CN102614918B - Preparation method of dispersant modified iron nanoparticles - Google Patents
Preparation method of dispersant modified iron nanoparticles Download PDFInfo
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- CN102614918B CN102614918B CN201210058806.7A CN201210058806A CN102614918B CN 102614918 B CN102614918 B CN 102614918B CN 201210058806 A CN201210058806 A CN 201210058806A CN 102614918 B CN102614918 B CN 102614918B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 title abstract description 16
- 150000002505 iron Chemical class 0.000 title abstract 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 257
- 229910052742 iron Inorganic materials 0.000 claims abstract description 126
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- 238000000034 method Methods 0.000 claims abstract description 42
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
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- 238000005406 washing Methods 0.000 claims description 6
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 8
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- 206010022998 Irritability Diseases 0.000 description 1
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- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 235000003891 ferrous sulphate Nutrition 0.000 description 1
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- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of dispersant modified iron nanoparticles. According to the preparation method, high polymer, a cationic surfactant or anionic polymer electrolyte is used as a dispersant to perform surface modification on particles in a preparation process of the iron nanoparticles so as to prepare the dispersant modified iron nanoparticles. The iron nanoparticles prepared by the method have good dispersion stability; the hard agglomeration of the iron nanoparticles in an aqueous medium is reduced; the dispersion degree of the iron nanoparticles is increased; the method can also be used for performing dispersion modification on iron base bimetallic particles; and the method can be applied to pollution remediation of chlorinated organic compounds in an environmental medium and has broad application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of nano iron particles of dispersant modification, belong to nano material and technical field of water pollution control.
Background technology
Chlorinatedorganic refers to the product after one or more hydrogen in the molecular structure of aliphatic hydrocarbon, fragrant hydrocarbons and their derivates is replaced by chlorine, there is the feature such as high volatile volatile and lipides solubility, easily by eating, suck, accumulating in vivo through modes such as skin absorptions, thereby produce teratogenesis, carcinogenic, mutagenic " three cause effect ", very big to environment and healthy potential risk, become one of hot issue of current research.
Traditional method for governing pollution has Physical, bioanalysis and chemical method.Wherein, chemical reduction method particularly Zero-valent Iron reducing process from the 1980s be found application since, replace gradually traditional pollution control technology, and prove (the Muftikian etc. after the dechlorination rate that can greatly promote system for handling that add of palladium at Muftikian, Water Research, 1995, 29 (10): 2434-2439), start in the world with iron-based nanoscale bimetallic particles (as Pd/Fe at once, Ni/Fe, Cu/Fe etc.) be catalytic reducer, seek environmental protection, the research boom of the reduction dechlorination method of economical and efficient, make remarkable progress.But nano iron particles is due to the effect of Van der Waals force and self magnetic force, between particle, there is the trend that keeps best Thermodynamically stable state simultaneously, make new synthetic nano iron particles easily oxidized, and agglomeration is serious, being applied to original position reparation shows as and is easy to be adsorbed on soil or sedimental surface, transporting and poor stability.
In recent years, association area researcher has attempted the whole bag of tricks Nanoscale Iron has been carried out to modification, comprise with microwave, mechanical agitation and supersonic synergic are main physics auxiliary law, with surfactant, polymer, organic solvent is main chemical addition agent method and the load fixation take natural or artificial synthetic organic-inorganic material as carrier etc., obtain certain effect, but based on current achievement in research, also do not have a kind of method of definite moulding can continue degradating chloro organic matter efficiently, material modified effect and environmental behaviour thereof to Nanoscale Iron degradating chloro organic-compound system, bio-toxicity, the aspects such as ecological risk remain in dispute, main manifestations is:
(1) though physics auxiliary law can be by strengthening or weaken some effect of system, reach to a certain extent the object of strengthening mass transfer and surface reaction, improvement system degradation effect, but its complicated operation cost is high, to hardware facility require high, be difficult to be applied to large-scale production practices, can not adapt to soil the requirement that the original position of underground water is repaired.
