CN109988928A - A kind of silicon material and preparation method prepared with photovoltaic cutting waste material - Google Patents
A kind of silicon material and preparation method prepared with photovoltaic cutting waste material Download PDFInfo
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- CN109988928A CN109988928A CN201910315139.8A CN201910315139A CN109988928A CN 109988928 A CN109988928 A CN 109988928A CN 201910315139 A CN201910315139 A CN 201910315139A CN 109988928 A CN109988928 A CN 109988928A
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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Abstract
The present invention relates to a kind of methods for preparing alusil alloy using photovoltaic cutting waste material comprising: S1.1, by photovoltaic cutting waste material: water: bonding agent 100:10~30:2~8 in mass ratio are uniformly mixed, and obtain mixture;Mixture is pressed into material block by S1.2;The dehydration of material block, de- organic matter are obtained the material block for being dehydrated de- organic matter by S1.3, are dehydrated material block, that is, silicon material of de- organic matter.Method provided by the invention with photovoltaic cutting waste material preparation silicon material, realizes the regeneration of photovoltaic industry waste material, turns waste into wealth.During handling waste material, die mould can reduce total volume, be conducive to transport and subsequent operation, reduce process loss;Bonding agent prevents spallation for being formed.Low temperature dewatering, high temperature take off organic matter, and convenient for collecting moisture and organic matter respectively, discharge is utilized respectively.Simultaneously it is also processing material block, makes it possible to for melting.
Description
Technical field
The present invention relates to open pit mining technical field, especially a kind of silicon material prepared with photovoltaic cutting waste material, also
Provide a kind of preparation method of silicon material.
Background technique
Aluminium alloy possesses many merits, such as light weight, and it is most widely used non-ferrous alloy that specific strength is high.Wherein,
Alusil alloy is the essential intermediate alloy of aluminium processing industry, and the market demand is vigorous.1~July in 2014, China's alusil alloy
The industry output value increases by 29.2% on a year-on-year basis up to 256.16 hundred million yuan.
Alar can be divided into deformation Al-Si alloy and casting Al-Si alloy two major classes.Wherein, Al-Si alloy is deformed
Si content be generally 4.5%~13.5%, it is main by forging or die-casting process molding;The Si content of casting Al-Si alloy
Mostly 4%~22%, mainly formed by routine casting mode.It is shown according to statistics in 2010, casts Al-Si in aluminium alloys for automobile
Alloy accounting is up to 50%, and wherein metallic silicon dosage is up to 7%~12%.
Alar has excellent casting character and lesser volume change coefficient, and specific gravity is small, intensity is high, thermally conductive
It is good, and wear-resisting property is preferable, so being widely used in the important industry such as aviation, traffic, building, automobile, is also used for manufacturing
The complex-shaped casting of low, middle intensity, such as cover board, motor casing, bracket.
There are mainly two types of production methods for alusil alloy at present: mix-melting method and electric reduction process.
1, mix-melting method
Using industrial pure silicon and fine aluminium as raw material, the production of alusil alloy is carried out by the method for melting.The simple process is fitted
It is wide with property.According to the difference of production process, which can be divided into following a few classes:
(1) high temperature adds silicon process
Aluminium block is melted, is then wrapped up broken silico briquette (granularity is 15~20mm) using aluminium foil, then with the graphite of preheating
Bell jar presses it into molten aluminum, cools down after held for some time, and it is stand-by to pour into ingot casting after degasification slagging-off.
The fusing point of Si is up to 1414 DEG C, and the density of silicon is less than aluminium, when preparing alloy silicon can float on molten aluminum surface and
Surface can generate layer of silicon dioxide film, and melting temperature is up to 1703 DEG C, completely cut off contact of the silicon with molten aluminum, prevent alloy from
Smoothly formed.
(2) eutectic method
Silico briquette and aluminium block are placed on the bottom of smelting furnace simultaneously, and it is using most common one that the common thawing that heats up, which prepares alloy,
The upper surface of kind method, since the fusing point of aluminium is more much lower than silicon, so aluminium takes the lead in melting, after aluminium melts, and be covered on silicon, silicon exists
It is slowly melted under the package of molten aluminum.
