CN106115714A - A kind of preparation method of metallic silicon - Google Patents
A kind of preparation method of metallic silicon Download PDFInfo
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- CN106115714A CN106115714A CN201610468000.3A CN201610468000A CN106115714A CN 106115714 A CN106115714 A CN 106115714A CN 201610468000 A CN201610468000 A CN 201610468000A CN 106115714 A CN106115714 A CN 106115714A
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- metallic silicon
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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
- C01B33/037—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention discloses the preparation method of a kind of metallic silicon, aim to solve the problem that and carry out the silica flour garbage that silicon wafer cut by diamond wire produces processing the technical problem being prepared as metallic silicon, comprise the following steps: the silica flour garbage pickling reaction first produced by silicon wafer cut by diamond wire, remove the metal in garbage and metal-oxide, again by its sedimentation concentration in inclined tube, then in centrifuge, it is centrifuged processed and washs, remove reacted metal and metal-oxide and regulate pH value simultaneously, again by gained material granulation and be vacuum dried, then smelt in smelting furnace, and the silico briquette after smelting is carried out broken and screening process, the silicon metal purity obtained is more than 99.5%, granularity meets the market demand.The method strong operability, using value is high, prepares metallic silicon from the silica flour garbage of diamond wire cutting, it is achieved comprehensive utilization of resources also is avoided polluting environment, has the strongest application value.
Description
Technical field
The invention belongs to silicon materials purification processes technical field, be specifically related to the preparation method of a kind of metallic silicon.
Background technology
The silicon chip of solar energy power generating generally use mode that line cuts by silico briquette dicing, and diamond wire cutting
Silicon chip technology, as at present the most novel most advanced technology, has that cutting speed is fast, cut quality is high, section yield rate
High, section consumes the advantages such as low, thus gradually starts at present to be applied in photovoltaic silicon wafer cuts.But silico briquette passes through Buddha's warrior attendant
Can produce tiny silicon bits after line dicing, according to statistics, often one ton of silico briquette of cutting has the silicon bits generation of about 35～45%, cuts
The silicon bits cutting generation are enriched in sedimentation tank formation silica flour garbage.This silica flour garbage key component contain 60～the silicon of 75%,
Various metals and the oxide thereof such as 5～the copper of the ferrum of the silicon dioxide of 10%, 15～25%, 15～30%, nickel, magnesium, aluminum, calcium, it is deposited
The environment such as soil, water resource, air are being worked the mischief, additionally in this silica flour garbage rich in silica flour have higher additional
Value.Metallic silicon is often referred to the purity silicon more than 99%, it as a kind of raw material of industry be widely used in refractory material, powder metallurgy,
The fields such as organic silicon chemical, monocrystal silicon son's material, industrial reduction agent, have higher using value and application.If by gold
The silica flour garbage that just line cutting silicon chip produces carries out process and is prepared as metallic silicon, has the most both been avoided that environmental pollution, has created again
It is worth, thus realizes comprehensive utilization of resources.
Summary of the invention
For problem above, the present invention provides a kind of and purifies silica flour from the silica flour garbage that silicon wafer cut by diamond wire produces
The method preparing metallic silicon.
For solving above-mentioned technical problem, the present invention is achieved through the following technical solutions:
Design the preparation method of a kind of metallic silicon, comprise the following steps:
(1) by silica flour garbage and water by 1:(10～15) weight ratio be mixed and stirred for uniformly；
(2) add acid and stir reaction 36～48 hours, gained slip being carried out in inclined tube sedimentation concentration 10～20 hours, extremely
Bottom inclined tube, the solid content of slip is 50～70wt%；
(3) remove the clear liquid on inclined tube top, and enriching slurry bottom inclined tube is centrifuged processed, be passed through water to material simultaneously
Slurry washs, and washing to pH value is 5～7, and to make final material moisture be 5～15wt%；
(4) gained material being carried out pelletize, be simultaneously introduced additive, pelletize particle diameter is 1～5cm；
(5) by step (4) gained granule temperature be 50～70 DEG C, vacuum be dried under the conditions of 0.01～0.02MPa 12～
24 hours so that it is moisture is not more than 0.04wt%；
(6) being smelted by step (5) gained granule, smelting temperature controls 2600～3000K；Smelt select white carbon black, bituminous coal,
At least one in petroleum coke is as reducing agent, and preferably white carbon black, bituminous coal, petroleum coke are with weight ratio 1:(1～2): (0.1～0.5)
Mixture, its addition is the 1～10% of particle weight to be smelted；
(7) gained silico briquette after smelting is crushed, and carry out sizing so that it is grain needed for crushing and screening to each industrial circle
Degree scope.
