CN102614918A - Preparation method of dispersant modified iron nanoparticles - Google Patents
Preparation method of dispersant modified iron nanoparticles Download PDFInfo
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- CN102614918A CN102614918A CN2012100588067A CN201210058806A CN102614918A CN 102614918 A CN102614918 A CN 102614918A CN 2012100588067 A CN2012100588067 A CN 2012100588067A CN 201210058806 A CN201210058806 A CN 201210058806A CN 102614918 A CN102614918 A CN 102614918A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
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- 150000002505 iron Chemical class 0.000 title abstract 3
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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 is meant the product after one or more hydrogen are replaced by chlorine in the molecular structure of aliphatic hydrocarbon, aromatic hydrocarbon and derivative thereof; Have characteristics such as high volatile volatile and lipides solubility; Be prone to through eat, suck, through mode such as skin absorption and accumulation in vivo; Thereby produce teratogenesis, carcinogenic, mutagenic " three cause effect ", very big to environment with healthy potential risk, become one of hot issue of current research.
Traditional method for governing pollution has physics method, bioanalysis and chemical method.Wherein, Chemical reduction method particularly the Zero-valent Iron reducing process from the 1980s come to light use since, replaced traditional pollution control technology gradually, and can promote (Muftikian etc. after the dechlorination rate of system for handling in the adding of Muftikian proof palladium greatly; Water Research; 1995,29 (10): 2434-2439), having started with iron-based bimetallic nano particle (like Pd/Fe, Ni/Fe, Cu/Fe etc.) at once in the world is catalytic reducer; Seek the research boom of the reduction dechlorination method of environmental protection, economical and efficient, make remarkable progress.But nano iron particles is because the effect of Van der Waals force and self magnetic force; There is the trend that keeps best Thermodynamically stable state simultaneously between particle; Make new synthetic nano iron particles be prone to oxidized; And agglomeration is serious, is applied to the original position reparation and then shows as and be easy to be adsorbed on soil or sedimental surface, transmission property and poor stability.
In recent years; Association area researcher has attempted the whole bag of tricks nanometer iron has been carried out modification; Comprised with the microwave radiation; Mechanical agitation and supersonic synergic be main physics auxiliary law, be master's chemical addition agent method and with load fixation natural or that the artificial organic-inorganic material that synthesizes is a carrier etc. with surfactant, polymer, organic solvent; Obtained certain effect, but, also do not had a kind of method of definite moulding can continue degradating chloro organic matter efficiently based on present achievement in research; Aspects such as material modified effect and environmental behaviour thereof, bio-toxicity, ecological risk to nanometer iron degradating chloro organic-compound system remain in dispute, mainly show as:
(1) though the physics auxiliary law can be through strengthening or weakens some effect of system; Reach the purpose of reinforcing mass transfer and surface reaction, improvement system degradation effect to a certain extent; But its complicated operation cost is high, and is high to the requirement of hardware facility, is difficult to be applied to large-scale production practices; Can not adapt to soil the requirement that phreatic original position is repaired.
(2) mostly surfactant is in the system of nano particle degraded target contaminant, to add surfactant to the application aspect the chlorinatedorganic removal efficient at enhancing nanometer iron; Utilize its surface that reduces solid liquid interface ability; Strengthen the physical attractiveness of nano particle; Thereby strengthen its adsorptivity, improve the dechlorination efficiency of system target contaminant.Its limitation is: on the one hand, the kind of surfactant is numerous, and they remain in dispute the promotion or the inhibitory action of dechlorination system; On the other hand, size and the dispersion stabilization that surfactant is controlled nano particle underused in present application.
(3) polymer such as polyethylene glycol, polyacrylic acid, carboxymethyl cellulose, polyvinylpyrrolidone etc. are to reducing the size of nanometer palladium/iron double metal particle; Strengthening its dispersion stabilization aspect plays an important role; But the concentration dose the during modified nanoparticles of polymer, the complexity that has form, synthesis mode of polymer etc. becomes one of barrier of this technical 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, regeneration wait and also to have big problem, and load also can to run into hydraulic conductivity when fixedly the nano iron particles of modification is applied to soil or the reparation of phreatic original position low; Problems such as transmission property difference make this method of modifying be difficult to apply.
