CN1994877A - Chemical method for promoting silicon metal purity - Google Patents
Chemical method for promoting silicon metal purity Download PDFInfo
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- CN1994877A CN1994877A CN 200610170726 CN200610170726A CN1994877A CN 1994877 A CN1994877 A CN 1994877A CN 200610170726 CN200610170726 CN 200610170726 CN 200610170726 A CN200610170726 A CN 200610170726A CN 1994877 A CN1994877 A CN 1994877A
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Abstract
The invention discloses a manufacturing method of chemical improved metal silicon purity with silicon purity more than 99. 97%, aluminium less than 0.01%, iron less than 0.003% and calcium less than 0.01%, which comprises the following steps: a. disposing raw material; b. breaking; c. grinding to 200 order; d sieving; magnifying; removing the magnetic material in the silicon powder; e. proceeding chemical purifying; placing silicon powder without magnetic material in the preservative tank; washing through distilled water; adding nitric acid solution to immerse; draining nitric acid; adding alcaine to react; adding hydrocyanic acid to react with hydrogen dioxide solution; f. drying; g. proceeding precise magnetic cobbing.
Description
Technical field
The present invention relates to electronic industry, semiconductor material, specifically a kind of chemistry improves the production method of silicon metal purity.
Background technology
Silicon is one of the widest element of distributed in nature, and the industrial silicon (HIGH-PURITY SILICON) that is applied to electron trade has tangible semiconductor property, is a kind of good semiconductor material, is the requisite starting material of unicircuit, electronic component of national encourage growth.Improve silicon metal purity and become one of current important industrial technology developing material project both at home and abroad with application, highly purified Pure Silicon Metal has been widely used in each industrial circle such as metallurgy, chemical industry, electronic information, machinofacture, space flight and aviation, shipbuilding, energy development, is the especially requisite material of high-tech industry of modern industry.
When being used to produce IC semiconductor, make materials such as solar cell, require the siliceous purity height of product, require siliceous purity greater than 99.99 (weight) more than the %.
The Pure Silicon Metal range of application that siliceous purity is high is quite extensive, and consumption is increasing, but at China's there be limited evidence currently of the producer that can produce this Pure Silicon Metal product is arranged, and most of dependence on import has consumed a large amount of foreign exchanges.
No matter the industrial silicon that present China is produced is that the overwhelming majority all is to be used to prepare aluminum silicon alloy for domestic needs or outlet, belongs to this kind of metallurgical grade silicon.From situation in recent years, the consumption of industrial silicon aspect organosilicon and semi-conductor increases the fastest, and in the international market, chemistry per ton is higher about 200 dollars than general metallurgical grade silicon price with silicon.
Along with the development of aluminium alloy, ferrous metallurgy, chemical industry and semi-conductor industry, to the output of industrial silicon particularly quality have higher requirement.In order to improve the purity of industrial silicon, though can adopt the high raw material of purity to smelt, be subjected to the restriction of resource and cost, purifying method commonly used has: gas refinement method (as chlorination process) and flux method.Method with this selective chlorination or the oxidation of selection row is effectively to aluminium and the calcium of removing in the industrial silicon, but all can not removes the impurity iron in the industrial silicon.
The impurity element of industrial silicon mainly is iron, aluminium, calcium, silicon under liquid state can with elementary composition eutectic such as iron, aluminium, calcium, after chlorination was refining, aluminium can be removed about 60 (weight) %, calcium can be removed about 90 (weight) %, and iron can't be removed.Therefore iron is the major impurity element that influences the industrial silicon quality product, and it is to influence the inhomogeneity principal element of industrial silicon product that iron produces segregation.
In recent years, industrial silicon electronics and chemical aspect application more and more widely, along with the expansion and the variation of industrial silicon range of application, both at home and abroad the industrial silicon user has proposed more hi-tech requirement to quality product.The chemistry silicon of country variant is to produce by different standards according to actual needs, in various countries' commerciality standard chemical ingredients and granularity is all had requirement.For example: the patent CN1562744A of Jiangsu Province discloses a kind of ultrapure superfine silica powder and preparation method thereof.This method limitation is very big, complex process.
