CN107445168A - A kind of method of fused silica crucible recycling after polycrystalline silicon ingot casting - Google Patents
A kind of method of fused silica crucible recycling after polycrystalline silicon ingot casting Download PDFInfo
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- CN107445168A CN107445168A CN201710454818.4A CN201710454818A CN107445168A CN 107445168 A CN107445168 A CN 107445168A CN 201710454818 A CN201710454818 A CN 201710454818A CN 107445168 A CN107445168 A CN 107445168A
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- crucible
- fused silica
- ingot casting
- silica crucible
- silicon ingot
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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
- C01B33/025—Preparation by reduction of silica or free silica-containing material with carbon or a solid carbonaceous material, i.e. carbo-thermal process
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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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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- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention belongs to resource regeneration technical field, relate to a kind of method that HIGH-PURITY SILICON is prepared using fused silica crucible after polycrystalline silicon ingot casting.Concretely comprise the following steps：1) primary breakup is carried out to fused silica crucible；2) crucible fragment is cleaned；3) two-stage crushing is carried out to the crucible fragment after removal of impurities；4) ball milling is carried out to crucible fragment, obtains the quartz powder of the mesh of particle diameter distribution 800~1000；5) sic powder and binding agent are added in quartz powder slurry, it is compressing, it is dried for standby；6) mixture after compacting is smelted in mineral hot furnace or electric arc furnaces high temperature, directional solidification, prepares industrial silicon, HIGH-PURITY SILICON or solar level crystalline silicon.The present invention efficiently utilizes discarded fused silica crucible, cost of the enterprise in processing waste quartz crucible is not only saved, also using waste quartz crucible as raw material, prepare the silicon product of various different stages, realize resource regeneration, meet the feature of recycling economy, there is larger economic value and social effect.
Description
Technical field
The invention belongs to resource regeneration technical field, is related to fused silica crucible recycling after a kind of polycrystalline silicon ingot casting
Method.
Background technology
With the development of society, the photovoltaic industry using polysilicon solar cell as representative has obtained development at full speed.And
Polycrystalline silicon ingot casting is to prepare one of important step of polysilicon solar cell, and used silica crucible is then in this course
It is disposable product, consumption is especially big.After ingot casting completion, the silica crucible of melting is converted into cristobalite material, and into
For trade waste.Past processing mode is usually that simple crushing is used as building filler to use afterwards, is had developed at present
Pay the freight ability someone is needed to be ready to pull away.From now on, with the constantly improve of environmental protection policy, will also be used as at Industrial Solid Waste
Manage and pay huge disposal costs.The great wasting of resources is so not only caused, while also add and prepare polycrystal silicon cell
Cost.Therefore, how effectively photovoltaic industry urgent problem to be solved is turned into using useless silica crucible.If can be by useless crucible
High value added product is transformed into by certain processing, can not only save the expense spent in the past on the useless crucible of processing simultaneously
Solve the environmental problem that industrial residue is brought, can also bring certain income.
The granted patent " fused silica crucible renovation process after polycrystalline silicon ingot casting " that Chinese invention patent specification is announced, specially
Profit number for " ZL201410155232.4 " and " it is a kind of using waste quartz crucible preparation cristobalite matter electroceramics ", Patent No.
The method that " ZL2012105532204.0 " describes two kinds of disposal fused silica crucibles respectively.But both approaches are required for
High-temperature calcination is carried out to silica crucible, production cost is high, and its value-added content of product is relatively low, and economic feasibility is poor.
The content of the invention
It is an object of the invention to solve the handling problems of fused silica crucible, a kind of crucible reconstituted product and its system are developed
Preparation Method, the Industrial Solid Waste for needing payment process originally is converted into the crucible reconstituted product with compared with high added value, realized
The purpose of resource regeneration.Fused silica crucible belongs to Industrial Solid Waste after the completion of ingot casting, and current processing mode is only broken
After build the road use, serious waste resource, and also need to pay related freight charges.The technology that we are provided obtains discarded crucible
Sufficiently utilize, the problem of not only solving Industrial Solid Waste, and accomplished recycling for resource, while create certain
Benefit, there is highly important economic value and social effect.
