CN114735708A - Method for preparing low-iron-aluminum-calcium-content silicon - Google Patents
Method for preparing low-iron-aluminum-calcium-content silicon Download PDFInfo
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- 239000010703 silicon Substances 0.000 title claims abstract description 124
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000012535 impurity Substances 0.000 claims abstract description 121
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 111
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000011701 zinc Substances 0.000 claims abstract description 83
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 83
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 55
- 229910052742 iron Inorganic materials 0.000 claims abstract description 55
- 239000011575 calcium Substances 0.000 claims abstract description 54
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 54
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 230000009471 action Effects 0.000 claims abstract description 13
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 6
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims abstract description 6
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical class [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 49
- 238000007670 refining Methods 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000009423 ventilation Methods 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 5
- 229910000882 Ca alloy Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- -1 iron aluminum calcium Chemical compound 0.000 claims 4
- 238000004064 recycling Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003723 Smelting Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001576 calcium mineral Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
Classifications
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
Description
技术领域technical field
本发明属于工业硅冶炼技术领域，具体涉及一种制备低铁铝钙含量硅的方法。The invention belongs to the technical field of industrial silicon smelting, and particularly relates to a method for preparing silicon with low iron, aluminum, and calcium content.
背景技术Background technique
在工业硅冶炼过程中，原料包含Fe、Al、Ca、B、P等杂，这些杂质元素在硅石还原的过程中随着硅元素一起被还原而进入工业硅,在硅熔体冷凝之后作为杂质沉积在工业硅中,从而降低了工业硅的纯度。为了减少工业硅中杂质的含量，提高工业硅的品质,就需对工业硅进行炉外精炼,去除工业硅中的大部分杂质。随着科技的进步，对工业硅的纯度要求越来越高。In the industrial silicon smelting process, the raw materials contain impurities such as Fe, Al, Ca, B, P, etc. These impurity elements are reduced together with the silicon element in the process of silica reduction and enter the industrial silicon, and are used as impurities after the silicon melt is condensed. It is deposited in industrial silicon, thereby reducing the purity of industrial silicon. In order to reduce the content of impurities in industrial silicon and improve the quality of industrial silicon, it is necessary to carry out out-of-furnace refining of industrial silicon to remove most of the impurities in industrial silicon. With the advancement of science and technology, the requirements for the purity of industrial silicon are getting higher and higher.
目前，在工业硅厂最常用的杂质去除方法是工业硅在抬包中进行炉外精炼，往抬包中吹入氯气、氮气、氧气和压缩空气或者上述气体的混合气体进行精炼，去除大部分Al、Ca、B、C等杂质，但是并不能去除Fe等其他杂质。At present, the most common impurity removal method in industrial silicon plants is that industrial silicon is refined outside the furnace in a ladle, and chlorine, nitrogen, oxygen and compressed air or a mixture of the above gases are blown into the ladle for refining to remove most of the Impurities such as Al, Ca, B, and C cannot be removed, but other impurities such as Fe cannot be removed.
另外一种常用的杂质去除方法为造渣剂精炼方法，往抬包中加入氧化钙、氧化硅、氧化铝、氧化镁、氟化钙等氧化物的组合成分或者含有上述氧化物的矿物原石，利用造渣剂将硅中的部分杂质去除，但是同样存在对于Fe等杂质的去除效果不理想，同时造渣精炼后硅与渣的分离难度较大影响硅的得率。Another commonly used impurity removal method is the slag-forming agent refining method, adding a combination of oxides such as calcium oxide, silicon oxide, aluminum oxide, magnesium oxide, calcium fluoride, or mineral rough stones containing the above oxides into the ladle, The slagging agent is used to remove some impurities in silicon, but the removal effect of Fe and other impurities is also unsatisfactory. At the same time, the difficulty of separating silicon and slag after slagging refining affects the yield of silicon.
第三种常用方法为定向凝固方法，将工业硅倒入单向散热的坩埚中，从底部向上慢慢凝固已达到利用偏析的原理去除工业硅中分凝系数较大的金属杂质，该方法虽然除杂效果较好，但是凝固时间长，能耗高。The third commonly used method is the directional solidification method. Pour industrial silicon into a crucible with one-way heat dissipation, and slowly solidify from the bottom to the top. The principle of segregation is used to remove metal impurities with a large segregation coefficient in industrial silicon. Although this method The impurity removal effect is good, but the solidification time is long and the energy consumption is high.
