CN101941068A - Silica micropowder loaded type nano zerovalent iron particle and preparation method thereof - Google Patents
Silica micropowder loaded type nano zerovalent iron particle and preparation method thereof Download PDFInfo
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- CN101941068A CN101941068A CN200910069677XA CN200910069677A CN101941068A CN 101941068 A CN101941068 A CN 101941068A CN 200910069677X A CN200910069677X A CN 200910069677XA CN 200910069677 A CN200910069677 A CN 200910069677A CN 101941068 A CN101941068 A CN 101941068A
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Abstract
The invention belongs to the technical field of nano material preparation and relates to a silica micropowder loaded type nano zerovalent iron particle and a preparation method thereof. The method comprises the following steps of: (1) preparing modified silica micropowder; (2) removing oxygen; (3) preparing a nano iron solution; and (4) preparing nano zerovalent iron particles. In the invention, a liquid-phase reduction method is adopted to prepare the silica micropowder loaded type nano zerovalent iron particles, and a strong reducing agent KBH4 or NaBH4 is used for reducing Fe<3+> to obtain Fe<0>; loading is carried out through the silica micropowder to ensure that the agglomeration resistance of the nano zerovalent iron particle is greatly improved; the prepared nano zerovalent iron particles are uniformly distributed and have small mean grain size and large specific surface area; and the pollutant removal capacity of the nano zerovalent iron particles is far higher than that unloaded nano iron, and the nano zerovalent iron particles have stronger mobility in simulated soil, and can be widely applied to the field of environmental modification.
Description
Technical field
The invention belongs to the nano material preparation technical field, relate in particular to a kind of silicon powder loaded nano nulvalent iron particle and preparation method thereof.
Background technology
Adopting the nano zero valence iron reduction to remove environmental contaminants is technology that domestic and international in recent years broad research is used.Nano zero valence iron is compared with common iron powder, have the advantages that particle diameter is little, specific area big, the surface can be big, with the reaction of other material in have higher activity, treatment effect is far superior to common iron powder, have good application prospects, but the sp act of nano zero valence iron makes it need harsh operating condition in preparation and use.
The preparation method of nanometer nulvalent iron particle mainly comprises gas phase process, liquid phase process and solid phase method at present.
The nanometer nulvalent iron particle of gas phase process preparation, its purity height, particle diameter be little, be uniformly dispersed, but equipment is had relatively high expectations, and apparatus expensive requires HTHP simultaneously, operates dangerous; Though method for preparing solid phase is fairly simple, workable, reunite easily, and the particle diameter skewness etc.
Principle is simple, equipment is simple though liquid phase reduction has, workable, characteristics such as production cost is low, but therefore defectives such as also existing the particle diameter skewness, reunite easily, reactivity is lower must overcome this defective by adding certain dispersant.In order to solve the problem that nano-iron particle is reunited easily, generally adopt load or coating method that the nanometer nulvalent iron particle of preparation is modified.The nano-iron particle loaded article adopts inorganic material usually, as polymer resin, and active carbon, graphite, silica gel etc.; Coating adopts organic material usually, as sodium carboxymethylcellulose (CMC), starch (Starch), shitosan etc.Yet the method for this class clad nano nulvalent iron particle can not prevent to reunite fully, and perhaps the additive cost is higher.
Particle is tiny owing to having for silicon powder, big (the about 25-30m of specific area
2/ g), SiO
2Good physicochemical properties such as the high and strong pozzolanic activity of purity become a kind of important nano-micrometre level Inorganic Non-metallic Materials, are widely used in industries such as building, chemical industry, metallurgy, are called as " magical material " abroad.The present invention carries out load by silicon powder, make the anti-reunion performance of nanometer nulvalent iron particle obtain bigger raising, the ability of removing pollutant strengthens, and has stronger animal migration in simulated soil, and does not study report about the preparation with silicon powder loaded nano nulvalent iron particle
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of silicon powder loaded nano nulvalent iron particle and preparation method thereof, a kind of loaded nano nulvalent iron particle of more specifically saying so and utilizing the improvement liquid phase reduction to prepare the method preparation of silicon powder loaded nano Zero-valent Iron and obtaining.This method equipment needed thereby is simple, technology is easy, and obtained silicon powder loaded nano nulvalent iron particle has better soil animal migration and reactivity; In addition, used loaded article silicon powder belongs to refuse reclamation, and is environment friendly and pollution-free.