In technique scheme, step (2) adds acid and stirring can make ferrum in silica flour garbage and copper, nickel, magnesium,
The acid reaction of the various metals such as aluminum, calcium and oxide thereof and addition, and make the metal in silica flour garbage and metal-oxide miscellaneous
Matter is soluble in water.Reacted slip is first carried out sedimentation concentration process by step (2), then will be dissolved in through step (3) centrifuge dehydration
Metal and metal oxide impurities in water remove, and first sedimentation concentration carries out dehydration again can reduce time and the reduction of centrifuge dehydration
The energy consumption of centrifuge dehydration.Metal soluble in water and gold after pickling can be reacted by washing is carried out while step (3) centrifuge dehydration
Belong to oxide fully to remove, the pH value of silica flour is adjusted simultaneously.Step (3) gained silica flour is carried out pelletize by step (4), keeps away
Melting is impacted by the silicon bits exempting from granularity tiny.Silicon and air contact generation oxygen when step (5) vacuum drying can be avoided being dried
Change reaction.Step (6), by smelting, makes silicon generation reduction reaction, and then improves the purity of silicon further so that it is purity is more than
99.5%, meet the purity requirement of metallic silicon, the smelting furnace of 12000KVA power and the use of ultra high power graphite electrode permissible
Drop the energy consumption of low silicon smelting further, and the safety and stability smelted can be provided by submerged arc and the electrically heated use of direct current
Ensure.Step (7) carries out broken and screening process to the silico briquette smelted so that it is granularity meets metallic silicon industrial application granularity
Demand.
Preferably, step (1) and step (3) described water are deionized water, and its electrical conductivity is 0.1～0.5 μ s/cm.
Preferably, step (1) is carried out in pickling still, and its material is 316L rustless steel.
Preferably, step (2) described acid be 35～37% hydrochloric acid, 95～98% sulphuric acid and 95～98% in nitric acid at least one
Kind, its addition is the 5～10% of described silica flour garbage weight, the more preferably mixture of hydrochloric acid, sulphuric acid, nitric acid, its ratio
For weight ratio 1:(1～5): (1～3).
Preferably, described in step (3), centrifugal rotational speed is 4000～5000 revs/min, and the number of times of described washing is 5～10
Secondary, described in be passed through the flow velocity of water be 0.5～1 meter per second.
Preferably, described in step (4), additive is the one in acetone, ethanol, white carbon black, acetaldehyde, and its addition is for making
The 0.01～0.1% of grain weight of material.
Preferably, smelting furnace power used in smelting described in step (6) is 12000KVA；It is furthermore preferred that smelting furnace
Electrode selects ultra high power graphite electrode, and its resistivity is 1.5～3 μ Ω m；Described smelting is carried out under submerged arc；Described smelting
Employing unidirectional current heats.
The present invention actively has the beneficial effects that:
The invention provides the method preparing metallic silicon from the silica flour garbage that silicon wafer cut by diamond wire produces, it is to avoid silica flour gives up
The environment such as soil, water resource, air are worked the mischief by gurry, and can realize the comprehensive utilization of resources of silica flour garbage；The method
Strong operability, using value is high, is highly suitable for industrialization promotion.
Detailed description of the invention
The detailed description of the invention of the present invention is described below in conjunction with embodiment, but following example are used only to describe in detail
The present invention, and limit the scope of the present invention never in any form.
Embodiment 1:
From the silica flour garbage that silicon wafer cut by diamond wire produces, metallic silicon is prepared according to the following step:
(1) by silica flour garbage in pickling still (316L rustless steel) with the deionized water that electrical conductivity is 0.2 μ s/cm by 1:12's
Weight ratio is mixed and stirred for uniformly；
(2) adding mass concentration in the pickling still of step (1) is the hydrochloric acid of 36%, and its addition is silica flour garbage weight used
The 8% of amount, and stir reaction 40 hours；Gained slip is carried out sedimentation concentration 15 hours in inclined tube, is concentrated into bottom inclined tube and expects
The solid content of slurry is 60wt%；
(3) remove the clear liquid on inclined tube top after sedimentation concentration, and enriching slurry bottom inclined tube is passed through rotating speed is 4500 revs/min
Centrifuge is centrifuged processed, be passed through in centrifuge simultaneously flow velocity be 0.6 meter per second, electrical conductivity be 0.2 μ s/cm
Slip in centrifuge is washed 6 times by deionized water, and after washing, pH value is between 5～7, centrifuge dehydration gained moisture content of material
It is 10%；
(4) by the pelletize in comminutor of step (3) gained material, adding additive acetone during pelletize, its addition is pelletize weight
The 0.5% of amount, granulated pellet granularity is 1～5cm；
(5) by step (4) gained granule baking temperature be 60 DEG C, vacuum be in the vacuum drier under the conditions of 0.015MPa
It is dried 15 hours so that it is moisture weight percentage composition≤0.04%；
(6) granule after step (5) being vacuum dried carries out unidirectional current heating submerged arc smelting in power is 12000KVA smelting furnace
Refining, the electrode of smelting furnace be resistivity be the ultra high power graphite electrode of 1.5～3 μ Ω m, smelting temperature control 2600～
3000K, smelts and selects white carbon black as reducing agent, and its addition is treat smelting Si particle weight 5%；
(7) gained silico briquette after smelting carried out in kibbler roll broken and in vibrosieve, carry out sizing so that it is be broken
Broken it is sized to each industrial circle desired particle size range.
