CN106191467A - A kind of method that former Smelting magnesium prepares porous silicon simultaneously - Google Patents
A kind of method that former Smelting magnesium prepares porous silicon simultaneously Download PDFInfo
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- CN106191467A CN106191467A CN201610547063.8A CN201610547063A CN106191467A CN 106191467 A CN106191467 A CN 106191467A CN 201610547063 A CN201610547063 A CN 201610547063A CN 106191467 A CN106191467 A CN 106191467A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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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
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of method that former Smelting magnesium prepares porous silicon simultaneously, belong to metal smelt and porous silicon preparing technical field.The present invention reduces the method that elemental magnesium produced by light magnesium oxide in atmospheric conditions, and the magnesium steam simultaneously produced with high temperature reacts for reducing agent with purified silicious earth, is porous silicon by reducing silica, and this porous silicon can be used for battery to be prepared and the field such as photoelectron.Former Smelting magnesium is carried out under condition of normal pressure of the present invention; and former Smelting magnesium " is united two into one " with porous silicon preparation technology; greatly simplify operating procedure, whole process is carried out at ambient pressure, overcomes tradition process for smelting magnesium and needs the deficiency of vacuum condition; simplify production equipment; protection gas reusable edible, reduces production cost, and prepared porous silicon remains kieselguhr original natural hole structure; residue magnesium Steam Recovery, becomes commodity magnesium.The present invention can also prepare high-purity porous silicon, has higher economic worth and application prospect.
Description
Technical field
The invention belongs to metal smelt and porous silicon preparing technical field；It is specifically related to a kind of former Smelting magnesium and prepares many simultaneously
The method of hole silicon.
Background technology
The method of current former Smelting magnesium technique mainly has methods such as chemical method, fused salt electrolysis process and thermal reduction, wherein,
Pidgeon process in thermal reduction is always the conventional method of the current process for smelting magnesium of China, production of magnesium by pidgeonprocess technological process and equipment
Relatively simple, production cost is low, and the magnesium purity produced is high.For production of magnesium by pidgeonprocess, the consumption of high temperature steel alloy reduction furnace
Can be high, major part white silk magnesium technique is using coal as fuel, and the thermal efficiency is low, virtually adds production cost, uses external heat, interior
The method of portion's vacuum, is affected by heating power and vacuum condition, and body of heater is susceptible to deformation, and the requirement to reduction furnace is higher.
Chinese patent CN102534251A discloses a kind of Pidgeon process magnesium metal crude magnesium and increases production and improves productivity smelting process, uses height
Matter magnesium grog is raw material, with ferrosilicon, the specific proportioning of fluorite after pressure ball, in 1200 DEG C of vacuum reduction tanks reaction prepare magnesium metal,
The described effect that increases production and improves productivity is obvious, but has continued to use original production equipment and operational approach, does not evade vacuum condition
The problem that lower operation easier is big.
The method that Chinese patent CN1584076A and CN1664135A produces magnesium metal with different reducing agents respectively, improves
The yield of magnesium metal, reduces production cost, but two kinds of Smelting magnesium techniques operates the most under vacuum conditions, add high temperature bar
Part, the requirement to equipment is high, virtually adds operation easier.
Chinese patent CN105420516A discloses the new process of a kind of continuity method electric furnace smelting magnesium metal, the method
Instead of coal fuel with electricity, furnace body temperature is easily controlled, and environmental is little, but remains a need for vacuum condition operation, does not has
Reduce the equipment requirements of electric furnace.
Summary of the invention
The present invention is directed to the problem that current former Smelting magnesium exists, it is provided that a kind of novel its preparation process, to solve
The problem that the vacuumizing condition of above-mentioned patent Central Plains Smelting magnesium is high to equipment requirements, realizes former Smelting magnesium mistake under condition of normal pressure
Journey, the magnesium steam simultaneously produced, the reducing agent prepared as porous silicon, two courses of reaction are required under protective atmosphere complete
Becoming, it is possible to achieve " uniting two into one " of two processes, the magnesium steam that the most former Smelting magnesium produces is passed directly in magnesiothermic reduction equipment, profit
With this magnesium steam, kieselguhr being reduced to porous silicon, prepared porous silicon purity is high, decreases power consumption.