And applied range of the present invention, little power consumption, product purity height, technology are simple, easy to operate, the low profit height of cost; The present invention is applicable to the customer requirements of each kind, can reach the purity of Pure Silicon Metal.
Summary of the invention
The object of the present invention is to provide a kind of chemistry to improve the production method of silicon metal purity,, improve the purity of Pure Silicon Metal effectively to reduce production costs.
According to technical scheme provided by the present invention, the siliceous purity of this Pure Silicon Metal greater than 99.97 (weight) %, iron less than 0.003 (weight) %, aluminium less than 0.01 (weight) %, calcium less than 0.01 (weight) %, remain and be other impurity.
The present invention provides (1) a kind of chemistry to improve the production method of silicon metal purity for achieving the above object, wherein: with high-purity technical silicon is raw material, bed material in the silico briquette is removed, make above-mentioned raw materials through following processing step: Hubei Province is broken, abrasive dust, screening and magnetic separation, chemical purification, drying and oven dry, precise magnetic cobbing, obtains highly purified Pure Silicon Metal then.
But also provide following embodiment preferred.
(2) a kind of chemistry improves the production method of silicon metal purity, and wherein said high-purity technical silicon can be " 2202 " high-purity technical silicon.Described " 2202 " high-purity technical silicon is the commercially available prod, and its composition content is: Si:99 (weight) %Fe:0.20 (weight) %Al:0.20 (weight) %Ca:0.02 (weight) %.
(3) a kind of chemistry improves the production method of silicon metal purity, and the broken step in wherein said Hubei Province is that silico briquette is broken into particle diameter is 0-15 centimetre.
(4) a kind of chemistry improves the production method of silicon metal purity, and wherein said abrasive dust is that silico briquette is worn into smaller or equal to 200 purpose silica flours.The sieve that is adopted is 200 mesh standard sieves.
(5) a kind of chemistry improves the production method of silicon metal purity, and wherein said screening and magnetic separation be, above-mentioned silica flour is screened on sieve apparatus, enters smaller or equal to 200 purpose silica flours again and carries out magnetic separation in the magnetic separator, to remove the magnetic substance in the silica flour.
(6) a kind of chemistry improves the production method of silicon metal purity, wherein will grind greater than 200 purpose silica flours in described screening and the magnetic separation again.
(7) a kind of chemistry improves the production method of silicon metal purity, wherein said chemical purification is, one, the silica flour that will remove magnetic substance is put into preservative tank, behind distilled water flushing, add nitric acid dousing more than 48 hours, bleed off nitric acid then, add the hydrochloric acid soln reaction, stir, soak more than 7 hours; Two, adding hydrochloric acid soln reaction then again in former preservative tank, stir, soak and place more than 7 hours, after slowly adding prussic acid and hydrogen peroxide again, treating intense reaction, stir, soak placement more than 48 hours, is 7 with distilled water flushing to pH value.
(8) a kind of chemistry improves the production method of silicon metal purity, when chemical purification, is 7 with distilled water flushing to pH value wherein, till not showing the chlorion reaction with the Silver Nitrate check.
(9) a kind of chemistry improves the production method of silicon metal purity, and wherein said precise magnetic cobbing adopts the static magnetic separation.
(10) a kind of chemistry improves the production method of silicon metal purity, the high purity metal silicon product that wherein adopts aforesaid method to obtain, its siliceous purity greater than 99.97 (weight) %, iron less than 0.003 (weight) %, aluminium less than 0.01 (weight) %, calcium less than 0.01 (weight) %, remain and be other impurity.
(11) a kind of chemistry improves the production method of silicon metal purity, and wherein when drying and dry, equipment used is respectively whizzer and drying kiln.
