電熱法制備高純硅的基礎(chǔ)研究
發(fā)布時(shí)間：2018-12-14 03:15
【摘要】：全球的石油、煤炭等傳統(tǒng)能源在日益枯竭,可再生能源太陽(yáng)能因其資源豐富、分布廣泛、清潔無(wú)害等特點(diǎn),而成為了21世紀(jì)最重要的新能源。太陽(yáng)能產(chǎn)業(yè)的迅猛發(fā)展,使得太陽(yáng)能級(jí)多晶硅的需求量迅速增加。而制備多晶硅的主要技術(shù)改良西門子法主要壟斷在美、日、德等國(guó)手中。我國(guó)因沒有掌握該法的核心技術(shù),多晶硅主要依賴于進(jìn)口。冶金法制備太陽(yáng)能級(jí)多晶硅具有能耗低、成本低和環(huán)境友好的特點(diǎn)。研究冶金法制備多晶硅對(duì)我國(guó)擁有自主知識(shí)產(chǎn)權(quán)及發(fā)展光伏產(chǎn)業(yè)有著重要的意義。 本文首次采用粉體原料,研究用電熱法制備高純硅的工藝,為下一步制備太陽(yáng)能級(jí)多晶硅奠定基礎(chǔ)。本文主要的內(nèi)容包括：研究了石油焦原料的除雜工藝；研究了粉體原料的制團(tuán)和焦化；測(cè)定了球團(tuán)的物理性能；在100kVA的礦熱爐內(nèi),探索了用粉體原料制備高純硅的工藝。 (1)石油焦原料的除雜。本論文詳細(xì)研究了石油焦粉的酸浸除雜,考察了原料粒度、鹽酸濃度、酸浸時(shí)間、酸浸溫度、酸浸液固比和攪拌速度對(duì)除雜的影響。得到的最佳工藝條件為：石油焦粉顆�？刂圃�150μm以下,鹽酸濃度為5wt%,水浴溫度為70℃,反應(yīng)時(shí)間5h,浸出液固比10：1,攪拌速度40r/min。在此最佳工藝條件下,石油焦粉中元素鐵的浸出率可高達(dá)97.73%、元素鋁的浸出率達(dá)75.36%。 (2)球團(tuán)的制備和焦化。本論文優(yōu)化了制團(tuán)粘結(jié)劑和物料配比,分別使用淀粉和水玻璃為粘結(jié)劑對(duì)粉體原料進(jìn)行球團(tuán)的制備。所制備的球團(tuán)具有一定的機(jī)械強(qiáng)度。同時(shí)采用焦化處理的方法制備焦化球團(tuán)。 (3)球團(tuán)物理性能的研究。對(duì)以淀粉和水玻璃的為粘結(jié)劑所制備球團(tuán)的物理性能進(jìn)行了研究。研究表明：用水玻璃作為粘結(jié)劑所制球團(tuán)的抗壓強(qiáng)度優(yōu)于用淀粉的球團(tuán),但是水玻璃球團(tuán)的氣孔率則比淀粉球團(tuán)的氣孔率要小。在球團(tuán)的電阻率方面二者相差不大。綜合考慮,選用水玻璃為粘結(jié)劑較為合適。用水玻璃作為粘結(jié)劑制團(tuán)的最佳工藝條件為：原料粒徑150μm、球團(tuán)壓制壓力15MPa、模數(shù)為3.1的水玻璃的用量為原料的5wt%、粘結(jié)劑配水量1：1。在此條件下,得到的生球團(tuán)的抗壓強(qiáng)度為3.25MPa,氣孔率為15.0%,電阻率為15.6Ω·cm。 (4)粉體原料熔煉硅的初探。本文采用粉體的石英和石油焦為原料,探索電熱法制備高純硅工藝的可行性。在100kVA的礦熱爐進(jìn)行了3次半工業(yè)化的試驗(yàn),得到以下結(jié)論： 第一次的開爐實(shí)驗(yàn)證明,在投入批料之前,礦熱爐爐底溫度不可太低,否則就會(huì)在爐底生成大量的碳化硅,堵塞爐眼,硅液無(wú)法流出。 從第二次的開爐實(shí)驗(yàn)中可以得到：合理設(shè)計(jì)石墨坩堝是非常重要的,同時(shí)提高砌筑爐子的質(zhì)量是非常必要的。 第三次開爐實(shí)驗(yàn)連續(xù)運(yùn)行18小時(shí),熔煉球團(tuán)80kg,共出爐6次,其中單爐出硅的質(zhì)量最高達(dá)到2.7kg。實(shí)踐證明采用粉體原料制備高純硅的工藝是完全可行的。 本研究實(shí)現(xiàn)了用粉體原料采用電熱法制備高純硅的工藝,這為將來(lái)用高純粉體原料制備太陽(yáng)能多晶硅奠定了基礎(chǔ)。
[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.
【學(xué)位授予單位】：東北大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2010
【分類號(hào)】：TQ127.2
本文編號(hào)：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.
【學(xué)位授予單位】：東北大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2010
【分類號(hào)】：TQ127.2
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