The present invention is achieved through the following technical solutions:
A kind of silicon powder loaded nano nulvalent iron particle is to be core with the modification silicon powder, evenly is stained with the very little nanometer nulvalent iron particle of particle diameter on its surface.
And the particle size distribution range of described nanometer nulvalent iron particle is 2-18nm, and average grain diameter is 6-8nm.
A kind of preparation method of silicon powder loaded nano nulvalent iron particle may further comprise the steps:
(1) preparation modification silicon powder:
Prepare silicon micro mist slurries add hydrochloric acid solution then, stir, and natural subsidence 2-3h gets the upper strata slurries, and centrifugation obtains the modification silicon powder;
(2) deoxygenation:
Above-mentioned modification silicon powder is dissolved in contains anhydrous FeCl
3Pure water mixed solution in, the molar concentration that makes iron ion is 0.01-0.03mol/L, feeds nitrogen deoxygenation 20-40min, mechanical agitation 9-11min obtains mixed solution so that mix then;
(3) preparation nanometer ferrous solution:
Under mechanical agitation to the freshly prepd KBH of mixed solution and dripping
4Solution or NaBH
4Solution reacts 30-40min, obtains the nanometer ferrous solution of black;
(4) preparation nanometer nulvalent iron particle:
The nanometer ferrous solution is isolated nanometer nulvalent iron particle through magnetic method, promptly gets silicon powder loaded nano nulvalent iron particle with distilled water washing, ethanol washing, vacuum drying.
And described hydrochloric acid solution addition is 1.2-1.8mol/L.
And volume ratio of alcohol to water is 3: 7 in the described pure water mixed solution, and alcohol is selected ethanol for use.
And, the freshly prepd KBH of the described mixed solution and dripping that after deoxygenation, obtains
4Solution or NaBH
4The molar concentration of solution is 4-6 a times of iron ion molar concentration.
Advantage of the present invention and beneficial effect are:
1, equipment required for the present invention is simple, and technology is easy, and reaction is finished at normal temperatures, and product is a solid phase, and reaction system is a liquid phase, and product separates easily, is applicable to large-scale industrial production.
2, it is cheap and easy to get that the present invention prepares the support materials silicon powder that silicon powder loaded nano nulvalent iron particle adopted, belong to refuse reclamation and, carry out load by silicon powder and make the anti-reunion performance of nanometer nulvalent iron particle obtain bigger raising environment nonhazardous effect.
3, the prepared silicon powder loaded nano of the present invention nulvalent iron particle is evenly distributed, average grain diameter is little, particle size distribution range is 2-18nm, average grain diameter is 6-8nm, specific area is big, not only in simulated soil, have stronger animal migration and to the removal ability of pollutant far above the nano zero valence iron of load not, can be widely used in the environment remediation field.
Description of drawings
Fig. 1 is the silicon powder loaded nano nulvalent iron particle transmission electron microscope photo of the present invention's preparation;
Fig. 2 removes Cr in the water for the silicon powder loaded nano nulvalent iron particle of the present invention preparation and loaded with nano Zero-valent Iron not
6+The performance comparison diagram;
Fig. 3 is the silicon powder loaded nano nulvalent iron particle of the present invention preparation and the soil migration performance comparison diagram of loaded with nano Zero-valent Iron not.
The specific embodiment
The present invention is described in further detail in conjunction with the accompanying drawings by following examples, but the technology contents that present embodiment is narrated is illustrative, rather than determinate, should not limit to protection scope of the present invention according to this.
This silicon powder loaded nano nulvalent iron particle is to be core with the modification silicon powder, evenly is stained with the very little nanometer nulvalent iron particle of particle diameter on its surface, and the particle size distribution range of nanometer nulvalent iron particle is 2-18nm, and average grain diameter is 6-8nm.