随着现代工业的发展，很多下游企业对于精炼硅中的杂质提出了更高的要求，尤其是硅钢工业用的特级硅对于硅中的铁、铝、钙杂质要求较高，但是，现有的炉外精炼技术无法有效分离工业硅产品中的主要金属杂质铁、铝、钙，进而导致铁、铝、钙杂质成为了直接影响工业硅牌号的关键杂质元素，针对此问题采用的通用方法主要是通过控制生产原料和冶炼过程中实现工业硅产品中杂质铁、铝、钙含量的控制。然而，由于原料成分和炉况的波动，通过此方法实现的工业硅产品质量的调控效果并不稳定，进而导致工业硅产品的质量存在显著的不稳定性，因此，亟需寻找一种更加经济有效的工业硅除杂方法。With the development of modern industry, many downstream enterprises have put forward higher requirements for impurities in refined silicon, especially the special-grade silicon used in the silicon steel industry has higher requirements for iron, aluminum and calcium impurities in silicon. However, the existing The out-of-furnace refining technology cannot effectively separate the main metal impurities iron, aluminum and calcium in industrial silicon products, which leads to iron, aluminum and calcium impurities becoming the key impurity elements that directly affect the industrial silicon grades. The general methods used to solve this problem are mainly By controlling the production raw materials and the smelting process, the control of the impurity iron, aluminum and calcium content in industrial silicon products is realized. However, due to fluctuations in raw material composition and furnace conditions, the quality control effect of industrial silicon products achieved by this method is not stable, which in turn leads to significant instability in the quality of industrial silicon products. Therefore, it is urgent to find a more economical method. Effective industrial silicon impurity removal method.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术的缺点，提供一种操作简单、成本低的炉外精炼去除工业硅熔体中杂质铁、铝、钙的方法。The purpose of the present invention is to overcome the shortcomings of the prior art, and to provide a method for removing impurities iron, aluminum and calcium in industrial silicon melts by refining outside the furnace with simple operation and low cost.
本发明的目的通过以下技术方案来实现：一种制备低铁铝钙含量硅的方法，抬包中通入压缩气体，将抬包中待除杂的工业硅熔体中加入固体锌，保持硅熔体的温度在1700℃以上，固体锌在高温下转化为气体锌，气体锌与杂质反应形成的化合物通过挥发去除，多余的气体锌在压缩气体的作用下进入管道，达到除去工业硅熔体中杂质的目的。The object of the present invention is achieved by the following technical solutions: a method for preparing silicon with low iron, aluminum and calcium content, feeding compressed gas into the ladle, adding solid zinc to the industrial silicon melt to be removed in the ladle, keeping the silicon The temperature of the melt is above 1700 °C, the solid zinc is converted into gaseous zinc at high temperature, the compounds formed by the reaction of gaseous zinc and impurities are removed by volatilization, and the excess gaseous zinc enters the pipeline under the action of compressed gas to remove industrial silicon melt. the purpose of impurities.
进一步地，所述的压缩气体为压缩氩气。Further, the compressed gas is compressed argon.
进一步地，所述通入压缩气体的通气压力为0.2～0.3MPa，气体流量为800～1200L/h，通气时间为20～60min。Further, the ventilation pressure of the compressed gas introduced is 0.2-0.3 MPa, the gas flow is 800-1200 L/h, and the ventilation time is 20-60 min.
进一步地，气体锌与杂质铁、铝、钙的反应时间为30～60min。Further, the reaction time of gaseous zinc and impurities iron, aluminum and calcium is 30-60 minutes.
进一步地，加入锌的质量为工业硅质量的0.15～0.3%。Further, the mass of added zinc is 0.15-0.3% of the mass of industrial silicon.
进一步地，所述工业硅熔体的温度为1700℃，采用挥发的方法去除锌与杂质反应形成的化合物。Further, the temperature of the industrial silicon melt is 1700° C., and the compound formed by the reaction of zinc and impurities is removed by a method of volatilization.
进一步地， 所述工业硅熔体中杂质铁的含量为200ppm～350ppm，杂质铝的含量为150ppm～220ppm，杂质钙的含量为100ppm～150ppm。Further, the content of impurity iron in the industrial silicon melt is 200ppm-350ppm, the content of impurity aluminum is 150ppm-220ppm, and the content of impurity calcium is 100ppm-150ppm.