The present invention is to solve caused fused silica crucible after a kind of insufficient polycrystalline silicon ingot casting provided of current techniques
The technology of recycling, it is different according to the purity of product reconstituted product, it is divided into industrial silicon (98~99%), HIGH-PURITY SILICON (99.9
~99.999%), solar level crystalline silicon (more than 99.9999%).
The method of fused silica crucible recycling, comprises the following steps after a kind of polycrystalline silicon ingot casting：
(1) fused silica crucible after ingot casting is first carried out to physics slightly to break, obtains crucible fragment；
(2) crucible fragment is put into weak acid or water and soaked, then carry out ultrasonic removal of impurities, removed micro on crucible fragment
Impurity；
(3) secondary thin broken is carried out to the crucible fragment after impurity elimination using jaw crusher；；
(4) ball milling is carried out to crucible fragment using ball mill, using ultra-fine powder technology, obtains quartz powder；
(5) quartzy slurry is made in the quartz powder that step (4) obtains, sic powder is added in quartzy slurry and is glued
Agent is tied, carries out mix, it is compressing, it is standby to be dried to water content≤5%；
(6) compound after drying is put into mineral hot furnace or electric arc furnaces, carries out high melt, industrial silico briquette or high-purity is made
Silico briquette；
(7) in vacuum≤1000Pa, temperature>1460 DEG C, under the conditions of cooldown rate≤200mm/min, by step (6)
To industrial silico briquette or high-purity silico briquette be oriented solidification, the impurity at silicon ingot bottom and top is removed after cooling of coming out of the stove, is obtained too
Positive energy level crystalline silicon.
In step (1), physics is carried out to vitreous silica earthenware using technical grade impact drill electric hammer and slightly broken, obtained crucible fragment
Size is 15~30cm.
In step (2), the weak acid needs immersion 6 hours, is soaked 12 hours in water；The weak acid is citric acid solution,
PH is 3~5.
In step (3), fragment is changed into 1~2cm of particle diameter crucible fragment after secondary thin broken.
In step (4), the particle diameter distribution of the quartz powder obtained after ball milling is 800~1000 mesh.
In step (5), the quartzy slurry, sic powder and weight of binder ratio are 3：2：(0.02~0.05)；Institute
The moisture content for stating quartzy slurry is 30%.
In step (6), the temperature of the high melt is more than 1400 DEG C.
In step (7), obtained solar level crystalline silicon purity is more than 99.9999%.
The method have the characteristics that：
(1) using fused silica crucible after polycrystalline silicon ingot casting as " silicon " source, it is high, reserves foot free purity had both been obtained
" silicon " source, and can allow this to be that the silica crucible of Industrial Solid Waste is turned waste into wealth, resource regeneration.
(2) the characteristics of reacting to obtain elemental silicon at high temperature using silica and carborundum, different stage is obtained
Silicon reconstituted product.
Fused silica crucible recycling method after the polycrystalline silicon ingot casting of the present invention, for being melted after existing polycrystalline silicon ingot casting
Fused silica crucible disposal difficulties problem, using resource regeneration, the thinking of comprehensive utilization, simply to chemically react, by tekite
English crucible is converted into the silicon reconstituted product of different stage, and the added value of the reconstituted product is high, and economic feasibility is big, for exploitation
New direction is opened using the trade waste in photovoltaic industry.
Brief description of the drawings
Fig. 1：For the flow chart of fused silica crucible recycling method after polycrystalline silicon ingot casting of the present invention.
Embodiment
Below according to the flow of accompanying drawing 1, embodiment of the invention is provided.Made by implementation of the example to the present invention
Further instruction.
Embodiment 1
Fused silica crucible after a kind of polycrystalline silicon ingot casting, its main component are silica 99.5%, carborundum
0.3%, alundum (Al2O3) 0.2%.