(2) mostly surfactant is the application aspect chlorinatedorganic removal efficiency to add surfactant in the system of nano particle degraded target contaminant at enhancing Nanoscale Iron, surface energy that utilizes it to reduce solid liquid interface, strengthen the physical attractiveness of nano particle, thereby strengthen its adsorptivity to target contaminant, improve the dechlorination efficiency of system.Its limitation is: on the one hand, the kind of surfactant is numerous, and their promotion or inhibitory action to dechlorination system remain in dispute; On the other hand, size and the dispersion stabilization of surfactant control nano particle underused in current application.
(3) polymer is if polyethylene glycol, polyacrylic acid, carboxymethyl cellulose, polyvinylpyrrolidone etc. are to reducing the size of Technique of Nano Pd/iron double metal particle, strengthening its dispersion stabilization aspect plays an important role, but the concentration dose when modified nanoparticles of polymer, the complexity that has form, synthesis mode of polymer etc. becomes one of barrier of this technology application.
(4) load fixation can be controlled the size of nano particle effectively, and can keep certain dispersion stabilization, but the selection of carrier material and the hydrophilic modification of itself, also there is larger problem in regeneration etc., and it is low that the original position that the nano iron particles of the fixing modification of load is applied to soil or underground water also can run into hydraulic conductivity while reparation, the problems such as transporting is poor, make this method of modifying be difficult to apply.
Publication number CN101579745A discloses take cetyl ammonium bromide as surfactant, n-butanol is cosurfactant, isooctane is oil phase, the configuration microemulsion take ferrous sulfate and the potassium borohydride aqueous solution as water, in microemulsion take azodiisobutyronitrile as initator, trigger monomer methyl methacrylate in-situ polymerization generates PMMA, prepares the Nanoscale Iron of macromolecule clad, increases its aerial stability.But the method preparation process must could realize the modification of PMMA to Nanoscale Iron by in-situ polymerization.
The method that chlorinatedorganic in water is removed in dispersant modified Nano iron particle reduction of the present invention is devoted to overcome the defect with said method; be intended to utilize dispersant directly the Nanoscale Iron in aqueous medium to be carried out to disperse modified; it is being realized on the basis that nanoparticulate dispersed is stable; further reduce particle diameter; improve the degradation efficiency to chlorinatedorganic in water; to seek, a kind of technique is simple, economical and efficient, and is easy to the preparation method of the dispersant modified Nano iron particle that engineering extensively implements and apply.
Summary of the invention
The invention provides a kind of preparation method of dispersant modification nano iron particles, the method adopts liquid phase reduction, using polymer, cationic surfactant or anionic polymer electrolyte as dispersant, in nano iron particles preparation process, carry out surface modified to particle, thereby reduce its hard aggregation in aqueous medium, increase its decentralization, make dispersant modified Nano iron particle.
The present invention completes by following concrete steps:
(1) prepare certain density dispersant solution; The FeSO that is 0.1-0.15mol/L by dispersant solution and concentration
4solution mixes and stirs, wherein dispersant solution and FeSO
4the volume ratio of solution is 1:20-1:25;
(2) mixed liquor is added dropwise in solution of potassium borohydride 0.20-0.3mol/L (for guaranteeing FeSO
4completely and NaBH
4reaction, adds excessive KBH according to reaction equation
4solution), stir while dripping, stir 10-15min until mixed liquor dropwises rear continuation, by the solution filter reacting completely, deionized water drip washing 2-3 all over after drain, obtain the zeroth order nano iron particles of stable dispersion;
(3) by the nano iron particles after draining, with absolute ethyl alcohol drip washing 2 – 3 times, acetone soln drip washing 1 time, after suction filtration, grinds under logical nitrogen condition after dry 6-8h at vacuum 100-105 ℃, and sealing is preserved, and obtains the nano iron particles of dispersant modification.
Dispersant described in the present invention is a kind of in polymethyl methacrylate, polyacrylic acid, softex kw solution.
The polymethyl methacrylate solution of dispersant described in the present invention, take methyl phenyl ethers anisole as solvent, is mixed with the methyl phenyl ethers anisole solution of the polymethyl methacrylate (PMMA) of mass percentage concentration between 7-10%.
