As shown in Figure 4, the particle diameter of gained Ni nanoparticle of the present invention/Fe-charcoal composite is 20～70nm.
The preparation method of embodiment 4 Ni nanoparticle/Fe-charcoal composite
1) with the alcoholic solution preparation 100ml0.1mol/LFeSO of 50%v/v4·7H2The solution of O, add PVP K30 (mass ratio of PVP K30 and Fe element is 0.5:1), 5min is stirred with the speed of 300rpm, so as to dissolve mixing, the charcoal granule (mass ratio of Fe element and charcoal is 1:0.5) embodiment 2 prepared again adds wherein, stir 40min with the speed of 300rpm, so as to dissolve mixing, obtain solution A;
2) with the sodium borohydride solution of the alcoholic solution preparation 50ml0.2mol/L of 50%v/v; under protective atmosphere (nitrogen); limit stirring condition is dropwise added drop-wise in solution A; continue the speed stirring reaction 40min with 300rpm; then separate by magnetic method; add the ethanol water of 50ml50% after washing, obtain solution B.
3) with the NiCl of the alcoholic solution preparation 50ml0.1mol/L of 50%v/v2·6H2O solution, is quickly adding in solution B 600rpm under agitation and stirs 20min, isolates resulting material, the dry 8h of washing final vacuum, obtains Ni nanoparticle/Fe-charcoal composite, can be used for the in-situ immobilization of PBDEs contaminated soil.
The preparation method of embodiment 5 Ni nanoparticle/Fe-charcoal composite
1) with the alcoholic solution preparation 100ml0.1mol/LFeSO of 30%v/v4·7H2The solution of O, add polyvinylpyrrolidone K60 (mass ratio of polyvinylpyrrolidone K60 and Fe element is 2:1), 5min is stirred with the speed of 300rpm, so as to dissolve mixing, the charcoal granule (mass ratio of Fe element and charcoal is 1:1.5) embodiment 2 prepared again adds wherein, stir 80min with the speed of 600rpm, so as to dissolve mixing, obtain solution A;
2) with the sodium borohydride solution of the alcoholic solution preparation 50ml0.6mol/L of 30%v/v; under protective atmosphere (nitrogen); limit stirring condition is dropwise added drop-wise in solution A; continue the speed stirring reaction 20min with 600rpm; then separate by magnetic method; add the ethanol water of 50ml40% after washing, obtain solution B.
3) with the NiCl of the alcoholic solution preparation 50ml0.3mol/L of 40%v/v2·6H2O solution, is quickly adding in solution B 600rpm under agitation and stirs 20min, isolates resulting material, the dry 8h of washing final vacuum, obtains Ni nanoparticle/Fe-charcoal composite, can be used for the in-situ immobilization of PBDEs contaminated soil.
The preparation method of embodiment 6 Ni nanoparticle/Fe-charcoal composite
1) with the alcoholic solution preparation 100ml0.1mol/LFeSO of 30%v/v4·7H2The solution of O, add polyvinylpyrrolidone K60 (mass ratio of polyvinylpyrrolidone K60 and Fe element is 1:1), 5min is stirred with the speed of 300rpm, so as to dissolve mixing, the charcoal granule (mass ratio of Fe element and charcoal is 1:2) embodiment 2 prepared again adds wherein, stir 60min with the speed of 400rpm, so as to dissolve mixing, obtain solution A;
2) with the sodium borohydride solution of the alcoholic solution preparation 50ml0.4mol/L of 40%v/v; under protective atmosphere (nitrogen); limit stirring condition is dropwise added drop-wise in solution A; continue the speed stirring reaction 20min with 600rpm; then separate by magnetic method; add the ethanol water of 50ml40% after washing, obtain solution B.
3) with the NiCl of the alcoholic solution preparation 50ml0.3mol/L of 40%v/v2·6H2O solution, is quickly adding in solution B 500rpm under agitation and stirs 30min, isolates resulting material, the dry 6h of washing final vacuum, obtains Ni nanoparticle/Fe-charcoal composite, can be used for the in-situ immobilization of PBDEs contaminated soil.
