CN107324347A - A kind of utilization waste cement prepares the method and product of nano silicon material - Google Patents
A kind of utilization waste cement prepares the method and product of nano silicon material Download PDFInfo
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- CN107324347A CN107324347A CN201710659531.5A CN201710659531A CN107324347A CN 107324347 A CN107324347 A CN 107324347A CN 201710659531 A CN201710659531 A CN 201710659531A CN 107324347 A CN107324347 A CN 107324347A
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- 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
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
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- 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
Abstract
The invention provides the method and product that a kind of utilization waste cement prepares nano silicon material.Waste cement is the hydrated product of cement, and this method comprises the following steps：Waste cement powder is subjected to calcination and cooled down, then then the waste cement powder after calcination is added heating after concentrated acid is mixed and be evaporated and wash to prepare nano silicon with that can be mixed as the solid ammonium salt of water absorbing agent.Preparing gained nano silicon material has big specific surface area, hierarchical porous structure, is expected to apply in the field such as environment remediation and energy storage.This method is simple, efficient, cost is low, and short preparation period is conducive to the prepare with scale of nano-silicon.The present invention provides new method for the recycling of waste cement, provides new approaches again for the preparation of nano silicon material.
Description
Technical field
Prepared the present invention relates to inorganic nano silicon materials and solid waste comprehensive utilization of resources field, and more particularly to a kind of utilization
Waste cement prepares the method and product of nano silicon material.
Background technology
Cement is widely used in building, bridge, road as most engineering materials is produced and used in mankind's activity
In terms of, it is that the development of human society and welfare are made that tremendous contribution.Meanwhile, the widely using of cement also generates substantial amounts of
Waste cement.It data show, it is contemplated that the waste cement amount produced to the year two thousand twenty China is up to 2,000,000,000 tons.If to waste water
Mud is mishandling, and not only environment can be impacted, and is the waste to resource.At present, the processing disposal master of waste cement
If landfill or recycling.For example, using waste cement be raw material, prepared using certain technique regenerated aggregate or
Recycled cement, but the regeneration rate of current waste cement is relatively low.Current waste cement processing method of disposal is less, existing method
The derived material added value of preparation is not high, therefore, and further the resource utilization method of exploitation waste cement is still very necessary.
The content of the invention
It is an object of the invention to provide the method and product that a kind of utilization waste cement prepares nano silicon material, to solve
The problem of derived material added value prepared using waste cement is not high.
The present invention is solved its technical problem and realized using following technical scheme.
The invention provides a kind of method that utilization waste cement prepares nano silicon material, waste cement is the aquation of cement
Product, comprises the following steps：Waste cement powder is carried out calcination and to cool down, then by the waste cement powder after calcination with can
Mixed as the solid ammonium salt of water absorbing agent, then add heating after concentrated acid is mixed and be evaporated and wash to prepare nano silicon.
Present invention also offers the product that the above method is prepared.
The utilization waste cement of the embodiment of the present invention prepares the method for nano silicon material and the beneficial effect of product：With useless
Cement is abandoned for raw material, first calcination, then selective pickling, dehydration obtains nano silicon, then by metallothermic reduction and
Pickling again, can prepare nano silicon material.Preparing gained nano silicon material has big specific surface area, hierarchical porous structure, and being expected to should
Used in the field such as environment remediation and energy storage.This method is simple, efficient, cost is low, short preparation period, raw material range of choice
Greatly, the prepare with scale of nano-silicon is conducive to, it is easy to realize industrialization promotion and application.
There is nano silicon material prepared by the method for the present invention big specific surface area (to reach as high as about 110m2/ g) and hole body
Product (reaches as high as about 0.64cm3/ g), hierarchical porous structure (mesoporous and macropore), be expected to apply in environment remediation and energy storage etc.
Field.
The method of the present invention can turn waste into wealth, and new method is provided for the recycling of waste cement, be nanometer again
The preparation of silicon materials provides new approaches.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram for the nano silicon that embodiment 1 is prepared.
Fig. 2 is the scanning electron microscope diagram for the nano silicon that embodiment 1 is prepared.
Fig. 3 is the X-ray diffractogram for the nano silicon material that embodiment 1 is prepared.
