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 PDFInfo
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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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- 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)
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- 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
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- 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
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- 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
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a kind of methods preparing iron oxide and aerosil simultaneously from iron tailings.It is a kind of of low cost, the low recycling approach obtained to this solid waste of iron tailings of reaction condition.It includes the following steps：Iron tailings pre-treatment；Pickling carries iron；Alkali soluble carries silicon；Collosol and gel；Gel post-processes；Prepare ferric oxide powder and constant pressure and dry.Aerosil prepared by the present invention has lower density, higher porosity after tested；The ferric oxide powder of preparation has the characteristics that grain size is small and distribution is uniform.Thus show that the ferric oxide powder prepared and aerosil of the invention have excellent performance, have a wide range of applications value.Raw material sources of the present invention are extensive, cheap, and equipment requirement is low, and reaction condition is mild, are suitable for large-scale production.
Description
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. a kind of method preparing iron oxide and aerosil simultaneously from iron tailings, it is characterised in that including following step
Suddenly：
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 standing 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.
2. the method according to claim 1 for preparing iron oxide and aerosil simultaneously from iron tailings, feature
It is step 1）In the ingredient of iron tailings include SiO2, CaO, MgO, Al2O3, Fe2O3.
3. the method according to claim 1 for preparing iron oxide and aerosil simultaneously from iron tailings, feature
It is 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.
4. the method according to claim 1 for preparing iron oxide and aerosil simultaneously from iron tailings, feature
It is step 4）In filter residue and sodium hydroxide mass ratio be 1：1.4-2.2.
5. the method according to claim 1 for preparing iron oxide and aerosil simultaneously from iron tailings, feature
It is 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.
6. the method according to claim 1 for preparing iron oxide and aerosil simultaneously from iron tailings, feature
It is step 7）In gel Ageing solution be absolute ethyl alcohol and ethyl orthosilicate mixed liquor, the body of absolute ethyl alcohol and ethyl orthosilicate
Product is than being 8-12：1, preferably 10:1.
7. the method according to claim 1 for preparing iron oxide and aerosil simultaneously from iron tailings, feature
It is step 9）In modification liquid be n-hexane and trim,ethylchlorosilane mixed liquor, the volume ratio of n-hexane and trim,ethylchlorosilane
For 8-12：1, preferably 10:1.
8. the method according to claim 1 for preparing iron oxide and aerosil simultaneously from iron tailings, feature
It is step 9）In the obtained tap density of hydrophobic silica aerogel be 0.158-0.172g/cm3, porosity 93%-
94%, the average pore size of aerosil is 20-40 nm.
9. the method according to claim 1 for preparing iron oxide and aerosil simultaneously from iron tailings, feature
It is step 9）In the obtained tap density of ferric oxide nano powder be 1.098-1.132 g/cm3, grain size is less than 50nm.
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| CN116328716A (en) * | 2023-03-09 | 2023-06-27 | 哈尔滨工业大学 | Super-hydrophobic silica aerogel composite material prepared by taking casting slag as raw material, and preparation method and application thereof |
| CN116328716B (en) * | 2023-03-09 | 2024-05-07 | 哈尔滨工业大学 | Super-hydrophobic silica aerogel composite material prepared by taking casting slag as raw material, and preparation method and application thereof |
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