CN100566803C - A kind of process for dispersing of nano iron particles - Google Patents
A kind of process for dispersing of nano iron particles Download PDFInfo
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- CN100566803C CN100566803C CNB2008100276177A CN200810027617A CN100566803C CN 100566803 C CN100566803 C CN 100566803C CN B2008100276177 A CNB2008100276177 A CN B2008100276177A CN 200810027617 A CN200810027617 A CN 200810027617A CN 100566803 C CN100566803 C CN 100566803C
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Abstract
The invention discloses a kind of process for dispersing of nano iron particles, may further comprise the steps: (1) is that the superfine sheet nanometer iron powder of 10～200nm is mixed with the nano-hot metal solution that concentration is 1～5g/L with granularity; (2) by the active carbon of the particle behind 2: 1～1: 3 the iron charcoal mass ratio adding process hydrophilic modification less than 10 μ m; (3) disperseed 0.5～4 hour with high-energy mill, take out liquid phase, obtain the nanometer iron/activated carbon composite aqueous solution of stable dispersion.And the present invention adopts cheaply that mechanical milling method prepares nanometer iron powder, and dispersion effect is stable, does not reunite, does not precipitate with interior at several days, can be applied in the groundwater seepage wall.
Description
Technical field
The present invention relates to the process for dispersing of nano particle, specifically is a kind of process for dispersing of nano iron particles.
Background technology
The underground water in the most of city of China is polluted by various organic and inorganic harmful substances to some extent.Common organic pollution comprises the remains of pesticide of the water that permeates the ground, hydrocarbons such as alkane that leak the gas station and aromatic hydrocarbon, the chlorohydrocarbon of the discharging of factory and enterprise and drycleaner's.Therefore, very urgent to contaminated phreatic improvement reparation.Compare advantage such as the based technique for in-situ remediation that injects reactive materials to the poluted region has not must power, cost is low, do not destroy environment, repair time is short with traditional " extraction-processing " technology.Yet utilize traditional permeable reactive wall to repair underground water pollution its shortcoming is also arranged.At first, this technology can only be used to repair more shallow water-bearing layer, and this is because the ditch of construction depth above 8 meters is relatively more difficult.Secondly, traditional permeable reactive wall can not be used for directly repairing pollution sources, and can only be placed in the downstream of polluting plume.These shortcomings of tradition permeable reactive wall have been impelled and have been passed through to the development of underground injection reactive materials with the technology of formation reaction zone.By various method for implanting (splitting as waterpower system), the degree of depth that reactive materials is injected into is far longer than classical inverse and answers the degree of depth of wall (can reach about 40 meters at most).Nanometer iron is strong because of its respond, enters characteristics such as low permeability zone easily and is considered to a kind of reactive materials with wide application prospect.Because the specific area of ultra-fine grade zeroth order iron powder is much larger than iron filings, the efficient of its degradation of contaminant will be far above iron filings.In addition, because nano iron particles is very little, obtaining infiltration at Polluted area easily, is a kind of active material of desirable formation reaction zone.At present, the research report about nanometer iron powder degradating chloro hydrocarbon is also a lot.(Comparison of reductive dechlorination of p-chlorophenolusing Fe such as Cheng
0And nanosized Fe
0Journal of Hazardous Materials, 2007,144:334-339.) studied nano zero-valence iron powder and common zeroth order iron powder (grain graininess 100-300 order) degraded situation to the 4-chlorophenol, the result proves that the reactivity of nano zero-valence iron powder will be higher than common zeroth order iron powder far away.But,, can practical sixty-four dollar question be the stable dispersion in water body for nanometer iron powder.