Dispersant softex kw solution of the present invention, using mass percent concentration as 0-100% ethanol water is as solvent, is mixed with the softex kw solution of mass percentage concentration 7-10%.
Dispersant polyacrylic acid solution of the present invention, take deionized water as solvent, is mixed with the polyacrylic acid that concentration of volume percent is 0.1-5% (PAA) aqueous solution.
The inventive method also can be carried out disperse modified for iron-based bimetal granule, concrete operations are can pass through common metal displacement reaction making after dispersant modification zeroth order nano iron particles, make iron-based nanoscale bimetallic particles, as dispersant modified Nano palladium/iron double metal particle, dispersant modified Nano nickel/iron double metal particle, dispersant modified Nano copper/iron double metal particle, dispersant modified Nano zinc/iron double metal particle, dispersant modified Nano magnesium/iron double metal particle etc.
The present invention utilizes dispersant modification to improve the dispersiveness of nano iron particles in aqueous medium, reduces its hard aggregation, increases surface reaction activity point figure place, thereby improves the reduction dechlorination clearance of Nanoscale Iron to chlorinatedorganic in water.Dispersant modification method of the present invention, its mechanism of action is: the electrostatic stabilization effect, space steric effect and the rest potential inhibition effect that utilize polymethyl methacrylate (PMMA), softex kw (CTAB) and polyacrylic acid (PAA), utilize the winding effect of polymer long-chain to form the decentralization of gel networks increase Nanoscale Iron in aqueous medium, control particle diameter, increase specific area, the increase surface-active reaction position of nano iron particles, thereby improve dechlorination activity and the removal efficiency to chlorinatedorganic of system.
Compared with prior art, the advantage of the method for the invention is:
(1) dispersant that polymethyl methacrylate that the present invention adopts (PMMA) is Nanoscale Iron, prepares the more common nano iron particles stability of nano iron particles and improves, and degree of aggregation reduces.The swelling impact that is not subject to pH, temperature and ionic strength of irritability of dispersant PMMA, can form oleophylic boundary layer on Nanoscale Iron surface, promotes the absorption of target contaminant, also can suppress the corrosion oxidation of Nanoscale Iron under oxidizing condition simultaneously.When excite (as the concentration of target contaminant raises) that PMMA is subject to environmental condition, can get through gradually the structure of obstruction, discharge gradually effective iron.
(2) the present invention utilizes dispersant PMMA to carry out nano iron particles modification, without generating PMMA with MMA by home position polymerization reaction, thereby the inventive method to prepare the technical process feasibility of modification particle high, products obtained therefrom can be good at the original position showering of adapted soil, surface water and underground water, be easy to realize through engineering approaches application, there is very large implementation prospect.
(3) dressing agent softex kw of the present invention (CTAB) is cationic surfactant, can be preferentially adsorbed on particle by ion exchange.In the synthetic process of Nanoscale Iron, utilize its electrostatic stabilization effect and sterically hindered effect simultaneously, can reach the object of stably dispersing nano particle, be conducive to the acquisition of the nano particle that average grain diameter is less.In addition, CTAB can also reduce the surface energy of solid liquid interface, strengthens the physical attractiveness of nano particle, thereby strengthens its adsorptivity to target contaminant.
(4) the form Cheng Jian that the contained carboxyl of dressing agent polyacrylic acid of the present invention (PAA) can be built bridge with bidentate with metal ion, thus will prepare the predecessor Fe of nano-metal particle
2+be dispersed in " nano-reactor ", and at reducing agent KBH
4reduction is rapid nucleation down, finally obtains the nano particle of stable dispersion.In addition, excessive PAA can also pass through hydrogen bond, winding and crosslinked action and form gel networks, and its sterically hindered effect is large.Known by analyzing X-ray diffraction (XRD) spectrogram of polyacrylic acid modified nano iron particles, the crystalline structure of particle is α-Fe, and particle is purer, does not occur iron oxide impurity.
The present invention adopts dispersant to modify nano iron particles, the defects such as oxidizable, the easy reunion of common nano iron particles are effectively overcome, not only can realize the stably dispersing of nano iron particles, can also obtain the more catalytic reductive dechlorination efficiency of high-efficient and lasting of chlorinatedorganic in water.
