CN105189350A - 流化床反应器以及生产颗粒状多晶硅的方法 - Google Patents
流化床反应器以及生产颗粒状多晶硅的方法 Download PDFInfo
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Abstract
本发明涉及用于制备颗粒状多晶硅的流化床反应器,包括具有用于流化床的内反应器管和反应器底座的容器,所述流化床具有颗粒状多晶硅,用于加热该内反应器管中的该流化床的加热装置、在该反应器底座中用于供应流态化气体的至少一个开口以及在该反应器底座中用于供应反应气体的至少一个开口、用于排放反应器废气的装置、用于供应硅颗粒的供应装置以及用于颗粒状多晶硅的排出管道,安装在内反应器管的外侧的反应器底座中的至少一个开口的前方的拉瓦尔喷嘴,以便超临界膨胀供应的至少一个质量流。
Description
技术领域
本发明涉及流化床反应器以及用于生产颗粒状多晶硅的方法。
背景技术
多晶的硅颗粒或缩写的多晶硅颗粒是在西门子法中制备的多晶硅的替代。西门子法中的多晶硅作为圆柱形硅棒获得,在圆柱形硅棒进一步加工之前,其必须以一种费时且昂贵的方式研磨以得到所谓的芯片聚(chippoly)并且可能需要再次纯化,多晶硅颗粒具有粒状(bulk)材料性能并且可以直接用作原料,例如用于光电和电子行业的单晶产品。
在流化床反应器中生产多晶硅颗粒。这是通过经由在流化床中的气流来流态化硅颗粒而实现的,通过加热装置将所述流化床加热至高温。添加含硅的反应气体导致在热的颗粒表面上的热解反应。在该方法中,元素硅沉积于硅颗粒上并且单个颗粒加厚生长。通过已经生长的颗粒的规律的排出以及添加更小的硅颗粒作为晶种,(在本文献下文中称为“种子”),利用全部相关联的优点可以连续地进行本方法。描述了硅-卤素化合物(例如,氯硅烷或溴硅烷)、甲硅烷(SiH4),以及这些气体与氢气或其它惰性气体(例如,氮气)的混合物作为含硅的反应气体。例如,由美国4786477A已知用于此目的的这种沉积的方法和装置。
美国7922990B2描述了一种流化床反应器,该流化床反应器包括:承压套管(pressure-bearingcasing),由具有热辐射高传输的材料制成的内反应器管,用于硅颗粒的入口,用于进料包含气态的或蒸汽的硅化合物的反应气体的入口装置,用于供应流态化气体的气体分布器,用于未反应的反应气体、流态化气体以及此外在流化床表面上积聚的反应的气态的或蒸汽的产物的出口,用于产物的出口,加热装置和用于加热装置的能源供应。例如,公开了在具有770mm内径的耐压钢容器中放置了内反应器管(600mm内径和2200mm长的石英管)。在石英管的下端处,由石英制成并且配有开口的板形成了用于流态化气体的气体分布器。布置于具有直径为250mm的中央环中的内径为20mm和长度为250mm的4个另外的石英管从气体分布板突出进入内反应器中作为入口装置用于供应含硅气体或气体混合物。此外,石英板设置有两个开口用于移去产物。
美国2008/0299291A1公开了一种用于在流化床反应器中通过在硅颗粒上沉积反应气体来生产高纯度多晶硅颗粒的方法。由于一个或多个气体喷嘴垂直向上定向进入通过稀释气体弱流态化的流化床,在这种情况下,反应气体更精确地以一个或多个局部反应区域形成于流化床内的进料喷嘴的上方的方式注入,在这种局部反应区域中,在反应气体到达流化床围墙或流化床表面之前,反应气体事实上完全反应至化学平衡。优选地,经由在流化床的横截面上面尽可能均匀地分布的多个单独的喷嘴进料稀释气体。结果,在该弱流化区中,产生了高强度的湍流,因此可以有效地防止凝聚物的形成。这是重要的,尤其因为沉积的产物颗粒也是从该区域由流化床排出。稀释气体经由单独的喷嘴导入至流化床下游的区域,其中,局部喷射区形成在每个喷嘴处。这些单独的喷射流向上溶解以产生形成泡沫的流化床。,反应气体导入至通过反应器底部经由一种或多种反应气体进料导入至反应器,并且在稀释气体喷嘴的水平上方限定的高度处流入流化床。结果,在反应气体的气体出口和稀释气体喷嘴的气体出口之间形成流化床区域,通过该流化床区域稀释气体流动。此外,稀释气体喷嘴和反应气体进料由尽可能纯的材料构成(优选地由高纯度的石英的材料制成)使得尽可能少地污染硅颗粒。反应气体进料以环形间隙形成用于进料稀释气体的方式存在于中央反应气体喷嘴和围绕其的环形喷嘴的每个壳中。