Because nanometer iron powder has great specific area and higher surface energy, particle coalescence, reunion very easily take place in preparation, use, form offspring, make particle diameter become big, thereby (transmission electron microscope is measured the granularity and the distribution of nanometer iron powder under different dispersion conditions to lose the function that nanoparticle possesses, chemistry and bonding, 2005,27:251-252.).So it is also very important to the Study on dispersity of nanometer iron powder in the aqueous solution, (Delivery Vehicles forZerovalent Metal Nanoparticles in Soil and Groundwater such as Schrick, Chem.Mater, 2004,16:2187-2193) with FeSO
4H
2O mixes respectively and through the carbon black of hydrophilic modification or polyacrylic acid, adds deionized water and makes two kinds of different mixed solutions, adds strong reductant NaBH to mixed solution then
4, Fe
2+Be reduced into minimum nano iron particles very soon, the nano iron particles of this moment has very strong adsorptivity, carbon black or polyacrylic acid around can adsorbing, reaction has just been made iron/charcoal, iron/polyacrylic compound particle after finishing, and reaches the purpose that improves the nano iron particles dispersiveness with this.Open towards equality (microemulsion method prepares ultra-fine coated iron powder, applied chemistry, 2000,17:248-251) with neopelex (DBS)/isoamyl alcohol/normal heptane/H
2The O reaction system is with NaBH
4Make reducing agent, use FeCl
26H
2O prepares and is coated with DBS. nanoscale coated superfine iron powder, and has good stable.(the dispersive property research of nanometer iron powder such as sieve coltfoal China, foundry engieering, 2007,28:184-185.) to have studied lauryl sodium sulfate (SDS) and oleic acid be that surfactant is the nanometer iron powder of 50nm to the average grain diameter that adopts the preparation of hydrogen arc plasma process, dispersion effect in ethanolic solution, the result shows, oleic acid for nanometer iron powder in ethanol dispersion effect be better than lauryl sodium sulfate all the time.At present, for the method that nanometer iron powder disperses, a common feature is all arranged: used all is that grain graininess is very little, has the ball shaped nano iron particle of strong adsorptivity, and these methods then are not fine to the superfine sheet particle of research prepared by physical method.In addition, when adopting the very high spherical nano iron particles of organic surface active agent modified chemical activity, might be by its deoxidization, degradation, so that do not reach dispersion effect.
Adopt the nanometer iron powder of the preparation of Mechanical Method cheaply to be applied in the infiltration wall and have agglomeration traits equally.The nano iron particles of mechanical milling method preparation is the irregular laminated structure (see figure 1) in edge, and the broad particle distribution of particle, and the nano iron particles of chemical method preparation is spherical, and size distribution is also very narrow.The dispersing mode of the nanometer iron powder of Mechanical Method preparation is different from the nanometer iron powder of chemical method preparation, and the nanometer iron powder of stable dispersion mechanical milling method preparation is a current great difficult problem.
Summary of the invention
The object of the present invention is to provide a kind of process for dispersing of nano iron particles, it utilizes the characteristics of the pore passage structure of the shape characteristic of irregular flake nano iron powder and active carbon prosperity, the mechanical force of utilizing medium stirring mill to produce, active carbon behind itself and the hydrophilic modification combined be prepared into nanometer iron/activated carbon composite, and directly be distributed to aqueous phase, form stabilized nano iron/activated carbon composite aqueous solution.
The objective of the invention is to be achieved through the following technical solutions:
A kind of process for dispersing of nano iron particles may further comprise the steps:
(1) be that the superfine sheet nanometer iron powder of 10～200nm is mixed with the nano-hot metal solution that concentration is 1～5g/L with granularity;
(2) by the active carbon of the particle behind 2: 1～1: 3 the iron charcoal mass ratio adding process hydrophilic modification less than 10 μ m;
(3) disperseed 0.5～4 hour with high-energy mill, take out liquid phase, obtain the nanometer iron/activated carbon composite aqueous solution of stable dispersion.