(12) a kind of chemistry improves the production method of silicon metal purity, wherein adopts following processing step, and a, the highly purified industrial silicon of employing " 2202 " are made raw material, and the furnace burdening in the silico briquette is removed; Break in b, Hubei Province, and it is 0-15 centimetre that particle diameter is broken in silico briquette Hubei Province; C, abrasive dust become smaller or equal to 200 purpose silica flours through ball mill grinding; D, screening and magnetic separation are screened above-mentioned silica flour on sieve apparatus, carry out magnetic separation smaller or equal to 200 purpose silica flours in entering magnetic separator, to remove the magnetic substance in the silica flour; E, chemical purification are put into preservative tank with the silica flour of removing magnetic substance, behind distilled water flushing, add nitric acid dousing more than 48 hours, bleed off nitric acid then, add the hydrochloric acid soln reaction, stir, and soak more than 7 hours; Then in former preservative tank, add the hydrochloric acid soln reaction again, stir, soak, place more than 7 hours, after slowly adding prussic acid (or hydrofluoric acid) and hydrogen peroxide again, treating intense reaction, stir, soak, place more than 48 hours, with distilled water flushing to pH value is 7, obtain the siliceous purity of product greater than 99.97 (weight) %, iron less than 0.003 (weight) %, aluminium less than 0.01 (weight) %, calcium high purity metal silicon less than 0.01 (weight) %; F, drying and oven dry are put into whizzer with the silica flour after cleaning and are dried, at the oven dry kiln drying; G, precise magnetic cobbing adopt the static magnetic separation.
Can produce the high high-purity technical silicon of siliceous purity after utilizing the present invention, lay good basis for stepping into the solar level epoch.
Effect of the present invention, the impurity of removing is not limited to iron, aluminium, calcium.Carbon also is the impurity of removing by oxidizing reaction.
The present invention is that example is illustrated with " 2202 " smaller or equal to 200 purpose silica flours only, but is not restricted to this, and the present invention is equally applicable to the high-purity technical silicon of other granularity, as 140 orders, 150 orders, 180 orders etc.; The present invention is that example is illustrated with " 2202 " high-purity technical silicon only in addition, but is not restricted to this, and the present invention is equally applicable to the high-purity technical silicon raw material of other model classification, as " 421 ", " 3303 " etc.Therefore adopt other high purity still within the scope of the present invention.
Brief Description Of Drawings
Fig. 1 is the process flow sheet that this chemistry of explanation improves the production method of silicon metal purity.
Embodiment
Embodiment 1
1. starting material: select " 2202 " highly purified silico briquette for use.
2. Hubei Province is broken: it is 0-15 centimetre that " 2202 " silico briquette is broken into particle diameter.
3. grind: the silico briquette of fragmentation is ground to form smaller or equal to 200 purpose silica flours.
4. screening and magnetic separation: above-mentioned silica flour is screened on sieve apparatus, grind greater than 200 purposes again, enter smaller or equal to 200 purpose silica flours and carry out magnetic separation in the magnetic separator, to remove the magnetic substance in the silica flour, the elements such as iron that will be present in the silica flour are disposed.
5. chemical purification:
Below four kinds of materials concentration by percentage to the quality:
A. nitric acid content (65-68%)
B. content of hydrochloric acid (36-38%)
C. prussic acid content (2-3%) (or hydrofluoric acid)
D. hydrogen peroxide content (30%)
By mass percentage, above-mentioned four kinds of materials are respectively with respect to the add-on of grinding the back silica flour:
100 kilograms of silica flour add-ons:
The nitric acid amount is, with the whole wetting immersions of silica flour
Hydrochloric acid content is to add 20 kilograms
The prussic acid amount is to add 10 kilograms
The dioxygen water yield is to add 5 kilograms
In addition, adding the acid amount also decides according to silica flour raw material reaction situation.
E. stirring reaction: stirred once every 3 hours, add prussic acid and hydrogen peroxide after, can improve speed of response, with other impurity full scale clearance that exists in the silica flour.
F. clean with distilled water, wash to pH value be 7, till not showing chlorion and react with the Silver Nitrate check.
6. dry, above-mentioned silica flour is put into whizzer dry.
7. the silica flour after will drying is put into the oven dry kiln drying.
8. precise magnetic cobbing is selected the static magnetic separation for use.
9. packing must be up to the standards before packing, packs with automatic packing machine.
The main component of this Pure Silicon Metal is: siliceous purity is greater than 99.97 (weight) %, and iron is less than 0.003 (weight) %, and aluminium is less than 0.01 (weight) %, and calcium is less than 0.01 (weight) %, remains to be other impurity.