The preparation method of embodiment 7 Ni nanoparticle/Fe-charcoal composite
1) with the alcoholic solution preparation 100ml0.1mol/LFeSO of 30%v/v4·7H2The solution of O, add polyvinylpyrrolidone K60 (mass ratio of polyvinylpyrrolidone K60 and Fe element is 1:1), 5min is stirred with the speed of 300rpm, so as to dissolve mixing, the charcoal granule (mass ratio of Fe element and charcoal is 1:3) embodiment 2 prepared again adds wherein, stir 60min with the speed of 400rpm, so as to dissolve mixing, obtain solution A;
2) with the sodium borohydride solution of the alcoholic solution preparation 50ml0.3mol/L of 40%v/v; under protective atmosphere (nitrogen); limit stirring condition is dropwise added drop-wise in solution A; continue the speed stirring reaction 20min with 600rpm; then separate by magnetic method; add the ethanol water of 50ml40% after washing, obtain solution B.
3) with the NiCl of the alcoholic solution preparation 50ml0.2mol/L of 40%v/v2·6H2O solution, is quickly adding in solution B 500rpm under agitation and stirs 30min, isolates resulting material, the dry 10h of washing final vacuum, obtains Ni nanoparticle/Fe-charcoal composite, can be used for the in-situ immobilization of PBDEs contaminated soil.
The preparation method of embodiment 8 Ni nanoparticle/Fe-charcoal composite
1) with the alcoholic solution preparation 100ml0.1mol/LFeSO of 30%v/v4·7H2The solution of O, add polyvinylpyrrolidone K60 (mass ratio of polyvinylpyrrolidone K60 and Fe element is 1:1), 5min is stirred with the speed of 300rpm, so as to dissolve mixing, the charcoal granule (mass ratio of Fe element and charcoal is 1:5) embodiment 2 prepared again adds wherein, stir 60min with the speed of 400rpm, so as to dissolve mixing, obtain solution A;
2) with the sodium borohydride solution of the alcoholic solution preparation 50ml0.3mol/L of 40%v/v; under protective atmosphere (nitrogen); limit stirring condition is dropwise added drop-wise in solution A; continue the speed stirring reaction 20min with 600rpm; then separate by magnetic method; add the ethanol water of 50ml40% after washing, obtain solution B.
3) with the NiCl of the alcoholic solution preparation 50ml0.2mol/L of 40%v/v2·6H2O solution, is quickly adding in solution B 500rpm under agitation and stirs 30min, isolates resulting material, the dry 8h of washing final vacuum, obtains Ni nanoparticle/Fe-charcoal composite, can be used for the in-situ immobilization of PBDEs contaminated soil.
The method of 9 one kinds of in-situ immobilization PBDE contaminated soils of embodiment
Ni nanoparticle embodiment 3 prepared/Fe-charcoal composite is added in PBDE contaminated soil, and the mixing that adds water makes soil moisture content be 50%～90%;
Wherein, Ni nanoparticle/Fe-charcoal composite quality is more than 0.02 times (preferably 0.06～0.1 times) of contaminated soil.
Further effect detection done by the Ni nanoparticle below prepared by the present invention/Fe-charcoal composite.
One, in-situ immobilization PBDEs contaminated soil experiment
The preparation of manual simulation PBDEs contaminated soil:
1) adopt laboratory test, for examination soil for picking up from the unpolluted soil of Guangzhou university city, after collection, remove plant residue and the soil animals such as dry branches and fallen leaves root system, air-dry, cross 60 mesh sieves, sealed storage is standby in exsiccator.
2) prepare BDE209 (decabromodiphenyl oxide) storing solution of 200mg/L with oxolane, weigh above-mentioned soil 50g in beaker, pipette a certain amount of BDE209 storing solution, be diluted to required concentration with oxolane, join in above-mentioned soil;
3) use magnetic stirring apparatus to be stirred uniformly in fume hood, treat that oxolane evaporates into antecedent soil moisture completely, be pollution soil sample;
4) soil sample is ground, be placed in wide mouthed bottle and seal keep in Dark Place;
5) after soil pollution adopts ultrasonic extraction method to extract, it is centrifuged and pours out supernatant, with the membrane filtration of 0.22 μm, with the content of BDE209 in high effective liquid chromatography for measuring extract, in final soil, the content of BDE209 is 8.6mg/kg, is PBDEs contaminated soil.