The method that a kind of former Smelting magnesium of the present invention prepares porous silicon simultaneously, first, dolomite carries out calcining, disappearing
The techniques such as change, carbonization prepare light magnesium oxide, make lamellar under a certain pressure with reducing agent etc., in same tube furnace, point
Do not carry out former Smelting magnesium and kieselguhr reduction reaction, the reduction prepared by magnesium steam produced by former Smelting magnesium as porous silicon
Agent, under conditions of being passed through protective atmosphere, it is achieved operating process, and the method that described a kind of former Smelting magnesium prepares porous silicon simultaneously is
Carry out in the steps below:
Step one, light magnesium oxide is mixed with reducing agent, be fully ground after adding calcium fluoride (purpose be mixing all
Even), then powder is pressed into lamellar, vacuum drying, obtain light magnesium oxide sheet；
Step 2, light magnesium oxide sheet is placed in smelting tube furnace in, purified silicious earth be placed in reaction tube furnace in, reaction
Tube furnace is rotatable, smelts tube furnace and reaction tube furnace reacts under protection gas shielded,
In smelting tube furnace, with 5～10 DEG C/min heating rate, temperature is risen to 500～700 DEG C, is incubated 0.5～3h,
With 5～10 DEG C/min heating rate, temperature is risen to 700～900 DEG C again, be incubated 0.1～2h, finally with 3～8 DEG C/min liter
Temperature is risen to 1200～1400 DEG C by temperature speed, produces magnesium steam,
Simultaneous reactions tube furnace is warming up to constant temperature 500～900 DEG C, and controls to rotate with the speed of 10～20r/min (to rotate
Purpose is to ensure that magnesium steam is fully contacted with kieselguhr.), smelt tube furnace generation magnesium steam and be passed through reaction under strength effect
In tube furnace, kieselguhr generation redox reaction during heated at constant temperature, unnecessary magnesium steam blowout stove condensed exterior is Crystalline Magnesium,
After reaction terminates, naturally cool to room temperature, take out reaction tube furnace product；I.e. obtain porous silicon.
The reaction tube furnace product that step 2 obtains is put in acid solution, spends under magnetic agitation after water bath with thermostatic control heating
Ionized water washs 1～5 time, vacuum drying；I.e. obtain porous silicon；Wherein said acid solution is hydrochloric acid, sulphuric acid, nitric acid or phosphorus
Acid solution, acid solution concentration is 1～10mol/L；Water bath with thermostatic control temperature is 50～100 DEG C；Magnetic agitation speed be 150～
300r/min, the magnetic force time is 6～10h (water bath with thermostatic control heating is that to remove unnecessary ferrum oxide, aluminium oxide and magnesium oxide etc. miscellaneous
Matter)；Vacuum drying temperature is 70～120 DEG C, and the vacuum drying time is 6～8h.
The preparation method of light magnesium oxide described in step one is as follows: dolomite is 900～1200 DEG C of calcinings, in water bath with thermostatic control
Under the conditions of add water digestion, digestion time is 0.5～2h, obtains digesting emulsion, carries out normal pressure carbonic acid successively in transferring to carbonators
Changing and two sections of pressurized carbon acidifying normal pressure carbonation temperature are 30～50 DEG C, carbonization time is 10～40min, two sections of pressurized carbon acidifyings
Temperature is 30～50 DEG C, and carbonization time is 10～40min, and pressure is 0.2～0.5MPa, the titanium dioxide produced during dolime
Emulsion after carbonization, as normal pressure carbonating and the raw material of two sections of pressurized carbon acidifyings, then is carried out filtering to obtain heavy magnesium water by carbon,
Being passed through water vapour in heavy magnesium water to be pyrolyzed, obtain light magnesium carbonate serosity and filter, filtering residue is 600～700 in temperature
After calcining 20～60min under the conditions of DEG C, obtain light magnesium oxide；
The liquid-solid ratio during digestion of wherein said dolomite is (30～50): 1；Described carbonization final state emulsion pH be 7.0～
8.0。
Reducing agent described in step one is coking coal, coke or ferrosilicon, and magnesium oxide is (1～4) with the mol ratio of reducing agent: 1,
Calcium fluoride accounts for the 5%～25% of magnesium oxide and reducing agent gross mass.
