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CN108658130A - A method of preparing iron oxide and aerosil simultaneously from iron tailings - Google Patents

A method of preparing iron oxide and aerosil simultaneously from iron tailings Download PDF

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CN108658130A
CN108658130A CN201810790734.2A CN201810790734A CN108658130A CN 108658130 A CN108658130 A CN 108658130A CN 201810790734 A CN201810790734 A CN 201810790734A CN 108658130 A CN108658130 A CN 108658130A
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iron tailings
iron
hours
iron oxide
gel
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CN108658130B (en
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王建国
宋鑫
包志康
张志军
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/152—Preparation of hydrogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C01B33/1585—Dehydration into aerogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

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  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Silicon Compounds (AREA)
  • Compounds Of Iron (AREA)

Abstract

本发明公开了一种从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法。它是一种成本低廉，反应条件低得对铁尾矿这种固体废弃物的再利用途径。它包括如下步骤：铁尾矿前处理；酸洗提铁；碱溶提硅；溶胶凝胶化；凝胶后处理；制备氧化铁粉体及常压干燥。本发明制备的二氧化硅气凝胶经测试具有较低的密度，较高的孔隙率；制备的氧化铁粉体具有粒径小且分布均一的特点。由此得出本发明制备的氧化铁粉体及二氧化硅气凝胶具有优良的性能，有着广泛的应用价值。本发明原料来源广泛，价格低廉，设备要求低，反应条件温和，适用于大规模生产。

The invention discloses a method for simultaneously preparing iron oxide and silica airgel from iron tailings. It is a low-cost, low-reaction condition method for reusing solid waste such as iron tailings. It comprises the following steps: pretreatment of iron tailings; iron extraction by acid washing; silicon extraction by alkali dissolution; gelation of sol; post-treatment of gel; preparation of iron oxide powder and drying under normal pressure. The silica airgel prepared by the invention has lower density and higher porosity after testing; the prepared iron oxide powder has the characteristics of small particle size and uniform distribution. Thus, it can be concluded that the iron oxide powder and silica airgel prepared by the present invention have excellent properties and have wide application value. The invention has wide sources of raw materials, low price, low equipment requirements, mild reaction conditions and is suitable for large-scale production.

Description

A method of preparing iron oxide and aerosil simultaneously from iron tailings
Technical field
The invention belongs to technical field of inorganic material, and in particular to one kind preparing ferric oxide powder and titanium dioxide from iron tailings The method of silicon nano material.
Background technology
Iron tailings is that ore dressing plant is levigate by iron ore and choose the waste discharged after useful constituent.The stockpiling of iron tailings Large amount of land resources are not only taken up, and cause serious environmental pollution, there is also security risks for some older Tailings Dams. Since the main chemical compositions of iron tailings are silicon, aluminium, iron, magnesium, calcium etc., how the element rationally contained using it is to reach waste The effect of recycling is the problem put in face of people.
Ferric oxide powder is a kind of important raw material of industry, for painting, the coloring of rubber, plastics, building etc., is Inorganic pigment is used as rust resisting pigment in coatings industry.It is also precision instrument, the polishing agent of optical glass and manufacture magnetic material The raw material etc. of ferrite component.
Aerosil has big specific surface area and high hole ratio, while having extremely low density, just because of It has these unique properties, before so that it is had a wide range of applications in fields such as aerospace, building, medicine and catalyst Scape.Silica aerogel material is best in the world one of heat-insulating flame-retardant solid material.It, which is prepared, generally uses positive silicic acid Esters（Ethyl orthosilicate, methyl orthosilicate）, Ludox, waterglass, and more cheap rice husk or flyash etc..Wherein just Silicic acid lipid has the factors such as strong toxicity, expensive to be allowed to be unable to mass production, and cheap rice husk or flyash etc. There is reaction route complicated so that final products quality is not high.
The drying of aerosil generally uses supercritical drying, supercritical drying to have many advantages, such as：Sample is shunk It is small, can completely preserve tridimensional network, quality of finished is high.But simultaneously supercritical drying have again energy consumption is big, equipment investment is more, The factors such as drying condition harshness make the aerosil cost of production greatly increase.
Background in view of the above technology does not have also using iron tailings as raw material while preparing ferric oxide powder and hydrophobic silica The play-by-play of aeroge, the present invention prepare ferric oxide powder and honest and clean while largely processing this waste of iron tailings Valence silicon source, and can be dried to obtain aerosil under normal pressure, there is very big Significance for Environment and economic implications.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide one kind using iron tailings as raw material, while preparing oxygen The method for changing iron powder body and aerosil, this environmentally harmful solid of iron tailings can largely be handled by, which having, gives up Gurry, raw material sources are extensive, mild condition, are easy to industrialized advantage.