The preparation process of above-mentioned nanometer iron powder can be: take by weighing a certain amount of reduced iron powder, be equipped with abrading-ball by 30: 1～70: 1 ratios of grinding media to material, with the lightweight organic matter is the liquid phase abrasive media, and add 5～10% polyethylene glycol (with respect to the mass percent of reduced iron powder) as grinding aid, adopt planetary mills to grind 40～120 hours, making granularity is the superfine sheet nanometer iron powder of 10～200nm, and described lightweight organic matter is absolute ethyl alcohol, ethylene glycol, acetone, methyl alcohol.
The front is mentioned, and Schrick etc. (Delivery Vehicles for Zerovalent Metal Nanoparticles in Soil andGroundwater, Chem.Mater, 2004,16:2187-2193) with FeSO
4H
2O mixes respectively and through the carbon black of hydrophilic modification or polyacrylic acid, adds deionized water and makes two kinds of different mixed solutions, adds strong reductant NaBH to mixed solution then
4, Fe
2+Be reduced into minimum nano iron particles very soon, the nano iron particles of this moment has very strong adsorptivity, carbon black or polyacrylic acid around can adsorbing, reaction has just been made iron/charcoal, iron/polyacrylic compound particle after finishing, and reaches the purpose that improves the nano iron particles dispersiveness with this.Here the nano iron particles of being mentioned is the chemical method preparation, and cost is very high.And the present invention adopts cheaply that mechanical milling method prepares nanometer iron powder, and dispersion effect is stable, can realize large-scale application.The active carbon that the present invention adopts is different with above-mentioned carbon black, and activated carbon surface has a lot of pore passage structures, and carbon black does not then have, and the fineness ratio active carbon of carbon black is much smaller.
According to process for dispersing of the present invention, the nanometer that obtains iron/activated carbon composite aqueous solution can stably exist, and does not reunite, does not precipitate with interior at several days, can be applied in the groundwater seepage wall.
Description of drawings
Fig. 1 is that mechanical milling method prepares flake nano iron particulate scan sem image.
The specific embodiment
Further specify the present invention by the following examples.
The preparation process of hydrophilic modification active carbon is:
(2.1) get a certain amount of active carbon, its refinement in pulverizer is pulverized, make its particle less than 10 μ m;
(2.2) active carbon being made into mass percent concentration is 5～10% the aqueous solution; Add modifier then, described modifier is nitric acid, hypochlorous acid or hydrogen peroxide, constantly stirs it fully to be reacted in 8～12 hours;
(2.3) the modification charcoal solution concentration after will reacting completely with deionized water is diluted to originally 50%～30%, is under 5000～8000r/min centrifugal about 10 minutes at rotating speed, removes supernatant;
(2.4) behind the repeating step (2.3) 2～3 times, with the gained black precipitate at 80～120 ℃ of following bone dries.
Among the comparative example, be not added into the active carbon after the modification in the dispersed nanometer ferrous solution.
Embodiment 1:
Take by weighing the 10g reduced iron powder, put into polyurethane material grinding pot, add absolute ethyl alcohol as liquid phase medium, and add 10% polyethylene glycol (with respect to the mass percent of reduced iron powder) as grinding aid, be equipped with the abrasive media (ratio of grinding media to material 70: 1) of carbide alloy, the rotating speed with 450rpm grinds 120h in planetary mills then.Liquid is dried in vacuum drying oven, obtain the solid metal powder (meso-position radius is 120nm) of black nano iron powder.The nano-hot metal solution of preparation 2g/L, add the hydrophilic modification active carbon by 1: 3 iron charcoal mass ratio, mechanical dispersion in the Perl Mill PML-H/V type medium stirring mill that German Draiswerke company produces, after grinding stirring 3h, take out 20mL solution with range and pour in the test tube, and test tube is placed the sedimentation situation of observation solution on the horizontal table top.The result shows that solution can be stablized and kept 58 hours.