Embodiment 2:
Metallic silicon is prepared according to the same manner as in Example 1 from the silica flour garbage that silicon wafer cut by diamond wire produces, difference
Place is, step (1) deionized water electrical conductivity is 0.5 μ s/cm, and the weight ratio that silica flour garbage mixes with deionized water is 1:
15；What step (2) added is the sulphuric acid of 97% for mass concentration, and its addition is the 10% of silica flour garbage weight and stirs reaction
48 hours；Step (3) the sedimentation concentration time is 20 hours, and the solid content of bottom slurry is 70%；Step (4) centrifuge speed is
5000 revs/min, being passed through deionization electrical conductivity of water is 0.5 μ s/cm, and its flow velocity is 1 meter per second；Add during step (5) pelletize adds
Adding agent is ethanol, and addition is the 0.1% of pelletize weight；The baking temperature of step (6) is 70 DEG C, vacuum is 0.02MPa condition
Under, 24 hours vacuum drier time；Step (7) is smelted and is selected bituminous coal as reducing agent, and its addition is for treating smelting Si granule
The 10% of weight.
Embodiment 3:
Metallic silicon is prepared according to the same manner as in Example 1 from the silica flour garbage that silicon wafer cut by diamond wire produces, difference
Place is, step (1) deionized water electrical conductivity is 0.1 μ s/cm, and the weight ratio that silica flour garbage mixes with deionized water is 1:
10；The nitric acid for weight fraction 97% that step (2) adds also stirs reaction 36 hours, and the sedimentation concentration time is 10 hours, bottom
The solid content of slip is 50%；Step (3) centrifuge speed is 4000 revs/min, and being passed through deionization electrical conductivity of water is 0.1 μ s/
Cm, its flow velocity is 0.5 meter per second；The additive added during step (4) pelletize is white carbon black, and addition is the 0.01% of pelletize weight；
The baking temperature of step (5) is 50 DEG C, vacuum be 0.01MPa under the conditions of, 12 hours vacuum drier time；Step (6) smelting
Refining selects petroleum coke as reducing agent, and its addition is treat smelting Si particle weight 1%.
Embodiment 4:
Metallic silicon is prepared according to the same manner as in Example 1 from the silica flour garbage that silicon wafer cut by diamond wire produces, difference
Place is, step (2) add for hydrochloric acid, sulphuric acid, the mixture of nitric acid, its ratio is weight ratio 1:3:2, and its addition is silicon
The 9% of powder garbage weight；The additive added during step (4) pelletize is acetaldehyde, and its addition is the 0.06% of pelletize weight.Step
Suddenly the reducing agent that (6) add is also white carbon black, bituminous coal, the mixture of petroleum coke three, and its mixed proportion is white carbon black: bituminous coal: oil
Jiao is 1:1.5:0.2, and its addition is treat smelting Si particle weight 5%.
Embodiment 5:
Metallic silicon is prepared according to the same manner as in Example 4 from the silica flour garbage that silicon wafer cut by diamond wire produces, difference
Place is, step (2) add for hydrochloric acid, sulphuric acid, the mixture of nitric acid, its ratio is weight ratio 1:5:3, and its addition is silicon
The 7% of powder garbage weight；The additive added during step (4) pelletize is acetone, and its addition is the 0.03% of pelletize weight.Step
Suddenly the reducing agent that (6) add is also white carbon black, bituminous coal, the mixture of petroleum coke three, and its mixed proportion is white carbon black: bituminous coal: oil
Jiao is 1:2:0.1, and its addition is treat smelting Si particle weight 7%.