With 9～18kgf/cm in step one2Pressure tabletting.
Step one is vacuum dried 3～6h under the conditions of 80～120 DEG C.
Protecting gas described in step 2 is nitrogen, argon, helium, and gas flow rate is 0.1～1L/min, capable of circulation in system
Recycling.
Described former Smelting magnesium and kieselguhr preparation process, all in same tube furnace, operate under condition of normal pressure.
Described technological operation must assure that sealing, midway can not leak into air.
Former Smelting magnesium process of the present invention, be to carry out in atmospheric conditions, it is to avoid vacuum condition pair in traditional handicraft
The operation high deficiency of equipment requirements, protective atmosphere serves vital effect in kieselguhr oxidation-reduction process, meanwhile,
Under protective atmosphere, magnesium steam can be condensed into Crystalline Magnesium by outside unnecessary magnesium steam blowout stove, operating process can realize again
Protective atmosphere reuse, saves material, reduces production cost.
Of the present invention reduce under the high temperature conditions with kieselguhr with the magnesium prepared by former Smelting magnesium for reducing agent
Porous silicon is prepared in reaction, successfully " is united two into one " with porous silicon preparation technology by former Smelting magnesium, greatly simplify operative employee
Skill, whole process is carried out at ambient pressure, overcomes tradition process for smelting magnesium and needs the deficiency of vacuum condition, simplifies production equipment, produce
Raw magnesium enters kieselguhr reaction zone as a vapor, it is not necessary to again heats, compared with traditional handicraft, greatly reduces energy
Consumption, reduces production cost, and prepared porous silicon purity height, remains kieselguhr original natural hole structure, improve
The productivity of porous silicon, it is achieved that industrialization prepared by porous silicon.
The magnesium metal that the present invention is produced is widely used in the field such as military, civilian, simultaneously prepared by porous silicon can answer
For fields such as battery preparation and photoelectrons.
Accompanying drawing explanation
Fig. 1 specific embodiment 1 diatomite original soil SEM scanned picture (amplifies 450 times)；
Fig. 2 diatomite original soil SEM scanned picture (amplifies 2500 times)；
Fig. 3 is the porous silicon SEM scanned picture (amplifying 10000 times) prepared by specific embodiment 1；
Fig. 4 is the porous silicon XRD figure spectrum prepared by specific embodiment 1.
Detailed description of the invention
The following is and be embodied as case, the invention will be further described, contributes to professional and technical personnel and is more fully understood that
And operation, but limit the present invention the most in any form.
Embodiment 1: a kind of method that in the present embodiment, former Smelting magnesium prepares porous silicon simultaneously is carried out in the steps below:
(1) light magnesium oxide is produced: dolomite 900 DEG C of calcinings, add water under the conditions of water bath with thermostatic control digestion, dolomite disappears
Liquid-solid ratio during change is 30:1, and digestion time is 0.5h, obtains digesting emulsion, carries out normal pressure carbonic acid successively in transferring to carbonators
Changing and two sections of pressurized carbon acidifyings, carburizing temperature is 30 DEG C, and carbonization time is 10min, and carbonization final state emulsion pH is 7.0.
Emulsion after carbonization, as carbonized stock, then is carried out filtering by the carbon dioxide that now dolime produces
Heavy magnesium water, is passed through water vapour in heavy magnesium water and is pyrolyzed, obtain light magnesium carbonate serosity and filter, and filtering residue in temperature is
After calcining 20min under the conditions of 600 DEG C, obtain light magnesium oxide.