Embodiment 2
(major impurity content is in this raw material: Fe:0.40 (weight) %Al:0.20 (weight) %Ca:0.1 (weight) % when raw material adopts " 421 " high-purity technical silicon, after utilizing the processing step purification identical with embodiment 1, Fe:0.0029 (weight) %Al:0.0067 (weight) %Ca:0.0014 (weight) %.
Claims (12)
1. a chemistry improves the production method of silicon metal purity, it is characterized in that: with high-purity technical silicon is raw material, bed material in the silico briquette is removed, make above-mentioned raw materials through following processing step: Hubei Province is broken, abrasive dust, screening and magnetic separation, chemical purification, drying and oven dry, precise magnetic cobbing, obtains highly purified Pure Silicon Metal then.
2. production method as claimed in claim 1 is characterized in that: described high-purity technical silicon can be " 2202 " high-purity technical silicon.
3. as production method arbitrary among the claim 1-2, it is characterized in that: the broken step in described Hubei Province is that silico briquette is broken into particle diameter is 0-15 centimetre.
4. as production method arbitrary among the claim 1-3, it is characterized in that: described abrasive dust is that silico briquette is worn into smaller or equal to 200 purpose silica flours.
5. as production method arbitrary among the claim 1-4, it is characterized in that: described screening and magnetic separation be, above-mentioned silica flour is screened on sieve apparatus, enters smaller or equal to 200 purpose silica flours again and carry out magnetic separation in the magnetic separator, to remove the magnetic substance in the silica flour.
6. as production method arbitrary among the claim 1-5, it is characterized in that: will grind again greater than 200 purpose silica flours in described screening and the magnetic separation.
7. as production method arbitrary among the claim 1-6, it is characterized in that: described chemical purification is,
One, the silica flour that will remove magnetic substance is put into preservative tank, behind distilled water flushing, adds nitric acid dousing more than 48 hours, bleeds off nitric acid then, adds the hydrochloric acid soln reaction, stirs, and soaks more than 7 hours;
Two, in former preservative tank, add the hydrochloric acid soln reaction then again, stir, soak and place more than 7 hours, after slowly adding prussic acid or hydrofluoric acid and hydrogen peroxide again, treating intense reaction, stirring, soak and place more than 48 hours, is 7 with distilled water flushing to pH value.
8. as production method arbitrary among the claim 1-7, it is characterized in that: when chemical purification, be 7, till not showing the chlorion reaction with the Silver Nitrate check with distilled water flushing to pH value.
9. as production method arbitrary among the claim 1-8, it is characterized in that: described precise magnetic cobbing, adopt the static magnetic separation.
10. as production method arbitrary among the claim 1-9, it is characterized in that: the high purity metal silicon product that adopts aforesaid method to obtain, its siliceous purity greater than 99.97 (weight) %, iron less than 0.003 (weight) %, aluminium less than 0.01 (weight) %, calcium less than 0.01 (weight) %, remain and be other impurity.
11. the production method as arbitrary among the claim 1-10 is characterized in that: when drying and dry, equipment used is respectively whizzer and drying kiln.
12. a chemistry improves the production method of silicon metal purity, it is characterized in that: adopt following processing step, a, employing " 2202 " high-purity technical silicon are made raw material, and the furnace burdening in the silico briquette is removed; Break in b, Hubei Province, and it is 0-15 centimetre that particle diameter is broken in silico briquette Hubei Province; C, abrasive dust become smaller or equal to 200 purpose silica flours through ball mill grinding; D, screening and magnetic separation are screened above-mentioned silica flour on sieve apparatus, carry out magnetic separation smaller or equal to 200 purpose silica flours in entering magnetic separator, to remove the magnetic substance in the silica flour; E, the silica flour of removing magnetic substance is put into preservative tank, behind distilled water flushing, added nitric acid dousing 48 hours, bleed off nitric acid then, add the hydrochloric acid soln reaction, stir, soak more than 7 hours, obtain siliceous purity for greater than 99.94 (weight) %, iron high purity metal silicon less than 0.04 (weight) %; Then in former preservative tank, add the hydrochloric acid soln reaction again, stir, soak, place more than 7 hours, after slowly adding prussic acid or hydrofluoric acid and hydrogen peroxide again, treating intense reaction, stir, soak, place more than 48 hours, with distilled water flushing to pH value is 7, obtain the siliceous purity of product greater than 99.97 (weight) %, iron less than 0.003 (weight) %, aluminium less than 0.01 (weight) %, calcium high purity metal silicon less than 0.01 (weight) %; F, drying and oven dry are put into whizzer with the silica flour after cleaning and are dried, at the oven dry kiln drying; G, precise magnetic cobbing adopt the static magnetic separation.
