CN103357884A - Method for preparing porous nano-iron by brown iron ore - Google Patents

Method for preparing porous nano-iron by brown iron ore Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
iron
limonite ore
nano
ore
limonite
Prior art date
Application number
CN2013102817169A
Other languages
Chinese (zh)
Inventor
陈斌
陈天虎
庆承松
邹雪华
刘海波
谢晶晶
Original Assignee
合肥工业大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 合肥工业大学 filed Critical 合肥工业大学
Priority to CN2013102817169A priority Critical patent/CN103357884A/en
Publication of CN103357884A publication Critical patent/CN103357884A/en

Links

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

A kind of method for preparing porous nano iron with limonite ore
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.
CN2013102817169A 2013-07-07 2013-07-07 Method for preparing porous nano-iron by brown iron ore CN103357884A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2013102817169A CN103357884A (en) 2013-07-07 2013-07-07 Method for preparing porous nano-iron by brown iron ore

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2013102817169A CN103357884A (en) 2013-07-07 2013-07-07 Method for preparing porous nano-iron by brown iron ore

Publications (1)

Publication Number Publication Date
CN103357884A true CN103357884A (en) 2013-10-23

Family

ID=49360618

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2013102817169A CN103357884A (en) 2013-07-07 2013-07-07 Method for preparing porous nano-iron by brown iron ore

Country Status (1)

Country Link
CN (1) CN103357884A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
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

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62156202A (en) * 1985-12-27 1987-07-11 Mitsui Toatsu Chem Inc Ferromagnetic metallic powder treated with amines
JPH02156001A (en) * 1988-12-09 1990-06-15 Tosoh Corp Manufacture of ferromagnetic iron powder
JPH0820809A (en) * 1994-07-07 1996-01-23 Akira Honda Production of chromium-base alloy powder
CN1827268A (en) * 2006-04-07 2006-09-06 北京科技大学 Process for preparing nano iron powder
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62156202A (en) * 1985-12-27 1987-07-11 Mitsui Toatsu Chem Inc Ferromagnetic metallic powder treated with amines
JPH02156001A (en) * 1988-12-09 1990-06-15 Tosoh Corp Manufacture of ferromagnetic iron powder
JPH0820809A (en) * 1994-07-07 1996-01-23 Akira Honda Production of chromium-base alloy powder
CN1827268A (en) * 2006-04-07 2006-09-06 北京科技大学 Process for preparing nano iron powder
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘雨等: "氢气还原针铁矿制备的纳米铁去除硝酸盐的研究", 《中国给水排水》 *

Cited By (7)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
Nanda et al. Fabrication of mesoporous CuO/ZrO2-MCM-41 nanocomposites for photocatalytic reduction of Cr (VI)
Yang et al. A novel visible-light-driven In-based MOF/graphene oxide composite photocatalyst with enhanced photocatalytic activity toward the degradation of amoxicillin
Yang et al. Fabrication and characterization of hydrophilic corn stalk biochar-supported nanoscale zero-valent iron composites for efficient metal removal
Ibrahim et al. Synthesis of magnetically recyclable spinel ferrite (MFe2O4, M= Zn, Co, Mn) nanocrystals engineered by sol gel-hydrothermal technology: High catalytic performances for nitroarenes reduction
He et al. Waste eggshell membrane-templated CuO-ZnO nanocomposites with enhanced adsorption, catalysis and antibacterial properties for water purification
Wang et al. Removal of cadmium (II) from aqueous solution: A comparative study of raw attapulgite clay and a reusable waste–struvite/attapulgite obtained from nutrient-rich wastewater
Chen et al. Biochar modification significantly promotes the activity of Co3O4 towards heterogeneous activation of peroxymonosulfate
Tang et al. Fabrication of AgFeO2/g-C3N4 nanocatalyst with enhanced and stable photocatalytic performance
Chen et al. Influence of pyrolysis temperature on characteristics and heavy metal adsorptive performance of biochar derived from municipal sewage sludge
Behnajady et al. Synthesis of mesoporous NiO nanoparticles and their application in the adsorption of Cr (VI)
Shen et al. Superior adsorption capacity of g-C3N4 for heavy metal ions from aqueous solutions
Mohan et al. Lead sorptive removal using magnetic and nonmagnetic fast pyrolysis energy cane biochars
Shao et al. Amorphous TiO2 doped with carbon for visible light photodegradation of rhodamine B and 4-chlorophenol
Luo et al. Fabrication uniform hollow Bi2S3 nanospheres via Kirkendall effect for photocatalytic reduction of Cr (VI) in electroplating industry wastewater
Yao et al. Synthesis of novel flower-like layered double oxides/carbon dots nanocomposites for U (VI) and 241Am (III) efficient removal: batch and EXAFS studies
Li et al. Enhanced visible-light photo-oxidation of nitric oxide using bismuth-coupled graphitic carbon nitride composite heterostructures
Huang et al. Kinetics, isotherm, thermodynamic, and adsorption mechanism studies of La (OH) 3-modified exfoliated vermiculites as highly efficient phosphate adsorbents
Lei et al. Effect of calcination temperature on the structure and visible-light photocatalytic activities of (N, S and C) co-doped TiO2 nano-materials
Raizada et al. Magnetically retrievable Bi2WO6/Fe3O4 immobilized on graphene sand composite for investigation of photocatalytic mineralization of oxytetracycline and ampicillin
Yang et al. Enhanced adsorption of Congo red dye by functionalized carbon nanotube/mixed metal oxides nanocomposites derived from layered double hydroxide precursor
Jin et al. Nickel nanoparticles encapsulated in porous carbon and carbon nanotube hybrids from bimetallic metal-organic-frameworks for highly efficient adsorption of dyes
Luo et al. Nanocomposites of graphene oxide-hydrated zirconium oxide for simultaneous removal of As (III) and As (V) from water
Zhang et al. Fe2O3/3DOM BiVO4: High-performance photocatalysts for the visible light-driven degradation of 4-nitrophenol
Ye et al. Facile fabrication of magnetically separable graphitic carbon nitride photocatalysts with enhanced photocatalytic activity under visible light
Xiao et al. Synthesis of stable burger-like α-Fe2O3 catalysts: formation mechanism and excellent photo-Fenton catalytic performance

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20131023

C02 Deemed withdrawal of patent application after publication (patent law 2001)