Embodiment 6:
Metallic silicon is prepared according to the same manner as in Example 4 from the silica flour garbage that silicon wafer cut by diamond wire produces, difference
Place is, step (2) add for hydrochloric acid, sulphuric acid, the mixture of nitric acid, its ratio is weight ratio 1:2:2, and its addition is silicon
The 8% of powder garbage weight；The additive added during step (4) pelletize is ethanol, and its addition is the 0.07% of pelletize weight.Step
Suddenly the reducing agent that (6) add is also white carbon black, bituminous coal, the mixture of petroleum coke three, and its mixed proportion is white carbon black: bituminous coal: oil
Jiao is 1:1:0.3, and its addition is treat smelting Si particle weight 5%.
From the silica flour garbage that silicon wafer cut by diamond wire produces, metallic silicon is prepared through the embodiment of the present invention 1～6 method,
The purity of gained metallic silicon is more than 99.5%, meets the metallic silicon use requirement to silicon purity, meets the purity requirement of metallic silicon,
Realize the comprehensive utilization of resources of silica flour garbage, it is to avoid pollute environment.When vacuum drying can be avoided being dried, silicon is sent out with air contact
Raw oxidation reaction.Metal soluble in water and metal-oxide after pickling can be reacted by washing is carried out abundant while centrifuge dehydration
Remove, the pH value of silica flour is adjusted simultaneously.After smelting, silico briquette is carried out broken and screening process so that it is meet metallic silicon work
Industry application, to the demand without granularity, is highly suitable for industrial applications.
It addition, first sedimentation concentration is centrifuged dehydration again can reduce the energy consumption of centrifuge, powerful smelting furnace and super
The energy consumption of low silicon smelting can drop in the use of high power graphite electrode further, thus reduces production cost, and submerged arc and direct current
The safety and stability smelted can be provided safeguard by electrically heated use.
Instrument and equipment involved in above example if no special instructions, is routine instrument device；Involved work
Industry raw material if no special instructions, is commercially available regular industrial raw material.
Above in conjunction with embodiment, the present invention is described in detail, but, person of ordinary skill in the field can
Understand, on the premise of without departing from present inventive concept, it is also possible to each design parameter in above-described embodiment is changed, shape
Become multiple specific embodiment, be the common excursion of the present invention, describe in detail the most one by one at this.
Claims (10)
1. the preparation method of a metallic silicon, it is characterised in that comprise the following steps:
(1) by silica flour garbage and water by 1:(10～15) weight ratio be mixed and stirred for uniformly；
(2) add acid and stir reaction 36～48 hours, gained slip being carried out in inclined tube sedimentation concentration 10～20 hours, extremely
Bottom inclined tube, the solid content of slip is 50～70wt%；
(3) remove the clear liquid on inclined tube top, and enriching slurry bottom inclined tube is centrifuged processed, be passed through water to material simultaneously
Slurry washs, and washing to pH value is 5～7, and to make final material moisture be 5～15wt%；
(4) gained material being carried out pelletize, be simultaneously introduced additive, pelletize particle diameter is 1～5cm；
(5) by step (4) gained granule temperature be 50～70 DEG C, vacuum be dried under the conditions of 0.01～0.02MPa 12～
24 hours so that it is moisture is not more than 0.04wt%；
(6) being smelted by step (5) gained granule, smelting temperature controls 2600～3000K；Smelt select white carbon black, bituminous coal,
At least one in petroleum coke is as reducing agent；
(7) gained silico briquette after smelting is crushed, and carry out sizing so that it is grain needed for crushing and screening to each industrial circle
Degree scope.
The preparation method of metallic silicon the most according to claim 1, it is characterised in that: in described step (1) and step (3)
In, described water is deionized water, and its electrical conductivity is 0.1～0.5 μ s/cm.
The preparation method of metallic silicon the most according to claim 1, it is characterised in that: step (1) is carried out in pickling still, its
Material is 316L rustless steel.
The preparation method of metallic silicon the most according to claim 1, it is characterised in that: in step (2), described acid be 35～
37% hydrochloric acid, 95～98% concentrated sulphuric acid and 95～98% at least one in concentrated nitric acid, its addition is described silica flour garbage weight
5～10%.
The preparation method of metallic silicon the most according to claim 4, it is characterised in that: in step (2), described acid is salt
Acid, sulphuric acid, the mixture of nitric acid, its ratio is weight ratio 1:(1～5): (1～3).