Accompanying drawing explanation
Fig. 1 is the relatively schematic diagram of transmission electron microscope photo of the PMMA disperse modified nano iron particles prepared of the present invention and common nano iron particles; Wherein (a) is PMMA disperse modified nano iron particles; (b) be common nano iron particles.
Fig. 2 is PAA disperse modified nano iron particles XRD spectra prepared by the present invention.
Fig. 3 is that PMMA disperse modified nano iron particles and common nano iron particles prepared by the present invention removed relatively schematic diagram of chlorinatedorganic effect in water.
Fig. 4 is relatively schematic diagram of chlorinatedorganic effect in PMMA disperse modified Technique of Nano Pd/iron particle of preparing of the present invention and common Technique of Nano Pd/iron particle removal water.
Fig. 5 is relatively schematic diagram of chlorinatedorganic effect in CTAB disperse modified nano nickel/iron particle of preparing of the present invention and common nano nickel/iron particle removal water.
Fig. 6 is that PAA disperse modified nano iron particles and common nano iron particles prepared by the present invention removed relatively schematic diagram of chlorinatedorganic effect in water.
The specific embodiment
Below by drawings and Examples, the present invention is described in further detail, but protection domain of the present invention is not limited to described content.
Embodiment 1: the preparation of polymetylmethacrylate disperse modified nano iron particles and the removal to multiple chlorinatedorganic in water thereof, particular content is as follows:
(1) preparation of PMMA disperse modified nano iron particles and dechlorination effect thereof
Methyl phenyl ethers anisole solution 10mL and the 200mL concentration of getting mass percent and be 7% PMMA are 0.1mol/L FeSO
4after solution mixes, stir 10min, in above-mentioned mixed solution, dropwise add excessive 0.2mol/L KBH
4in solution 200mL, also stir, after dropwising, time delay is stirred 15min to reacting completely, and filters and drains through vacuum filtration device, by washed with de-ionized water 3 times, suction filtration is extremely dry, then washes 3 times with absolute ethyl alcohol successively, and acetone is washed 1 time, after draining, put it in vacuum drying chamber in 100 ℃ of dry 6h, and grind under logical nitrogen condition, sealing is preserved, and obtains PMMA disperse modified nano iron particles.
PMMA disperse modified nano iron particles is added in the waste water water sample containing target contaminant, under normal temperature and pressure, react 4h, the dosage of dispersant modified Nano iron particle is 5g/L, the initial concentration of pollutant is 20mg/L, the original ph of reactant liquor is 7, after reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation of common nano iron particles and dechlorination effect thereof
The KBH that is 0.2mol/L by 250mL concentration
4it is the FeSO of 0.1mol/L that solution dropwise adds 200mL concentration
4in solution, limit edged magnetic stirrer FeSO
4solution, after dropwising, time delay is stirred 15min to reacting completely, and filters and drains through vacuum filtration device, uses washed with de-ionized water 3 times, wash 3 times with absolute ethyl alcohol successively draining the zero-valent iron particle obtaining, acetone is washed 1 time, puts it into vacuum drying chamber interior in 100 ℃ of dry 6h, and grind under logical nitrogen condition after draining, sealing is preserved, and obtains unmodified nano iron particles.
Common nano iron particles is added in the waste water water sample containing target contaminant, under normal temperature and pressure, react 4h, the dosage of Nanoscale Iron bimetal granule is 5g/L, the initial concentration of pollutant is 20mg/L, the original ph of reactant liquor is 7, after reaction result, measure chlorinatedorganic concentration, calculate clearance.
By more known, PMMA disperse modified nano iron particles improves 27%, 18% and 25% (seeing Fig. 1 and 3) than common nano iron particles respectively to the clearance of 2,4-chlorophenesic acid, carbon tetrachloride and chloroform.