进一步地，它还包括精制的步骤，具体为硅凝固后未挥发的杂质化合物会偏聚在晶界处，将凝固后的工业硅进行破碎，破碎到晶界处的锌铁、锌铝、锌钙合金裸露在外边，将破碎后的工业硅料浸泡在酸溶液中，晶界处的锌铁、锌铝、锌钙合金与酸反应生成无机盐而溶解掉，进而达到去除杂质化合物的目的。Further, it also includes a refining step, specifically, the impurity compounds that are not volatilized after the silicon is solidified will segregate at the grain boundary, the solidified industrial silicon will be broken, and the zinc-iron, zinc-aluminum, zinc The calcium alloy is exposed outside, and the crushed industrial silicon material is immersed in an acid solution, and the zinc-iron, zinc-aluminum, zinc-calcium alloy at the grain boundary reacts with the acid to form inorganic salts and dissolves, thereby achieving the purpose of removing impurity compounds.
进一步地，它还包采用冷凝的方式对管道中的气体锌进行回收的过程。Further, it also includes the process of recovering the gaseous zinc in the pipeline by means of condensation.
本发明具有以下优点：本发明公开了一种制备低铁铝钙含量硅的方法，该方法突破了现有技术通过控制生产原料中杂质含量方法获得高品质硅的途径，由于硅在锌中的溶解度很低，锌在硅中的溶解度也很低，在常温下基本互不相容，采用工业锌在炉外进行精炼，工业硅中的杂质铁、铝、钙与锌发生反应形成低熔点的化合物，利用硅熔体本身的高温将化合物挥发逸出达到除杂的目的，硅凝固后未挥发的锌铁、锌铝、锌钙化合物偏析在晶界处，破碎后采用酸洗除去，并且多余的锌在高温下变成气体在压缩气体的作用下分离；本发明方法能够有效去除硅熔体中的杂质铁、铝、钙，且不引入新的杂质，解决了现有工业硅生产对原料的依赖，该方法成本低、操作简单，可对多余的锌进行回收再利用，节能环保，适用于工业化大规模生产。The present invention has the following advantages: the present invention discloses a method for preparing silicon with low iron, aluminum, and calcium content, which breaks through the method of obtaining high-quality silicon by controlling the impurity content in the production raw materials in the prior art. The solubility of zinc is very low, and the solubility of zinc in silicon is also very low. It is basically incompatible at room temperature. Industrial zinc is used for refining outside the furnace. The impurities iron, aluminum and calcium in industrial silicon react with zinc to form low melting point. Compound, the high temperature of the silicon melt itself is used to volatilize and escape the compound to achieve the purpose of impurity removal. After the silicon solidifies, the unvolatile zinc-iron, zinc-aluminum, and zinc-calcium compounds segregate at the grain boundary, and are removed by pickling after crushing, and the excess is removed. The zinc that has been added is converted into gas at high temperature and separated under the action of compressed gas; the method of the invention can effectively remove the impurities iron, aluminum and calcium in the silicon melt without introducing new impurities, which solves the problem of the existing industrial silicon production on raw materials. The method is low in cost, simple in operation, can recycle and reuse excess zinc, saves energy and is environmentally friendly, and is suitable for industrialized large-scale production.
具体实施方式Detailed ways
下面结合实施例对本发明做进一步的描述，本发明的保护范围不局限于以下所述：Below in conjunction with embodiment, the present invention is further described, protection scope of the present invention is not limited to the following:
实施例1：一种制备低铁铝钙含量硅的方法，抬包中通入压缩气体氩气，通气压力为0.2MPa，气体流量为800L/h，通气时间为20min，将抬包中待除杂质的工业硅熔体中加入锌，加入工业锌的质量为工业硅质量的0.15%，反应30min，保持硅熔体的温度在1700℃，锌与杂质铁、铝、钙反应形成的化合物通过挥发去除；锌与杂质反应形成的未挥发掉的化合物会在硅凝固后晶界处偏析，破碎后采用盐酸洗除去，达到除去工业硅熔体中杂质铁、铝、钙的目的，多余的气体锌在压缩气体的作用下进入管道，采用冷凝的方式对管道中的气体锌进行回收。Embodiment 1: a method for preparing silicon with low iron, aluminum and calcium content, the compressed gas argon is introduced into the ladle, the ventilation pressure is 0.2MPa, the gas flow rate is 800L/h, and the ventilation time is 20min. Zinc is added to the impurity industrial silicon melt, and the mass of the added industrial zinc is 0.15% of the industrial silicon mass, and the reaction is carried out for 30 minutes, keeping the temperature of the silicon melt at 1700 ℃, and the compounds formed by the reaction of zinc with impurities iron, aluminum and calcium are evaporated Removal; the non-volatile compounds formed by the reaction of zinc and impurities will segregate at the grain boundaries after the silicon solidifies, and are washed with hydrochloric acid after crushing to achieve the purpose of removing the impurities iron, aluminum and calcium in the industrial silicon melt, and the excess gas zinc Under the action of compressed gas, it enters the pipeline, and the gaseous zinc in the pipeline is recovered by condensation.