(2) light magnesium oxide tabletting: be first that 1:1 mix with coking coal according to mol ratio by light magnesium oxide, add fluorination
Calcium (calcium fluoride accounts for the 5% of magnesium oxide and reducing agent gross mass), is fully ground, and makes each component mix homogeneously, then by mixture
Send into tablet machine, with 9kgf/cm2Powder is pressed into lamellar by pressure, puts in vacuum drying oven, 80 DEG C of vacuum drying 3h.
(3) former Smelting magnesium and the preparation of porous silicon: tube furnace is divided into two regions, A district is former Smelting magnesium district, and B district is silicon
Diatomaceous earth reaction zone, B district body of heater is rotatable, and light magnesium oxide sheet and purified silicious earth are respectively fed to tube furnace respective reaction zones,
Be passed through nitrogen as protection gas, gas flow rate is 0.1L/min, in A district, with 5 DEG C/min heating rate, temperature is risen to 500
DEG C, and it is incubated 0.5h, then with 5 DEG C/min heating rate, temperature is risen to 700 DEG C, and it is incubated 0.1h, finally with 3 DEG C/min liter
Temperature is risen to 1200 DEG C by temperature speed, produces magnesium steam, enters B district under strength effect, and now B district temperature rises to constant temperature
500 DEG C, adjusting B district body of heater rotary speed is 10r/min, and kieselguhr generation redox reaction, unnecessary magnesium steam is through indifferent gas
Body blowout stove condensed exterior is Crystalline Magnesium, after reaction terminates, naturally cools to room temperature, takes out B district product, be porous silicon.
(4) porous silicon post processing: the porous silicon of reaction preparation is put in the hydrochloric acid solution that concentration is 1mol/L, with 50 DEG C
Water bath with thermostatic control is heated, and 150r/min speed magnetic agitation 6h removes the impurity such as unnecessary ferrum oxide, aluminium oxide and magnesium oxide, uses
Deionized water wash 3 times, 70 DEG C of vacuum drying 6h, obtain purification porous silicon.
Fig. 1～3 is the figure of embodiment 1, kieselguhr the porous silicon prepared, and surface covers abundant pore structure, and impurity contains
Amount is few, and after XRD tests, in spectral line, the peak intensity of elemental silicon is obvious, and porous silicon purity is higher.
Embodiment 2: a kind of method that in the present embodiment, former Smelting magnesium prepares porous silicon simultaneously is carried out in the steps below:
(1) light magnesium oxide is produced: dolomite 1000 DEG C of calcinings, add water under the conditions of water bath with thermostatic control digestion, dolomite
Liquid-solid ratio during digestion is 35:1, and digestion time is 1h, obtains digesting emulsion, carries out normal pressure carbonic acid successively in transferring to carbonators
Changing and two sections of pressurized carbon acidifyings, the carburizing temperature of normal pressure carbonating and two sections of pressurized carbon acidifyings is 30 DEG C, and carbonization time is
20min, the pressure of two sections of pressurized carbon acidifyings is 0.5MPa, and carbonization final state emulsion pH is 7.0.
Emulsion after carbonization, as carbonized stock, then is carried out filtering by the carbon dioxide that now dolime produces
Heavy magnesium water, is passed through water vapour in heavy magnesium water and is pyrolyzed, obtain light magnesium carbonate serosity and filter, and filtering residue in temperature is
After calcining 30min under the conditions of 600 DEG C, obtain light magnesium oxide.
(2) light magnesium oxide tabletting: be first that 1:1 mix with coke according to mol ratio by light magnesium oxide, add fluorination
Calcium (calcium fluoride accounts for the 5% of magnesium oxide and reducing agent gross mass), is fully ground, and makes each component mix homogeneously, then by mixture
Send into tablet machine, with 9kgf/cm2Powder is pressed into lamellar by pressure, puts in vacuum drying oven, 80 DEG C of vacuum drying 3h.