Fig. 4 is the Si 2p high-resolution X-ray fluorescence spectra figures for the nano silicon material that embodiment 1 is prepared.
Fig. 5 is the scanning electron microscope diagram for the nano silicon material that embodiment 1 is prepared.
Fig. 6 is the nitrogen adsorption desorption curve for the nano silicon material that embodiment 1 is prepared.
Fig. 7 is the graph of pore diameter distribution for the nano silicon material that embodiment 1 is prepared.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
Inventor has found：Nano-silicon causes everybody concern, including Energy Section due to unique property in numerous areas
Learn (battery electrode material and catalyst for preparing hydrogen), environment remediation (chemical sensor and different-phase catalyst), biological medicine (it is biological into
Picture and pharmaceutical carrier).Compared with buik silicon, nano-silicon can provide bigger ratio table for the load of goal response or active material
Face, accelerates interfacial mass transfer process, shortens diffusion length.In addition, for some specific reaction (embedding lithiums in such as discharge and recharge/de-
Lithium process), the vesicular structure of nano-silicon can effectively during adaptive response silicon volumetric expansion, strengthen its stability.
It is mainly nano silicon, silane, siliceous organic matter etc. in terms of silicon precursor selection.These presomas are actual
On both be from quartzite, be quartzite is prepared by complicated physical and chemical process.High cost and complicated preparation process limit
The large-scale production of nano-silicon is made, it is difficult to realize industrial applications.
The method and product that prepare nano silicon material using waste cement to the embodiment of the present invention are carried out specifically below
It is bright.
Present embodiments provide for a kind of method that utilization waste cement prepares nano silicon material, waste cement is cement
Hydrated product, comprises the following steps：
S1.1：By the waste cement of solid-like is broken and grind into powder, can be carried out using existing means it is broken and
Grinding, will not be repeated here.Cement be it is a kind of using tricalcium silicate, dicalcium silicate, tricalcium aluminate and tetra calcium aluminoferrite for mainly into
The powdery hydraulicity inorganic coagulation material divided, hydration reaction can be occurred by meeting water.Waste cement is then the hydrated product of cement, mainly
By CaO-SiO2-H2O gels, calcium hydroxide, entringite etc. are constituted.Waste cement is generally into bulk, if directly purchase adds
Work crosses into powdered waste cement, then can omit step S1.1.
S1.2：Waste cement powder is subjected to calcination and cooled down.
The temperature of calcination waste cement can be 300~800 DEG C, and corresponding calcination time can be 0.5~3 hour.Can
Choosing, the temperature of calcination waste cement is 400~800 DEG C.Optionally, the temperature of calcination waste cement is 500~800 DEG C.Bar
The situation calcination temperature that part allows can be above 800 DEG C, but the temperature of calcination waste cement is unsuitable too high, otherwise can be formed
It is difficult to the high-temperature-phase being acid washed, is impacted to subsequent step.
The type of cooling can use natural cooling, or other conventional chilling modes.Room temperature can be cooled to or close
Room temperature.
S1.3：Using the waste cement powder after calcination and cooling with that can be mixed as the solid ammonium salt of water absorbing agent.
First waste cement powder and solid ammonium salt are mixed before addition concentrated acid, the waste cement powder after calcination can be avoided
Grab concentrated acid reclaimed water mitogenetic into gel.Can be as the main function of the solid ammonium salt of water absorbing agent：Using solid ammonium salt and cement
Powder is mixed, and when adding concentrated acid, using the strong absorptive of solid ammonium salt, waste cement powder is not formed gel.And then
So that metal ion is difficult to be mixed into gel, metal ion clearance is higher.
It is possible to further which waste cement powder and solid ammonium salt are adjusted to suitable ratio.For example solid ammonium salt with
The mass ratio of waste cement is more than or equal to 3:1.It is further alternative, the mass ratio of solid ammonium salt and waste cement for 5~
10:1。
Optionally, at least one of ammonium chloride and ammonium nitrate can be included as the solid ammonium salt of water absorbing agent.It is preferred to use
Ammonium chloride, ammonium chloride cost is low, and easily reclaims.
