电热法制备高纯硅的基础研究
发布时间：2018-12-14 03:15
【摘要】：全球的石油、煤炭等传统能源在日益枯竭,可再生能源太阳能因其资源丰富、分布广泛、清洁无害等特点,而成为了21世纪最重要的新能源。太阳能产业的迅猛发展,使得太阳能级多晶硅的需求量迅速增加。而制备多晶硅的主要技术改良西门子法主要垄断在美、日、德等国手中。我国因没有掌握该法的核心技术,多晶硅主要依赖于进口。冶金法制备太阳能级多晶硅具有能耗低、成本低和环境友好的特点。研究冶金法制备多晶硅对我国拥有自主知识产权及发展光伏产业有着重要的意义。 本文首次采用粉体原料,研究用电热法制备高纯硅的工艺,为下一步制备太阳能级多晶硅奠定基础。本文主要的内容包括：研究了石油焦原料的除杂工艺；研究了粉体原料的制团和焦化；测定了球团的物理性能；在100kVA的矿热炉内,探索了用粉体原料制备高纯硅的工艺。 (1)石油焦原料的除杂。本论文详细研究了石油焦粉的酸浸除杂,考察了原料粒度、盐酸浓度、酸浸时间、酸浸温度、酸浸液固比和搅拌速度对除杂的影响。得到的最佳工艺条件为：石油焦粉颗粒控制在150μm以下,盐酸浓度为5wt%,水浴温度为70℃,反应时间5h,浸出液固比10：1,搅拌速度40r/min。在此最佳工艺条件下,石油焦粉中元素铁的浸出率可高达97.73%、元素铝的浸出率达75.36%。 (2)球团的制备和焦化。本论文优化了制团粘结剂和物料配比,分别使用淀粉和水玻璃为粘结剂对粉体原料进行球团的制备。所制备的球团具有一定的机械强度。同时采用焦化处理的方法制备焦化球团。 (3)球团物理性能的研究。对以淀粉和水玻璃的为粘结剂所制备球团的物理性能进行了研究。研究表明：用水玻璃作为粘结剂所制球团的抗压强度优于用淀粉的球团,但是水玻璃球团的气孔率则比淀粉球团的气孔率要小。在球团的电阻率方面二者相差不大。综合考虑,选用水玻璃为粘结剂较为合适。用水玻璃作为粘结剂制团的最佳工艺条件为：原料粒径150μm、球团压制压力15MPa、模数为3.1的水玻璃的用量为原料的5wt%、粘结剂配水量1：1。在此条件下,得到的生球团的抗压强度为3.25MPa,气孔率为15.0%,电阻率为15.6Ω·cm。 (4)粉体原料熔炼硅的初探。本文采用粉体的石英和石油焦为原料,探索电热法制备高纯硅工艺的可行性。在100kVA的矿热炉进行了3次半工业化的试验,得到以下结论： 第一次的开炉实验证明,在投入批料之前,矿热炉炉底温度不可太低,否则就会在炉底生成大量的碳化硅,堵塞炉眼,硅液无法流出。 从第二次的开炉实验中可以得到：合理设计石墨坩埚是非常重要的,同时提高砌筑炉子的质量是非常必要的。 第三次开炉实验连续运行18小时,熔炼球团80kg,共出炉6次,其中单炉出硅的质量最高达到2.7kg。实践证明采用粉体原料制备高纯硅的工艺是完全可行的。 本研究实现了用粉体原料采用电热法制备高纯硅的工艺,这为将来用高纯粉体原料制备太阳能多晶硅奠定了基础。
[Abstract]:The world's traditional energy sources, such as oil and coal, are increasingly depleted, and the renewable energy solar energy has become the most important new energy in the 21st century because of its rich resources, wide distribution, and clean and harmless. The rapid development of the solar industry has led to a rapid increase in demand for solar-grade polysilicon. The main technology for preparing polycrystalline silicon is that the Siemens method is mainly monopolized in the hands of the United States, Japan and Germany. Because of the lack of the core technology of the law, the polysilicon mainly depends on the import. The method for preparing the solar-grade polycrystalline silicon by the metallurgical method has the characteristics of low energy consumption, low cost and environment-friendly. The research of the preparation of polycrystalline silicon by the method of metallurgy is of great significance to our country's own intellectual property rights and the development of the photovoltaic industry. In this paper, the powder raw materials are used for the first time, and the technology of preparing the high pure silicon by the electric heating method is studied, and the base of the solar-grade polycrystalline silicon is prepared for the next step. The main contents of this paper are as follows: the impurity removal process of the petroleum coke raw materials is studied, the system and the coking of the powder raw materials are studied, and the physical properties of the pellets are determined; in the 100kVA submerged arc furnace, the process of preparing the high pure silicon with the powder raw materials is explored. Art. (1) Petroleum coke raw material In this paper, the acid leaching and impurity removal of petroleum coke powder were studied in detail. The granularity of the raw material, the hydrochloric acid concentration, the acid leaching time, the acid leaching temperature, the solid ratio of the acid liquid and the stirring speed were studied. The obtained optimum process conditions are as follows: the petroleum coke powder particles are controlled to be below 150 & mu; m, the hydrochloric acid concentration is 5wt%, the water bath temperature is 70 DEG C, the reaction time is 5h, the solid ratio of the leaching solution is 10: 1, and the stirring speed 40r/ and the leaching rate of the elemental iron in the petroleum coke powder can reach 97. 