Example 2:
Take by weighing the 7g reduced iron powder, put into polyurethane material grinding pot, add absolute ethyl alcohol as liquid phase medium, and add 8% polyethylene glycol (with respect to the mass percent of reduced iron powder) as grinding aid, be equipped with the abrasive media (ratio of grinding media to material 50: 1) of carbide alloy, the rotating speed with 420rpm grinds 100h in planetary mills then.Liquid is dried in vacuum drying oven, obtain the solid metal powder of black nano iron powder.The nanometer ferrous solution of preparation 3g/L, add the hydrophilic modification active carbon by 1: 2 iron charcoal mass ratio, mechanical dispersion in the Perl Mill PML-H/V type medium stirring mill that German Draiswerke company produces, after grinding stirring 2h, take out 20mL solution with range and pour in the test tube, and test tube is placed the sedimentation situation of observation solution on the horizontal table top.The result shows that solution can be stablized and kept 52 hours.
Example 3:
Take by weighing the 8g reduced iron powder, put into polyurethane material grinding pot, add absolute ethyl alcohol as liquid phase medium, and add 6% polyethylene glycol (with respect to the mass percent of reduced iron powder) as grinding aid, be equipped with the abrasive media (ratio of grinding media to material 60: 1) of carbide alloy, the rotating speed with 380rpm grinds 80h in planetary mills then.Liquid is dried in vacuum drying oven, obtain the solid metal powder of black nano iron powder.The nanometer ferrous solution of preparation 4g/L, add the hydrophilic modification active carbon by 1: 1 iron charcoal mass ratio, mechanical dispersion in the Perl Mill PML-H/V type medium stirring mill that German Draiswerke company produces, after grinding stirring 1h, take out 20mL solution with range and pour in the test tube, and test tube is placed the sedimentation situation of observation solution on the horizontal table top.The result shows that solution can be stablized and kept 48 hours.
Example 4:
Take by weighing the 5g reduced iron powder, put into polyurethane material grinding pot, add absolute ethyl alcohol as liquid phase medium, and add 7% polyethylene glycol (with respect to the mass percent of reduced iron powder) as grinding aid, be equipped with the abrasive media (ratio of grinding media to material 40: 1) of carbide alloy, the rotating speed with 400rpm grinds 60h in planetary mills then.Liquid is dried in vacuum drying oven, obtain the solid metal powder of black nano iron powder.The nanometer ferrous solution of preparation 1g/L, add the hydrophilic modification active carbon by 2: 1 iron charcoal mass ratioes, mechanical dispersion in the Perl Mill PML-H/V type medium stirring mill that German Draiswerke company produces, after grinding stirring 4h, take out 20mL solution with range and pour in the test tube, and test tube is placed the sedimentation situation of observation solution on the horizontal table top.The result shows that solution can be stablized and kept 40 hours.
Example 5:
Take by weighing the 6g reduced iron powder, put into polyurethane material grinding pot, add absolute ethyl alcohol as liquid phase medium, and add 5% polyethylene glycol (with respect to the mass percent of reduced iron powder) as grinding aid, be equipped with the abrasive media (ratio of grinding media to material 40: 1) of carbide alloy, the rotating speed with 380rpm grinds 40h in planetary mills then.Liquid is dried in vacuum drying oven, obtain the solid metal powder of black nano iron powder.The nanometer ferrous solution of preparation 5g/L, add the hydrophilic modification active carbon by 2: 1 iron charcoal mass ratioes, mechanical dispersion in the Perl Mill PML-H/V type medium stirring mill that German Draiswerke company produces, after grinding stirring 0.5h, take out 20mL solution with range and pour in the test tube, and test tube is placed the sedimentation situation of observation solution on the horizontal table top.The result shows that solution can be stablized and kept 12 hours.