实施例2：一种制备低铁铝钙含量硅的方法，抬包中通入压缩气体氩气，通气压力0.3MPa，气体流量为1200L/h，通气时间为60min，将抬包中待除杂质的工业硅熔体中加入锌，加入工业锌的质量为工业硅质量的0.3%，反应35min，保持硅熔体的温度在1800℃，锌与杂质铁、铝、钙反应形成的化合物通过挥发去除；锌与杂质反应形成的未挥发掉的化合物会在硅凝固后晶界处偏析，破碎后采用硫酸洗除去，达到除去工业硅熔体中杂质铁、铝、钙的目的，多余的气体锌在压缩气体的作用下进入管道，采用冷凝的方式对管道中的气体锌进行回收。Example 2: A method for preparing silicon with low iron, aluminum, and calcium content. The compressed gas argon is introduced into the ladle, the ventilation pressure is 0.3MPa, the gas flow rate is 1200L/h, and the ventilation time is 60min. The impurities to be removed in the ladle are removed. Zinc was added to the industrial silicon melt, and the mass of the added industrial zinc was 0.3% of the mass of industrial silicon. The reaction was performed for 35 minutes, and the temperature of the silicon melt was kept at 1800 ° C. The compounds formed by the reaction of zinc with impurities such as iron, aluminum and calcium were removed by volatilization. ; The non-volatile compounds formed by the reaction of zinc and impurities will segregate at the grain boundaries after the silicon solidifies, and then use sulfuric acid washing to remove them after crushing, so as to achieve the purpose of removing impurities iron, aluminum and calcium in industrial silicon melts. Under the action of compressed gas, it enters the pipeline, and the gaseous zinc in the pipeline is recovered by condensation.
实施例3：一种制备低铁铝钙含量硅的方法，抬包中通入压缩气体氩气，通气压力为0.25MPa，气体流量为1000L/h，通气时间为30min，将抬包中待除杂质的工业硅熔体中加入锌，加入工业锌的质量为工业硅质量的0.2%，反应40min，保持硅熔体的温度在2000℃，锌与杂质铁、铝、钙反应形成的化合物通过挥发去除；锌与杂质反应形成的未挥发掉的化合物会在硅凝固后晶界处偏析，破碎后采用盐酸洗除去，达到除去工业硅熔体中杂质铁、铝、钙的目的，多余的气体锌在压缩气体的作用下进入管道，采用冷凝的方式对管道中的气体锌进行回收。Example 3: A method for preparing silicon with low iron, aluminum and calcium content. The compressed gas argon is introduced into the ladle, the ventilation pressure is 0.25MPa, the gas flow rate is 1000L/h, and the ventilation time is 30min. Zinc was added to the impurity industrial silicon melt, and the mass of the added industrial zinc was 0.2% of the industrial silicon mass, and the reaction was carried out for 40 minutes, keeping the temperature of the silicon melt at 2000 ° C. Removal; the non-volatile compounds formed by the reaction of zinc and impurities will segregate at the grain boundaries after the silicon solidifies, and are washed with hydrochloric acid after crushing to achieve the purpose of removing the impurities iron, aluminum and calcium in the industrial silicon melt, and the excess gas zinc Under the action of compressed gas, it enters the pipeline, and the gas zinc in the pipeline is recovered by condensation.