It is surfactant that publication number CN101579745A discloses with the cetyl ammonium bromide; N-butanol is a cosurfactant, and isooctane is an oil phase, is water configuration microemulsion with the ferrous sulfate and the potassium borohydride aqueous solution; In microemulsion, be initator with the azodiisobutyronitrile; Trigger monomer methyl methacrylate in-situ polymerization generates PMMA, prepares the nanometer iron of macromolecule clad, increases its aerial stability.But this method preparation process must could realize the modification of PMMA to nanometer iron by in-situ polymerization.
The method that chlorinatedorganic in the water is removed in dispersant modified Nano iron particle reduction according to the invention is devoted to overcome the defective with said method; Be intended to utilize dispersant directly the nanometer iron in the aqueous medium to be disperseed modification; It is being realized on the stable basis of nanoparticulate dispersed; Further reduce particle diameter; Raising is to the degradation efficiency of chlorinatedorganic in the water, and a kind of technology is simple to seek, 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; This method adopts liquid phase reduction; With polymer, cationic surfactant or anionic polymer electrolyte as dispersant, nano iron particles prepare in the process particle is carried out surface modified, thereby reduce its hard aggregation in aqueous medium; Increase its decentralization, make dispersant modified Nano iron particle.
The present invention accomplishes by following concrete steps:
(1) prepares certain density dispersant solution; With dispersant solution and concentration is the FeSO of 0.1-0.15mol/L
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 among the solution of potassium borohydride 0.20-0.3mol/L (for guaranteeing FeSO
4Fully and NaBH
4Reaction adds excessive KBH according to reaction equation
4Solution), stir, dropwise continued until mixed liquor and stir 10-15min, the solution that reacts completely is filtered while dripping, deionized water drip washing 2-3 all over after drain, obtain the zeroth order nano iron particles of stable dispersion;
(3) nano iron particles after will draining, with absolute ethyl alcohol drip washing 2 – 3 times, acetone soln drip washing 1 time, behind the suction filtration, vacuum 100-105 ℃ is ground under the logical nitrogen condition behind the dry 6-8h down, and sealing is preserved, and promptly gets the nano iron particles of dispersant modification.
Dispersant described in the present invention is a kind of in polymethyl methacrylate, polyacrylic acid, the softex kw solution.
The polymethyl methacrylate solution of dispersant described in the present invention is solvent with the methyl phenyl ethers anisole, 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 according to the invention with the mass percent concentration be the 0-100% ethanol water as solvent, be mixed with the softex kw solution of mass percentage concentration 7-10%.
Dispersant polyacrylic acid solution according to the invention is a solvent with the deionized water, is mixed with the polyacrylic acid that concentration of volume percent is 0.1-5% (PAA) aqueous solution.
The inventive method also can be disperseed modification to the iron-based bimetal granule; Concrete operations are after processing dispersant modification zeroth order nano iron particles, can pass through the common metal displacement reaction; Make iron-based bimetallic nano particle, like 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 the 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 nanometer iron to chlorinatedorganic in the water.Dispersant modification method according to the 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 nanometer iron in aqueous medium; The particle diameter of control nano iron particles, increase specific area, increase surface-active reaction position, thus the dechlorination activity that improves system reaches the removal efficient to chlorinatedorganic.
Compared with prior art, the advantage of the method for the invention is:
(1) polymethyl methacrylate that the present invention adopts (PMMA) is the dispersant of nanometer iron, prepares the more common nano iron particles stability of nano iron particles and improves, and degree of aggregation reduces.The irritability swelling of dispersant PMMA does not receive the influence of pH, temperature and ionic strength, can form the oleophylic boundary layer at the nanometer iron surface, promotes the absorption of target contaminant, also can suppress the corrosion oxidation of nanometer iron under oxidizing condition simultaneously.When excite (concentration like target contaminant raises) that PMMA receives environmental condition, can get through the structure of obstruction gradually, discharge effective iron gradually.