Embodiment 1:
A kind of silicon powder loaded nano nulvalent iron particle preparation method may further comprise the steps:
(1) preparation modification silicon powder:
The silicon powder slurries of configuration 13g/L add the hydrochloric acid solution of 1.7mol/L then, stir, and natural subsidence 3h gets the slurries centrifugation on upper strata.
(2) deoxygenation:
Above-mentioned centrifugal good silicon powder is dissolved in contains anhydrous FeCl
3Mixed solution in (volume ratio of alcohol to water is 3: 7), the molar concentration that makes iron ion is 0.011mol/L, feeds nitrogen deoxygenation 20min, mechanical agitation 10min obtains mixed solution so that mix fully.
(3) preparation nanometer ferrous solution:
Under mechanical agitation to the freshly prepd KBH of mixed solution and dripping 10ml 0.268mol/L
4Solution reacts 30min, obtains the nanometer ferrous solution of black.
(4) preparation nanometer nulvalent iron particle:
The nanometer ferrous solution is isolated nanometer nulvalent iron particle through magnetic method, fully washs three times with distilled water, and alcohol is given a baby a bath on the third day after its birth time, and vacuum drying promptly gets silicon powder loaded nano nulvalent iron particle.
Embodiment 2:
When the nanometer ferrous solution of preparation black, its reactant adopts NaBH
4Solution substitutes KBH
4Solution gets final product, and other all are same as embodiment 1.
Embodiment 3:
A kind of silicon powder loaded nano nulvalent iron particle preparation method may further comprise the steps:
(1) preparation modification silicon powder:
The silicon powder slurries of configuration 13g/L add the hydrochloric acid solution of 1.3mol/L then, stir, and natural subsidence 2.5h gets the slurries centrifugation on upper strata.
(2) deoxygenation:
Above-mentioned centrifugal good silicon powder is dissolved in contains anhydrous FeCl
3Mixed solution in (volume ratio of alcohol to water is 3: 7), the molar concentration that makes iron ion is 0.014mol/L, feeds nitrogen deoxygenation 30min, mechanical agitation 10min obtains mixed solution so that mix fully.
(3) preparation nanometer ferrous solution:
Under mechanical agitation to the freshly prepd KBH of mixed solution and dripping 10ml 0.358mol/L
4Solution reacts 35min, obtains the nanometer ferrous solution of black.
(4) preparation nanometer nulvalent iron particle:
The nanometer ferrous solution is isolated nanometer nulvalent iron particle through magnetic method, fully washs three times with distilled water, and alcohol is given a baby a bath on the third day after its birth time, and vacuum drying promptly gets silicon powder loaded nano nulvalent iron particle.
Embodiment 4:
When the nanometer ferrous solution of preparation black, its reactant adopts NaBH
4Solution substitutes KBH
4Solution gets final product, and other all are same as embodiment 3.
Embodiment 5:
A kind of silicon powder loaded nano nulvalent iron particle preparation method may further comprise the steps:
(1) preparation modification silicon powder:
The silicon powder slurries of configuration 13g/L add the 1.5mol/L hydrochloric acid solution then, stir, and natural subsidence 2h gets the slurries centrifugation on upper strata.
(2) deoxygenation:
Above-mentioned centrifugal good silicon powder transferred to contain anhydrous FeCl
3Solution in (volume ratio of alcohol to water is 3: 7), the molar concentration that makes iron ion is 0.018mol/L, feeds nitrogen deoxygenation 40min, mechanical agitation 10min obtains mixed solution so that mix fully.
(3) preparation nanometer ferrous solution:
Under mechanical agitation to the freshly prepd KBH of mixed solution and dripping 10ml 0.448mol/L
4Solution reacts 40min, obtains the nanometer ferrous solution of black.
(4) preparation nanometer nulvalent iron particle:
The nanometer ferrous solution is isolated nanometer nulvalent iron particle through magnetic method, fully washs three times with distilled water, and alcohol is given a baby a bath on the third day after its birth time, and vacuum drying promptly gets silicon powder loaded nano nulvalent iron particle.
Embodiment 6:
When the nanometer ferrous solution of preparation black, its reactant adopts NaBH
4Solution substitutes KBH
4Solution gets final product, and other all are same as embodiment 5.