A kind of method preparing iron oxide and aerosil simultaneously from iron tailings, it is characterised in that including Following steps：
1）Iron tailings is ground and is sieved with 100 mesh sieve, obtain it is levigate after iron tailings；
2）By step 1）It is levigate after iron tailings be put into Muffle furnace and be heated to 850-950 DEG C and activated, keep the temperature 4.5-5.5 Hour, the iron tailings powder after activation is made；
3）By step 2）In activation after iron tailings powder and mixed in hydrochloric acid and be stirred to react, filter after reaction, filter residue into Row drying, filtrate container collection；
4）By step 3）In filter residue and sodium hydrate particle be mixed and stirred for uniformly, being put into Muffle furnace and keeping for 500-600 DEG C 1.5-2.5 hours, the iron tailings after alkali fusion reaction is made；
5）By step 4）In alkali fusion reaction after iron tailings incorporate water in carry out heating reaction, filter to obtain thick silicon after reaction Solution；
6）By step 5）In thick silicon solution cross cation exchange resin, then it is 6.5- to adjust thick silicon solution ph with ammonia spirit 7.5, stand to obtain gel；
7）Gel aging：In step 6）In gel obtained be added in gel Ageing solution, stand aging in 20-26 hours at room temperature, Obtain silica hydrogel；
8）Exchange of solvent：By step 7）Silica hydrogel after middle aging immerses 22-26 hours will be in gel in n-hexane Water cement out, obtain colloid；
9）Surface is modified：By step 8）In gel immerse modification liquid and be stored at room temperature 12-24 hours, and by modified gel obtained Constant pressure and dry 5-7 hours at 85-95 DEG C, it is hydrophobic silica aerogel prepared by raw material to be able to iron tailings；
10）By step 3）In filtrate to be adjusted to pH with ammonium hydroxide under ultrasound environments be 7-8, there are a large amount of precipitations, mistake after standing Filter, filter residue and drying are spare；
11）By step 10）Filter residue after middle drying is put into Muffle furnace, and it is small that 1.5-2.5 is roasted at a temperature of 600 DEG C -700 DEG C When, ferric oxide nano powder is finally made.
The method that the slave iron tailings prepares iron oxide and aerosil simultaneously, it is characterised in that step 1）In The ingredient of iron tailings include SiO2, CaO, MgO, Al2O3, Fe2O3.
The method that the slave iron tailings prepares iron oxide and aerosil simultaneously, it is characterised in that step 2）In Concentration of hydrochloric acid be 1-3mol/L, preferably 2mol/L, the volume ratio of iron tailings powder and hydrochloric acid is 1：1.5-2.2, preferably 1.6-1.8。
The method that the slave iron tailings prepares iron oxide and aerosil simultaneously, it is characterised in that step 4）In Filter residue and sodium hydroxide mass ratio be 1：1.4-2.2.
The method that the slave iron tailings prepares iron oxide and aerosil simultaneously, it is characterised in that step 5）In Alkali soluble reaction after iron tailings and water solid-to-liquid ratio be 1:3-7, heating temperature are 60 DEG C -85 DEG C.
The method that the slave iron tailings prepares iron oxide and aerosil simultaneously, it is characterised in that step 7）In Gel Ageing solution be absolute ethyl alcohol and ethyl orthosilicate mixed liquor, the volume ratio of absolute ethyl alcohol and ethyl orthosilicate is 8-12： 1, preferably 10:1.
The method that the slave iron tailings prepares iron oxide and aerosil simultaneously, it is characterised in that step 9）In Modification liquid be n-hexane and trim,ethylchlorosilane mixed liquor, the volume ratio of n-hexane and trim,ethylchlorosilane is 8-12：1, it is excellent It is selected as 10:1.
The method that the slave iron tailings prepares iron oxide and aerosil simultaneously, it is characterised in that step 9）In The tap density of obtained hydrophobic silica aerogel is 0.158-0.172g/cm3, porosity 93%-94%, silica The average pore size of aeroge is 20-40 nm.