(2) the present invention utilizes dispersant PMMA to carry out the nano iron particles modification; Need not to generate PMMA through home position polymerization reaction with MMA; Thereby the inventive method prepares the technical process feasibility height of modification particle; Products obtained therefrom can be good at adapted soil, surface water and the reparation of phreatic original position dystopy, is easy to realize the through engineering approaches application, has very big implementation prospect.
(3) the dressing agent softex kw (CTAB) that the present invention adopted is a cationic surfactant, can be preferentially adsorbed on the particle through ion exchange.In the synthetic process of nanometer iron, utilize its electrostatic stabilization effect and sterically hindered effect simultaneously, can reach the purpose of stably dispersing nano particle, help the acquisition of the less nano particle of average grain diameter.In addition, CTAB can also reduce the surface ability 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 the dressing agent polyacrylic acid (PAA) that the present invention adopted 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 big.X-ray diffraction (XRD) spectrogram through analyzing polyacrylic acid modified nano iron particles can know that the crystalline structure of particle is α-Fe, and particle is purer, the oxidation iron tramp do not occur.
The present invention adopts dispersant that nano iron particles is modified; Defectives such as the easy oxidation of common nano iron particles, easy reunion have effectively been overcome; Not only can realize the stably dispersing of nano iron particles, can also obtain the catalytic reductive dechlorination efficient of high-efficient and lasting more of chlorinatedorganic in the water.
Description of drawings
Fig. 1 disperses the transmission electron microscope photo of modified Nano iron particle and common nano iron particles to compare sketch map for the PMMA of the present invention's preparation; Wherein (a) disperses modified Nano iron particle for PMMA; (b) be common nano iron particles.
Fig. 2 disperses modified Nano iron particle XRD spectra for the PAA of the present invention's preparation.
Fig. 3 disperses modified Nano iron particle and common nano iron particles to remove chlorinatedorganic effect comparison sketch map in the water for the PMMA of the present invention's preparation.
Fig. 4 disperses chlorinatedorganic effect comparison sketch map in modified Nano palladium/iron particle and the common nanometer palladium/iron particle removal water for the PMMA of the present invention's preparation.
Fig. 5 disperses chlorinatedorganic effect comparison sketch map in modified Nano nickel/iron particle and the common nanometer nickel/iron particle removal water for the CTAB of the present invention's preparation.
Fig. 6 disperses modified Nano iron particle and common nano iron particles to remove chlorinatedorganic effect comparison sketch map in the water for the PAA of the present invention's preparation.
The specific embodiment
Through accompanying drawing and embodiment the present invention is done further explain below, but protection domain of the present invention is not limited to said content.
Embodiment 1: polymetylmethacrylate disperses the preparation of modified Nano iron particle and to the removal of multiple chlorinatedorganic in the water, particular content is following:
(1) PMMA disperses the preparation and the dechlorination effect thereof of modified Nano iron particle
The 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
4Also stir among the solution 200mL, after dropwising, time-delay is stirred 15min to reacting completely; Filter through the vacuum filtration device and to drain, with washed with de-ionized water 3 times, suction filtration is to dried; Wash 3 times with absolute ethyl alcohol successively, acetone is washed 1 time again, puts it into after draining in the vacuum drying chamber in 100 ℃ of dry 6h; And under logical nitrogen condition, grind, sealing is preserved, and obtains PMMA and disperses modified Nano iron particle.