(3) former Smelting magnesium and the preparation of porous silicon: tube furnace is divided into two regions, A district is former Smelting magnesium district, and B district is silicon
Diatomaceous earth reaction zone, B district body of heater is rotatable, and light magnesium oxide sheet and purified silicious earth are respectively fed to tube furnace respective reaction zones,
Be passed through nitrogen as protection gas, gas flow rate is 0.3L/min, in A district, with 5 DEG C/min heating rate, temperature is risen to 500
DEG C, and it is incubated 0.5h, then with 5 DEG C/min heating rate, temperature is risen to 700 DEG C, and it is incubated 0.1h, finally with 3 DEG C/min liter
Temperature is risen to 1200 DEG C by temperature speed, produces magnesium steam, enters B district under strength effect, and now B district temperature rises to constant temperature
500 DEG C, adjusting B district body of heater rotary speed is 10r/min, and kieselguhr generation redox reaction, unnecessary magnesium steam is through indifferent gas
Body blowout stove condensed exterior is Crystalline Magnesium, after reaction terminates, naturally cools to room temperature, takes out B district product, be porous silicon.
(4) porous silicon post processing: the porous silicon of reaction preparation is put in the sulfuric acid solution that concentration is 1mol/L, with 50 DEG C
Water bath with thermostatic control is heated, and 150r/min speed magnetic agitation 6h removes the impurity such as unnecessary ferrum oxide, aluminium oxide and magnesium oxide, uses
Deionized water wash 3 times, 70 DEG C of vacuum drying 6h, obtain purification porous silicon.
Embodiment 3: a kind of method that in the present embodiment, former Smelting magnesium prepares porous silicon simultaneously is carried out in the steps below:
(1) light magnesium oxide is produced: dolomite 1100 DEG C of calcinings, add water under the conditions of water bath with thermostatic control digestion, dolomite
Liquid-solid ratio during digestion is 35:1, and digestion time is 0.5h, obtains digesting emulsion, carries out normal pressure carbon successively in transferring to carbonators
Acidifying and two sections of pressurized carbon acidifyings, normal pressure carbonating and two sections of pressurized carbon acidifying carburizing temperatures are 40 DEG C, and carbonization time is
30min, the pressure of two sections of pressurized carbon acidifyings is 0.5MPa, and carbonization final state emulsion pH is 7.5.
Emulsion after carbonization, as carbonized stock, then is carried out filtering by the carbon dioxide that now dolime produces
Heavy magnesium water, is passed through water vapour in heavy magnesium water and is pyrolyzed, obtain light magnesium carbonate serosity and filter, and filtering residue in temperature is
After calcining 40min under the conditions of 650 DEG C, obtain light magnesium oxide.
(2) light magnesium oxide tabletting: be first that 2:1 mix with coking coal according to mol ratio by light magnesium oxide, add fluorination
Calcium (calcium fluoride accounts for the 10% of magnesium oxide and reducing agent gross mass), is fully ground, and makes each component mix homogeneously, then by mixture
Send into tablet machine, with 13kgf/cm2Powder is pressed into lamellar by pressure, puts in vacuum drying oven, 80 DEG C of vacuum drying 3h.
(3) former Smelting magnesium and the preparation of porous silicon: tube furnace is divided into two regions, A district is former Smelting magnesium district, and B district is silicon
Diatomaceous earth reaction zone, B district body of heater is rotatable, and light magnesium oxide sheet and purified silicious earth are respectively fed to tube furnace respective reaction zones,
Be passed through nitrogen as protection gas, gas flow rate is 0.3L/min, in A district, with 8 DEG C/min heating rate, temperature is risen to 600
DEG C, and it is incubated 1.5h, then with 8 DEG C/min heating rate, temperature is risen to 800 DEG C, and it is incubated 1h, finally heat up with 5 DEG C/min
Temperature is risen to 1300 DEG C by speed, produces magnesium steam, enters B district under strength effect, and now B district temperature rises to constant temperature
650 DEG C, adjusting B district body of heater rotary speed is 15r/min, and kieselguhr generation redox reaction, unnecessary magnesium steam is through indifferent gas
Body blowout stove condensed exterior is Crystalline Magnesium, after reaction terminates, naturally cools to room temperature, takes out B district product, be porous silicon.