With reference to figure 1, the method for fused silica crucible recycling after a kind of polycrystalline silicon ingot casting of the present embodiment, including such as
Lower step：
The 1st, the fused silica crucible of sheet is broken into 15~30cm crucible fragment using technical grade impact drill electric pick；
2nd, crucible fragment is put into weak acid and soaked 6 hours, then carry out ultrasonic removal of impurities；
3rd, crucible fragment is put into jaw crusher, carries out secondary thin broken, be broken into crucible fragment of the particle diameter in 1~2cm；
4th, using ultra-fine powder technology, crucible fragment is ground into stone of the particle diameter distribution in 800 mesh or so in ball mill
English powder, the powdery pulp injection raw material stock tank of gained are standby；
5th, sic powder and binding agent are added in quartzy powdery pulp, weight is than 3：2：0.02, it is compressing, it is put into
Water content is dried in baking oven less than 5%；
6th, the compound after drying is put into electric arc furnaces, is heated to 1700 degrees Celsius, be incubated more than 1 hour, obtain siliceous
Rate is higher than 98% industrial silico briquette.
Embodiment 2
With reference to figure 1, the method for fused silica crucible recycling after a kind of polycrystalline silicon ingot casting of the present embodiment, including such as
Lower step：
The 1st, the fused silica crucible of sheet is broken into 15-30cm crucible fragment using technical grade impact drill electric pick；
2nd, crucible fragment is put into water and soaked 12 hours, then carry out ultrasonic removal of impurities；
3rd, the crucible fragment after impurity elimination is put into jaw crusher, carries out secondary thin broken, be broken into particle diameter 1~2cm's
Crucible fragment；
4th, using ultra-fine powder technology, crucible fragment is ground into stone of the particle diameter distribution in 1000 mesh or so in ball mill
English powder, the powdery pulp injection raw material stock tank of gained are standby；
5th, sic powder and binding agent are added in quartzy powdery pulp, weight is than 3：2：0.05, it is compressing, it is put into
Water content is dried in baking oven less than 5%；
6th, the compound after drying is put into electric arc furnaces, is heated to 2200 degrees Celsius, be incubated more than 2 hours, obtain siliceous
Rate is higher than 99.9% high-purity silico briquette.
Embodiment 3
With reference to figure 1, the method for fused silica crucible recycling after a kind of polycrystalline silicon ingot casting of the present embodiment, including such as
Lower step：
The 1st, the fused silica crucible of sheet is broken into 15-30cm crucible fragment using technical grade impact drill electric pick；
2nd, crucible fragment is put into water and soaked 12 hours, then carry out ultrasonic removal of impurities；
3rd, the crucible fragment after impurity elimination is put into jaw crusher, carries out secondary thin broken, be broken into particle diameter 1~2cm's
Crucible fragment；
4th, using ultra-fine powder technology, crucible fragment is ground into stone of the particle diameter distribution in 1000 mesh or so in ball mill
English powder, the powdery pulp injection raw material stock tank of gained are standby；
5th, sic powder and binding agent are added in quartzy powdery pulp, weight is than 3：2：0.05, it is compressing, it is put into
Water content is dried in baking oven less than 5%；
6th, the compound after drying is put into electric arc furnaces, is heated to 2200 degrees Celsius, be incubated more than 2 hours, obtain siliceous
Rate is higher than 99.9% high-purity silico briquette.
7th, it is 1460 degrees Celsius in temperature, under the conditions of cooldown rate≤150mm/min, high-purity silico briquette is oriented solidifying
Gu until removing the impurity above and below silicon ingot after cooling completely, the solar level crystalline silicon that purity is higher than 99.9999% is obtained.
Claims (8)
1. a kind of method of fused silica crucible recycling after polycrystalline silicon ingot casting, it is characterised in that comprise the following steps：
(1) fused silica crucible after ingot casting is first carried out to physics slightly to break, obtains crucible fragment；
(2) crucible fragment is put into weak acid or water and soaked, then carry out ultrasonic removal of impurities；
(3) secondary thin broken is carried out to the crucible fragment after impurity elimination using jaw crusher；
(4) ball milling is carried out to crucible fragment using ball mill, using ultra-fine powder technology, obtains quartz powder；
(5) quartzy slurry is made in the quartz powder that step (4) obtains, sic powder and bonding is added in quartzy slurry
Agent, mix is carried out, it is compressing, it is standby to be dried to water content≤5%；
(6) compound after drying is subjected to high melt, industrial silico briquette or high-purity silico briquette is made；
(7) in vacuum≤1000Pa, temperature>1460 DEG C, under the conditions of cooldown rate≤200mm/min, step (6) is obtained
Industrial silico briquette or high-purity silico briquette are oriented solidification, and the impurity at silicon ingot bottom and top is removed after cooling of coming out of the stove, obtains solar energy
Level crystalline silicon.