The method that the slave iron tailings prepares iron oxide and aerosil simultaneously, it is characterised in that step 9）In The tap density of obtained ferric oxide nano powder is 1.098-1.132 g/cm3, grain size is less than 50nm.By using above-mentioned skill Art, compared with prior art, the present invention have the advantages that：
1）The present invention uses the solid waste such as iron tailings for raw material, has carried out reasonable utilization to wherein iron, element silicon, has passed through profit With the cheap silicon source in iron tailings, hydrophobic silica aerogel is prepared；The iron in iron tailings is recycled simultaneously, is made Iron oxide, hydrophobic silica aerogel and iron oxide are used for the comprehensive utilization of next step, to realize a large amount of processing iron tailings Purpose, on the one hand alleviate environmental pressure, reduce environmental pollution, while improving recovery utilization rate, meet environmentally protective It is required that；
2）The present invention exchanges obtained silica hydrogel using organic solvent-normal hexane, and the water in gel is cemented out, It greatly reduces water in the drying process and hydrophobically modified is carried out at the same time to the surface tension of gel structure, make titanium dioxide obtained Silica aerogel has preferable pore structure and hydrophobic performance；
3）The present invention replaces supercritical drying when aerosil is dried, by using constant pressure and dry, effectively prevents It is big that supercritical drying is faced with energy consumption, the unfavorable factors such as condition harshness；The advantages of constant pressure and dry has mild condition, and low energy consumption, It is easy to mass produce.
Description of the drawings
Fig. 1 is implementing procedure figure of the present invention；
Fig. 2 is the SEM figures of aerosil obtained in the embodiment of the present invention 1；
Fig. 3 is that the Fourier of aerosil made from present example 1 is infrared（FTIR）Analysis chart；
Fig. 4 is the SEM figures of ferric oxide powder made from present example 1.
Specific implementation mode
Technical scheme of the present invention is described further with specific embodiment below, but protection scope of the present invention is unlimited In this：
Embodiment 1 prepares ferric oxide powder and aerosil
The embodiment of the present invention 1 prepares ferric oxide powder and aerosil by raw material of iron tailings, as shown in Figure 1, including Following steps：
（1）Raw material includes at least North China's iron tailings（Its constituent mass percentage composition is as follows：SiO245.43%、CaO 13.81%, MgO 13.10%, Al2O3 11.35%, Fe2O3 10.13%, surplus are impurity）, sodium hydroxide, hydrochloric acid, n-hexane, Trim,ethylchlorosilane, absolute ethyl alcohol, concentrated ammonia liquor；
（2）Iron tailings after will be levigate sieves with 100 mesh sieve, and is put into later in Muffle furnace and is heated to 850 DEG C, keeps temperature 4.5 hours, The iron tailings powder after activation is made；
（3）It is 1 by volume by mine tailing and the 2mol/L hydrochloric acid after activation:1.6 are mixed and stirred for 2 hours, filter to take to obtain filter Slag is dried, filtrate container collection；
（4）It is 1 in mass ratio by filter residue and sodium hydrate particle:1.4 are mixed and stirred for uniformly, 500 DEG C of holdings in Muffle furnace Iron tailings after obtained alkali fusion reaction in 1.5 hours；
（5）Iron tailings after alkali fusion is reacted incorporates in water, is 1 by solid-to-liquid ratio:3 are stirred to react 24 hours under 60 DEG C of oil baths, Through thick silicon solution is obtained by filtration；
（6）By step（5）In thick silicon solution obtained cross storng-acid cation exchange resin, in being adjusted to later with ammonia spirit Property near, standing wait for its gel；
（7）Gel aging：Gel Ageing solution is added to gel obtained（Absolute ethyl alcohol presses 8 with ethyl orthosilicate:1 volume ratio is mixed It closes）, aging in 20 hours is stood at room temperature；
（8）Exchange of solvent：Gel after aging is immersed in n-hexane 22 hours, the water in colloid is cemented out；
（9）Surface is modified：Colloid after exchange of solvent is immersed into modification liquid（N-hexane presses 8 with trim,ethylchlorosilane:1 volume ratio Mixing）, 12 hours are stood at room temperature, finally by 85 DEG C of gel constant pressure and dry 5 hours obtained, the final one kind that obtains is with iron tailings The hydrophobic silica aerogel prepared for raw material；
（10）By step（3）In filtrate be adjusted to pH=7 with ammonium hydroxide under ultrasound environments, there are a large amount of precipitations, stand 2 hours After filter, container collection is used after filter residue and drying；
（11）Filter residue after drying is put into Muffle furnace, is roasted at a temperature of 600 DEG C 1.5 hours, iron oxide is finally made Nano-powder.