73%, and the leaching rate of the elemental aluminum is up to 75. 36%. (2) Pellets In this paper, the binder and the ratio of materials were optimized, and the raw materials of the powder were prepared by using starch and water glass as the binder, respectively. The preparation of the pellets has the advantages that the prepared pellets have a certain effect, mechanical strength at the same time using coker treatment (3) Pellets A study on the physical properties of pellets prepared by using starch and water glass as binder The performance of the pellets is studied. The results show that the compressive strength of the pellets made by using water glass as a binder is superior to that of the starch pellets, but the porosity of the water glass ball group is higher than that of the starch ball. The porosity of the mass is to be small. The resistivity of the pellets The phase difference of the two surfaces is not large. The water glass is selected as the comprehensive consideration. The optimum process conditions of the water glass as the binder are as follows: the particle size of the raw material is 150. m u.m, the pressing pressure of the pellets is 15MPa, and the amount of the water glass with the modulus of 3. 1 is 5wt% of the raw material, and the bonding agent In this condition, the compressive strength of the obtained pellets is 3. 25MPa, the porosity is 15. 0%, and the resistivity is 1. 5. 6 惟 路 cm. (4) Powder A preliminary study on the smelting of silicon from bulk raw materials is carried out in this paper. The quartz and petroleum coke of the powder are used as the raw materials, and the preparation of the electric heating method is explored. The feasibility of a high pure silicon process is carried out at a submerged arc furnace of 100kVA. The test has the following conclusions: the first open-furnace experiment proves that the bottom temperature of the furnace bottom of the submerged arc furnace is not too low before the batch material is put into the batch material, otherwise a large amount of silicon carbide is generated at the bottom of the furnace, It is very important to design a graphite crucible in a reasonable way, and at the same time, it is important to design a graphite crucible. The quality of the built-in furnace is very necessary. The third open-furnace experiment runs continuously for 18 hours, and the smelting pellet is 80kg. It is out of the furnace for 6 times. The quality of the silicon in the furnace is up to 2.7kg. It has been proved that the powder is used The process of preparing the high pure silicon by using the material is completely feasible. The process of preparing the high pure silicon by the electric heating method is realized by using the powder raw material, which is high pure silicon in the future.