Experiment 1: the ability of Ni nanoparticle/Fe-charcoal composite repair contaminated soil prepared by different embodiments
The contaminated soil weighing the above-mentioned preparation of 2g adds in reaction bulb, deionized water is added by the solid-to-liquid ratio of 1:2, add the Ni nanoparticle/Fe-charcoal composite of 0.12g embodiment 3～7 preparation respectively, in the composite of embodiment 3～7 preparation, Fe element (i.e. nano zero valence iron) is followed successively by 1:1 with the mass ratio of charcoal, 1:0.5, 1:1.5, 1:2 and 1:3, cover politef lid, shaking table shakes, the speed of shaking table is 300r/min, temperature is 25 DEG C, sample bottle is taken out after reaction 72h, add appropriate acetonitrile solvent concussion 30min, then ultrasonic extraction is carried out, the ultrasonic extraction time is 30min.Repeating twice, be then followed by centrifugation step, centrifugal rotational speed is 2000r/min, and centrifugal force is 716g, and the time is 8min. Merging twice extract, take the filtering with microporous membrane that 2mL is with 0.22 μm, HPLC analyzes the concentration of BDE209.
Testing result is as it is shown in figure 5, wherein mFe 0:mBCRepresent the mass ratio of ferrum element (i.e. nano zero valence iron) and charcoal, there it can be seen that as the material (m of example example 3 preparationFe 0:mBCMass ratio is 1:1), the clearance of BDE209 is the highest, reaches 86.32%, compares embodiment 4 material (mFe 0:mBCMass ratio be 1:0.5) time add 6.67%; Work as mFe:mBCMass ratio reach 1:1 after, increase along with charcoal, the clearance of BDE209 is downward trend by composite, this is likely due to excessive charcoal and occupies the avtive spot of bimetallic nano, hinder contacting of BDE209 and bimetallic nano, cause that remediation efficiency reduces, therefore best m in compositeFe 0:mBCMass ratio be 1:1.
Test the impact on soil remediation of the 2 Ni nanoparticle/Fe-charcoal composite amount ratio with contaminated soil
The contaminated soil weighing the above-mentioned preparation of 2g adds in reaction bulb, deionized water is added by the solid-to-liquid ratio of 1:2, it is separately added into Ni nanoparticle/Fe-charcoal the composite of 0g, 0.04g, 0.08g, 0.12g, 0.16g, 0.2g embodiment 3 preparation again, covers politef lid, shaking table shakes, the speed of shaking table is 300r/min, temperature is 25 DEG C, takes out sample bottle after reaction 72h, adds appropriate acetonitrile solvent concussion 30min, then carrying out ultrasonic extraction, the ultrasonic extraction time is 30min. Repeating twice, be then followed by centrifugation step, centrifugal rotational speed is 2000r/min, and centrifugal force is 716g, and the time is 8min. Merging twice extract, take the filtering with microporous membrane that 2mL is with 0.22 μm, HPLC analyzes the concentration of BDE209.
Testing result as shown in Figure 6, by it can be seen that along with the increase of composite dosage, the clearance of BDE209 is increasing trend. When the dosage of composite is 0.02g/g, the clearance of BDE209 only has 43.81%, and when increasing to 0.06g/g along with dosage, the clearance of BDE209 has reached 86.21%, adds 42.4%; When continuing the dosage increasing composite to 0.1g/g, BDE20 clearance is 94.83%, when being 0.06g/g compared to dosage, merely add 8.62%, increases inconspicuous, therefore selecting optimum dosage is 0.06g/g.
Test the impact on repairing polluted soil of 3 different water cuts
For the removal effect of PBDEs in the soil of research different water cut, determine optimum moisture content, 4 groups of experimental grouies of this Setup Experiments, often group weighs 2.00g soil, three Duplicate Samples, preparation soil moisture content is 33% respectively, 50%, 66.7%, the reaction system of 71%, the dosage pressing 0.06g/g respectively adds the Ni nanoparticle/Fe-charcoal composite of embodiment 3 preparation, after the concussion reaction 72h with speed for the shaking table of 300r/min, after taking-up sample bottle addition acetonitrile solution carries out ultrasonic extraction, centrifugal, then the filtering with microporous membrane that 2mL is with 0.22 μm is taken, HPLC analyzes the concentration of BDE209.