(4) porous silicon post processing: the porous silicon of reaction preparation is put in the hydrochloric acid solution that concentration is 1mol/L, with 50 DEG C
Water bath with thermostatic control is heated, and 200r/min speed magnetic agitation 6h removes the impurity such as unnecessary ferrum oxide, aluminium oxide and magnesium oxide, uses
Deionized water wash 3 times, 70 DEG C of vacuum drying 6h, obtain purification porous silicon.
Embodiment 4: a kind of method that in the present embodiment, former Smelting magnesium prepares porous silicon simultaneously is carried out in the steps below:
(1) light magnesium oxide is produced: dolomite 1200 DEG C of calcinings, add water under the conditions of water bath with thermostatic control digestion, dolomite
Liquid-solid ratio during digestion is 40:1, and digestion time is 2h, obtains digesting emulsion, carries out normal pressure carbonic acid successively in transferring to carbonators
Changing and two sections of pressurized carbon acidifyings, normal pressure carbonating and two sections of pressurized carbon acidifying carburizing temperatures are 50 DEG C, and carbonization time is 20min,
The pressure of two sections of pressurized carbon acidifyings is 0.5MPa, and carbonization final state emulsion pH is 7.5.
Emulsion after carbonization, as carbonized stock, then is carried out filtering by the carbon dioxide that now dolime produces
Heavy magnesium water, is passed through water vapour in heavy magnesium water and is pyrolyzed, obtain light magnesium carbonate serosity and filter, and filtering residue in temperature is
After calcining 50min under the conditions of 700 DEG C, obtain light magnesium oxide.
(2) light magnesium oxide tabletting: be first that 4:1 mix with coking coal according to mol ratio by light magnesium oxide, add fluorination
Calcium (calcium fluoride accounts for the 5% of magnesium oxide and reducing agent gross mass), is fully ground, and makes each component mix homogeneously, then by mixture
Send into tablet machine, with 18kgf/cm2Powder is pressed into lamellar by pressure, puts in vacuum drying oven, 80 DEG C of vacuum drying 3h.
(3) former Smelting magnesium and the preparation of porous silicon: tube furnace is divided into two regions, A district is former Smelting magnesium district, and B district is silicon
Diatomaceous earth reaction zone, B district body of heater is rotatable, and light magnesium oxide sheet and purified silicious earth are respectively fed to tube furnace respective reaction zones,
Be passed through argon as protection gas, gas flow rate is 1L/min, in A district, with 5 DEG C/min heating rate, temperature is risen to 700 DEG C,
And it is incubated 0.5h, then with 5 DEG C/min heating rate, temperature is risen to 900 DEG C, and it is incubated 0.1h, finally heat up with 3 DEG C/min
Temperature is risen to 1300 DEG C by speed, produces magnesium steam, enters B district under strength effect, and now B district temperature rises to constant temperature
650 DEG C, adjusting B district body of heater rotary speed is 15r/min, and kieselguhr generation redox reaction, unnecessary magnesium steam is through indifferent gas
Body blowout stove condensed exterior is Crystalline Magnesium, after reaction terminates, naturally cools to room temperature, takes out B district product, be porous silicon.
(4) porous silicon post processing: the porous silicon of reaction preparation is put in the hydrochloric acid solution that concentration is 1mol/L, with 50 DEG C
Water bath with thermostatic control is heated, and 150r/min speed magnetic agitation 6h removes the impurity such as unnecessary ferrum oxide, aluminium oxide and magnesium oxide, uses
Deionized water wash 3 times, 70 DEG C of vacuum drying 6h, obtain purification porous silicon.