The advantages of such method is after molten aluminum wraps silico briquette, to have completely cut off contact of the silicon with air, to prevent silicon
The oxidational losses of the oxidation of block, silicon reduces, and improves alloy preparation efficiency.But at 400 DEG C vigorous oxidation will occur for silicon, although
Aluminium block can play a protective role to silico briquette after melting, but the fusing point of aluminium is 660 DEG C, therefore can not be to silicon before aluminium block thawing
Block plays a protective role, and the silica of generation not only affects the purity of alloy, but also mechanical property and surface to alloy
Quality has an impact, and can shorten die life.
(3) stir casting
The basic principle of stirring casting are as follows: silicon particle is put into the molten aluminum of thawing, melts silicon rapidly simultaneously by stirring
It is distributed in molten aluminum.Liquid metal stirring casting method is the alloy preparation method of nowadays mainstream, easy to operate low in cost etc. excellent
Point promotes its rapid development.
Stir casting there are the problem of primarily to increasing the speed of dissolution, general silicon particle can be processed relatively thin,
It since the wettability of silicon grain and molten aluminum is poor, is not easily accessible in molten aluminum and forms alloy, furthermore silicon grain is easy to reunite, causes in alloy
It is serious that silicon is unevenly distributed uniform segregation.
2, electric reduction process
On electric arc furnaces, with kaolin, aluminium oxide or bauxite and blue spar ore etc. for raw material, bituminous coal and petroleum coke are also
Former agent, acid system spent pulping liquor or clay are the technique that binder produces alusil alloy.
The main reason for preparing aluminum-silicon alloy by electrothermal process is not promoted on a large scale is that fusion process difficulty is grasped, reason
It is as follows:
(1) at a lower temperature, carbon and silica produce silicon carbide first, and decomposition temperature is higher than reduction reaction institute
The temperature needed.Carbon and aluminium oxide can generate the carbide of aluminium when generating the temperature of metallic aluminium lower than carbon and aluminium oxide.Exactly
Due to silicon carbide difficult decomposition easily generated in reduction process, very big difficulty is brought to smelting process, it is easy to furnace bottom rising is caused, it is real
In the generating process of border silicon carbide to smelting, to impact degree bigger than the carbide of aluminium.
(2) melting under 2000 DEG C of high temperature, misoperation easily cause Al and Si and its low oxide gaseous state to volatilize and damage
It loses, and makes the rate of recovery of aluminium, silicon low.
(3) it needs using low ferrallite mine, otherwise iron content is high in product, and the alusil alloy of acquisition cannot be directly used to give birth to
Casting alloy is produced, deoxidizer in steel production etc. can only be used as.The high raw material of iron content, needs to pre-process before smelting, the crude aluminum silicon of acquisition
Alloy will be refined, and the oxide slag in melt is removed.
Electrothermal way produces aluminium silicon compared with mix-melting method at present, the still shortage market competitiveness, therefore the life of existing alusil alloy
Production. art mostly to be electrolysed raw aluminum liquid and silicon ingot as raw material, is made by mix-melting method.
Simultaneously as existing mix-melting method uses fine aluminium and pure simple substance silicon for raw material, thus, production cost is higher.
When photovoltaic industry cutting pure silicon stick is in blocks, incision can generate a large amount of cutting waste materials, cutting waste material powdering, particulate
Shape, bits shape etc., volume is big, density is small, extremely fluffy.Surface area ratio is larger when existing cutting waste material is dehydrated de- organic matter, oxidation
Rate is higher.Waste gas treatment process is extensive.When melting alusil alloy, there are the wettability of cutting waste material and molten aluminum is poor, be not easy into
Entering and forms alloy into molten aluminum, cutting waste material reunion causes Silicon In Alloys to be unevenly distributed the problems such as uniform segregation is serious,
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provide it is a kind of using photovoltaic cutting waste material, at low cost, pollution
The method of low preparation silicon material.Silicon material good manufacturability provided by the invention, is readily transported, stores, operates, craftsmanship when alloy molten
It is good.