2. the method for fused silica crucible recycling, its feature after a kind of polycrystalline silicon ingot casting according to claim 1
It is, in step (1), physics is carried out to fused silica crucible using technical grade impact drill electric hammer and slightly broken, obtained crucible fragment
Size is 15~30cm.
3. the method for fused silica crucible recycling, its feature after a kind of polycrystalline silicon ingot casting according to claim 1
It is, in step (2), the weak acid needs immersion 6 hours, is soaked 12 hours in water；The weak acid is citric acid solution, and pH is
3~5.
4. the method for fused silica crucible recycling, its feature after a kind of polycrystalline silicon ingot casting according to claim 1
It is, in step (3), fragment is changed into 1~2cm of particle diameter crucible fragment after secondary thin broken.
5. the method for fused silica crucible recycling, its feature after a kind of polycrystalline silicon ingot casting according to claim 1
It is, in step (4), the particle diameter distribution of the quartz powder obtained after ball milling is 800~1000 mesh.
6. the method for fused silica crucible recycling, its feature after a kind of polycrystalline silicon ingot casting according to claim 1
It is, in step (5), the quartzy slurry, sic powder and weight of binder ratio are 3：2：(0.02~0.05)；The stone
The moisture content of English slurry is 30%.
7. the method for fused silica crucible recycling, its feature after a kind of polycrystalline silicon ingot casting according to claim 1
It is, in step (6), the temperature of the high melt is more than 1400 DEG C.
8. the method for fused silica crucible recycling, its feature after a kind of polycrystalline silicon ingot casting according to claim 1
It is, in step (7), obtained solar level crystalline silicon purity is more than 99.9999%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531368A (en) * | 2009-04-10 | 2009-09-16 | 华南师范大学 | Method for preparing cristobalite material by taking quartz crucible as raw material |
| JP5148784B1 (en) * | 2012-02-13 | 2013-02-20 | シャープ株式会社 | Silicon purification equipment |
| CN103112862A (en) * | 2012-03-16 | 2013-05-22 | 江苏融汇石英材料科技有限公司 | Method for producing fused obtuse quartz sand from quartz crucibles |
| CN103613103A (en) * | 2013-12-04 | 2014-03-05 | 南京工业大学东海先进硅基材料研究院 | Method for preparing filler-level silicon micropowder by using waste quartz crucibles as raw materials |
| CN103964677A (en) * | 2014-04-17 | 2014-08-06 | 江苏盎华光伏工程技术研究中心有限公司 | Method for regenerating fused quartz crucible through fused quartz crucible fragments after polycrystalline silicon ingoting |
| 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 |
-
2017
- 2017-06-16 CN CN201710454818.4A patent/CN107445168B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531368A (en) * | 2009-04-10 | 2009-09-16 | 华南师范大学 | Method for preparing cristobalite material by taking quartz crucible as raw material |
| JP5148784B1 (en) * | 2012-02-13 | 2013-02-20 | シャープ株式会社 | Silicon purification equipment |
| CN103112862A (en) * | 2012-03-16 | 2013-05-22 | 江苏融汇石英材料科技有限公司 | Method for producing fused obtuse quartz sand from quartz crucibles |
| CN103613103A (en) * | 2013-12-04 | 2014-03-05 | 南京工业大学东海先进硅基材料研究院 | Method for preparing filler-level silicon micropowder by using waste quartz crucibles as raw materials |
| CN103964677A (en) * | 2014-04-17 | 2014-08-06 | 江苏盎华光伏工程技术研究中心有限公司 | Method for regenerating fused quartz crucible through fused quartz crucible fragments after polycrystalline silicon ingoting |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 何允平 等: "《工业硅生产》", 30 June 1989 * |
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Effective date of registration: 20221020 Address after: No.198 Guangming Road, Yangzhong Economic Development Zone, Zhenjiang City, Jiangsu Province Patentee after: Jiangsu Meike Solar Energy Technology Co.,Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: JIANGSU University |
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