Principle of the present invention:
The present invention utilizes strong reductant KBH
4Or NaBH
4Reduction Fe
3+Obtain Fe
0, its reaction equation is:
Experimental verification is as follows:
(1) use TEM (transmission electron microscope) to measure the form and the particle size of the silicon powder loaded nano nulvalent iron particle of the present invention's preparation.Interpretation of result is as follows:
TEM result shows that this loaded nano nulvalent iron particle is to be core with the silicon powder, is adhering to the very little nano-iron particle of particle diameter uniformly on its surface; The nanometer nulvalent iron particle particle size distribution range is 2-18nm, and average grain diameter is 6-8nm, as shown in Figure 1.
(2) the performance comparative test of removing Cr (VI) in the water of the silicon powder loaded nano Zero-valent Iron of the present invention preparation and loaded with nano Zero-valent Iron not is as follows:
In being Cr (VI) solution of 40mg/L, the 100ml initial concentration adds the 0.03g silicon powder loaded nano nulvalent iron particle and the nano zero valence iron of load not respectively, normal temperature and pressure is reaction down, adopt diphenyl carbazide spectrophotometry to measure residual Cr (VI) in the solution, add dosage in the loaded nano Zero-valent Iron and equal under the condition of loaded with nano Zero-valent Iron not, its removal effect is better than the nano zero valence iron of not load far away.As shown in Figure 2.
(3) the silicon powder loaded nano Zero-valent Iron of the present invention's preparation is as follows with the nano zero valence iron soil migration performance test of not load:
Be that the top of 0.39 quartz sand column adds the silicon powder support type of 10ml2.5mg/L and the nanometer ferrous solution of load not respectively at porosity, wash away ionized water by constant flow pump on quartz sand column top then, flow velocity is 14ml/min, and the turbidity by the nanometer iron that moves calculates the transmitance of nanometer iron at quartz sand column.The animal migration of silicon powder loaded nano Zero-valent Iron in quartz sand column is much larger than the nano zero valence iron of load not.As shown in Figure 3.
Claims (6)
1. silicon powder loaded nano nulvalent iron particle is characterized in that: be to be core with the modification silicon powder, evenly be stained with the very little nanometer nulvalent iron particle of particle diameter on its surface.
2. silicon powder loaded nano nulvalent iron particle according to claim 1 is characterized in that: the particle size distribution range of described nanometer nulvalent iron particle is 2-18nm, and average grain diameter is 6-8nm.
3. the preparation method of a silicon powder loaded nano nulvalent iron particle as claimed in claim 1, it is characterized in that: the preparation method may further comprise the steps:
(1) preparation modification silicon powder:
Prepare silicon micro mist slurries add hydrochloric acid solution then, stir, and natural subsidence 2-3h gets the upper strata slurries, and centrifugation obtains the modification silicon powder;
(2) deoxygenation:
Above-mentioned modification silicon powder is dissolved in contains anhydrous FeCl
3Pure water mixed solution in, the molar concentration that makes iron ion is 0.01-0.03mol/L, feeds nitrogen deoxygenation 20-40min, mechanical agitation 9-11min obtains mixed solution so that mix then;
(3) preparation nanometer ferrous solution:
Under mechanical agitation to the freshly prepd KBH of mixed solution and dripping
4Solution or NaBH
4Solution reacts 30-40min, obtains the nanometer ferrous solution of black;
(4) preparation nanometer nulvalent iron particle:
The nanometer ferrous solution is isolated nanometer nulvalent iron particle through magnetic method, promptly gets silicon powder loaded nano nulvalent iron particle with distilled water washing, ethanol washing, vacuum drying.
4. the preparation method of silicon powder loaded nano nulvalent iron particle according to claim 3 is characterized in that: described hydrochloric acid solution addition is 1.2-1.8mol/L.
5. the preparation method of silicon powder loaded nano nulvalent iron particle according to claim 3 is characterized in that: volume ratio of alcohol to water is 3: 7 in the described pure water mixed solution, and alcohol is selected ethanol for use.