实施例4：一种制备低铁铝钙含量硅的方法，抬包中通入压缩气体氩气，通气压力为0.2MPa，气体流量为1100L/h，通气时间为50min，将抬包中待除杂质的工业硅熔体中加入锌，加入工业锌的质量为工业硅质量的0.2%，反应60min，保持硅熔体的温度在1900℃，锌与杂质铁、铝、钙反应形成的化合物通过挥发去除；锌与杂质反应形成的未挥发掉的化合物会在硅凝固后晶界处偏析，破碎后采用硫酸洗除去，达到除去工业硅熔体中杂质铁、铝、钙的目的，多余的气体锌在压缩气体的作用下进入管道，采用冷凝的方式对管道中的气体锌进行回收。Example 4: A method for preparing silicon with low iron, aluminum and calcium content. The compressed gas argon is introduced into the ladle, the ventilation pressure is 0.2MPa, the gas flow rate is 1100L/h, and the ventilation time is 50min. Zinc is added to the impurity industrial silicon melt, and the mass of the added industrial zinc is 0.2% of the mass of the industrial silicon, and the reaction is performed for 60 minutes. Removal; the non-volatile compounds formed by the reaction of zinc and impurities will segregate at the grain boundary after the silicon solidifies, and after crushing, it is removed by sulfuric acid washing to achieve the purpose of removing the impurities iron, aluminum and calcium in the industrial silicon melt, and the excess gas zinc Under the action of compressed gas, it enters the pipeline, and the gaseous zinc in the pipeline is recovered by condensation.
以下通过实验说明本发明的有益效果：The beneficial effects of the present invention are described below through experiments:
实验例1：Experimental example 1:
抬包中通入压缩气体氩气，通气压力0.25MPa、气体流量1000L/h、通气时间20min。将抬包中待除杂质的工业硅熔体中加入锌，加入工业锌粒总质量为工业硅质量的0.1%，一次性加入，加入工业锌后静置反应30min，保持硅熔体的温度在1800℃，锌与杂质铁、铝、钙反应形成的化合物通过挥发去除；锌与杂质反应形成的未挥发掉的化合物会在硅凝固后晶界处偏析，破碎后采用盐酸洗除去，达到除去工业硅熔体中杂质的铁、铝、钙目的，多余的气体锌在压缩气体的作用下进入管道，采用冷凝的方式对管道中的气体锌进行回收。Compressed gas argon was introduced into the bag, the ventilation pressure was 0.25MPa, the gas flow was 1000L/h, and the ventilation time was 20min. Zinc was added to the industrial silicon melt to be removed from impurities in the ladle, and the total mass of the added industrial zinc particles was 0.1% of the mass of the industrial silicon. At 1800°C, the compounds formed by the reaction of zinc with impurities iron, aluminum and calcium are removed by volatilization; the non-volatile compounds formed by the reaction of zinc with impurities will segregate at the grain boundaries after the silicon solidifies, and are washed with hydrochloric acid after crushing to achieve industrial removal. For the purpose of iron, aluminum and calcium impurities in the silicon melt, the excess gaseous zinc enters the pipeline under the action of compressed gas, and the gaseous zinc in the pipeline is recovered by condensation.
除杂前工业硅中的杂质铁的含量为330ppm，杂质铝的含量220 ppm，杂质钙含量为100ppm；精炼后杂质铁含量为218ppm，精炼后杂质铝含量为102ppm，精炼后杂质钙含量为52ppm。The content of impurity iron in the industrial silicon before impurity removal is 330 ppm, the content of impurity aluminum is 220 ppm, and the content of impurity calcium is 100 ppm; the content of impurity iron after refining is 218 ppm, the content of impurity aluminum after refining is 102 ppm, and the content of impurity calcium after refining is 52 ppm .
实验例2：Experimental example 2:
抬包中通入压缩氩气，通气压力0.25MPa、气体流量1000L/h、通气时间20min。将抬包中待除杂的工业硅熔体中加入锌，加入工业锌粒总质量为工业硅质量的0.2%，分批次逐渐加入，加入工业锌后静置反应30min，保持硅熔体的温度在1800℃，锌与杂质铁、铝、钙反应形成的化合物通过挥发去除；锌与杂质反应形成的未挥发掉的化合物会在硅凝固后晶界处偏析，破碎后采用盐酸洗除去，达到除去工业硅熔体中杂质铁、铝、钙的目的，多余的气体锌在压缩气体的作用下进入管道，采用冷凝的方式对管道中的气体锌进行回收。Compressed argon gas was introduced into the bag, the ventilation pressure was 0.25MPa, the gas flow was 1000L/h, and the ventilation time was 20min. Zinc was added to the industrial silicon melt to be removed in the ladle, and the total mass of the added industrial zinc particles was 0.2% of the mass of the industrial silicon, and gradually added in batches. When the temperature is 1800°C, the compounds formed by the reaction of zinc with impurities such as iron, aluminum and calcium are removed by volatilization; the non-volatile compounds formed by the reaction of zinc with impurities will segregate at the grain boundaries after the silicon solidifies, and are washed with hydrochloric acid after crushing. For the purpose of removing impurities iron, aluminum and calcium in industrial silicon melt, the excess gaseous zinc enters the pipeline under the action of compressed gas, and the gaseous zinc in the pipeline is recovered by condensation.