The present invention to obtained by the embodiment ferric oxide nano powder and aerosil carried out performance parameter survey It is fixed, it is specific as follows：
1）Aerosil scanning electron microscope prepared by embodiment 1（SEM）Analysis is as shown in Fig. 2, Fig. 2 is SiO2Gas Morphology of the gel under electronic scanner microscope, it can be seen from the figure that SiO2Aeroge is by nano level micro- Grain be formed by connecting, have the characteristics that it is porous, belong to typically three-dimensional netted nano-porous structure；
2）Aerosil Fourier prepared by embodiment 1 is infrared（FTIR）Analysis is as shown in figure 3, Fig. 3 is SiO2Airsetting The Fourier transform infrared spectroscopy figure of glue.As can be seen from Figure 3：In 1098 cm-1Locate strong and wide peak to vibrate for Si-O-Si Peak；In 1402 cm-1Place is Si-CH3Stretching vibration peak；Prove the three-dimensional that the aerosil is made of Si-O-Si Reticular structure；
3）Ferric oxide nano powder scanning electron microscope prepared by embodiment 1（SEM）Analysis is as shown in figure 4, Fig. 4 is iron oxide Morphology of the powder under electronic scanner microscope.It can be seen from the figure that ferric oxide powder is corynebacterium particle, grain Diameter distribution is uniform, is less than 50nm, belongs to nano material scope.
4）The silicon rate of recovery of aerosil prepared by embodiment 1 is 56%；It is 81% to aoxidize iron recovery.
Embodiment 2 prepares ferric oxide powder and aerosil
The embodiment of the present invention 2 prepares ferric oxide powder and aerosil by raw material of iron tailings, includes the following steps：
（1）Raw material include at least North China's iron tailings, sodium hydroxide, hydrochloric acid, n-hexane, trim,ethylchlorosilane, absolute ethyl alcohol, Concentrated ammonia liquor；
（2）Iron tailings after will be levigate sieves with 100 mesh sieve, and is put into later in Muffle furnace and is heated to 950 DEG C, keeps temperature 5.5 hours, The mine tailing after activation is made；
（3）It is 1 by volume by mine tailing and the 1.5mol/L hydrochloric acid after activation:2.2 are mixed and stirred for 2 hours, filter to take Filter residue is dried, filtrate container collection；
（4）It is 1 in mass ratio by filter residue and sodium hydroxide:2.2 are mixed and stirred for uniformly, and 600 DEG C of holdings 2.5 are small in Muffle furnace When be made alkali fusion reaction after iron tailings；
（5）Iron tailings after alkali fusion is reacted incorporates in water, is 1 by solid-to-liquid ratio:7 are stirred to react 24 hours under 85 DEG C of oil baths, Through thick silicon solution is obtained by filtration；
（6）By step（5）In thick silicon solution obtained cross storng-acid cation exchange resin, in being adjusted to later with ammonia spirit Property near, standing wait for its gel；
（7）Gel aging：Gel Ageing solution is added to gel obtained（Absolute ethyl alcohol presses 12 with ethyl orthosilicate:1 volume ratio is mixed It closes）, aging in 26 hours is stood at room temperature；
（8）Exchange of solvent：Gel after aging is immersed in n-hexane 26 hours, the water in colloid is cemented out；
（9）Surface is modified：Colloid after exchange of solvent is immersed into modification liquid（N-hexane presses 12 with trim,ethylchlorosilane:1 volume ratio Mixing）, 24 hours are stood at room temperature, finally by 95 DEG C of gel constant pressure and dry 8 hours obtained, the final one kind that obtains is with iron tailings The hydrophobic silica aerogel prepared for raw material；
（10）By step（3）In filtrate be adjusted to pH=8 with ammonium hydroxide under ultrasound environments, there are a large amount of precipitations, stand 2 hours After filter, container collection is used after filter residue and drying；
（11）Filter residue after drying is put into Muffle furnace, is roasted at a temperature of 700 DEG C 2.5 hours, iron oxide is finally made Nano-powder.And iron oxide to gained and aerosil enter measured performance parameter with embodiment 1.Final products The silicon rate of recovery be 58%；It is 80% to aoxidize iron recovery.
Embodiment 3 prepares ferric oxide powder and aerosil
The embodiment of the present invention 3 prepares ferric oxide powder and aerosil by raw material of iron tailings, includes the following steps：
（1）Raw material include at least North China's iron tailings, sodium hydroxide, hydrochloric acid, n-hexane, trim,ethylchlorosilane, absolute ethyl alcohol, Concentrated ammonia liquor；
（2）Iron tailings after will be levigate sieves with 100 mesh sieve, and is put into later in Muffle furnace and is heated to 900 DEG C, keeps temperature 5 hours, system Mine tailing after must activating；
（3）It is 1 by volume by mine tailing and the 2mol/L hydrochloric acid after activation:1.7 are mixed and stirred for 4 hours, filter to take to obtain filter Slag is dried, filtrate container collection；
（4）It is 1 in mass ratio by filter residue and sodium hydroxide:1.8 are mixed and stirred for uniformly, are kept for 2 hours for 550 DEG C in Muffle furnace The iron tailings after alkali fusion reaction is made.