【学位授予单位】：东北大学
【学位级别】：硕士
【学位授予年份】：2010
【分类号】：TQ127.2
本文编号：2377810
[Abstract]:The world's traditional energy sources, such as oil and coal, are increasingly depleted, and the renewable energy solar energy has become the most important new energy in the 21st century because of its rich resources, wide distribution, and clean and harmless. The rapid development of the solar industry has led to a rapid increase in demand for solar-grade polysilicon. The main technology for preparing polycrystalline silicon is that the Siemens method is mainly monopolized in the hands of the United States, Japan and Germany. Because of the lack of the core technology of the law, the polysilicon mainly depends on the import. The method for preparing the solar-grade polycrystalline silicon by the metallurgical method has the characteristics of low energy consumption, low cost and environment-friendly. The research of the preparation of polycrystalline silicon by the method of metallurgy is of great significance to our country's own intellectual property rights and the development of the photovoltaic industry. In this paper, the powder raw materials are used for the first time, and the technology of preparing the high pure silicon by the electric heating method is studied, and the base of the solar-grade polycrystalline silicon is prepared for the next step. The main contents of this paper are as follows: the impurity removal process of the petroleum coke raw materials is studied, the system and the coking of the powder raw materials are studied, and the physical properties of the pellets are determined; in the 100kVA submerged arc furnace, the process of preparing the high pure silicon with the powder raw materials is explored. Art. (1) Petroleum coke raw material In this paper, the acid leaching and impurity removal of petroleum coke powder were studied in detail. The granularity of the raw material, the hydrochloric acid concentration, the acid leaching time, the acid leaching temperature, the solid ratio of the acid liquid and the stirring speed were studied. The obtained optimum process conditions are as follows: the petroleum coke powder particles are controlled to be below 150 & mu; m, the hydrochloric acid concentration is 5wt%, the water bath temperature is 70 DEG C, the reaction time is 5h, the solid ratio of the leaching solution is 10: 1, and the stirring speed 40r/ and the leaching rate of the elemental iron in the petroleum coke powder can reach 97. 73%, and the leaching rate of the elemental aluminum is up to 75. 36%. (2) Pellets In this paper, the binder and the ratio of materials were optimized, and the raw materials of the powder were prepared by using starch and water glass as the binder, respectively. The preparation of the pellets has the advantages that the prepared pellets have a certain effect, mechanical strength at the same time using coker treatment (3) Pellets A study on the physical properties of pellets prepared by using starch and water glass as binder The performance of the pellets is studied. The results show that the compressive strength of the pellets made by using water glass as a binder is superior to that of the starch pellets, but the porosity of the water glass ball group is higher than that of the starch ball. The porosity of the mass is to be small. The resistivity of the pellets The phase difference of the two surfaces is not large. The water glass is selected as the comprehensive consideration. The optimum process conditions of the water glass as the binder are as follows: the particle size of the raw material is 150. m u.m, the pressing pressure of the pellets is 15MPa, and the amount of the water glass with the modulus of 3. 1 is 5wt% of the raw material, and the bonding agent In this condition, the compressive strength of the obtained pellets is 3. 25MPa, the porosity is 15. 0%, and the resistivity is 1. 5. 6 惟 路 cm. (4) Powder A preliminary study on the smelting of silicon from bulk raw materials is carried out in this paper. The quartz and petroleum coke of the powder are used as the raw materials, and the preparation of the electric heating method is explored. The feasibility of a high pure silicon process is carried out at a submerged arc furnace of 100kVA. The test has the following conclusions: the first open-furnace experiment proves that the bottom temperature of the furnace bottom of the submerged arc furnace is not too low before the batch material is put into the batch material, otherwise a large amount of silicon carbide is generated at the bottom of the furnace, It is very important to design a graphite crucible in a reasonable way, and at the same time, it is important to design a graphite crucible. The quality of the built-in furnace is very necessary. The third open-furnace experiment runs continuously for 18 hours, and the smelting pellet is 80kg. It is out of the furnace for 6 times. The quality of the silicon in the furnace is up to 2.7kg. It has been proved that the powder is used The process of preparing the high pure silicon by using the material is completely feasible. The process of preparing the high pure silicon by the electric heating method is realized by using the powder raw material, which is high pure silicon in the future.
【学位授予单位】：东北大学
【学位级别】：硕士
【学位授予年份】：2010
【分类号】：TQ127.2
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