(2) technical solution
In order to achieve the above object, the present invention provides a kind of method for preparing alusil alloy using photovoltaic cutting waste material,
It include: S1.1, by photovoltaic cutting waste material: water: bonding agent 100:10~30:2~8 in mass ratio are uniformly mixed, and obtain mixture;
Mixture is pressed into material block by S1.2;The dehydration of material block, de- organic matter are obtained the material block for being dehydrated de- organic matter, are dehydrated by S1.3
Material block, that is, silicon material of de- organic matter.
Preferably, S1.3 includes S1.31, the material block that will expect that block is dehydrated;The material block of dehydration is placed in by S1.32
At 120 to 350 DEG C, until the material block no longer volatile fume of dehydration, obtains the material block for being dehydrated de- organic matter.
Further, in S1.31, material block is dehydrated using the mode of heating, dehydration temperaturre is 80 to 150 DEG C, dehydration
Time 5 is to 20h.
It further, further include the organic matter in combustion fumes after S1.32.
Further, the dewatering space hot gas generated after burning being transmitted back to where expecting block in S1.31.
Preferably, the bonding agent includes one of starch, dextrin, bentonite and cellulose or several.
Preferably, the photovoltaic cutting waste material: water: the mass ratio of bonding agent is 100:20:5.
Preferably, in S1.2, the pressure of compacting is 10~40MPa.
The present invention also provides a kind of silicon materials, are prepared by the method above-mentioned with photovoltaic cutting waste material preparation silicon material
It arrives.
(3) beneficial effect
The present invention provides a kind of method with photovoltaic cutting waste material preparation silicon material, realizes making profits again for photovoltaic industry waste material
With turning waste into wealth.During handling waste material, die mould can reduce total volume, be conducive to transport and subsequent operation, reduce process damage
Consumption;Bonding agent prevents spallation for being formed.Low temperature dewatering, high temperature take off organic matter, convenient for collecting moisture and organic matter respectively, point
It Pai Chu not utilize.Simultaneously it is also processing material block, makes it possible to for melting.
Water and organic matter remove respectively, can collect or discharge respectively, are convenient for exhaust-gas treatment.In heating process, due to silicon
Material is compaction state, and oxygenation efficiency substantially reduces.
Thermal dehydration is also taken in dehydration, can be used in conjunction with the equipment for heating de- organic matter, save the energy.By organic object point
Combustion, one reduces environmental pollution, and two discharge heat, reduce cost.The dehydration that the hot gas generated after burning is led to feed back block is empty
Between, the moisture of material block dewatering space can be taken away faster.
The bonding agent heatproof of selection, will not fragmentation, failure when thermal dehydration takes off organic matter.Meanwhile when silicon material is for melting
When refining, the bonding agent having can crack failure under smelting temperature, and silicon material outer layer first separates, generates molten alloy and expand
It dissipates, the bonding agent of silicon material internal layer connects failure, discharges element silicon, not will cause the reunion of silicon powder as stir casting, melting
Alloy it is high-quality.
Photovoltaic cutting waste material: water: the mass ratio of bonding agent is 100:20:5, and more strict material block can be generated, and postorder is de-
The moisture removal time is short.
The pressure range of compacting material block is suitble to the process of present invention material block.
Silicon material density provided by the invention is big, material is clean.Melt fast, silicon in melting and disseminates that fast, reaction surface is uniform greatly.
And the waste material of photovoltaic industry is utilized, silicon material cost is far below pure silicon.
Detailed description of the invention
Fig. 1 is a kind of flow chart of method that alusil alloy is prepared with photovoltaic cutting waste material.
Specific embodiment
In order to preferably explain the present invention, in order to understand, below with reference to Fig. 1, by specific embodiment, to the present invention
It is described in detail.
Embodiment 1
S1.1, by photovoltaic cutting waste material: water: cellulose 100:10:2 in mass ratio is uniformly mixed, and obtains mixture;
Mixture is pressed into material block with the pressure of 10MPa by S1.2, expects that the size of block is 3mm, shape is granular;
Material block is placed at 120 DEG C and is dehydrated, takes off organic matter by S1.3, after expecting block no longer volatile fume, obtains taking off organic
The material block of object is dehydrated material block, that is, silicon material of de- organic matter.
