CN102558214B - 一种用于处理直接合成有机氯硅烷中的液体残余物的方法 - Google Patents
一种用于处理直接合成有机氯硅烷中的液体残余物的方法 Download PDFInfo
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- C07F7/125—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving both Si-C and Si-halogen linkages, the Si-C and Si-halogen linkages can be to the same or to different Si atoms, e.g. redistribution reactions
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Abstract
本发明提供一种在无铝的含有二氧化硅的颗粒的流化床中用氯化氢热裂解直接Müller-Rochow合成中的高沸点残余物以得到硅烷的方法。
Description
技术领域
本发明涉及一种用氯化氢热裂解直接Müller-Rochow合成中的高沸点残余物以得到硅烷的方法。
背景技术
在从硅金属和烷基氯直接合成式RaHbSiCl4-a-b的有机氯硅烷中,其中a=1以及b=0、1或2,R更优选为甲基,形成低聚硅烷、碳硅烷、硅氧烷和高沸点裂解产物作为副产物。另外存在于蒸馏残余物中的有直接合成得到的固体,其是极其细小的,甚至用旋风分离器和过滤器也不能保留。所述固体由硅、金属氯化物、金属硅化物和烟灰组成。
这些蒸馏残余物的主要部分由低聚硅烷,特别是其中c=0-6的乙硅烷RcCl6-cSi2组成。因此在早期开发了将乙硅烷转化为甲硅烷的方法。这可通过用氯化氢进行氨催化裂解,如在US 2,709,176中所描述。但是,这种方法只能裂解含有少于4个甲基的乙硅烷。此外,需要事先将乙硅烷从固体残余物中移出,因为这些残余物例如氯化铝是催化剂毒物。
为了也利用不可裂解的乙硅烷,开发了将不可裂解的乙硅烷转化为可裂解的乙硅烷并随后裂解的方法,例如US 4,393,229,其中这些乙硅烷用HCl在通常含有贵金属的特定催化剂上直接裂解,例如DE 44 31 995,或者其中乙硅烷在金属催化剂上用氢气裂解,例如US 4,079,071。氢化的优点是R’3Si-CH2-SiR’3型的碳硅烷,其中R’=H、C1-C4烷基或者卤素,也能够裂解成含氢的甲硅烷。金属催化转化的缺点是催化剂容易被来自残余物中的杂质毒化。氢化还需要相对高压。这明显增加了设备的复杂性。
在一个步骤中结合后续步骤在US 5,430,168中描述,其中可避免添加金属催化剂,但是没有避免相对高压。
DE 936 444公开了一种方法,其中直接合成甲基氯硅烷的相对高沸点残余物,在400-900℃下用氯化氢在高压釜或者空管中完全热转化成单体硅烷而不需要催化。此处使用管式反应器的很大的优点是低的焦化倾向,因此所述方法可以进行更长的时间。
但是,需要对残余物进行预处理,否则由于其固含量能很快导致反应管的堵塞。DE 10354262描述了通过经由氯化氢流而不是经由设备夹套来引入所需的反应温度进行裂解,最小化了在反应器壁上的固体残余物。
DE 19711693另外描述了在反应管中可旋转的内部构件,其刮掉了焦化物质。
根据DE 10039172,在硅流化床上用氯化氢裂解含有固体的高沸点甲基氯硅烷残余物得到了好的裂解结果,但是在该方法中可得到的包含三氯硅烷、四氯化硅和甲基氯硅烷的产物混合物需要更复杂的分离方法,因为在工业规模上,其既不适于三氯硅烷工厂也不适于甲基氯硅烷工厂。EP 635510描述了在移动床中在含铂的氧化铝载体、氯化铝载体或者沸石即铝硅酸盐上,转变含固体的高沸物混合物。但是,贵金属催化剂非常昂贵。在所述方法条件下,氯化铝载体和沸石释放氯化铝,将其从制备的硅烷混合物移除非常困难。
发明内容
本发明提供了一种用于在无铝的含有二氧化硅的颗粒的流化床中用氯化氢热裂解直接Müller-Rochow合成中的高沸点残余物以得到硅烷的方法。
具体实施方式