（5）Iron tailings after alkali fusion is reacted incorporates in water, is 1 by solid-to-liquid ratio:5 under 70 DEG C of oil baths to be stirred to react 25 small When, through thick silicon solution is obtained by filtration；
（6）By step（5）In thick silicon solution obtained cross storng-acid cation exchange resin, in being adjusted to later with ammonia spirit Property near, standing wait for its gel；
（7）Gel aging：Gel Ageing solution is added to gel obtained（Absolute ethyl alcohol presses 10 with ethyl orthosilicate:1 volume ratio is mixed It closes）, aging in 25 hours is stood at room temperature；
（8）Exchange of solvent：Gel after aging is immersed in n-hexane 25 hours, the water in colloid is cemented out；
（9）Surface is modified：Colloid after exchange of solvent is immersed into modification liquid（N-hexane presses 10 with trim,ethylchlorosilane:1 volume ratio Mixing）, 25 hours are stood at room temperature, finally by 90 DEG C of gel constant pressure and dry 6 hours obtained, the final one kind that obtains is with iron tailings The hydrophobic silica aerogel prepared for raw material；
（10）By step（3）In filtrate be adjusted to pH=8 with ammonium hydroxide under ultrasound environments, there are a large amount of precipitations, stand 2 hours After filter, container collection is used after filter residue and drying；
（11）Filter residue after drying is put into Muffle furnace, is roasted at a temperature of 650 DEG C 2.5 hours, iron oxide is finally made Nano-powder.And iron oxide to gained and aerosil enter measured performance parameter with embodiment 1.Final products The silicon rate of recovery be 53%；It is 78% to aoxidize iron recovery.
Embodiment 4 prepares ferric oxide powder and aerosil
The embodiment of the present invention 4 prepares ferric oxide powder and aerosil by raw material of iron tailings, includes the following steps：
（1）Raw material include at least North China's iron tailings, sodium hydroxide, hydrochloric acid, n-hexane, trim,ethylchlorosilane, absolute ethyl alcohol, Concentrated ammonia liquor；
（2）Iron tailings after will be levigate sieves with 100 mesh sieve, and is put into later in Muffle furnace and is heated to 920 DEG C, keeps temperature 5 hours, system Mine tailing after must activating；
（3）It is 1 by volume by mine tailing and the 2.5mol/L hydrochloric acid after activation:2 are mixed and stirred for 2 hours, filter to take to obtain filter Slag is dried, filtrate container collection；
（4）It is 1 in mass ratio by filter residue and sodium hydroxide:1.6 are mixed and stirred for uniformly, are kept for 2 hours for 570 DEG C in Muffle furnace The iron tailings after alkali fusion reaction is made；
（5）Iron tailings after alkali fusion is reacted incorporates in water, is 1 by solid-to-liquid ratio:6 are stirred to react 24 hours under 80 DEG C of oil baths, Through thick silicon solution is obtained by filtration；
（6）By step（5）In thick silicon solution obtained cross storng-acid cation exchange resin, in being adjusted to later with ammonia spirit Property near, standing wait for its gel；
（7）Gel aging：Gel Ageing solution is added to gel obtained（Absolute ethyl alcohol presses 9 with ethyl orthosilicate:1 volume ratio is mixed It closes）, aging in 23 hours is stood at room temperature；
（8）Exchange of solvent：Gel after aging is immersed in n-hexane 23 hours, the water in colloid is cemented out；
（9）Surface is modified：Colloid after exchange of solvent is immersed into modification liquid（N-hexane presses 9 with trim,ethylchlorosilane:1 volume ratio Mixing）, 23 hours are stood at room temperature, finally by 90 DEG C of gel constant pressure and dry 7 hours obtained, the final one kind that obtains is with iron tailings The hydrophobic silica aerogel prepared for raw material；
（10）By step（3）In filtrate be adjusted to pH=8 with ammonium hydroxide under ultrasound environments, there are a large amount of precipitations, stand 2 hours After filter, container collection is used after filter residue and drying；
（11）Filter residue after drying is put into Muffle furnace, is roasted at a temperature of 680 DEG C 2 hours, iron oxide is finally made and receives Rice flour body.And iron oxide to gained and aerosil enter measured performance parameter with embodiment 1.Final products The silicon rate of recovery is 61%；It is 85% to aoxidize iron recovery.