The preparation of embodiment 2:PMMA disperse modified Technique of Nano Pd/iron particle and the removal to multiple chlorinatedorganic in water thereof, particular content is as follows:
(1) preparation and the dechlorination effect thereof of PMMA disperse modified Technique of Nano Pd/iron double metal particle
Methyl phenyl ethers anisole solution 10mL and the 200mL concentration of getting mass percent and be 8% PMMA are 0.1mol/L FeSO
4after solution mixes, stir 10min, in above-mentioned mixed solution, dropwise add excessive 0.2mol/LKBH
4in solution 200mL, also stir, after dropwising, time delay is stirred 15min to reacting completely, filter and drain through vacuum filtration device, by washed with de-ionized water 3 times, pour in the ethanolic solution of palladium draining the zeroth order nano iron particles obtaining, under magnetic agitation, react 30min, product is placed in to core filter suction filtration to dry, wash 3 times with absolute ethyl alcohol successively, acetone is washed 1 time, after draining, put it in vacuum drying chamber in 100 ℃ of dry 6h, and grind under logical nitrogen condition, sealing is preserved, obtain PMMA disperse modified Technique of Nano Pd/iron double metal particle.
PMMA disperse modified Technique of Nano Pd/iron double metal particle is added in the waste water water sample containing target contaminant, under normal temperature and pressure, react 4h, the dosage of dispersant modified Nano palladium/iron double metal particle is 5g/L, the initial concentration of pollutant is 20mg/L, the original ph of reactant liquor is 7, after reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation and the dechlorination effect thereof of common Technique of Nano Pd/iron double metal particle
The KBH that is 0.2mol/L by 250mL concentration
4it is the FeSO of 0.1mol/L that solution dropwise adds 200mL concentration
4in solution, limit edged magnetic stirrer FeSO
4solution, after dropwising, time delay is stirred 15min to reacting completely, filter and drain through vacuum filtration device, by washed with de-ionized water 3 times, pour in palladium palladium liquid draining the zero-valent iron particle obtaining, under magnetic agitation, react 30min, product is placed in to core filter suction filtration to dry, washes 3 times successively with absolute ethyl alcohol, acetone is washed 1 time, after draining, put it in vacuum drying chamber in 100 ℃ of dry 6h, and grind under logical nitrogen condition, sealing is preserved, and obtains unmodified Technique of Nano Pd/iron particle.Then common Technique of Nano Pd/iron particle is added in the waste water water sample containing target contaminant, under normal temperature and pressure, react 4h, the dosage of Technique of Nano Pd/iron double metal particle is 5g/L, the initial concentration of pollutant is 20mg/L, the original ph of reactant liquor is 7, after reaction result, measure chlorinatedorganic concentration, calculate clearance.
By more known, PMMA disperse modified Technique of Nano Pd/iron particle improves 34%, 16% and 28% (seeing Fig. 4) than common Technique of Nano Pd/iron particle respectively to the clearance of 2,4-chlorophenesic acid, carbon tetrachloride and chloroform.
The preparation of embodiment 3:CTAB disperse modified nano nickel/iron particle and the removal to multiple chlorinatedorganic in water thereof, particular content is as follows:
(1) preparation and the dechlorination effect thereof of CTAB disperse modified nano nickel/iron double metal particle
Softex kw solution (making solvent with the ethanol of mass percent concentration 70%) 10mL and the 250mL concentration of getting mass percentage concentration 10% are 0.15mol/L FeSO
4after solution mixes, stir 10min, in above-mentioned mixed solution, dropwise add excessive 0.3mol/LKBH
4in solution 200mL and stir, after dropwising, time delay is stirred 12min to reacting completely, and filters and drains through vacuum filtration device, by washed with de-ionized water 2 times, immerses by draining the zeroth order nano iron particles obtaining the nickel chloride (NiCl that concentration is 120mg/L
2) in solution, under magnetic agitation, react 30min, product is placed in to core filter suction filtration to dry, wash 2 times with absolute ethyl alcohol successively, acetone is washed 1 time, puts it into vacuum drying chamber interior in 105 ℃ of dry 7h, and grind under logical nitrogen condition after draining, sealing is preserved, and obtains CTAB disperse modified nano nickel/iron double metal particle.