Testing result as it is shown in fig. 7, by it can be seen that along with the increase of moisture content, in soil, the clearance of BDE209 increases along with the increase of soil moisture content. When soil moisture content is 33%, the clearance of BDE209 in soil is only had 33.74% by composite, and when moisture content increases to 50%, clearance is 45.75%;When continuation increase moisture content is 66.7%, clearance reaches 86.39%. When moisture content is 71%, clearance continues to increase to 91.29%. Owing in soil, the response rate of BDE209 is subject to the impact of soil moisture content, therefore selecting optimum moisture content is 66.7%.
Test 4 three kinds of different materials to the comparison of the remediation efficiency of PBDEs in soil
For probing into the Ni nanoparticle/Fe bimetallic of embodiment 1 preparation, the charcoal of embodiment 2 preparation and the composite prepared of the present invention to the impact of the remediation efficiency of PBDEs in soil, three kinds of materials are selected to repair PBDEs contaminated soils respectively. The dosage that the fixing bimetallic dosage of Ni nanoparticle/Fe is the Ni nanoparticle/Fe-charcoal compound that dosage is 0.06g/g, embodiment 3 preparation of 0.06g/g, charcoal is 0.06g/g, soil moisture content is 66.7%, and method described in above-mentioned experiment 3 reacts.
As shown in Figure 8, there it can be seen that the BDE209 in soil is all had certain repair by material, and along with the increase of repair time, the remediation efficiency of BDE209 in soil is improved experimental result by material therewith. But for three kinds of materials, composite repair best results, next to that Ni nanoparticle/Fe bimetallic, it is finally charcoal. After repairing 72h, the removal effect of BDE209 in soil is 86.32%, 63.91%, 16.28% by three kinds of materials respectively. The repairing effect of three kinds of materials of contrast, hence it is evident that find out that the repairing effect of composite is best. Show that composite has given full play to the advantage of both Ni nanoparticle/Fe and charcoal, enhance material to the repairing effect of PBDEs in soil.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of Ni nanoparticle/Fe-charcoal composite, it is characterised in that: include following preparation method:
1) iron salt or ferrous salt and polyvinylpyrrolidone are dissolved in ethanol water, mixing, add charcoal granule, stirring and evenly mixing, obtain solution A;
2) ethanol water containing reducing agent is joined in solution A, after stirring reaction is complete, isolate product, add in ethanol water after washes clean, obtain solution B;
3) ethanol water containing nickel salt is added drop-wise in solution B, after stirring reaction is complete, isolates resulting material, wash, namely obtain Ni nanoparticle/Fe-charcoal composite after drying.
2. method according to claim 1, it is characterised in that: in described ethanol water, the concentration of ethanol is 20～50%v/v.
3. method according to claim 1, it is characterised in that: ferrum element in described iron salt or ferrous salt, polyvinylpyrrolidone, charcoal mass ratio be 1:(0.5～2): (0.5～5).
4. method according to claim 1, it is characterised in that: after step 1) adds charcoal granule, with 300～600rpm stirring and evenly mixing 40 ~ 80min, obtain solution A.
5. method according to claim 1, it is characterised in that: in step 2) in, when protective atmosphere, the ethanol water containing reducing agent is joined in solution A, add the stirring of fashionable limit.
6. method according to claim 1, it is characterised in that: in nickel salt described in step 3), nickel element is (0.5～1.5) with the mol ratio of Fe element: 1.
7. method according to claim 1; it is characterized in that: the preparation method of described charcoal is: after broken for agricultural wastes; dry, put in crucible, be placed in the Muffle furnace of protective atmosphere; it is warming up to 600 ~ 800 DEG C with 15～25 DEG C/min; continue pyrolysis 1 ~ 3h at such a temperature, be cooled to room temperature, take out black solid; grind, sieve.
8. method according to claim 7, it is characterised in that: described agricultural wastes are bagasse.
9. the arbitrary described Ni nanoparticle of claim 1～8/Fe-charcoal composite application in PBDE contaminated soil in-situ immobilization.