Disperse modified Nano iron particle to be added in the waste water water sample that contains target contaminant PMMA; React 4h down in normal temperature and pressure, the dosage of dispersant modified Nano iron particle is 5g/L, and the initial concentration of pollutant is 20mg/L; The initial pH value of reactant liquor is 7; Behind the reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation of common nano iron particles and dechlorination effect thereof
With 250mL concentration is the KBH of 0.2mol/L
4Solution dropwise adds the FeSO that 200mL concentration is 0.1mol/L
4In the solution, the limit edged is used magnetic stirrer FeSO
4Solution, after dropwising, time-delay is stirred 15min to reacting completely; Filter through the vacuum filtration device and to drain,, wash 3 times with absolute ethyl alcohol successively draining the zero-valent iron particle that obtains with washed with de-ionized water 3 times; Acetone is washed 1 time, puts it into after draining in the vacuum drying chamber in 100 ℃ of dry 6h, and under logical nitrogen condition, grinds; Sealing is preserved, and obtains unmodified nano iron particles.
Common nano iron particles is added in the waste water water sample that contains target contaminant; React 4h down in normal temperature and pressure, the dosage of nanometer iron double metal particle is 5g/L, and the initial concentration of pollutant is 20mg/L; The initial pH value of reactant liquor is 7; Behind the reaction result, measure chlorinatedorganic concentration, calculate clearance.
Through relatively knowing, PMMA disperses modified Nano iron particle to 2, and the clearance of 4-chlorophenesic acid, carbon tetrachloride and chloroform improves 27%, 18% and 25% (seeing Fig. 1 and 3) than common nano iron particles respectively.
Embodiment 2:PMMA disperses the preparation of modified Nano palladium/iron particle and to the removal of multiple chlorinatedorganic in the water, particular content is following:
(1) PMMA disperses the preparation and the dechlorination effect thereof of modified Nano palladium/iron double metal particle
The 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
4Also stir among the solution 200mL, after dropwising, time-delay is stirred 15min to reacting completely; Filter through the vacuum filtration device and to drain,, pour in the ethanolic solution of palladium draining the zeroth order nano iron particles that obtains with washed with de-ionized water 3 times; Under magnetic agitation, react 30min, place core filter suction filtration to doing product, wash 3 times with absolute ethyl alcohol successively; Acetone is washed 1 time, puts it into after draining in the vacuum drying chamber in 100 ℃ of dry 6h, and under logical nitrogen condition, grinds; Sealing is preserved, and obtains PMMA and disperses modified Nano palladium/iron double metal particle.
Disperse modified Nano palladium/iron double metal particle to be added in the waste water water sample that contains target contaminant PMMA; React 4h down in normal temperature and pressure, the dosage of dispersant modified Nano palladium/iron double metal particle is 5g/L, and the initial concentration of pollutant is 20mg/L; The initial pH value of reactant liquor is 7; Behind the reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation and the dechlorination effect thereof of common nanometer palladium/iron double metal particle
With 250mL concentration is the KBH of 0.2mol/L
4Solution dropwise adds the FeSO that 200mL concentration is 0.1mol/L
4In the solution, the limit edged is used magnetic stirrer FeSO
4Solution, after dropwising, time-delay is stirred 15min to reacting completely; Filter through the vacuum filtration device and to drain,, pour in the palladium palladium liquid draining the zero-valent iron particle that obtains with washed with de-ionized water 3 times; Under magnetic agitation, react 30min, place core filter suction filtration to doing product, wash 3 times with absolute ethyl alcohol successively; Acetone is washed 1 time, puts it into after draining in the vacuum drying chamber in 100 ℃ of dry 6h, and under logical nitrogen condition, grinds; Sealing is preserved, and obtains unmodified nanometer palladium/iron particle.Then common nanometer palladium/iron particle is added in the waste water water sample that contains target contaminant; React 4h down in normal temperature and pressure, the dosage of nanometer palladium/iron double metal particle is 5g/L, and the initial concentration of pollutant is 20mg/L; The initial pH value of reactant liquor is 7; Behind the reaction result, measure chlorinatedorganic concentration, calculate clearance.
Through relatively knowing, PMMA disperses modified Nano palladium/iron particle to 2, and the clearance of 4-chlorophenesic acid, carbon tetrachloride and chloroform improves 34%, 16% and 28% (see figure 4) than common nanometer palladium/iron particle respectively.