在开始处提及的装置和方法中,已经发现,在流化床中随时间变化的压力条件引起进料的气体质量流的波动。这导致化学工艺和温度分布的不稳定性。还观察到局部悬浮流化,并且因此,例如,在热表面上烧结。在流化床中的局部波动的压力条件具有相同的效果,特别是当气体质量流通过多个开口,如,例如在分布于横截面上喷嘴进料时。
出于结构、加工和质量的原因,在流化床反应器中使用硅烷(SiHnXl4-n,其中,X=卤素,例如F、Cl、I;N=0-4)沉积硅过程中,不可能使用常规的气体分布器板,经由该板可以进料所有的气体质量流。气体经由其进料至流化床的开口并不具有足够的压降用于以与时间和位置相一致的方式分布相应的质量流。
美国7490785B2公开了一种由硅颗粒生产硅晶种的装置,包括具有圆柱形横截面的竖直布置的喷射室以及在喷射室的底座处的喷射喷嘴、通过该喷射喷嘴可以将研磨(milling)气体流引入至喷射室、直接跟随喷射室的逆流重力筛和用于硅颗粒的入口,其特征在于,喷射室具有足以使研磨气体流膨胀至喷射室的横截面的长度,并且喷射室具有比逆流重力筛更小的流道截面。优选地,这是流化床气流研磨机(jetmill)。在这种情况下,研磨气体经由喷射喷嘴(布置在研磨室的底座处构造为简单喷嘴或拉瓦尔喷嘴)进料。进料材料经由入口侧向进料至研磨室。在研磨室中,流化床形成研磨气体和颗粒,其中,颗粒通过具有其他颗粒的气体喷射胶体加速并分解。
美国7850102B2公开了通过研磨系统(研磨设备)(优选包括喷射研磨机的研磨系统)研磨无定形固体的方法,其特征在于,研磨机在具有选自由以下各项组成的组的中的操作介质的研磨相中进行操作:气体和/或蒸汽,优选蒸汽,和/或包含蒸汽的气体,以及特征在于在加热相(即在利用操作介质进行实际操作之前)以研磨室和/或研磨机出口中的温度高于蒸汽和/或操作介质的露点的方式加热研磨室。该方法在研磨系统(研磨设备)中,优选在包括喷射研磨机的研磨系统中,特别优选在包括对撞喷射研磨机的研磨系统中进行。为了这个目的,待粉碎的进料材料在膨胀的高速的气体喷射中加速并且通过颗粒-颗粒碰撞粉碎。所使用的喷射研磨机特别优选地是流化床对撞喷射研磨机或密实床喷射研磨机或螺旋喷射研磨机。在特别优选的流化床对撞喷射研磨机的情况下,两个或更多个研磨喷射入口优选地研磨喷嘴的形式位于研磨室的下三分之一,该研磨喷嘴优选地位于水平平面。使用的研磨喷嘴可以是拉瓦尔喷嘴。
使用的与用于制备晶种的流化床喷射研磨机有关的拉瓦尔喷嘴在现有技术中是已知的,该晶种通过研磨硅颗粒用于多晶硅的沉积。拉瓦尔喷嘴是具有初始会聚以及随后发散的横截面的流元件,其中,从一部分至另一部分的转变逐步进行。在每个点处的横截面表面被认为是圆形的,因此流过的流体可以加速至超音速而不发生强的压缩震动。声音的速度恰好到达喷嘴的最窄的横截面。
由以上描述的在多晶硅颗粒的制备过程中随着时间和/或地点改变的流化床中的压力条件的问题导致本发明的目的。
发明内容
本发明的目的通过用于制备颗粒状多晶硅的流化床反应器来实现,所述流化床反应器包括具有用于流化床的具有内反应器管以及反应器底座的容器(该流化床具有颗粒状多晶硅)、用于加热该内反应器管中的该流化床的加热装置、在该反应器底座中用于进料流态化气体的至少一个开口,以及在该反应器底座中用于进料反应气体的至少一个开口、用于去除反应器废气的装置、用于进料硅颗粒的进料设备,以及此外用于颗粒状多晶硅的排出管道,其中,拉瓦尔喷管位于内反应器管外侧的反应器底座中的至少一个开口的上游,适用于超临界膨胀进料的至少一个质量流。