Comparative example 1 prepares ferric oxide powder and aerosil
Comparative example 1 of the present invention prepares ferric oxide powder and aerosil by raw material of iron tailings, includes the following steps：
（1）Raw material include at least North China's iron tailings, sodium hydroxide, hydrochloric acid, n-hexane, trim,ethylchlorosilane, absolute ethyl alcohol, Concentrated ammonia liquor；
（2）Iron tailings after will be levigate sieves with 100 mesh sieve, and is put into later in Muffle furnace and is heated to 900 DEG C, keeps temperature 5 hours, system Mine tailing after must activating；
（3）It is 1 by volume by mine tailing and the 2mol/L hydrochloric acid after activation:1.6 are mixed and stirred for 2 hours, filter to take to obtain filter Slag is dried；
（4）It is 1 in mass ratio by filter residue and sodium hydroxide:1.4 are mixed and stirred for uniformly, are kept for 2 hours for 500 DEG C in Muffle furnace The iron tailings after alkali fusion reaction is made；
（5）Iron tailings after alkali fusion is reacted incorporates in water, is 1 by solid-to-liquid ratio:5 are stirred to react 24 hours under 70 DEG C of oil baths, Through thick silicon solution is obtained by filtration；
（6）By step（5）In thick silicon solution obtained cross storng-acid cation exchange resin, in being adjusted to later with ammonia spirit Property near, standing wait for its gel；
（7）Gel aging：Gel Ageing solution is added to gel obtained（Absolute ethyl alcohol presses 10 with ethyl orthosilicate:1 volume ratio is mixed It closes）, aging in 24 hours is stood at room temperature；
（8）Surface is modified：Colloid after exchange of solvent is immersed into modification liquid（N-hexane presses 10 with trim,ethylchlorosilane:1 volume ratio Mixing）, 12 hours are stood at room temperature, finally by 90 DEG C of gel constant pressure and dry 6 hours obtained, the final one kind that obtains is with iron tailings The hydrophobic silica aerogel prepared for raw material.
Comparative example 2 prepares ferric oxide powder and aerosil
Comparative example 2 of the present invention prepares ferric oxide powder and aerosil by raw material of iron tailings, includes the following steps：
（1）Raw material include at least North China's iron tailings, sodium hydroxide, hydrochloric acid, n-hexane, trim,ethylchlorosilane, absolute ethyl alcohol, Concentrated ammonia liquor；
（2）Iron tailings after will be levigate sieves with 100 mesh sieve, and is put into later in Muffle furnace and is heated to 900 DEG C, keeps temperature 5 hours, system Mine tailing after must activating；
（3）It is 1 by volume by mine tailing and the 2mol/L hydrochloric acid after activation:1.8 are mixed and stirred for 4 hours, filter to take to obtain filter Slag is dried, filtrate container collection；
（4）It is 1 in mass ratio by filter residue and sodium hydroxide:2.2 are mixed and stirred for uniformly, are kept for 4 hours for 500 DEG C in Muffle furnace The iron tailings after alkali fusion reaction is made；
（5）Iron tailings after alkali fusion is reacted incorporates in water, is 1 by solid-to-liquid ratio:6 are stirred to react 24 hours under 85 DEG C of oil baths, Through thick silicon solution is obtained by filtration；
（6）By step（5）In thick silicon solution obtained cross storng-acid cation exchange resin, in being adjusted to later with ammonia spirit Property near, standing wait for its gel；
（7）Gel aging：Gel Ageing solution is added to gel obtained（Absolute ethyl alcohol presses 10 with ethyl orthosilicate:1 volume ratio is mixed It closes）, aging in 20 hours is stood at room temperature；
（8）By wet gel obtained with 120 DEG C of constant pressure and dries 6 hours, a kind of two prepared as raw material using iron tailings are finally obtained Silica aerogel.
The property of aerosil, ferric oxide nano powder obtained by 1-4 of the embodiment of the present invention and comparing embodiment 1-2 Energy parameter is as shown in table 1.
The performance parameter table of 1 aerosil of table, ferric oxide nano powder
As can be drawn from Table 1, the Monolithic aerogel volume-diminished that two comparative examples of the invention obtain is serious, and density is larger, nor It is often hard, it is scanned through Electronic Speculum（SEM）It can be seen that silica dioxide granule stacks seriously, porosity is very low, this is because wet gel Do not pass through solvent exchange operation or aeroge is modified operation, makes wet gel in the drying process due to the surface tension effects of water By the three-dimensional network be collapsed of silica, obtained aeroge volume-diminished, density is caused to increase, heat-insulation and heat-preservation ability drops significantly Low, it is very necessary that this explanation exchange of solvent and surface when preparing aerosil are modified operation；And the embodiment of the present invention 1-4's the results show that the method limited through the invention, is recycled iron tailings, obtained iron oxide vibration density Degree is 1.116g/cm3Hereinafter, grain size is respectively less than 50nm, aerosil tap density 0.172g/cm3Hereinafter, average hole Diameter is not more than 40nm, 93% or more porosity.