S1.4：Heating after concentrated acid is mixed is added to be evaporated to prepare nano silicon.Waste cement and energy after concentrated acid effect
Generate silicic acid and soluble chloride, wherein silicic acid (SiO2·H2O) easily exist in colloidal form in aqueous, by adding
Solid ammonium salt and heating, which are evaporated, can separate out its overwhelming majority dehydration, so as to be separated with other components in solution.
The consumption of concentrated acid is a small amount of, and alternatively, the volume mass ratio of concentrated acid and waste cement is 4~10mL/g.Concentrated acid
Mass concentration can be 36%-38%.Optionally, concentrated acid is any of the concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid, or dense sulphur
At least two mixture in acid, concentrated nitric acid and concentrated hydrochloric acid.
Contain Fe in the product obtained after wherein S1.33+、Al3+Plasma.Due to Fe3+、Al3+Plasma is too high in temperature
Shi Rongyi hydrolysis generation slightly solubility basic salt, is mixed into silicic acid gel and is difficult to separate, therefore, temperature is strictly controlled during being evaporated
Degree.Optionally, temperature when heating is evaporated is 80-100 DEG C.
S1.5：Then it can will be evaporated product to be washed to neutrality, dry, produce more pure nano silicon.In order to
Moisture removal is removed in quickening, and processing is dried after can first being centrifuged after washing again.
Nano silicon can be obtained after above-mentioned steps, if it is desired to further obtain nano-silicon, can carried out
Following step.
S2.1：Also include sealing the mixture of nano silicon, metallic reducing agent and salt formation under protective atmosphere
Heat and be incubated.
Mixture can have nano silicon, metallic reducing agent and salt according to mol ratio 1：0.2~3：3~12 mix
It is made.
Above-mentioned heating-up temperature can be 300~900 DEG C, and soaking time can be 1~20h.Optionally, heating-up temperature is
650~800 DEG C, soaking time is 4~5h.
Above-mentioned salt forms fused salt after heatingization is molten, and fused salt can absorb released in reduction process many as heat absorbent
Waste heat amount, the generation of high temperature dephasign and the melting of nano silicon particles aggregation caused by effectively preventing temperature too high.
Above-mentioned salt can select the salt of alkali metal or the salt of alkaline-earth metal.It is possible to further select potassium chloride, sodium chloride,
One or more combinations in aluminium chloride, zinc chloride, lithium chloride and magnesium chloride.
In addition, metallic reducing agent is also possible to prevent the generation of high temperature dephasign and the oxidation of silicon.The selection of metallic reducing agent is former
It is then that its fusing point is less than more than 50 DEG C of the fusing point of selected salt, and ensures that there is reproducibility at the heating temperature.Metallic reducing agent can
To select one or more kinds of groups in magnesium metal, metallic sodium, metallic zinc, metallic aluminium, metallic potassium, calcium metal or metallic iron
Close.Optionally, metallic reducing agent is selected from magnesium metal and metallic aluminium.
Optionally, diluted acid include hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid in one or more, volumetric concentration used be 5~
20%.Optionally, the volumetric concentration of diluted acid is 8-20%.Optionally, the volumetric concentration of diluted acid is 15-20%.Optionally, diluted acid
Volumetric concentration be 8-15%.
Optionally, protective gas is one or more kinds of combinations in nitrogen and rare gas.
Closed environment can be provided by closed container, further, can select stainless steel reactor.
S2.2：Dilute acid wash again is first washed with water after thing cooling to be mixed.
The salt of generation is heated in step S2.1 to be recycled by way of evaporative crystallization.
S2.3 mixtures are after weak acid scrubbing, then wash with diluted hydrofluoric acid or ammonium hydrogen fluoride solution immersion more than 2 minutes,
Then it is washed with water to neutral and dries.
Inventor has found, in mixture after weak acid scrubbing, then is soaked with diluted hydrofluoric acid or ammonium hydrogen fluoride solution
The product quality obtained afterwards is preferable.During possible the reason for is the product obtained after S2.2, silicon face there may be silicon oxide compound
And/or the SiO not reacted away completely2.And after diluted hydrofluoric acid or ammonium hydrogen fluoride solution immersion, can remove the silica of silicon face
Compound and/or the SiO not reacted away completely2, further reduce impurity.