The comparative example:
Take by weighing the 10g reduced iron powder, put into polyurethane material grinding pot, add absolute ethyl alcohol as liquid phase medium, and add 8% polyethylene glycol (with respect to the mass percent of reduced iron powder) as grinding aid, be equipped with the abrasive media (ratio of grinding media to material 70: 1) of carbide alloy, the rotating speed with 420rpm grinds 40h then.Liquid is dried in vacuum drying oven, obtain the solid metal powder of black nano iron powder.The nanometer ferrous solution of preparation 2g/L, mechanical dispersion in the Perl MillPML-H/V type medium stirring mill that German Draiswerke company produces, after grinding stirring 3h, take out 20mL solution with range and pour in the test tube, and test tube is placed the sedimentation situation of observation solution on the horizontal table top.The result shows that solution has become transparent after 30 minutes, illustrates that nanometer iron precipitates substantially fully.
Compare with the comparative example, far better according to nanometer iron/activated carbon composite aqueous stability that the inventive method dispersion obtains.
Claims (5)
1, a kind of process for dispersing of nano iron particles is characterized in that may further comprise the steps:
(1) be that the superfine sheet nanometer iron powder of 10～200nm is mixed with the nano-hot metal solution that concentration is 1～5g/L with granularity;
(2) by the active carbon of the particle behind 2: 1～1: 3 the iron charcoal mass ratio adding process hydrophilic modification less than 10 μ m;
(3) disperseed 0.5～4 hour with high-energy mill, take out liquid phase, obtain the nanometer iron/activated carbon composite aqueous solution of stable dispersion;
The preparation process of the described active carbon of step (2) is:
(2.1) get a certain amount of active carbon, its refinement in pulverizer is pulverized, make its particle less than 10 μ m;
(2.2) active carbon being made into mass percent concentration is 5～10% the aqueous solution; Add modifier then, described modifier is nitric acid, hypochlorous acid or hydrogen peroxide, constantly stirs it fully to be reacted in 8～12 hours;
(2.3) the modification charcoal solution concentration after will reacting completely with deionized water is diluted to originally 50%～30%, is under 5000～8000r/min centrifugal about 10 minutes at rotating speed, removes supernatant;
(2.4) behind the repeating step (2.3) 2～3 times, with the gained black precipitate at 80～120 ℃ of following bone dries.
2, the process for dispersing of nano iron particles according to claim 1, the preparation process that it is characterized in that nanometer iron powder described in the step (1) is: take by weighing a certain amount of reduced iron powder, be equipped with abrading-ball by 30: 1～70: 1 ratios of grinding media to material, with the lightweight organic matter is the liquid phase abrasive media, and add polyethylene glycol as grinding aid, the consumption of polyethylene glycol is 5～10% of a reduced iron powder quality, adopt planetary mills to grind 40～120 hours, making granularity is the superfine sheet nanometer iron powder of 10～200nm, and described lightweight organic matter is absolute ethyl alcohol, ethylene glycol, acetone, methyl alcohol.
3, the process for dispersing of nano particle according to claim 1 and 2 is characterized in that disperseing 1～3 hour with high-energy mill in the step (3).
4, the process for dispersing of nano particle according to claim 3 is characterized in that the concentration of nano-hot metal solution in the step (1) is configured to 2～4g/L.
5, the process for dispersing of nano particle according to claim 1 and 2 is characterized in that the concentration of nano-hot metal solution in the step (1) is configured to 2～4g/L.
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| CN101481155B (en) * | 2009-03-03 | 2011-03-09 | 同济大学 | Composite material for water treatment, and preparation and use thereof |
| CN101830471B (en) * | 2010-04-02 | 2012-09-26 | 吉林大学 | Method for preventing nano particles from being agglomerated during processing nano particles at high temperature |
| CN103394699B (en) * | 2013-08-19 | 2015-08-19 | 上海富大同诺环境科技有限公司 | The preparation method of nano iron particles and application thereof |
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| CN113560586B (en) * | 2021-07-27 | 2023-07-04 | 上海爱仑倍思环境科技有限公司 | Preparation device of irregular flaky zero-valent iron-based nano material |
| CN115364823A (en) * | 2022-08-23 | 2022-11-22 | 中南大学 | Nano zero-valent iron slurry capable of repairing arsenic pollution of underground water and preparation method and application thereof |
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