CTAB disperse modified nano nickel/iron double metal particle is added in the waste water water sample containing target contaminant, under normal temperature and pressure, react 4h, the dosage of dispersant modified Nano nickel/iron double metal particle is 5g/L, the initial concentration of pollutant is 20mg/L, the original ph of reactant liquor is 7, after reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation and the dechlorination effect thereof of common nano nickel/iron double metal particle
The KBH that is 0.2mol/L by 250mL concentration
4it is the FeSO of 0.1mol/L that solution dropwise adds 200mL concentration
4in solution, limit edged magnetic stirrer FeSO
4solution, after dropwising, time delay is stirred 15min to reacting completely, and filters and drains through vacuum filtration device, uses washed with de-ionized water 2 times, immerses by draining the zeroth order nano iron particles obtaining the nickel chloride (NiCl that concentration is 120mg/L
2) in solution, under magnetic agitation, react 30min, product is placed in to core filter suction filtration to dry, wash 2 times with absolute ethyl alcohol successively, acetone is washed 1 time, puts it into vacuum drying chamber interior in 105 ℃ of dry 7h, and grind under logical nitrogen condition after draining, sealing is preserved, and obtains unmodified common nano nickel/iron particle.
Common nano nickel/iron particle is added in the waste water water sample containing target contaminant, under normal temperature and pressure, react 4h, the dosage of nano nickel/iron double metal particle is 5g/L, the initial concentration of pollutant is 20mg/L, the original ph of reactant liquor is 7, after reaction result, measure chlorinatedorganic concentration, calculate clearance.
By more known, CTAB disperse modified nano nickel/iron particle improves 28%, 10% and 22% (seeing Fig. 5) than common nano nickel/iron particle respectively to the clearance of 2,4-chlorophenesic acid, carbon tetrachloride and chloroform.
The preparation of embodiment 4:PAA disperse modified Technique of Nano Pd/iron particle and the removal to multiple chlorinatedorganic in water thereof, particular content is as follows:
(1) preparation process and the dechlorination effect thereof of PAA disperse modified Technique of Nano Pd/iron double metal particle
Getting mass percent and be 0.5% PAA solution 10mL and 220mL concentration is 0.12mol/L FeSO
4after solution mixes, stir 10min, in above-mentioned mixed solution, dropwise add excessive 0.25mol/LKBH
4in solution 200mL, also stir, after dropwising, time delay is stirred 10min to reacting completely, filter and drain through vacuum filtration device, by washed with de-ionized water 3 times, pour in the ethanolic solution of palladium draining the zeroth order nano iron particles obtaining, under magnetic agitation, react 30min, product is placed in to core filter suction filtration to dry, washes 3 times successively with absolute ethyl alcohol, acetone is washed 1 time, after draining, put it in vacuum drying chamber in 102 ℃ of dry 8h, and grind under logical nitrogen condition, sealing is preserved, and obtains PAA decorated nanometer palladium/iron double metal particle.
PAA decorated nanometer palladium/iron double metal particle is added in the waste water water sample containing target contaminant, under normal temperature and pressure, react 4h, the dosage of dispersant modified Nano palladium/iron double metal particle is 5g/L, the initial concentration of pollutant is 20mg/L, the original ph of reactant liquor is 7, after reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation and the dechlorination effect thereof of common Technique of Nano Pd/iron double metal particle, method is with embodiment 2.
By more known, PAA disperse modified Technique of Nano Pd/iron particle improves 17%, 14% and 20% than common Technique of Nano Pd/iron particle respectively to the clearance of 2,4-chlorophenesic acid, carbon tetrachloride and chloroform.
The preparation of embodiment 5:PAA disperse modified nano iron particles and the removal to multiple chlorinatedorganic in water thereof, particular content is as follows:
(1) preparation of PAA disperse modified nano iron particles and dechlorination effect thereof
Getting mass percent and be 5% PAA solution 10mL and 230mL concentration is 0.13mol/L FeSO
4after solution mixes, stir 10min, in above-mentioned mixed solution, dropwise add 0.2mol/L KBH
4in solution 230mL, also stir, after dropwising, time delay is stirred 12min to reacting completely, and filters and drains through vacuum filtration device, by washed with de-ionized water 2 times, suction filtration is extremely dry, then washes 2 times with absolute ethyl alcohol successively, and acetone is washed 1 time, after draining, put it in vacuum drying chamber in 105 ℃ of dry 8h, and grind under logical nitrogen condition, sealing is preserved, and obtains PAA disperse modified nano iron particles.