Further, the volumetric concentration of hydrofluoric acid can be 1%~5%.During using ammonium hydrogen fluoride solution, can use and
The equivalent amount of hydrofluoric acid.The mass fraction of such as ammonium hydrogen fluoride solution is 1%~20%.
Embodiments of the present invention also provide the product that a kind of above method is prepared.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of method that utilization waste cement prepares nano silicon material, comprises the following steps：
First by waste water clod is broken, grind into powder, calcination 1h, natural cooling at 500 DEG C are placed in Muffle furnace；Then
Take the waste cement powder after 5g calcinations and 30g solid ammonium chlorides well mixed, plus 25mL concentrated hydrochloric acids, after stirring, 105 DEG C
Heating water bath is evaporated, and with milli-Q water to neutrality, is centrifuged, is dried, obtains nano silicon.
Take 1g nano silicons obtained above, 0.8g metal magnesium powders and 5g sodium chloride well mixed, be transferred to stainless
Steel reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, 700 DEG C under argon gas protection
Heating, is incubated 4h, after cooling, first with milli-Q water, is then washed with volumetric concentration for 8% watery hydrochloric acid, then with 1% dilute hydrogen fluorine
Acid soak 10min, finally with milli-Q water to neutrality, centrifuges, dries, produce nano silicon material.
Embodiment 2
A kind of method that utilization waste cement prepares nano silicon material, comprises the following steps：
First by waste water clod is broken, grind into powder, calcination 0.5h, natural cooling at 800 DEG C are placed in Muffle furnace；So
Take the waste cement powder after 4g calcinations and 25g solid ammonium chlorides well mixed afterwards, plus 20mL concentrated hydrochloric acids, after stirring, 100
DEG C heating water bath is evaporated, with milli-Q water to neutrality, centrifugation, is dried, and obtains nano silicon.
Take 1g nano silicons obtained above, 1g metallic aluminium powders and 3g sodium chloride well mixed, be transferred to stainless steel
Reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, 800 DEG C add under argon gas protection
Heat, is incubated 5h, after cooling, first with milli-Q water, is then washed with volumetric concentration for 15% watery hydrochloric acid, then with 2% dilute hydrogen fluorine
Acid soak 5min, finally with milli-Q water to neutrality, centrifuges, dries, produce nano silicon material.
Gained nano silicon material has preferable crystal formation, with hierarchical porous structure, and BET specific surface area is 105m2/ g, total hole body
Product is 0.61cm3/g。
Embodiment 3
A kind of method that utilization waste cement prepares nano silicon material, comprises the following steps：
First by waste water clod is broken, grind into powder, calcination 3h, natural cooling at 400 DEG C are placed in Muffle furnace；Then
Take the waste cement powder after 10g calcinations and 50g solid ammonium chlorides well mixed, plus 50mL concentrated hydrochloric acids, after stirring, 102
DEG C heating water bath is evaporated, with milli-Q water to neutrality, centrifugation, is dried, and obtains nano silicon.
Take 2g nano silicons obtained above, 2g metal magnesium powders and 12g sodium chloride well mixed, be transferred to stainless steel
Reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, 650 DEG C add under argon gas protection
Heat, is incubated 5h, after cooling, first with milli-Q water, is then washed with volumetric concentration for 20% watery hydrochloric acid, then with 1.5% dilute hydrogen
Fluoric acid soaks 8min, finally with milli-Q water to neutrality, centrifuges, dries, produces nano silicon material.
Gained nano silicon material has preferable crystal formation, with hierarchical porous structure, and BET specific surface area is 98m2/ g, total hole body
Product is 0.54cm3/g。
Embodiment 4
A kind of method that utilization waste cement prepares nano silicon material, comprises the following steps：
First by waste water clod is broken, grind into powder, calcination 3h, natural cooling at 400 DEG C are placed in Muffle furnace；Then
Take the waste cement powder after 10g calcinations and 30g solid ammonium nitrates well mixed, plus the 50mL concentrated sulfuric acids, after stirring, 102
DEG C heating water bath is evaporated, with milli-Q water to neutrality, centrifugation, is dried, and obtains nano silicon.