优选地,流化床反应器包括在各自具有位于上游的拉瓦尔喷嘴的反应器底座中的至少两个开口。
优选地,流化床反应器包括在反应器底座中的至少一组开口,包括至少两个开口,其中,在每一种情况下,拉瓦尔喷嘴位于至少一组开口的上游。
优选地,流化床反应器包括在反应器底座中的至少一组开口,每一种情况下包括在至少两个开口,其中,在每一种情况下,一个拉瓦尔喷嘴以在每一种情况下至少一组拉瓦尔喷嘴包括至少两个拉瓦尔喷嘴的结果的方式位于各自开口的上游,其中,在每一种情况下,一个拉瓦尔喷嘴连接至少一组拉瓦尔喷嘴的各自上游。
优选地,在拉瓦尔喷嘴位于其上游的反应器底座中的至少一个开口是气体分布器装置。
优选地,在拉瓦尔喷嘴位于其上游的反应器底座中的至少一个开口是在底板中的孔、阀或喷嘴。
通过用于在根据本发明的装置中或在根据任一上述优选的实施方式的装置中制备颗粒状多晶硅的方法也可以实现本发明目的,该方法包括通过在经由加热装置加热至850-1200℃的温度的流化床中的流态化气体流态化硅颗粒,添加含硅的反应气体以及在硅颗粒上沉积硅。
本发明还涉及一种用于在流化床反应器制备颗粒状多晶硅的方法,该方法包括通过经由流化床中的流化床反应器的反应器底座中的至少一个开口进料的流态化气体流态化硅颗粒,该流化床经由加热装置加热至850-1200℃的温度,添加经由流化床反应器的反应器底座中的至少一个开口进料的含硅的反应气体,以及在硅颗粒上沉积硅,其中,进料的流态化气体或反应气体的中至少一个质量流是超临界膨胀的。
流态化气体优选是H2以及含硅的反应气体优选是TCS。
优选地,拉瓦尔喷嘴位于反应器底座中的至少一个开口中的上游以便通过存在于拉瓦尔喷嘴中的过压超临界膨胀进料的至少一个质量流。还可以使用具有喷嘴几何结构的穿孔的(perforated)板、喷嘴板、阀板或偶尔具有限定的压降的多孔板用于流化床中气体质量流的均匀分布。通过气体分步器的压降显著抑制了通过流化床的压力波动诱导的在供应侧上的压力和质量流波动。此外,在气体进料管道中可以使用圆形孔以防止气体入口开口的压降不足够。
在本发明中没有单独经由通过其压降的气体分配器板,而是经由拉瓦尔喷嘴(优选在超临界压力比处操作)确保随着时间进料至流化床的一种或多种气体质量流和所有入口开口的均匀分布。
在某些流化床应用中,由于结构的,工艺相关的或质量的原因,经由使用的气体分配器板或阀或喷嘴,不可能确保用于气体均匀分布的所需的压降。
位于上游的拉瓦尔喷嘴具有这样的优点,即它们可以用于在时间和位置方面协调进料的气体质量流的这类应用,而不干涉流化床设备、气体分步器板,喷嘴或阀门的几何结构。
进料至流化床的至少一个气体质量流的均匀分布经由位于上游的拉瓦尔喷嘴进行。
在拉瓦尔喷嘴中,限定的压降由横截面压缩以及随后的膨胀产生。如果在入口侧和出口侧之间的压差增加超过一定比率(临界压力比),拉瓦尔喷嘴中的流体在最窄的横截面中加速至音速,以及在出口侧加速至超音速。在超临界流中,质量流以恒定的喷嘴入口压力保持恒定,即,在连结至流化床设备的拉瓦尔喷嘴的出口侧上的压力变化不会对穿过的质量流产生影响。
附图说明
在拉瓦尔喷嘴和开口(例如,在底板、阀或喷嘴中的孔)的布置中,在下文中参考图1-5示出了各种可能的结果。
使用的参考标记的列表
1流化床
2用于将气体质量流进料至流化床的开口
3拉瓦尔喷嘴
4进料气体质量流
5废气质量流
6进料的其它气体质量流
7气体分配器架(rest)(具有多个开口)
图1示出了具有位于上游的拉瓦尔喷嘴的开口的一种实施方式。
图2示出了具有各自具有位于上游的拉瓦尔喷嘴的两个或多个开口的一种实施方式。
图3示出了具有一组或多组开口的一种实施方式,其中的每个组具有至少两个开口。拉瓦尔喷嘴位于每个组的上游。
图4示出了具有两个或多个开口的一种实施方式,其中,拉瓦尔喷嘴位于每个开口的上游并且它们组合以形成各自具有位于上游的拉瓦尔喷嘴的一个或多个组。