PAA disperse modified nano iron particles is added in the waste water water sample containing target contaminant, under normal temperature and pressure, react 4h, the dosage of dispersant modified Nano iron particle is 5g/L, the initial concentration of pollutant is 20mg/L, the original ph of reactant liquor is 7, after reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation of common nano iron particles and dechlorination effect thereof, method is with embodiment 1.
By more known, PAA disperse modified nano iron particles improves 25%, 15% and 20% (seeing Fig. 2, Fig. 6) than common nano iron particles respectively to the clearance of 2,4-chlorophenesic acid, carbon tetrachloride and chloroform.
Claims (2)
1. the preparation method of a dispersant modified Nano iron particle, it is characterized in that: using high polymer, cationic surfactant or anionic polymer electrolyte as dispersant, in nano iron particles preparation process, carry out surface modified to particle, thereby reduce its hard aggregation in aqueous medium, increase its decentralization, make dispersant modified Nano iron particle;
The concrete operations of said method are as follows:
(1) FeSO that is 0.1-0.15mol/L by dispersant solution and concentration
4solution mixes and stirs, wherein dispersant solution and FeSO
4the volume ratio of solution is 1:20-25;
(2) mixed liquor is added dropwise in 0.2-0.3mol/L solution of potassium borohydride, stir while dripping, stir 10-15min until mixed liquor dropwises rear continuation, by the solution filter reacting completely, after deionized water drip washing 2-3 time, drain, obtain the zeroth order nano iron particles of stable dispersion;
(3) by the nano iron particles after draining, with absolute ethyl alcohol drip washing 2-3 time, acetone soln drip washing 1 time, after suction filtration, grinds under logical nitrogen condition after dry 6-8h at vacuum 100-105 ℃, and sealing is preserved, and obtains the nano iron particles of dispersant modification;
Described dispersant is a kind of in polymethyl methacrylate, softex kw solution;
Described polymethyl methacrylate solution is the methyl phenyl ethers anisole solution of the polymethyl methacrylate of mass percent concentration 7-10%;
Described softex kw solution, using mass percent concentration as 0-100% ethanol water is as solvent, is mixed with the softex kw solution of mass percent concentration 7-10%.
2. the preparation method of dispersant modified Nano iron particle according to claim 1, is characterized in that: after making dispersant modification zeroth order nano iron particles, pass through metal displacement reaction, make the modifying iron based nanoscale bimetallic particles of dispersant.
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| CN103100721A (en) * | 2013-01-23 | 2013-05-15 | 昆明理工大学 | Method for preparing modified nanometer-palladium/iron duplex-metal particles |
| CN104858425B (en) * | 2015-05-13 | 2017-02-22 | 同济大学 | Method for weakening oxidization of metal nanoparticles |
| CN105502604A (en) * | 2015-12-22 | 2016-04-20 | 中国人民大学 | Preparation of modified nano-iron and application of modified nano-iron in antibiotic drug manufacture wastewater treatment |
| CN105562708B (en) * | 2016-01-06 | 2018-01-12 | 昆明理工大学 | A kind of dispersant modified Nano Zero-valent Iron and its preparation method and application |
| CN109304470B (en) * | 2017-07-28 | 2020-07-10 | 华中科技大学 | Surface-modified amorphous zero-valent iron, and preparation method and application thereof |
| CN107715844B (en) * | 2017-10-23 | 2020-06-16 | 青岛理工大学 | Preparation method and application of methyl parathion adsorption material |
| CN108298502B (en) * | 2018-01-15 | 2021-06-01 | 东南大学 | Method for preparing dispersed nano metal oxide and nano metal powder |
| CN109449442B (en) * | 2018-10-25 | 2021-08-27 | 贵州梅岭电源有限公司 | Composite electronic conductive agent for thermal battery anode material |
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