Embodiment 5: a kind of method that in the present embodiment, former Smelting magnesium prepares porous silicon simultaneously is carried out in the steps below:
(1) light magnesium oxide is produced: dolomite 1200 DEG C of calcinings, add water under the conditions of water bath with thermostatic control digestion, dolomite
Liquid-solid ratio during digestion is 50:1, and digestion time is 2h, obtains digesting emulsion, carries out normal pressure carbonic acid successively in transferring to carbonators
Changing and two sections of pressurized carbon acidifyings, normal pressure carbonating and two sections of pressurized carbon acidifying carburizing temperatures are 50 DEG C, and carbonization time is 40min,
The pressure of two sections of pressurized carbon acidifyings is 0.5MPa, and carbonization final state emulsion pH is 8.0.
Emulsion after carbonization, as carbonized stock, then is carried out filtering by the carbon dioxide that now dolime produces
Heavy magnesium water, is passed through water vapour in heavy magnesium water and is pyrolyzed, obtain light magnesium carbonate serosity and filter, and filtering residue in temperature is
After calcining 60min under the conditions of 700 DEG C, obtain light magnesium oxide.
(2) light magnesium oxide tabletting: be first that 4:1 mix with ferrosilicon according to mol ratio by light magnesium oxide, add fluorination
Calcium (calcium fluoride accounts for the 25% of magnesium oxide and reducing agent gross mass), is fully ground, and makes each component mix homogeneously, then by mixture
Send into tablet machine, with 9kgf/cm2Powder is pressed into lamellar by pressure, puts in vacuum drying oven, 80 DEG C of vacuum drying 3h.
(3) former Smelting magnesium and the preparation of porous silicon: tube furnace is divided into two regions, A district is former Smelting magnesium district, and B district is silicon
Diatomaceous earth reaction zone, B district body of heater is rotatable, and light magnesium oxide sheet and purified silicious earth are respectively fed to tube furnace respective reaction zones,
Be passed through argon as protection gas, gas flow rate is 0.1L/min, in A district, with 5 DEG C/min heating rate, temperature is risen to 500
DEG C, and it is incubated 0.5h, then with 5 DEG C/min heating rate, temperature is risen to 800 DEG C, and it is incubated 0.1h, finally with 5 DEG C/min liter
Temperature is risen to 1400 DEG C by temperature speed, produces magnesium steam, enters B district under strength effect, and now B district temperature rises to constant temperature
900 DEG C, adjusting B district body of heater rotary speed is 20r/min, and kieselguhr generation redox reaction, unnecessary magnesium steam is through indifferent gas
Body blowout stove condensed exterior is Crystalline Magnesium, after reaction terminates, naturally cools to room temperature, takes out B district product, be porous silicon.
(4) porous silicon post processing: the porous silicon of reaction preparation is put in the hydrochloric acid solution that concentration is 5mol/L, with 50 DEG C
Water bath with thermostatic control is heated, and 300r/min speed magnetic agitation 6h removes the impurity such as unnecessary ferrum oxide, aluminium oxide and magnesium oxide, uses
Deionized water wash 3 times, 70 DEG C of vacuum drying 6h, obtain purification porous silicon.
Claims (10)
1. the method that a former Smelting magnesium prepares porous silicon simultaneously, it is characterised in that the method is carried out in the steps below:
Step one, light magnesium oxide is mixed with reducing agent, be fully ground after adding calcium fluoride, then powder be pressed into sheet
Shape, vacuum drying, obtain light magnesium oxide sheet；
Step 2, light magnesium oxide sheet is placed in smelting tube furnace in, purified silicious earth be placed in reaction tube furnace in, react tubular type
Stove is rotatable, smelts tube furnace and reaction tube furnace reacts under protection gas shielded,
In smelting tube furnace, with 5～10 DEG C/min heating rate, temperature is risen to 500～700 DEG C, insulation 0.5～3h, then with
Temperature is risen to 700～900 DEG C by 5～10 DEG C/min heating rate, is incubated 0.1～2h, finally heats up speed with 3～8 DEG C/min
Temperature is risen to 1200～1400 DEG C by rate, produces magnesium steam,
Simultaneous reactions tube furnace is warming up to constant temperature 500～900 DEG C, and controls to rotate with the speed of 10～20r/min, smelts tubular type
Stove produces magnesium steam and is passed through under strength effect in reaction tube furnace, and during heated at constant temperature, kieselguhr generation oxidoreduction is anti-
Should, unnecessary magnesium steam blowout stove condensed exterior is Crystalline Magnesium, after reaction terminates, naturally cools to room temperature, takes out reaction tube furnace and produces
Thing；I.e. obtain porous silicon.
