CN103357884A - Method for preparing porous nano-iron by brown iron ore - Google Patents
Method for preparing porous nano-iron by brown iron ore Download PDFInfo
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- CN103357884A CN103357884A CN2013102817169A CN201310281716A CN103357884A CN 103357884 A CN103357884 A CN 103357884A CN 2013102817169 A CN2013102817169 A CN 2013102817169A CN 201310281716 A CN201310281716 A CN 201310281716A CN 103357884 A CN103357884 A CN 103357884A
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- limonite ore
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Abstract
The invention discloses a method for preparing porous nano-iron by brown iron ore. The method is characterized in that the brown iron ore is ground into particles and the particles are subjected to hydrogen reduction at the temperature of 250-450 DEG C to prepare the nano-iron. The main phase of the nano-iron prepared by the method is zero-valent iron, and the nano-iron belongs to a porous nano active material with nanopores and micropores. The nano-iron can serve as a filter material or an underground permeation wall material to be applied to detoxification of organic pollutants-halogenated aromatics in underground water and purification of inorganic pollutants of nitrate, arsenic, hexavalent chromium and the like.
Description
One, technical field
The present invention relates to the method that the limonite resources processing prepares functional material.
Two, background technology
Nanoscale Iron refers to that particle diameter is the superfine iron powder of 1 ~ 100nm, because of its transitional region between the elementide of the Commen powder of macroscopic view and microcosmic, so present some unique character.
Research finds that Nanoscale Iron has good removal effect to arsenic, Cr VI, nitrate nitrogen.Nitrate nitrogen can be reduced to nitrogen, almost not have other intermediate products in the reacted water, be swift in response at ambient temperature, denitration is complete, and need not to regulate the pH value; Nanoscale Iron can make the detoxification of haloarene compounds dehalogenation.Therefore, Nanoscale Iron is obtaining extensive concern and application aspect groundwater treatment and the original position reparation.
The Nanoscale Iron particle diameter is little, active strong, and easily coalescent, easy oxidation all must isolated O when preparation and use
2, the method for preparing at present nano-iron particle both at home and abroad comprises physical vaporous deposition, high-energy ball milling method, chemical reduction method, pyrolysis carbonyl iron processes, electrochemical process.
Many bibliographical informations prepare Nanoscale Iron with sodium borohydride reduction ferric iron or ferrous ion, but the cost of this method preparation is very high, and per kilogram reaches 200 dollars.Publication number is to have proposed the technique that carbonyl iron steam prepares nanometer iron powder in the Chinese invention patent application specification of CN101138793, to be that 99.9% nitrogen carries out preheating in preheater with purity, the nitrogen that is preheated and carbonyl iron steam meet at the decomposer top, and decomposition reaction obtains nanometer iron powder; Publication number is to have proposed a kind of water in the Chinese invention patent application specification of CN101157136 to purify nano iron powder dedicated, in-5 ℃～-15 ℃ situation, utilize the high frequency cutting, number of times is set in per minute 3500 times-4000 times, it is nano iron powder dedicated to produce the drinking water cohesion, and purpose is with harmful substances such as the microorganism in its effective removing water, heavy metals; Publication number is to have proposed a kind of atmosphere-desulphurizing appropriative ferrous powder preparation technology in the Chinese invention patent application specification of CN101229588, in 20 ℃～35 ℃ situation, utilize the high frequency cutting, the high frequency cutting times is set in per minute 5000 times-6000 times, to produce nanometer iron powder, before coating, ferrous powder granules is carried out wet body infiltration in 460 ℃, make the surface of its ferrous powder granules form microporous cellular, then again to the anti-oxidation coating of ferrous powder granules; Publication number is the chemical preparation process that has proposed nanometer iron powder in the Chinese invention patent application of CN1751829, that molysite is dissolved in the mixed solution of ethanol, water or second alcohol and water, the molar concentration that makes iron ion is 0.02-1.0mol/L, adding molal quantity is that iron ion 15-50 NaOH and hydrazine content doubly is that iron ion molal quantity 8-30 mass concentration doubly is the hydrazine hydrate solution of 40-80%, after stirring, be back to the mother liquor water white transparency 80-120 ℃ of heating, can obtain nanometer iron powder; Publication number is to have proposed a kind of method that liquid phase reduction prepares nanometer nulvalent iron particle of improving in the Chinese invention patent application of CN1876294, is in the soluble iron saline solution, take polyvinylpyrrolidone as protective agent box particle diameter controlling agent, with NaBH
4Or KBH
4The aqueous solution is reducing agent, prepares Nanoscale Iron.
But, more than all can relate to poisonous and hazardous material among which kind of preparation technology, moreover, its complicated technique, expensive raw material have limited the extensive use of Nanoscale Iron in water treatment and underground water pollution are repaired equally.