By above example and comparative example it is found that the present invention provides one kind preparing iron oxide simultaneously using iron tailings as raw material The method of powder and silica nano material, including：Pickling and alkali soluble operation are carried out to iron tailings, by iron therein, silicon Element extraction comes out；Wherein ferro element is made ferric oxide powder through the precipitation method and further utilizes, and it is molten that sodium metasilicate is made in element silicon Liquid becomes cheap silicon source, and aerosil is made；To wet gel by aging, exchange of solvent, surface be modified etc. operations, The shortcomings of make to be dried under normal pressure, avoid severe reaction conditions in supercritical drying, and energy consumption is big.This hair The ferric oxide powder and aerosil preparation condition of bright offer are mild, and not high to equipment requirement, daily energy consumption is smaller, close Reason utilizes solid waste, reduces cost, is easy to industrialize.
The foregoing is merely the section Examples of the present invention, are not used for limiting the present invention.In every case according to the content of present invention institute The equivalent changes and modifications done, all for protection scope of the present invention within.

Claims (9)

1.一种从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法，其特征在于包括以下步骤：1. A method for simultaneously preparing iron oxide and silica airgel from iron tailings, characterized in that it may further comprise the steps: 1）将铁尾矿研磨粉碎并过100目筛，得到磨细后的铁尾矿；1) Grinding and pulverizing the iron tailings and passing through a 100-mesh sieve to obtain finely ground iron tailings; 2）将步骤1）的磨细后的铁尾矿放入马弗炉内加热到850-950℃进行活化，保温4.5-5.5小时，制得活化后的铁尾矿粉；2) Put the finely ground iron tailings in step 1) into a muffle furnace and heat to 850-950°C for activation, and keep warm for 4.5-5.5 hours to obtain activated iron tailings powder; 3）将步骤2）中的活化后的铁尾矿粉与盐酸混合并搅拌反应，反应结束后过滤，滤渣进行干燥，滤液用容器收集；3) Mix the activated iron tailings powder in step 2) with hydrochloric acid and stir for reaction, filter after the reaction, dry the filter residue, and collect the filtrate in a container; 4）将步骤3）中的滤渣与氢氧化钠颗粒混合并搅拌均匀，放入马弗炉中500-600℃保持1.5-2.5小时，制得碱熔反应后的铁尾矿；4) Mix the filter residue in step 3) with sodium hydroxide particles and stir evenly, put it in a muffle furnace at 500-600°C for 1.5-2.5 hours to obtain iron tailings after alkali fusion reaction; 5）将步骤4）中的碱熔反应后的铁尾矿融入水中进行加热反应，反应结束后过滤得粗硅溶液；5) Melt the iron tailings after the alkali fusion reaction in step 4) into water for heating reaction, and filter to obtain a crude silicon solution after the reaction; 6）将步骤5）中的粗硅溶液过阳离子交换树脂，再用氨水溶液调节粗硅溶液pH值为6.5-7.5，静置得凝胶；6) Pass the crude silicon solution in step 5) through a cation exchange resin, then use ammonia solution to adjust the pH of the crude silicon solution to 6.5-7.5, and let stand to obtain a gel; 7）凝胶老化：在步骤6）中制得的凝胶加入凝胶老化液中，室温下静置20-26小时老化，得二氧化硅水凝胶；7) Gel aging: add the gel prepared in step 6) to the gel aging solution, and leave it at room temperature for 20-26 hours to age to obtain a silica hydrogel; 8）溶剂交换：将步骤7）中老化后的二氧化硅水凝胶浸入正己烷中22-26小时将凝胶内的水置换出来，得胶体；8) Solvent exchange: immerse the aged silica hydrogel in step 7) in n-hexane for 22-26 hours to replace the water in the gel to obtain a colloid; 9）表面改性：将步骤8）中的凝胶浸入改性液室温静置12-24小时，并将制得的改性凝胶于85-95℃下常压干燥5-7小时，得以铁尾矿为原料制备的疏水二氧化硅气凝胶；9) Surface modification: immerse the gel in step 8) into the modification solution and let it stand at room temperature for 12-24 hours, and dry the prepared modified gel at 85-95°C under normal pressure for 5-7 hours to obtain Hydrophobic silica airgel prepared from iron tailings; 10）将步骤3）中的滤液在超声环境下用氨水调节至pH为7-8，出现大量沉淀，静置后过滤，滤渣干燥备用；10) Adjust the filtrate in step 3) to a pH of 7-8 with ammonia water in an ultrasonic environment, a large amount of precipitation occurs, filter after standing, and dry the filter residue for later use; 11）将步骤10）中干燥后的滤渣放入马弗炉内，在600℃-700℃的温度下焙烧1.5-2.5小时，最后制得氧化铁纳米粉体。