Take 2g nano silicons obtained above, 2g metallic aluminium powders and 12g potassium chloride well mixed, be transferred to stainless steel
Reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, 750 DEG C add under nitrogen protection
Heat, is incubated 5h, after cooling, first with milli-Q water, is then washed with volumetric concentration for 20% watery hydrochloric acid, then with 1.5% dilute hydrogen
Fluoric acid soaks 8min, finally with milli-Q water to neutrality, centrifuges, dries, produces nano silicon material.
Embodiment 5
A kind of method that utilization waste cement prepares nano silicon material, comprises the following steps：
First by waste water clod is broken, grind into powder, calcination 3h, natural cooling at 400 DEG C are placed in Muffle furnace；Then
Take the waste cement powder after 10g calcinations and 50g solid ammonium chlorides well mixed, plus 50mL concentrated hydrochloric acids, after stirring, 100
DEG C heating water bath is evaporated, with milli-Q water to neutrality, centrifugation, is dried, and obtains nano silicon.
Take 2g nano silicons obtained above, 2g metal magnesium powders and 9g sodium chloride well mixed, be transferred to stainless steel
Reactor, and it is closed, then the stainless steel reactor for filling mixture is placed in tube furnace, 650 DEG C add under argon gas protection
Heat, is incubated 3h, after cooling, first with milli-Q water, is then washed with volumetric concentration for 20% watery hydrochloric acid, then with 5% dilute hydrogen fluorine
Acid soak 5min, finally with milli-Q water to neutrality, centrifuges, dries, produce nano silicon material.
Test example 1
The nano silicon prepared using embodiment 1 obtains the X-ray diffractogram of the nano silicon as sample
(as shown in Figure 1), and the nano silicon scanning electron microscope diagram (as shown in Figure 2).
X-ray diffraction spectra (XRD) result shows (Fig. 1), an obvious Bao Feng occurs at~24 ° (2 θ), illustrates by giving up
Abandon the nano silicon predominantly amorphous silica of cement preparation.
In addition, have also appeared the characteristic peak of nano silicon in picture, illustrate there be least a portion of crystal two in product
Silica.Scanning electron microscope diagram spectrum (SEM) shows (Fig. 2), and nanoparticle aggregate pattern is presented in gained silica.
Test example 2
The nano-silicon obtained after metallothermic reduction and pickling using embodiment 1 obtains the X of the nano silicon material as sample
X ray diffration pattern x (as shown in Figure 3)；The Si 2p high-resolution X-ray fluorescence spectra figures (as shown in Figure 4) of the nano silicon material；Should
The scanning electron microscope diagram (as shown in Figure 5) of nano silicon material；The nitrogen adsorption desorption curve of the nano silicon material is (such as Fig. 6 institutes
Show)；The graph of pore diameter distribution (as shown in Figure 7) of the nano silicon material.
XRD results show (Fig. 3), and obvious elemental silicon characteristic diffraction peak is presented in products therefrom, corresponding to (111),
(220), (311), (400), (331) crystal face.
High-resolution X-ray fluorescence spectra figure (XPS) shows (Fig. 4), Si 2p peaks it is main by positioned at~99.1 and~
103.50eV two peaks are constituted, and are respectively belonging to simple substance Si and SiOx, and simple substance Si accounts for major part.
SEM results show (Fig. 5), prepare products therefrom and loose porous nanotopography is presented.Nitrogen adsorption desorption curve is shown
(Fig. 6), prepares gained nano silicon material and belongs to IV type thermoisopleths, stagnant ring is returned with H3 types.When relative pressure is higher, nitrogen is inhaled
Attached amount quickly increases, and shows that the material has macroporous structure.It is according to the specific surface area that BET formula calculating obtains the material
110m2/ g, total pore volume is 0.64cm3/g。
Graph of pore diameter distribution (Fig. 7) further demonstrates that the material has hierarchical porous structure, predominantly mesoporous and macropore.
To sum up, the result shows, this method is successfully prepared using waste cement and has bigger serface and multi-stage porous concurrently
The nano silicon material of structure.Raw material range of choice of the present invention is wide, cost is low, and preparation method is simple efficiently, energy consumption
It is low, short preparation period, suitable for prepare with scale, prospects for commercial application is wide.Provided newly for the recycling of waste cement
Method, provides new approaches for the preparation of nano silicon material again.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of method that utilization waste cement prepares nano silicon material, the waste cement is the hydrated product of cement, it is special
Levy and be, comprise the following steps：
Waste cement powder is subjected to calcination and cooled down, then using the waste cement powder after calcination with water absorbing agent can be used as
Solid ammonium salt mix, then add concentrated acid mix after heating be evaporated and wash to prepare nano silicon.