Embodiment 2
Such as the silicon material that the method for embodiment 1 makes, 98% or more silicone content.It can be used for the smelting of all kinds of silicon alloys.Such as
Antaciron, Si-Mg alloy, silicomangan.
Embodiment 3
S1 prepares silicon material:
S1.1, by photovoltaic cutting waste material: water: bentonite 100:20:5 in mass ratio is uniformly mixed, and obtains mixture;
Mixture is pressed into material block with the pressure of 20MPa by S1.2, expects that the size of block is 10mm, shape is square;It can also
In the form of according to pressing mold, it is pressed into item, piece or cone etc.;
S1.31, the material block that will expect that the mode of block vacuum dehydration is dehydrated;
The material block of dehydration is placed at 350 DEG C by S1.32, until the material block no longer volatile fume of dehydration, obtaining being dehydrated taking off has
The material block of machine object;
S2 smelts pretreatment:
The material block of the de- organic matter of dehydration needed for primary smelting is taken, it is whole to be wrapped with aluminium foil, alclad material block is made;
Aluminum feedstock to be smelted is melted into molten aluminum, and molten aluminum is warming up to 1500 DEG C;
Graphite bell jar is preheating to 400 DEG C;
S3 smelts:
S3.1, the molten aluminum after the indentation of alclad material block is heated up with preheated bell jar;
S3.2, the mixed liquor of molten aluminum Yu alclad material block is stirred with the mode of electromagnetic agitation, and mixed liquor keeps the temperature 2h, melted
Alusil alloy;
S3.3, after the alusil alloy degasification slagging-off of melting, casting obtains Al-Si alloy ingots.
Embodiment 4
Such as embodiment 3, the bentonite in S1.1 is substituted for the mixture of starch and dextrin, and the mass ratio of starch and dextrin is
1:2.The several combination being also possible in starch, dextrin, bentonite and cellulose, the combined ratio are any ratio
Example.
Embodiment 5
Such as embodiment 3, molten aluminum is warming up to 1200 DEG C in S2.In S3.2, mixed liquor keeps the temperature 3.5h.
Embodiment 6
As shown in Figure 1,
S1 prepares silicon material:
S1.1, by photovoltaic cutting waste material: water: dextrin 100:30:8 in mass ratio is uniformly mixed, and obtains mixture;
Mixture is pressed into material block with the pressure of 40MPa by S1.2, expects that the size of block is 30mm, shape is spherical;
S1.31 will expect that block is placed at 80 DEG C the material block for being dehydrated 20h and being dehydrated;
The material block of dehydration is placed at 300 DEG C by S1.32, until the material block no longer volatile fume of dehydration, obtaining being dehydrated taking off has
The material block of machine object;Organic matter in combustion fumes, it is possible to reduce pollute and can use the heat of burning release;
S2 smelts pretreatment:
The material block for taking the de- organic matter of dehydration needed for primary smelting, is divided into 3-5 parts and is wrapped respectively with aluminium foil, alclad is made
Expect block;
Aluminum feedstock to be smelted is melted into molten aluminum, and molten aluminum is warming up to 800 DEG C;
Graphite bell jar is preheating to 150 DEG C;
S3 smelts:
S3.1, the molten aluminum after the indentation of alclad material block is heated up with preheated bell jar;
S3.2 stirs the mixed liquor of molten aluminum Yu alclad material block with the mode for being passed through stirring of inert gas, and mixed liquor keeps the temperature 5h,
The alusil alloy melted;
S3.3, after the alusil alloy degasification slagging-off of melting, casting obtains Al-Si alloy ingots.
Embodiment 7
Such as embodiment 6, in S3.3, after the alusil alloy degasification slagging-off of melting, aluminium element silicon ratio, the aluminium of melting are detected
Fine aluminium is added in silicon alloy, adjusts alumina silica ratio example;And continue stirring, heat preservation, then casting obtains the alusil alloy of various criterion
Ingot casting.