The method that a kind of former Smelting magnesium the most according to claim 1 prepares porous silicon simultaneously, it is characterised in that step 2 obtains
The reaction tube furnace product obtained is put in acid solution, is washed with deionized 1～5 under magnetic agitation after water bath with thermostatic control heating
Secondary, vacuum drying；I.e. obtain porous silicon.
The method that a kind of former Smelting magnesium the most according to claim 2 prepares porous silicon simultaneously, it is characterised in that described acid
Property solution is hydrochloric acid, sulphuric acid, nitric acid or phosphoric acid solution, and acid solution concentration is 1～10mol/L.
The method that a kind of former Smelting magnesium the most according to claim 2 prepares porous silicon simultaneously, it is characterised in that water bath with thermostatic control
Temperature is 50～100 DEG C；Magnetic agitation speed is 150～300r/min, and the magnetic force time is 6～10h；Vacuum drying temperature is 70
～120 DEG C, the vacuum drying time is 6～8h.
5. the method simultaneously preparing porous silicon according to a kind of former Smelting magnesium described in claim 1,2,3 or 4, it is characterised in that step
Described in rapid one, the preparation method of light magnesium oxide is as follows: dolomite is 900～1200 DEG C of calcinings, add water under the conditions of water bath with thermostatic control
Digestion, digestion time is 0.5～2h, obtain digest emulsion, carry out normal pressure carbonating successively in transferring to carbonators and two sections add
Pressure carbonating, normal pressure carbonation temperature is 30～50 DEG C, and carbonization time is 10～40min, and two sections of pressurized carbon souring temperatures are 30
～50 DEG C, carbonization time is 10～40min, and pressure is 0.2～0.5MPa, and the carbon dioxide produced during dolime is as often
Pressure carbonating and the raw material of two sections of carbonatings, then carry out filtering to obtain heavy magnesium water by the emulsion after carbonization, be passed through in heavy magnesium water
Water vapour is pyrolyzed, and obtains light magnesium carbonate serosity and filters, and filtering residue is calcined under the conditions of temperature is 600～700 DEG C
After 20～60min, obtain light magnesium oxide.
The method that a kind of former Smelting magnesium the most according to claim 5 prepares porous silicon simultaneously, it is characterised in that described white clouds
Liquid-solid ratio during stone digestion is 30:1～50:1；Described carbonization final state emulsion pH is 7.0～8.0.
7. the method simultaneously preparing porous silicon according to a kind of former Smelting magnesium described in claim 1,2,3 or 4, it is characterised in that step
Reducing agent described in rapid one is coking coal, coke or ferrosilicon, and magnesium oxide is (1～4) with the mol ratio of reducing agent: 1, and calcium fluoride accounts for oxygen
Change the 5%～25% of magnesium and reducing agent gross mass.
8. the method simultaneously preparing porous silicon according to a kind of former Smelting magnesium described in claim 1,2,3 or 4, it is characterised in that step
With 9～18kgf/cm in rapid one2Pressure tabletting.
9. the method simultaneously preparing porous silicon according to a kind of former Smelting magnesium described in claim 1,2,3 or 4, it is characterised in that step
Rapid one is vacuum dried 3～6h under the conditions of 80～120 DEG C.
10. the method simultaneously preparing porous silicon according to a kind of former Smelting magnesium described in claim 1,2,3 or 4, it is characterised in that
Protecting gas described in step 2 is nitrogen, argon, helium, and gas flow rate is 0.1～1L/min.
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| CN108417819A (en) * | 2018-02-09 | 2018-08-17 | 武汉科技大学 | A kind of preparation method of silicon nanoparticle |
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