Three, summary of the invention
The present invention is for avoiding the existing weak point of above-mentioned prior art, provides that a kind of raw material reserves are abundant, with low cost, the simple Nanoscale Iron preparation method of method.
Technical solution problem of the present invention adopts following technical scheme:
Select goethite content greater than 80%, porosity is not less than 20%, the goethite crystals diameter is not more than 500nm limonite ore, through packing the nano-iron material that acquisition has loose structure after the cooling under fragmentation, screening, 350-650 ℃ hydrogen reducing calcining, the protective atmosphere.
The characteristics that the present invention utilizes limonite ore to prepare Nanoscale Iron are:
The inventor studies discovery, goethite crystals is that nanometer is to sub-micron needle-like form in the limonite ore, space (Fig. 3) between the mixed and disorderly heap-shaped granulating of acicular crystal, therefore, limonite ore has abundant nano-pore, recognize that limonite belongs to important nano-mineral resource, have very large prospect in the preparation of nano-mineral functional material with in using;
Find that goethite high temperature dehydration under reducing atmosphere also becomes Nanoscale Iron mutually, have nano-pore between the Nanoscale Iron crystal grain, therefore, the Nanoscale Iron for preparing with the inventive method has nanometer, sub-micron, micron hole, has higher porosity;
The a small amount of aluminium of ubiquity substitutes the iron phenomenon in the natural goethite, and there is more lattice defect in the nano-iron material that the alternative meeting of impurity aluminum causes preparing, is conducive to improve the chemism of nano-iron material and purifies the effect of removing pollutant.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention's method of preparing Nanoscale Iron is compared with the method for existing bibliographical information, the limonite ore reserves are huge, widely distributed, high-temperature hydrogen or the carbon monoxide reducing process is simple, efficient is high, reducing agent hydrogen and carbon monoxide very are easy to get, thereby make the preparation cost of product that significantly reduction be arranged equally.
2, goethite has nanometer, sub-micron in the limonite ore, and become mutually in the process of Nanoscale Iron because of the newly-increased nanostructured hole of dewatering in reduction, therefore, the Nanoscale Iron of the inventive method preparation has the nano-pore structure feature, and the Nanoscale Iron specific area of preparation is large.
3, because the alternative iron phenomenon of Aluminium In Goethite is extensive, the abundant fault of construction of Nanoscale Iron existence with the limonite preparation has than with the synthetic higher chemism of pure Nanoscale Iron of molysite, has the effect of better removal pollutant.
Four, description of drawings
The X ray diffracting spectrum of hydrogen reduction limonite product under Fig. 1 different temperatures.Show to form Nanoscale Iron more than 300 ℃, along with the degree of crystallinity rising of temperature rising Nanoscale Iron.
The specific area variation tendency of hydrogen reduction limonite product under Fig. 2 different temperatures.Show that the specific area of Nanoscale Iron diminishes along with temperature raises.
Fig. 3 is the limonite scanning electron microscope image, shows that goethite wherein has nanometer needle-like form, and there is nano-pore in intergranular
Fig. 4 is the images of transmissive electron microscope that 300 ℃ of hydrogen reducings prepare Nanoscale Iron, shows that the nanometer structure hole exists.
Five, the specific embodiment
Embodiment 1:
Choose the limonite ore of earthy porous, measure through the X-ray powder diffraction analysis, wherein the content of goethite is about 90%, and all the other impurity are bloodstone, clay mineral and quartzy about 10%; Porosity is greater than 20%, and goethite presents acicular crystal, and diameter is not more than 500nm.
Above-mentioned limonite ore is broken, screening obtain particle diameter 0.1-0.3mm; Above-mentioned granular material 10g is placed the tube furnace high temperature section, passes into hydrogen with the flow of 100mL/min, 250 ℃ of reduction until reduction furnace no longer produces condensed water in giving vent to anger, cool to room temperature under the hydrogen atmosphere, and pack at the hydrogen atmosphere lower seal.
Embodiment 2:
Broken, the screening of limonite ore that will be identical with embodiment obtains particle diameter 0.3-0.5mm; Above-mentioned granular material 10g is placed the tube furnace high temperature section, flow with 100mL/min passed into hydrogen, and the ratio that forms limonite equivalent proportion 1:1 according to hydrogen reduction is calculated, 450 ℃ of logical hydrogen reducings 15 minutes, cool to room temperature under the hydrogen atmosphere, and pack at the hydrogen atmosphere lower seal.
Embodiment 3:
Broken, the screening of limonite ore that will be identical with embodiment obtains particle diameter 2.0-10mm; Above-mentioned granular material 100g is placed the tube furnace high temperature section, flow with 100mL/min passed into hydrogen, and the ratio that forms limonite equivalent proportion 1:1 according to hydrogen reduction is calculated, 500 ℃ of logical hydrogen reducings 150 minutes, cool to room temperature under the hydrogen atmosphere, and pack at the hydrogen atmosphere lower seal.