Embodiment 3:CTAB disperses the preparation of modified Nano nickel/iron particle and to the removal of multiple chlorinatedorganic in the water, particular content is following:
(1) CTAB disperses the preparation and the dechlorination effect thereof of modified Nano nickel/iron double metal particle
Softex kw solution (ethanol with mass percent concentration 70% the is made solvent) 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
4Among the solution 200mL and stir, after dropwising, time-delay is stirred 12min to reacting completely, and filter through the vacuum filtration device and drain, with washed with de-ionized water 2 times, be the nickel chloride (NiCl of 120mg/L with draining the zeroth order nano iron particles immersion concentration that obtains
2) in the solution, under magnetic agitation, react 30min, place core filter suction filtration to doing product; Wash 2 times with absolute ethyl alcohol successively; Acetone is washed 1 time, puts it into after draining in the vacuum drying chamber in 105 ℃ of dry 7h, and under logical nitrogen condition, grinds; Sealing is preserved, and obtains CTAB and disperses modified Nano nickel/iron double metal particle.
Disperse modified Nano nickel/iron double metal particle to be added in the waste water water sample that contains target contaminant CTAB; React 4h down in normal temperature and pressure, the dosage of dispersant modified Nano nickel/iron double metal particle is 5g/L, and the initial concentration of pollutant is 20mg/L; The initial pH value of reactant liquor is 7; Behind the reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation and the dechlorination effect thereof of common nanometer nickel/iron double metal particle
With 250mL concentration is the KBH of 0.2mol/L
4Solution dropwise adds the FeSO that 200mL concentration is 0.1mol/L
4In the solution, the limit edged is used magnetic stirrer FeSO
4Solution, after dropwising, time-delay is stirred 15min to reacting completely, and filter through the vacuum filtration device and drain, with washed with de-ionized water 2 times, be the nickel chloride (NiCl of 120mg/L with draining the zeroth order nano iron particles immersion concentration that obtains
2) in the solution, under magnetic agitation, react 30min, place core filter suction filtration to doing product; Wash 2 times with absolute ethyl alcohol successively; Acetone is washed 1 time, puts it into after draining in the vacuum drying chamber in 105 ℃ of dry 7h, and under logical nitrogen condition, grinds; Sealing is preserved, and obtains unmodified common nanometer nickel/iron particle.
Common nanometer nickel/iron particle is added in the waste water water sample that contains target contaminant; React 4h down in normal temperature and pressure, the dosage of nanometer nickel/iron double metal particle is 5g/L, and the initial concentration of pollutant is 20mg/L; The initial pH value of reactant liquor is 7; Behind the reaction result, measure chlorinatedorganic concentration, calculate clearance.
Through relatively knowing, CTAB disperses modified Nano nickel/iron particle to 2, and the clearance of 4-chlorophenesic acid, carbon tetrachloride and chloroform improves 28%, 10% and 22% (see figure 5) than common nanometer nickel/iron particle respectively.
Embodiment 4:PAA disperses the preparation of modified Nano palladium/iron particle and to the removal of multiple chlorinatedorganic in the water, particular content is following:
(1) PAA disperses the preparation process and the dechlorination effect thereof of modified Nano palladium/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
4Also stir among the solution 200mL, after dropwising, time-delay is stirred 10min to reacting completely; Filter through the vacuum filtration device and to drain,, pour in the ethanolic solution of palladium draining the zeroth order nano iron particles that obtains with washed with de-ionized water 3 times; Under magnetic agitation, react 30min, place core filter suction filtration to doing product, wash 3 times with absolute ethyl alcohol successively; Acetone is washed 1 time, puts it into after draining in the vacuum drying chamber in 102 ℃ of dry 8h, and under logical nitrogen condition, grinds; 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 that contains target contaminant; React 4h down in normal temperature and pressure, the dosage of dispersant modified Nano palladium/iron double metal particle is 5g/L, and the initial concentration of pollutant is 20mg/L; The initial pH value of reactant liquor is 7; Behind the reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation and the dechlorination effect thereof of common nanometer palladium/iron double metal particle, method is with embodiment 2.