10. the method for an in-situ immobilization PBDE contaminated soil, it is characterised in that: being added in PBDE contaminated soil by the Ni nanoparticle of arbitrary for claim 1～8 preparation/Fe-charcoal composite, add water mixing; Wherein, Ni nanoparticle/Fe-charcoal composite quality is more than 0.02 times of contaminated soil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610131446.7A CN105670635B (en) | 2016-03-08 | 2016-03-08 | Application in Ni nanoparticle/Fe- biology carbon composite preparation method and its in situ reparation polybrominated diphenyl ethers contaminated soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610131446.7A CN105670635B (en) | 2016-03-08 | 2016-03-08 | Application in Ni nanoparticle/Fe- biology carbon composite preparation method and its in situ reparation polybrominated diphenyl ethers contaminated soil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105670635A true CN105670635A (en) | 2016-06-15 |
| CN105670635B CN105670635B (en) | 2019-04-30 |
Family
ID=56307254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610131446.7A Active CN105670635B (en) | 2016-03-08 | 2016-03-08 | Application in Ni nanoparticle/Fe- biology carbon composite preparation method and its in situ reparation polybrominated diphenyl ethers contaminated soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105670635B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107716942A (en) * | 2017-09-04 | 2018-02-23 | 绍兴文理学院 | The method for preparing ferronickel bimetallic material using nickel ion pollutant effluents original position is repaired |
| CN110003912A (en) * | 2019-04-18 | 2019-07-12 | 江西师范大学 | A kind of method of modifying of charcoal and its application 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 |
| US20210395159A1 (en) * | 2020-06-17 | 2021-12-23 | Iowa State University Research Foundation, Inc. | Biochar product, its use in fertilizers, and methods of making the biochar |
| CN115960611A (en) * | 2022-12-29 | 2023-04-14 | 北京建工环境修复股份有限公司 | Contaminated soil remediation agent and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1739822A (en) * | 2005-09-22 | 2006-03-01 | 中国科学院生态环境研究中心 | The method of nanometer iron powder fast polybrominated biphenyl ether degrading |
| CN101816828A (en) * | 2010-04-23 | 2010-09-01 | 华南理工大学 | Method for rapidly degrading decabromodiphenyl oxide in organic series by nano Pd/C catalyst |
| CN101844230A (en) * | 2010-05-19 | 2010-09-29 | 华南师范大学 | Nano zero-valent iron prepared by using iron and steel acid-cleaning wastewater and preparation method and application thereof |
| CN103157810A (en) * | 2013-03-11 | 2013-06-19 | 华南师范大学 | Manufacturing method and application of poly brominated diphenyl ethers polluted soil in-situ remediation material |
| CN104388094A (en) * | 2014-10-13 | 2015-03-04 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron-based bio-char material, preparation process thereof, and application thereof in soil pollution treatment |
-
2016
- 2016-03-08 CN CN201610131446.7A patent/CN105670635B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1739822A (en) * | 2005-09-22 | 2006-03-01 | 中国科学院生态环境研究中心 | The method of nanometer iron powder fast polybrominated biphenyl ether degrading |
| CN101816828A (en) * | 2010-04-23 | 2010-09-01 | 华南理工大学 | Method for rapidly degrading decabromodiphenyl oxide in organic series by nano Pd/C catalyst |
| CN101844230A (en) * | 2010-05-19 | 2010-09-29 | 华南师范大学 | Nano zero-valent iron prepared by using iron and steel acid-cleaning wastewater and preparation method and application thereof |
| CN103157810A (en) * | 2013-03-11 | 2013-06-19 | 华南师范大学 | Manufacturing method and application of poly brominated diphenyl ethers polluted soil in-situ remediation material |
| CN104388094A (en) * | 2014-10-13 | 2015-03-04 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron-based bio-char material, preparation process thereof, and application thereof in soil pollution treatment |
Non-Patent Citations (1)
| Title |
|---|
| PARMILA DEVI等: "Simultaneous adsorption and dechlorination of pentachlorophenol from effluent by Ni–ZVI magnetic biochar composites synthesized from paper mill sludge", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107716942A (en) * | 2017-09-04 | 2018-02-23 | 绍兴文理学院 | The method for preparing ferronickel bimetallic material using nickel ion pollutant effluents original position is repaired |
| 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 |
| CN110003912A (en) * | 2019-04-18 | 2019-07-12 | 江西师范大学 | A kind of method of modifying of charcoal and its application in soil remediation |