Claims (1)
1. a method for preparing porous nano ironwork material take limonite ore as raw material is characterized in that, screening broken satisfactory limonite ore, then prepares Nanoscale Iron at 350-650 ℃ of hydrogen reducing;
The content of goethite is greater than 80% in the described limonite ore, and all the other impurity are bloodstone, clay mineral and quartz;
Have nanometer and micron space in the described limonite ore, porosity is not less than 20%;
The goethite crystals diameter is not more than 500nm in the described limonite ore;
Described limonite ore prepares the method for Nanoscale Iron, it is characterized in that operating as follows:
A, described limonite ore is broken, screening obtain respectively the granular materials that particle diameter is 0.1-0.3mm, 0.3-0.5mm and 0.5-2.0mm, 2.0-10mm;
B, described variable grain material placed respectively the stove of airtight reducing atmosphere; the reduction furnace temperature remains between 350-650 ℃; until reduction furnace no longer produces condensed water in giving vent to anger, perhaps control the oxid-reduction equivalent of reducing agent and iron than being 1:1, pack after the cooling under the protective atmosphere.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803703A (en) * | 2014-02-25 | 2014-05-21 | 合肥工业大学 | Method for simultaneously removing phosphorous and nitrogen through synergistic effect of nanoscale-iron and microbes |
| CN105833850A (en) * | 2016-05-13 | 2016-08-10 | 合肥工业大学 | Method for preparing Fe/C composite porous structure material by using limonite |
| CN107186216A (en) * | 2017-06-02 | 2017-09-22 | 新冶高科技集团有限公司 | A kind of method that low cost low temperature direct-reduction prepares superfine iron powder |
| CN108746604A (en) * | 2018-06-26 | 2018-11-06 | 厦门理工学院 | A kind of air-stable type nano zero valence iron and its preparation method and application |
| CN110773195A (en) * | 2019-11-06 | 2020-02-11 | 合肥学院 | Nano zero-valent metal composite material prepared based on meteorite, and preparation method and application thereof |
| CN113499775A (en) * | 2021-07-29 | 2021-10-15 | 合肥学院 | Nano zero-valent copper-iron composite porous material and preparation method and application thereof |
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| CN1858264A (en) * | 2006-06-08 | 2006-11-08 | 王号德 | Method for producing iron powder by directly reducing hematite or limonite |
| CN103086460A (en) * | 2013-02-04 | 2013-05-08 | 合肥工业大学 | Phosphorus-removing method based on nano-grade iron |
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2013
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| JPS62156202A (en) * | 1985-12-27 | 1987-07-11 | Mitsui Toatsu Chem Inc | Ferromagnetic metallic powder treated with amines |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803703A (en) * | 2014-02-25 | 2014-05-21 | 合肥工业大学 | Method for simultaneously removing phosphorous and nitrogen through synergistic effect of nanoscale-iron and microbes |
| CN103803703B (en) * | 2014-02-25 | 2016-01-06 | 合肥工业大学 | A kind of Nanoscale Iron and microorganism act synergistically the method for synchronous denitrification dephosphorizing |
| CN105833850A (en) * | 2016-05-13 | 2016-08-10 | 合肥工业大学 | Method for preparing Fe/C composite porous structure material by using limonite |
| CN105833850B (en) * | 2016-05-13 | 2018-06-15 | 合肥工业大学 | A kind of method that Fe/C compound porous structure materials are prepared with limonite |
| CN107186216A (en) * | 2017-06-02 | 2017-09-22 | 新冶高科技集团有限公司 | A kind of method that low cost low temperature direct-reduction prepares superfine iron powder |
| CN107186216B (en) * | 2017-06-02 | 2019-07-23 | 新冶高科技集团有限公司 | A kind of method that low cost low temperature direct-reduction prepares superfine iron powder |
| CN108746604A (en) * | 2018-06-26 | 2018-11-06 | 厦门理工学院 | A kind of air-stable type nano zero valence iron and its preparation method and application |
| CN110773195A (en) * | 2019-11-06 | 2020-02-11 | 合肥学院 | Nano zero-valent metal composite material prepared based on meteorite, and preparation method and application thereof |
| CN110773195B (en) * | 2019-11-06 | 2022-06-17 | 合肥学院 | Nano zero-valent metal composite material prepared based on meteorite, and preparation method and application thereof |
| CN113499775A (en) * | 2021-07-29 | 2021-10-15 | 合肥学院 | Nano zero-valent copper-iron composite porous material and preparation method and application thereof |
| CN113499775B (en) * | 2021-07-29 | 2024-02-02 | 深圳万知达技术转移中心有限公司 | Nanometer zero-valent copper-iron composite porous material, and preparation method and application thereof |
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Application publication date: 20131023 |