Through relatively knowing, PAA disperses modified Nano palladium/iron particle to 2, and the clearance of 4-chlorophenesic acid, carbon tetrachloride and chloroform improves 17%, 14% and 20% than common nanometer palladium/iron particle respectively.
Embodiment 5:PAA disperses the preparation of modified Nano iron particle and to the removal of multiple chlorinatedorganic in the water, particular content is following:
(1) PAA disperses the preparation and the dechlorination effect thereof of modified Nano iron particle
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
4Also stir among the solution 230mL, after dropwising, time-delay is stirred 12min to reacting completely; Filter through the vacuum filtration device and to drain, with washed with de-ionized water 2 times, suction filtration is to dried; Wash 2 times with absolute ethyl alcohol successively, acetone is washed 1 time again, puts it into after draining in the vacuum drying chamber in 105 ℃ of dry 8h; And under logical nitrogen condition, grind, sealing is preserved, and obtains PAA and disperses modified Nano iron particle.
Disperse modified Nano iron particle to be added in the waste water water sample that contains target contaminant PAA; React 4h down in normal temperature and pressure, the dosage of dispersant modified Nano iron particle is 5g/L, and the initial concentration of pollutant is 20mg/L; The initial pH value of reactant liquor is 7; Behind the reaction result, measure chlorinatedorganic concentration, calculate clearance.
(2) preparation of common nano iron particles and dechlorination effect thereof, method is with embodiment 1.
Through relatively knowing, PAA disperses modified Nano iron particle to 2, and the clearance of 4-chlorophenesic acid, carbon tetrachloride and chloroform improves 25%, 15% and 20% than common nano iron particles respectively and (sees Fig. 2, Fig. 6).
Claims (7)
1. the preparation method of a dispersant modified Nano iron particle; It is characterized in that: with high polymer, cationic surfactant or anionic polymer electrolyte as dispersant; Prepare in the process at nano iron particles and to carry out surface modified particle; Thereby reduce its hard aggregation in aqueous medium, increase its decentralization, make dispersant modified Nano iron particle.
2. the preparation method of dispersant modified Nano iron particle according to claim 1 is characterized in that carrying out as follows:
(1) be the FeSO of 0.1-0.15mol/L with 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, dropwise continued until mixed liquor and stir 10-15min, the solution that reacts completely is filtered; Drain after deionized water drip washing 2-3 time, obtain the zeroth order nano iron particles of stable dispersion;
(3) nano iron particles after will draining, with absolute ethyl alcohol drip washing 2-3 time, acetone soln drip washing 1 time, behind the suction filtration, vacuum 100-105 ℃ is ground under the logical nitrogen condition behind the dry 6-8h down, and sealing is preserved, and promptly gets the nano iron particles of dispersant modification.
3. the preparation method of dispersant modified Nano iron particle according to claim 1 and 2 is characterized in that: dispersant is a kind of in polymethyl methacrylate, polyacrylic acid, the softex kw solution.
4. the preparation method of dispersant modified Nano iron particle according to claim 3 is characterized in that: polymethyl methacrylate solution is the methyl phenyl ethers anisole solution of the polymethyl methacrylate of mass percent concentration 7-10%.
5. the preparation method of dispersant modified Nano iron particle according to claim 3; It is characterized in that: softex kw solution with the mass percent concentration be the 0-100% ethanol water as solvent, be mixed with the softex kw solution of mass percent concentration 7-10%.
6. the preparation method of dispersant modified Nano iron particle according to claim 3 is characterized in that: polyacrylic acid solution is the polyacrylic acid aqueous solution of concentration of volume percent 0.1-5%.
7. the preparation method of dispersant modified Nano iron particle according to claim 1 and 2 is characterized in that: pass through metal displacement reaction after processing dispersant modification zeroth order nano iron particles, make the modifying iron based bimetallic nano particle of dispersant.
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