| 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 |
| US20210395159A1 (en) * | 2020-06-17 | 2021-12-23 | Iowa State University Research Foundation, Inc. | Biochar product, its use in fertilizers, and methods of making the biochar |
| 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 |
| CN115960611A (en) * | 2022-12-29 | 2023-04-14 | 北京建工环境修复股份有限公司 | Contaminated soil remediation agent and preparation method and application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105670635B (en) | 2019-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105670635A (en) | Preparation method of nano Ni/Fe-biochar composite material and application of nano Ni/Fe-biochar composite material in in-situ restoration of polybrominated diphenyl ether polluted soil | |
| Chowdhury et al. | Removal of lead ions (Pb2+) from water and wastewater: a review on the low-cost adsorbents | |
| Pant et al. | Green and facile method for the recovery of spent Lithium Nickel Manganese Cobalt Oxide (NMC) based Lithium ion batteries | |
| Bashir et al. | Efficiency of KOH-modified rice straw-derived biochar for reducing cadmium mobility, bioaccessibility and bioavailability risk index in red soil | |
| Elias et al. | Modified oil palm industry solid waste as a potential adsorbent for lead removal | |
| CN103861866A (en) | Fixed enrichment method for city life compost heavy metals through modified nanocarbon | |
| CN105670643B (en) | A kind of preparation and application of heavy metal cadmium soil remediation material | |
| CN103623782A (en) | Preparation method for composite magnetic adsorption material and method for removing heavy metal ions in waste water | |
| Jian et al. | Preparation of polydopamine nanofibers mat as a recyclable and efficient adsorbent for simultaneous adsorption of multiple tetracyclines in water | |
| CN106179216A (en) | The preparation method of a kind of Magnetic Activated hydro-thermal charcoal and application | |
| CN104525129B (en) | A kind of preparation method of the modified activated carbon for heavy metal containing wastewater treatment | |
| Niu et al. | Preparation and characterization of magnetic modified bone charcoal for removing Cu2+ ions from industrial and mining wastewater | |
| Linghu et al. | Macroscopic and spectroscopic exploration on the removal performance of titanate nanotubes towards Zn (II) | |
| CN103980907B (en) | Soil heavy metal passivator and preparation method thereof | |
| Chen et al. | Effect of tartaric acid on the adsorption of Pb (Ⅱ) via humin: Kinetics and mechanism | |
| CN106882852A (en) | A kind of method of charcoal Adsorption of Heavy Metals Cr (VI) prepared by utilization coffee grounds | |
| Du et al. | Performance and mechanisms of NaOH and ball-milling co-modified biochar for enhanced the removal of Cd2+ in synthetic water: A combined experimental and DFT study | |
| CN106186163A (en) | A kind of preparation method and application of PBDE pollution waters restoration material | |
| Taşçı et al. | Boron removal from aqueous solutions by chitosan/functionalized-SWCNT-COOH: Development of optimization study using response surface methodology and simulated annealing | |
| CN105251446B (en) | A kind of underground water Compound Heavy Metals repair materials | |
| Darama et al. | Leaching performance and zinc ions removal from industrial slag leachate using natural and biochar walnut shell | |
| CN113000012A (en) | Arsenic removal adsorption material, preparation method thereof and application of arsenic removal adsorption material in removal of As (III) in acidic wastewater | |
| JP2013160666A (en) | Method for safely disposing burned ash containing radioactive cesium | |
| Du et al. | Multifunctional magnetic bio-nanoporous carbon material based on zero-valent iron, Angelicae Dahuricae Radix slag and graphene oxide: an efficient adsorbent of pesticides | |
| CN107617425A (en) | A kind of modified cocoanut shell and the method using vanadium in its reduction water body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221010 Address after: 511518 No. 09, floor t0218, industrial building, Tian'an Zhigu science and Technology Industrial Park, No. 18, Chuangxing Avenue, high tech Industrial Development Zone, Qingyuan City, Guangdong Province Patentee after: Normal University (Qingyuan) Environmental Remediation Technology Co.,Ltd. Address before: 510006 No. 378 West Ring Road, Guangzhou University Town, Panyu District, Guangzhou City, Guangdong Province Patentee before: SOUTH CHINA NORMAL University |