2. according to the method described in claim 1, it is characterised in that the volume mass ratio of the concentrated acid and waste cement is 4~
10mL/g。
3. according to the method described in claim 1, it is characterised in that the mass concentration of the concentrated acid is 36%-38%；It is optional
, the concentrated acid is any of the concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid.
4. according to the method described in claim 1, it is characterised in that the mass ratio of the solid ammonium salt and the waste cement is big
In or equal to 3:1；Optionally, the mass ratio of the solid ammonium salt and the waste cement is 5~10:1；Optionally, it is described
Solid ammonium salt includes at least one of ammonium chloride and ammonium nitrate.
5. according to the method described in claim 1, it is characterised in that the temperature of waste cement described in calcination is 300~800 DEG C,
Calcination time is 0.5~3 hour；Optionally, the temperature of waste cement described in calcination is 400~800 DEG C；Optionally, calcination institute
The temperature for stating waste cement is 500~800 DEG C；Optionally, temperature when heating is evaporated is 80-100 DEG C.
6. according to the method described in claim 1, it is characterised in that be additionally included in the drying steps carried out after washing step.
7. the method according to claim any one of 1-6, it is characterised in that also including by the nano silicon, gold
Category reducing agent and the mixture of salt formation heated sealed and are incubated under protective atmosphere, are first washed with water after after mixture cooling
Wash dilute acid wash again；Optionally, the mixture be have the nano silicon, the metallic reducing agent and the salt by
According to mol ratio 1：0.2~3：3~12 mixings are made；Optionally, the mixture is after weak acid scrubbing, then with diluted hydrofluoric acid or
Ammonium hydrogen fluoride solution washing immersion more than 2 minutes, is then washed with water to neutral and dries.
8. method according to claim 7, it is characterised in that the metallic reducing agent includes magnesium metal, metallic sodium, metal
At least one of zinc, metallic aluminium, metallic potassium, calcium metal or metallic iron；Optionally, the metallic reducing agent be selected from magnesium metal and
Metallic aluminium；The salt is the salt of alkali metal or the salt of alkaline-earth metal；Optionally, the salt includes potassium chloride, sodium chloride, chlorination
At least one of aluminium, zinc chloride, lithium chloride or magnesium chloride；Optionally, described diluted acid includes hydrochloric acid, nitric acid, sulfuric acid or phosphorus
One or more in acid, volumetric concentration used is 5~20%；Optionally, the protective gas is nitrogen and rare gas
At least one of body；Optionally, the volumetric concentration of the hydrofluoric acid is 1%~5%, the quality point of the ammonium hydrogen fluoride solution
Number is 1%~20%.
9. method according to claim 7, it is characterised in that heating-up temperature is 300~900 DEG C, soaking time is 1~
20h；Optionally, heating-up temperature is 650~800 DEG C, and soaking time is 4~5h.
10. the product that a kind of method as described in claim any one of 1-9 is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109494399A (en) * | 2018-11-23 | 2019-03-19 | 浙江众泰汽车制造有限公司 | A kind of silicon/solid electrolyte nanocomposite and its preparation method and application |
| CN116768191A (en) * | 2023-06-25 | 2023-09-19 | 福建省鑫森炭业股份有限公司 | Nano-silicon modified mesoporous carbon material and preparation method and application thereof |
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| US20170073576A1 (en) * | 2013-10-30 | 2017-03-16 | Baker Hughes Incorporated | Proppants with improved strength |
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| CN109494399A (en) * | 2018-11-23 | 2019-03-19 | 浙江众泰汽车制造有限公司 | A kind of silicon/solid electrolyte nanocomposite and its preparation method and application |
| CN116768191A (en) * | 2023-06-25 | 2023-09-19 | 福建省鑫森炭业股份有限公司 | Nano-silicon modified mesoporous carbon material and preparation method and application thereof |
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