多晶硅还原炉进气中添加SiCl_4、SiH_2Cl_2工艺进展
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摘要
多晶硅产能近几年迅速扩张,副产物四氯化硅(SiCl_4,简写STC)和二氯二氢硅(SiH_2Cl_2,简写DCS)随之迅速增加。出于环境保护和生产经济性考虑,需对STC和DCS进行回收处理。对于STC的处理,冷氢化工艺应用日益广泛;同时,在还原炉进气中添加STC的研究也展示了良好前景。对于二氯二氢硅的处理,研究普遍采用反歧化法,使DCS和STC反应,生成三氯氢硅(SiHCl_3,简写TCS),重新进入还原生产,循环利用。从国内外相关技术研究看,可以在还原炉进气中适量添加STC或DCS,使STC或DCS转化成TCS,从而充分利用物料,降低回收处理系统负荷,达到节能降耗环保安全的目的。
The production capacity of polycrystalline silicon was expanded rapidly in recent years.The amount of byproducts SiCl_4(abbrev.STC) and SiH_2 Cl_2(abbrev.DCS) is greatly increased.In view of environmental conservation and economic producing,it is necessary to recycle and process STC and DCS.Of the methods to recycle and process STC,Low Temperature Hydrogenation is increasingly applied,and the research on adding STC into the feed gas mixture also shows a good prospect.At the present time,it is commonly studied to generate TCS by the Normalized Reaction between STC and DCS,and then SiHCl_3(abbrev.TCS) produced by the reaction is cyclically utilized into the producing system.Based on related researches at home and abroad,it should be used that adding proper STC or DCS into the feed gas mixture TCS/H_2,to convert STC and DCS to TCS,and thus to make full use of raw material,to decrease the CDI load,to achieve the energy-saving,cost-reducing and environmental-protecting production.
The production capacity of polycrystalline silicon was expanded rapidly in recent years.The amount of byproducts SiCl_4(abbrev.STC) and SiH_2 Cl_2(abbrev.DCS) is greatly increased.In view of environmental conservation and economic producing,it is necessary to recycle and process STC and DCS.Of the methods to recycle and process STC,Low Temperature Hydrogenation is increasingly applied,and the research on adding STC into the feed gas mixture also shows a good prospect.At the present time,it is commonly studied to generate TCS by the Normalized Reaction between STC and DCS,and then SiHCl_3(abbrev.TCS) produced by the reaction is cyclically utilized into the producing system.Based on related researches at home and abroad,it should be used that adding proper STC or DCS into the feed gas mixture TCS/H_2,to convert STC and DCS to TCS,and thus to make full use of raw material,to decrease the CDI load,to achieve the energy-saving,cost-reducing and environmental-protecting production.
引文
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[3]吴明明,谈瑛,侯清麟,等.四氯化硅的应用现状研究[J].湖南工业大学学报,2011,24(6):18-22.
[4]王跃林.多晶硅副产物四氯化硅的综合利用技术[J].精细与专用化学品,2009,17(2):22-24.
[5]陈涵斌,李育亮,印永祥.四氯化硅转化技术的现状与发展趋势[J].氯碱工业,2009,45(4):27-31.
[6]王跃,吴青友,印永祥.四氯化硅的氢化处理技术进展[J].四川化工,2011,14(1):13-17.
[7]陈宁.四氯化硅氢化技术进展[J].煤炭与化工,2011,34(12):48-51.
[8]黄友光,郑静,潘金花,等.四氯化硅热氢化制备三氯氢硅[J].现代化工,2015(10):75-77.
[9]龙雨谦,刘颖颖,梁斌,等.四氯化硅催化氢化制备三氯氢硅[J].工业催化,2012,20(8):26-30.
[10]岳晓宁,龙雨谦,蒋炜,等.四氯化硅催化氢化合成三氯氢硅机理研究[J].分子催化,2013,27(3):279-286.
[11]黄韬,唐思扬,刘颖颖,等.催化热氢化法制备三氯氢硅研究进展[J].工业催化,2015(1):8-14.
[12]梁国仑.特种气体贮运、应用、安全与特性-硅烷、砷烷、二氯二氢硅[J].低温与特气,1997(1):61-65.
[13]胡小冬,刘小锋,张东,等.多晶硅生产中Si H2Cl2的富集及处理方法[J].新材料产业,2013(12):44-47.
[14]孙福楠.高纯二氯二氢硅的生产和应用[J].化工新型材料,1996(11):27-28.
[15]侯二林,宋安宁,秦渊博.工艺因素对二氯二氢硅反歧化反应的影响[J].硅谷,2012(17):171.
[16]李仕扬,沈伟.一种二氯二氢硅反歧化生产三氯氢硅工艺[P].中国专利:公开号CN102923716A,2013-02-13.
[17]黄国强,孙帅帅.反歧化反应精馏处理二氯二氢硅[J].化学工程,2014,42(1):19-23.
[18]石何武,杨永亮,汤传斌,等.多晶硅副产物二氯二氢硅的应用研究[J].有色冶金节能,2014,30(3):53-55.
[19]路向平.二氯二氢硅反歧化装置在多晶硅生产中的应用[J].中国化工贸易,2014,6(13):189-190.
[20]丁国江.三氯氢硅和四氯化硅混合比对多晶硅生产的影响[J].四川有色金属,1998,(3):14-19.
[21]闻瑞梅,戴自忠,梁骏吾,等.用三氯氢硅和四氯化硅混合源生产多晶硅的方法[P].中国专利:公开号CN1403372,2005-10-12.
[22]方旭升,刘勇,陈吉,等.多晶硅生产原料中添加四氯化硅的工艺研究[J].现代化工,2012,32(7):85-87.
[23]MA RODGERS.Process for manufacturing pure polycrystalline silicon[P].U.S.Pat.Appl.No.:899,125,Apr.24,1978.
[24]张耀平,董燕军.反应精馏技术在二氯二氢硅逆歧化反应中的应用[J].内蒙古石油化工,2013,(12):102-103.
[25]HB BRADLEY.Manufacture of silicon metal from a mixture of chlorosilanes[P].U.S.Pat.Appl.No.:432,438,Jan.11,1974.