图5示出了具有各自具有两个或多个开口的一个或多个气体分布器装置的一种实施方式。拉瓦尔喷嘴位于每个气体分布器装置的上游。
具体实施方式
实施例
以下实施例表明流动通过拉瓦尔喷嘴的气体质量流取决于入口压力、喷嘴直径、气体组合物,喷嘴的温度和数量。
优选地,应当以普遍存在于拉瓦尔喷嘴中的超临界状态的方式选择压力p_外:
临界压力比可以计算如下
在这种情况下,κ是流动通过的气体的等熵系数。
流动通过具有最狭窄的开口横截面面积A的开口的质量流可以计算如下:
ρ内在此是指气体在气体入口侧(加压侧)上的密度。
实施例1是参考案例。在表1中可以发现参考案例以及另外的实施例的参数。
在实施例2中,增加喷嘴的横截面。用于相同的进气压力的更大的喷嘴横截面意味着更多的质量流通过,然而,其对p_外没有影响。
在实施例3中,气体组合物通过拉瓦尔喷嘴改变。发现质量流很大程度上取决于气体组合物,其中,具有较低摩尔质量的气体需要拉瓦尔喷嘴下游较低的压力并且可以通过较小的质量流。
在实施例4中,升高温度。这导致气体密度的降低,并且从而也降低了质量流。
另外,降低拉瓦尔喷嘴的入口压力导致能够流动通过喷嘴的较低的气体质量流。
表1
实施例6是基于图4的布置,其中,四个开口各自具有一个拉瓦尔喷嘴,组合每两个拉瓦尔喷嘴从而形成组,并且此外一个另外的拉瓦尔喷嘴连接至每个组的上游。
在表2的结果中示出了压力比和几何结构。
表2
实施例6 | |
组的上游的拉瓦尔喷嘴的最小直径[m] | 0.01 |
开口的上游的拉瓦尔喷嘴的最小直径[m] | 0.0092 |
x_H2[摩尔%] | 50 |
x_HCl[摩尔%] | 0 |
x_TCS[摩尔%] | 50 |
T_内[K] | 500 |
p_内[巴] | 15 |
p_中央[巴] | <8.572 |
p_外[巴] | <4.889 |
总质量流[kg/h] | 2102 |
质量流/组[kg/h] | 1051 |
质量流/_开口[kg/h] | 525 |
Claims (10)
1.一种用于生产颗粒状多晶硅的流化床反应器,所述流化床反应器包括具有用于具有颗粒状多晶硅的流化床的内反应器管和反应器底座的容器,用于加热所述内反应器管中的所述流化床的加热装置,在所述反应器底座中用于进料流态化气体的至少一个开口,以及在所述反应器底座中用于进料反应气体的至少一个开口,用于去除反应器废气的装置,用于进料硅颗粒的进料设备,以及此外用于颗粒状多晶硅的排出管道,其中,拉瓦尔喷嘴位于所述内反应器管外部的所述反应器底座中的至少一个开口的上游,适用于超临界膨胀所进料的至少一个质量流。
2.根据权利要求1所述的流化床反应器,包括在所述反应器底座中的至少两个开口,这两个开口各自具有位于上游的拉瓦尔喷嘴。
3.根据权利要求1所述的流化床反应器,包括在所述反应器底座中的至少一组开口,包括至少两个开口,其中,在每种情况下,拉瓦尔喷嘴位于所述至少一组开口的上游。
4.根据权利要求1所述的流化床反应器,包括在所述反应器底座中的至少一组开口,在每种情况下包括至少两个开口,其中,在每种情况下,一个拉瓦尔喷嘴以在每种情况下至少一组拉瓦尔喷嘴包括至少两个拉瓦尔喷嘴的结果的方式位于各开口的上游,其中,在每种情况下,一个拉瓦尔喷嘴连接至少一组拉瓦尔喷嘴的各自的上游。
5.根据权利要求1所述的流化床反应器,其中,在拉瓦尔喷嘴位于其上游的所述反应器底座中的所述至少一个开口是气体分布器装置。
6.根据权利要求1至5中任一项所述的流化床反应器,其中,在拉瓦尔喷嘴位于其上游的所述反应器底座中的所述至少一个开口是在底板中的孔、阀或喷嘴。
7.一种用于在流化床反应器中生产颗粒状多晶硅的方法,所述方法包括通过经由流化床中的所述流化床反应器的所述反应器底座中的至少一个开口进料的流态化气体流态化硅颗粒,所述流化床经由加热装置加热至850-1200℃的温度;添加经由所述流化床反应器的所述反应器底座中的至少一个开口进料的含硅的反应气体;以及在所述硅颗粒上沉积硅,其中,进料的流态化气体或反应气体中的至少一个质量流是超临界膨胀的。