除杂前工业硅中的杂质铁的含量为330ppm，杂质铝的含量220ppm，杂质钙含量为100ppm；精炼后杂质铁含量为176ppm，精炼后杂质铝含量为83ppm，精炼后杂质钙含量为41ppm。The content of impurity iron in the industrial silicon before impurity removal is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100ppm; the content of impurity iron after refining is 176ppm, the content of impurity aluminum after refining is 83ppm, and the content of impurity calcium after refining is 41ppm.
实验例3：Experimental example 3:
抬包中通入压缩氩气，通气压力0.25MPa、气体流量1000L/h、通气时间30min。将抬包中待除杂质的工业硅熔体中加入锌，加入工业锌粒总质量为工业硅质量的0.2%，分批次逐渐加入，加入工业锌后静置反应30min。保持硅熔体的温度在1800℃，锌与杂质铁、铝、钙反应形成的化合物通过挥发去除；锌与杂质反应形成的未挥发掉的化合物会在硅凝固后晶界处偏析，破碎后采用盐酸洗除去，达到除去工业硅熔体中杂质铁、铝、钙的目的，多余的气体锌在压缩气体的作用下进入管道，采用冷凝的方式对管道中的气体锌进行回收。Compressed argon gas was introduced into the bag, the ventilation pressure was 0.25MPa, the gas flow was 1000L/h, and the ventilation time was 30min. Zinc was added to the industrial silicon melt to be removed from impurities in the ladle, and the total mass of industrial zinc particles was 0.2% of the mass of industrial silicon, gradually added in batches, and then allowed to stand for 30 minutes after adding industrial zinc. Keep the temperature of the silicon melt at 1800°C, and the compounds formed by the reaction of zinc with impurities such as iron, aluminum and calcium are removed by volatilization; the non-volatile compounds formed by the reaction of zinc with impurities will segregate at the grain boundaries after the silicon is solidified, and after crushing, use It is washed with hydrochloric acid to achieve the purpose of removing impurities iron, aluminum and calcium in the industrial silicon melt. The excess gaseous zinc enters the pipeline under the action of compressed gas, and the gaseous zinc in the pipeline is recovered by condensation.
除杂前工业硅中的杂质铁的含量为330ppm，杂质铝的含量220ppm，杂质钙含量为100ppm；精炼后杂质铁含量为153ppm，精炼后杂质铝含量为72ppm，精炼后杂质钙含量为35ppm。The content of impurity iron in the industrial silicon before impurity removal is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100ppm; the content of impurity iron after refining is 153ppm, the content of impurity aluminum after refining is 72ppm, and the content of impurity calcium after refining is 35ppm.
实验例4：Experimental example 4:
抬包中通入压缩氩气，通气压力0.25MPa、气体流量1000L/h、通气时间30min。将抬包中待除杂的工业硅熔体中加入锌，加入工业锌粒总质量为工业硅质量的0.2%，分批次逐渐加入，加入工业锌后静置反应60min保持硅熔体的温度在1800℃，锌与杂质铁、铝、钙反应形成的化合物通过挥发去除；锌与杂质反应形成的未挥发掉的化合物会在硅凝固后晶界处偏析，破碎后采用盐酸洗除去，达到除去工业硅熔体中杂质铁、铝、钙的目的，多余的气体锌在压缩气体的作用下进入管道，采用冷凝的方式对管道中的气体锌进行回收。Compressed argon gas was introduced into the bag, the ventilation pressure was 0.25MPa, the gas flow was 1000L/h, and the ventilation time was 30min. Zinc is added to the industrial silicon melt to be removed in the ladle, and the total mass of the industrial zinc particles is 0.2% of the mass of the industrial silicon. Gradually add it in batches. After adding industrial zinc, let it stand for reaction for 60 minutes to maintain the temperature of the silicon melt. At 1800°C, the compounds formed by the reaction of zinc with impurities iron, aluminum and calcium are removed by volatilization; the non-volatilized compounds formed by the reaction of zinc with impurities will segregate at the grain boundary after the silicon solidifies, and after crushing, it is washed with hydrochloric acid to remove it. For the purpose of impurity iron, aluminum and calcium in industrial silicon melt, excess gas zinc enters the pipeline under the action of compressed gas, and the gas zinc in the pipeline is recovered by condensation.