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| CN200610170726A CN100584754C (en) | 2006-12-26 | 2006-12-26 | Chemical method for promoting silicon metal purity |
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| CN200610170726A CN100584754C (en) | 2006-12-26 | 2006-12-26 | Chemical method for promoting silicon metal purity |
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| CN100584754C CN100584754C (en) | 2010-01-27 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079524A (en) * | 2011-03-09 | 2011-06-01 | 云南云天化国际化工股份有限公司 | Wet purification method of silicon |
| CN102134077A (en) * | 2011-01-25 | 2011-07-27 | 云南乾元光能产业有限公司 | Method for purifying polycrystalline silicon by wet method |
| CN102247933A (en) * | 2011-03-22 | 2011-11-23 | 江西赛维Ldk太阳能高科技有限公司 | Method for purifying silicon powder |
| CN102862989A (en) * | 2012-10-11 | 2013-01-09 | 包头市山晟新能源有限责任公司 | Pretreatment method for purifying polycrystalline silicon by metallurgic method |
| CN104641009A (en) * | 2012-06-25 | 2015-05-20 | 希利柯尔材料股份有限公司 | Method to purify aluminum and use of purified aluminum to purify silicon |
| US9676632B2 (en) | 2012-06-25 | 2017-06-13 | Silicor Materials Inc. | Method for purifying silicon |
| CN107716431A (en) * | 2017-10-30 | 2018-02-23 | 镇江环太硅科技有限公司 | A kind of polycrystalline sheet stock cleaning method |
| CN111001577A (en) * | 2019-12-09 | 2020-04-14 | 宁晋晶兴电子材料有限公司 | Method for treating silicon scrap |
| CN112517244A (en) * | 2019-09-19 | 2021-03-19 | Cmcoeng有限公司 | Screening system of silicon raw material fragments |
-
2006
- 2006-12-26 CN CN200610170726A patent/CN100584754C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134077A (en) * | 2011-01-25 | 2011-07-27 | 云南乾元光能产业有限公司 | Method for purifying polycrystalline silicon by wet method |
| CN102134077B (en) * | 2011-01-25 | 2012-09-05 | 云南乾元光能产业有限公司 | Method for purifying polycrystalline silicon by wet method |
| CN102079524A (en) * | 2011-03-09 | 2011-06-01 | 云南云天化国际化工股份有限公司 | Wet purification method of silicon |
| CN102247933A (en) * | 2011-03-22 | 2011-11-23 | 江西赛维Ldk太阳能高科技有限公司 | Method for purifying silicon powder |
| CN104641009A (en) * | 2012-06-25 | 2015-05-20 | 希利柯尔材料股份有限公司 | Method to purify aluminum and use of purified aluminum to purify silicon |
| US9676632B2 (en) | 2012-06-25 | 2017-06-13 | Silicor Materials Inc. | Method for purifying silicon |
| US10773963B2 (en) | 2012-06-25 | 2020-09-15 | Silicor Materials Inc. | Method of purifying aluminum and use of purified aluminum to purify silicon |
| CN102862989A (en) * | 2012-10-11 | 2013-01-09 | 包头市山晟新能源有限责任公司 | Pretreatment method for purifying polycrystalline silicon by metallurgic method |
| CN107716431A (en) * | 2017-10-30 | 2018-02-23 | 镇江环太硅科技有限公司 | A kind of polycrystalline sheet stock cleaning method |
| CN112517244A (en) * | 2019-09-19 | 2021-03-19 | Cmcoeng有限公司 | Screening system of silicon raw material fragments |
| CN111001577A (en) * | 2019-12-09 | 2020-04-14 | 宁晋晶兴电子材料有限公司 | Method for treating silicon scrap |
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| CN100584754C (en) | 2010-01-27 |
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