8.根据权利要求7所述的方法,其中,所述流态化气体是H2并且所述含硅的反应气体是TCS。
9.根据权利要求7或权利要求8所述的方法,其中,拉瓦尔喷嘴位于所述反应器底座中的至少一个开口的上游以便通过存在于所述拉瓦尔喷嘴中的过压超临界膨胀进料的至少一个质量流。
10.根据权利要求7至9中任一项所述的方法,其中,使用根据权利要求1至6中任一项所述的流化床反应器。
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-
2013
- 2013-05-06 DE DE102013208274.6A patent/DE102013208274A1/de not_active Withdrawn
-
2014
- 2014-04-28 US US14/889,347 patent/US10899626B2/en active Active
- 2014-04-28 WO PCT/EP2014/058588 patent/WO2014180693A1/de active Application Filing
- 2014-04-28 KR KR1020157031974A patent/KR101819012B1/ko active IP Right Grant
- 2014-04-28 JP JP2016512281A patent/JP6149154B2/ja active Active
- 2014-04-28 ES ES14721307.8T patent/ES2627760T3/es active Active
- 2014-04-28 EP EP14721307.8A patent/EP2994420B1/de active Active
- 2014-04-28 MY MYPI2015002578A patent/MY171935A/en unknown
- 2014-04-28 CN CN201480026058.1A patent/CN105189350B/zh active Active
- 2014-05-05 TW TW103115934A patent/TWI532677B/zh active
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EP2994420A1 (de) | 2016-03-16 |
MY171935A (en) | 2019-11-07 |
SA515370069B1 (ar) | 2016-11-08 |
EP2994420B1 (de) | 2017-03-22 |
KR20150142008A (ko) | 2015-12-21 |
TW201505967A (zh) | 2015-02-16 |
JP2016522782A (ja) | 2016-08-04 |
US20160101982A1 (en) | 2016-04-14 |
WO2014180693A1 (de) | 2014-11-13 |
TWI532677B (zh) | 2016-05-11 |
US10899626B2 (en) | 2021-01-26 |
KR101819012B1 (ko) | 2018-01-16 |
CN105189350B (zh) | 2017-08-25 |
JP6149154B2 (ja) | 2017-06-14 |
ES2627760T3 (es) | 2017-07-31 |
DE102013208274A1 (de) | 2014-11-20 |
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