Embodiment 8
S1.1, by photovoltaic cutting waste material: water: dextrin 100:30:8 in mass ratio is uniformly mixed, and obtains mixture;
Mixture is pressed into material block with the pressure of 35MPa by S1.2, expects that the size of block is 25mm, shape is spherical;
S1.31 will expect that block is placed at 100 DEG C the material block for being dehydrated 15h and being dehydrated;
The material block of dehydration is placed at 180 DEG C by S1.32, until the material block no longer volatile fume of dehydration, obtaining being dehydrated taking off has
The material block of machine object;Organic matter in combustion fumes, and the thermal conductivity that burning is generated leads to the dewatering space of feed back block;
Dewatering space can be two sections of front and back in continuous oven with organic object space is taken off;It is also possible to two individually heating
Furnace, material block is first dehydrated in the same furnace, then de- organic matter, the interleaved step of process in two furnaces, takes off the furnace of organic matter to de-
The furnace of water leads to hot gas.
Embodiment 9
Such as embodiment 8, in S1.31, expect that the dehydration temperaturre of block reaches 150 DEG C, dewatering time 5h.
Upper embodiment is only presently preferred embodiments of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes in the specific implementation manner and application range, and this specification should not be construed as to limit of the invention
System.
Claims (9)
1. a kind of method with photovoltaic cutting waste material preparation silicon material, characterized in that it comprises:
S1.1, by photovoltaic cutting waste material: water: bonding agent 100:10~30:2~8 in mass ratio are uniformly mixed, and obtain mixture;
Mixture is pressed into material block by S1.2;
The dehydration of material block, de- organic matter are obtained the material block for being dehydrated de- organic matter by S1.3, are dehydrated material block, that is, silicon material of de- organic matter.
2. as described in claim 1 with the method for photovoltaic cutting waste material preparation silicon material, it is characterised in that: S1.3 includes,
S1.31, the material block that will expect that block is dehydrated;
The material block of dehydration is placed at 120 to 350 DEG C by S1.32, until the material block no longer volatile fume of dehydration, it is de- to obtain dehydration
The material block of organic matter.
3. as claimed in claim 2 with the method for photovoltaic cutting waste material preparation silicon material, it is characterised in that: in S1.31, will expect
Block is dehydrated using the mode of heating, and dehydration temperaturre is 80 to 150 DEG C, dewatering time 5 to 20h.
4. as claimed in claim 2 or claim 3 with the method for photovoltaic cutting waste material preparation silicon material, it is characterised in that: after S1.32 also
Including organic matter in combustion fumes.
5. as claimed in claim 4 with the method for photovoltaic cutting waste material preparation silicon material, it is characterised in that: by what is generated after burning
Hot gas is transmitted back to the dewatering space expected where block in S1.31.
6. as described in claim 1 with the method for photovoltaic cutting waste material preparation silicon material, it is characterised in that: the bonding agent includes
One of starch, dextrin, bentonite and cellulose are several.
7. as described in claim 1 with the method for photovoltaic cutting waste material preparation silicon material, it is characterised in that: the photovoltaic cutting is useless
Material: water: the mass ratio of bonding agent is 100:20:5.
8. as described in claim 1 with the method for photovoltaic cutting waste material preparation silicon material, it is characterised in that: in S1.2, compacting
Pressure be 10~40MPa.
9. a kind of silicon material, it is characterised in that: by any side with photovoltaic cutting waste material preparation silicon material of claim 1 to 8
Method is prepared.
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Cited By (1)
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CN111646477A (en) * | 2020-04-23 | 2020-09-11 | 北方民族大学 | Diamond wire-electrode cutting polycrystalline silicon waste material forming and drying method |
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CN109338125A (en) * | 2018-09-30 | 2019-02-15 | 东北大学 | A method of silicochromium is prepared using diamond wire sliced crystal scrap silicon |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN109338125A (en) * | 2018-09-30 | 2019-02-15 | 东北大学 | A method of silicochromium is prepared using diamond wire sliced crystal scrap silicon |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111646477A (en) * | 2020-04-23 | 2020-09-11 | 北方民族大学 | Diamond wire-electrode cutting polycrystalline silicon waste material forming and drying method |
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