6. the preparation method of silicon powder loaded nano nulvalent iron particle according to claim 3 is characterized in that: the freshly prepd KBH of the described mixed solution and dripping that obtains after deoxygenation
4Solution or NaBH
4The molar concentration of solution is 4-6 a times of iron ion molar concentration.
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| CN103007907A (en) * | 2012-12-21 | 2013-04-03 | 清华大学 | Preparation method of high-efficiency quantitative supported nano iron |
| CN103143705A (en) * | 2013-03-29 | 2013-06-12 | 湖南科技大学 | Alumina-clad iron nanoparticles and preparation method as well as application thereof |
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| CN104759635A (en) * | 2015-03-12 | 2015-07-08 | 中国科学院福建物质结构研究所 | Preparation method of load type nanometer zero-valent iron composite material |
| CN108862538A (en) * | 2018-05-30 | 2018-11-23 | 中国地质大学（武汉） | The method of nano zero valence iron activation sodium percarbonate degradation bisphenol-A |
| CN110097992A (en) * | 2019-05-09 | 2019-08-06 | 东华理工大学 | A kind of method that high-strength flour cladding nano zero valence iron removes uranium in nuclear waste |
| CN110153170A (en) * | 2019-05-23 | 2019-08-23 | 四川大学 | Composite material, preparation method and application for heavy metal-organic matter reparation |
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| CN103007907A (en) * | 2012-12-21 | 2013-04-03 | 清华大学 | Preparation method of high-efficiency quantitative supported nano iron |
| CN103192073B (en) * | 2013-03-29 | 2015-12-23 | 湖南科技大学 | A kind of nanometer iron silicon compound particle of three-layer nuclear shell structure and preparation method and application |
| CN103143705A (en) * | 2013-03-29 | 2013-06-12 | 湖南科技大学 | Alumina-clad iron nanoparticles and preparation method as well as application thereof |
| CN103192073A (en) * | 2013-03-29 | 2013-07-10 | 湖南科技大学 | Nanometer ferrosilicon composite particle of three-layer nuclear shell structure and preparing method and application thereof |
| CN103143705B (en) * | 2013-03-29 | 2015-08-19 | 湖南科技大学 | A kind of alumina-coated type nano-iron particle and preparation method thereof and application |
| CN103317144A (en) * | 2013-06-26 | 2013-09-25 | 昆明理工大学 | Production method for iron-based nanometer thermometal particles modified by surface modifiers |
| CN103317144B (en) * | 2013-06-26 | 2015-09-16 | 昆明理工大学 | The preparation method of the modifying iron based nanoscale bimetallic particles of a kind of coating material |
| CN104759635B (en) * | 2015-03-12 | 2016-09-14 | 中国科学院福建物质结构研究所 | A kind of preparation method of loaded nano zero-valent iron composite material |
| CN104759635A (en) * | 2015-03-12 | 2015-07-08 | 中国科学院福建物质结构研究所 | Preparation method of load type nanometer zero-valent iron composite material |
| CN108862538A (en) * | 2018-05-30 | 2018-11-23 | 中国地质大学（武汉） | The method of nano zero valence iron activation sodium percarbonate degradation bisphenol-A |
| CN110097992A (en) * | 2019-05-09 | 2019-08-06 | 东华理工大学 | A kind of method that high-strength flour cladding nano zero valence iron removes uranium in nuclear waste |
| CN110153170A (en) * | 2019-05-23 | 2019-08-23 | 四川大学 | Composite material, preparation method and application for heavy metal-organic matter reparation |
| CN110451597A (en) * | 2019-07-31 | 2019-11-15 | 武汉科技大学 | A kind of nano zero valence iron@molecular sieves compound material and preparation method thereof and purposes |
| CN113000851A (en) * | 2021-01-28 | 2021-06-22 | 南开大学 | Method for preparing superparamagnetic nano-iron with controllable particle size by using microchannel reactor |
| CN114307981A (en) * | 2021-12-30 | 2022-04-12 | 北京建工环境修复股份有限公司 | Aminated chitosan silica microsphere and preparation method and application thereof |
| CN115106519A (en) * | 2022-06-09 | 2022-09-27 | 南开大学 | Superparamagnetic nano-iron material, composite material thereof, preparation method and application |
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Application publication date: 20110112 |