11) Put the filter residue dried in step 10) into a muffle furnace, and roast at a temperature of 600°C-700°C for 1.5-2.5 hours, and finally obtain iron oxide nanopowder. 2.根据权利要求1所述的从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法，其特征在于步骤1）中的铁尾矿的成分包括SiO2、CaO、MgO、Al2O3、Fe2O3。2. The method for simultaneously preparing iron oxide and silica airgel from iron tailings according to claim 1, characterized in that the iron tailings in step 1) include SiO2, CaO, MgO, Al2O3, Fe2O3 . 3.根据权利要求1所述的从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法，其特征在于步骤2）中的盐酸浓度为1-3mol/L，优选为2mol/L，铁尾矿粉与盐酸的体积比为1：1.5-2.2，优选为1.6-1.8。3. The method for simultaneously preparing iron oxide and silica airgel from iron tailings according to claim 1, characterized in that the concentration of hydrochloric acid in step 2) is 1-3mol/L, preferably 2mol/L, The volume ratio of iron tailings powder to hydrochloric acid is 1:1.5-2.2, preferably 1.6-1.8. 4.根据权利要求1所述的从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法，其特征在于步骤4）中的滤渣与氢氧化钠的质量比为1：1.4-2.2。4. The method for simultaneously preparing iron oxide and silica airgel from iron tailings according to claim 1, characterized in that the mass ratio of filter residue to sodium hydroxide in step 4) is 1:1.4-2.2. 5.根据权利要求1所述的从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法，其特征在于步骤5）中的碱溶反应后的铁尾矿与水的固液比为1:3-7，加热温度为60℃-85℃。5. The method for simultaneously preparing iron oxide and silica airgel from iron tailings according to claim 1, characterized in that the solid-to-liquid ratio of the iron tailings and water after the alkali solution reaction in step 5) is 1:3-7, the heating temperature is 60°C-85°C. 6.根据权利要求1所述的从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法，其特征在于步骤7）中的凝胶老化液为无水乙醇和正硅酸乙酯混合液，无水乙醇和正硅酸乙酯的体积比为8-12：1，优选为10:1。6. The method for simultaneously preparing iron oxide and silica airgel from iron tailings according to claim 1, characterized in that the gel aging solution in step 7) is a mixed solution of absolute ethanol and tetraethyl orthosilicate , the volume ratio of absolute ethanol to ethyl orthosilicate is 8-12:1, preferably 10:1. 7.根据权利要求1所述的从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法，其特征在于步骤9）中的改性液为正己烷和三甲基氯硅烷混合液，正己烷与三甲基氯硅烷的体积比为8-12：1，优选为10:1。7. The method for simultaneously preparing iron oxide and silica airgel from iron tailings according to claim 1, characterized in that the modifying liquid in step 9) is a mixed liquid of n-hexane and trimethylchlorosilane, The volume ratio of n-hexane to trimethylchlorosilane is 8-12:1, preferably 10:1. 8.根据权利要求1所述的从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法，其特征在于步骤9）中得到的疏水二氧化硅气凝胶的振实密度为0.158-0.172g/cm3，孔隙率为93%-94%，二氧化硅气凝胶的平均孔径为20-40 nm。8. The method for simultaneously preparing iron oxide and silica airgel from iron tailings according to claim 1, characterized in that the tap density of the hydrophobic silica airgel obtained in step 9) is 0.158- 0.172g/cm 3 , the porosity is 93%-94%, and the average pore diameter of silica airgel is 20-40 nm. 9.根据权利要求1所述的从铁尾矿同时制备氧化铁和二氧化硅气凝胶的方法，其特征在于步骤9）中得到的氧化铁纳米粉体的振实密度为1.098-1.132 g/cm3，粒径小于50nm。9. The method for simultaneously preparing iron oxide and silica airgel from iron tailings according to claim 1, characterized in that the tap density of the iron oxide nanopowder obtained in step 9) is 1.098-1.132 g /cm 3 , the particle size is less than 50nm.
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