除杂前工业硅中的杂质铁的含量为330ppm，杂质铝的含量220ppm，杂质钙含量为100ppm；精炼后杂质铁含量为145ppm，精炼后杂质铝含量为65ppm，精炼后杂质钙含量为31ppm。The content of impurity iron in the industrial silicon before impurity removal is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100ppm; the content of impurity iron after refining is 145ppm, the content of impurity aluminum after refining is 65ppm, and the content of impurity calcium after refining is 31ppm.
实验例5：Experimental example 5:
抬包中通入压缩氩气，通气压力0.3MPa、气体流量1000L/h、通气时间20min。将抬包中待除杂的工业硅熔体中加入锌，加入工业锌粒总质量为工业硅质量的0.2%，分批次逐渐加入，加入工业锌后静置反应60min，保持硅熔体的温度在1800℃，锌与杂质铁、铝、钙反应形成的化合物通过挥发去除；锌与杂质反应形成的未挥发掉的化合物会在硅凝固后晶界处偏析，破碎后采用盐酸洗除去，达到除去工业硅熔体中杂质铁、铝、钙的目的，多余的气体锌在压缩气体的作用下进入管道，采用冷凝的方式对管道中的气体锌进行回收。Compressed argon gas was introduced into the bag, the ventilation pressure was 0.3 MPa, the gas flow was 1000 L/h, and the ventilation time was 20 min. Zinc was added to the industrial silicon melt to be removed in the ladle, and the total mass of the industrial zinc particles was 0.2% of the mass of the industrial silicon, and gradually added in batches. When the temperature is 1800°C, the compounds formed by the reaction of zinc with impurities such as iron, aluminum and calcium are removed by volatilization; the non-volatile compounds formed by the reaction of zinc with impurities will segregate at the grain boundaries after the silicon solidifies, and are washed with hydrochloric acid after crushing. For the purpose of removing impurities iron, aluminum and calcium in industrial silicon melt, the excess gaseous zinc enters the pipeline under the action of compressed gas, and the gaseous zinc in the pipeline is recovered by condensation.
除杂前工业硅中的杂质铁的含量为330ppm，杂质铝的含量220ppm，杂质钙含量为100ppm；精炼后杂质铁含量为110ppm，精炼后杂质铝含量为51ppm，精炼后杂质钙含量为20ppm。The content of impurity iron in the industrial silicon before the impurity removal is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100ppm; the content of impurity iron after refining is 110ppm, the content of impurity aluminum after refining is 51ppm, and the content of impurity calcium after refining is 20ppm.
对比例：Comparative ratio:
抬包中通入压缩氩气，通入压缩氩气，通气压力0.25MPa、气体流量1000L/h、通气时间20min，不加锌静置反应30min。工业硅中的杂质铁的含量为330ppm，杂质铝的含量220ppm，杂质钙含量为100ppm；精炼后杂质铁含量为328ppm，精炼后杂质铝含量为120ppm，精炼后杂质钙含量为65ppm。可见，反应前后基本无变化。Compressed argon gas was introduced into the ladle, and compressed argon gas was introduced. The ventilation pressure was 0.25MPa, the gas flow rate was 1000L/h, the ventilation time was 20min, and the reaction was allowed to stand for 30min without adding zinc. The content of impurity iron in industrial silicon is 330ppm, the content of impurity aluminum is 220ppm, and the content of impurity calcium is 100ppm; the content of impurity iron after refining is 328ppm, the content of impurity aluminum after refining is 120ppm, and the content of impurity calcium after refining is 65ppm. It can be seen that there is basically no change before and after the reaction.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都涵盖在本发明的保护范围之内。The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to this. Equivalent replacements or changes to the inventive concept thereof are all included within the protection scope of the present invention.
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