The preparation method of metallic silicon the most according to claim 1, it is characterised in that: described in step (3), centrifugal rotational speed is
4000～5000 revs/min, the number of times of described washing is 5～10 times, described in be passed through the flow velocity of water be 0.5～1 meter per second.
The preparation method of metallic silicon the most according to claim 1, it is characterised in that: in step (4), described additive is
One in acetone, ethanol, white carbon black, acetaldehyde, its addition is the 0.01～0.1% of pelletize weight of material.
The preparation method of metallic silicon the most according to claim 1, it is characterised in that: described reducing agent is white carbon black, bituminous coal, stone
Oil coke is with weight ratio 1:(1～2): the mixture of (0.1～0.5), its addition is the 1～10% of particle weight to be smelted.
The preparation method of metallic silicon the most according to claim 1, it is characterised in that: in step (6), institute in described smelting
Smelting furnace power be 12000KVA, described smelting furnace electrode is ultra high power graphite electrode, and its resistivity is 1.5～3 μ
Ω·m。
The preparation method of metallic silicon the most according to claim 9, it is characterised in that: described smelting uses unidirectional current heating,
Carry out under submerged arc.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108840339A (en) * | 2018-07-18 | 2018-11-20 | 大连理工大学 | A kind of high-efficient treatment method of Buddha's warrior attendant wire cutting silicon powder |
| CN109167044A (en) * | 2018-09-12 | 2019-01-08 | 山西中电科新能源技术有限公司 | The method for preparing lithium cell cathode material using Buddha's warrior attendant wire cutting waste silicon powder |
| CN109205626A (en) * | 2018-09-14 | 2019-01-15 | 四川永祥多晶硅有限公司 | A kind of silicon wafer cutting silicon mud recycling technique |
| CN111762787A (en) * | 2019-04-01 | 2020-10-13 | 新特能源股份有限公司 | Combined preparation method of chlorosilane and quartz |
| CN111807370A (en) * | 2020-07-21 | 2020-10-23 | 昆明理工大学 | Synergistic high-value utilization method for silicon wafer cutting waste material smelting and refining |
| CN112441588A (en) * | 2020-12-31 | 2021-03-05 | 重庆大学 | Deoxidation method for diamond wire cutting silicon waste |
| CN114890429A (en) * | 2022-05-18 | 2022-08-12 | 江苏新效新材料科技有限公司 | Purification method for removing resin impurities from solar silicon wafer cutting waste residues |
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| CN104512894A (en) * | 2013-09-27 | 2015-04-15 | 东莞市长安东阳光铝业研发有限公司 | Treatment method of silicon block |
| CN105523557A (en) * | 2016-02-14 | 2016-04-27 | 东北大学 | Method for recycling waste slurry produced during diamond wire cutting of crystalline silicon |
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- 2016-06-24 CN CN201610468000.3A patent/CN106115714A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104512894A (en) * | 2013-09-27 | 2015-04-15 | 东莞市长安东阳光铝业研发有限公司 | Treatment method of silicon block |
| CN105523557A (en) * | 2016-02-14 | 2016-04-27 | 东北大学 | Method for recycling waste slurry produced during diamond wire cutting of crystalline silicon |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108840339A (en) * | 2018-07-18 | 2018-11-20 | 大连理工大学 | A kind of high-efficient treatment method of Buddha's warrior attendant wire cutting silicon powder |
| CN109167044A (en) * | 2018-09-12 | 2019-01-08 | 山西中电科新能源技术有限公司 | The method for preparing lithium cell cathode material using Buddha's warrior attendant wire cutting waste silicon powder |
| CN109167044B (en) * | 2018-09-12 | 2021-03-26 | 山西中电科新能源技术有限公司 | Method for preparing lithium battery cathode material by using diamond wire cutting waste silicon powder |
| CN109205626A (en) * | 2018-09-14 | 2019-01-15 | 四川永祥多晶硅有限公司 | A kind of silicon wafer cutting silicon mud recycling technique |
| CN111762787A (en) * | 2019-04-01 | 2020-10-13 | 新特能源股份有限公司 | Combined preparation method of chlorosilane and quartz |
| CN111807370A (en) * | 2020-07-21 | 2020-10-23 | 昆明理工大学 | Synergistic high-value utilization method for silicon wafer cutting waste material smelting and refining |
| CN112441588A (en) * | 2020-12-31 | 2021-03-05 | 重庆大学 | Deoxidation method for diamond wire cutting silicon waste |
| CN114890429A (en) * | 2022-05-18 | 2022-08-12 | 江苏新效新材料科技有限公司 | Purification method for removing resin impurities from solar silicon wafer cutting waste residues |
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