所述方法非常容易进行。可以在低压下,处理直接Müller-Rochow合成有机氯硅烷中的所有液体残余物,甚至那些含有固体的液体残余物,并且将有机硅组分转变为可利用的甲硅烷。充分避免了固体沉积在反应器壁上。
所述直接合成中的残余物在1013hpa下的沸点优选为70℃以上,特别是至少100℃。
在所述方法中,优选将残余物中的高分子量组分裂解为甲硅烷。优选低聚硅烷,特别是通式RcCl6-cSi2的乙硅烷,其中c=0-6,R=烷基,被裂解。直接合成中的残余物可以包含溶解的或微细悬浮的金属或者其化合物。更特别地,残余物包含选自Al、Cu、Zn、Sn、Fe、Ti的金属和/或它们的化合物。残余物也可以包含其它固体,例如硅和烟灰。
优选地,在所述方法中没有催化剂,也没有进一步的给料。
优选制备通式为MeaHbSiCl4-a-b的甲基氯硅烷,其中Me为甲基,a为1、2或3的值,以及b是0或1的值。
所用的无铝的含有二氧化硅的颗粒可以是含有二氧化硅的陶瓷材料或矿物材料,例如石英、陶瓷或者酸洗的煅烧砂。二氧化硅的含量优选为至少90重量%,特别是至少99重量%。所述无铝的含有二氧化硅的颗粒含有优选最多0.1重量%,特别是最多0.01重量%的铝。石英是特别优选的。
所述颗粒以有利于所用反应器类型的粒径分布来使用。颗粒的粒径优选为至少50μm,特别是至少80μm,并且优选至多1000μm,特别是至多500μm。
直接合成中的具有70℃以上沸点的残余物与氯化氢一起加入到流化床反应器中。当使用圆锥形的流入盘(conical inflow plate)时,可以在反应器的上游或者在反应器内混合。如果流化床放置在气体分配盘上,氯化氢从盘下流入,而需要转化的液体残余物从盘的上方以合适的方式引入,任选用一部分氯化氢雾化。
所用的氯化氢的量至少是对应于存在于残余物中的低聚硅烷,尤其乙硅烷的摩尔当量,但是优选不高于保持流化床的用量。优选使用1.1-10倍的摩尔用量。残余物和氯化氢可以优选利用废热预热的形式或者在室温下计量加入到反应器中,所述流优选连续计量加入。
流化床反应器由可直接或间接加热至650℃的夹套组成。另外,反应器可以安装有一个或多个温度控制指针。可能的加热方法是耐高温载热油、电阻加热、感应加热或者它们的组合。
反应器优选在至少400℃,特别是至少500℃,并且优选至多650℃,特别是至多600℃下操作。
压力优选为至少50hPa,特别是至少1000hPa,并且优选至多10000hPa,特别是至多3000hPa。
流化床阻止任何结块并且粉碎结块的材料。在颗粒上的沉积物被粉碎并且随气体流排出。热处理的一个有利的副作用是固体颗粒的烧结,这使得难以过滤并且可以呈胶态分布的固体可以转变为可过滤的组分或者通过旋风分离器以粉末形式排出,并且可以用处理直接合成中的灰尘残余物的已知方法来处理。
输出的混合物优选是冷凝的并任选不含固体,并且可以重新加回到直接合成中得到的硅烷混合物中,或者单独分离成纯的物质。过量的氯化氢可以用已知的方法回收并重新返回到反应中。
在下面的实施例中,除非在每种情况中另外说明,所有的用量和百分比均是基于重量,所有的压力为1000hPa(绝对)并且所有的温度为20℃。实施例1(类似于DE 936444;非本发明的)
在室温和环境压力下,将180ml/h的硅烷合成中沸点>150℃的高沸点残余物与25l/h的气体氯化氢并流计量至放置在管式炉中的长度700mm和内径25mm的空的水平钢管中。管式炉设置为550℃的温度。高沸点残余物由80%乙硅烷(1,1,2,2-四氯二甲基乙硅烷、1,1,2-三氯三甲基乙硅烷和1,2-二氯四甲基乙硅烷的混合物)、2%固体和18%硅氧烷和碳硅烷组成。由于副产物很多,更精确的分配是困难的。经过17小时的操作后,测试停止,因为管式反应器在反应区域已经被固体和裂解产物堵塞。
测试的结果是具有下表1中所述组成的裂解硅烷:
实施例2-4(本发明的)
25l/h的气体氯化氢在室温和环境压力下通入到玻璃实验流化床反应器(长500mm,直径40mm)中,所述流化床反应器安装有玻璃料作为气体分配器并且填充有粒级(particle fraction)为100-315μm的270g石英粉以获得流化床。通过电加热将反应器加热至550℃。通过泵将要转化的高沸点混合物在玻璃料上方以60g/h雾化。甚至在操作50小时后,在反应器中或者在不变色石英上也没有发现沉积物。从不同的高沸点化合物混合物得到以下裂解的硅烷,产物混合物的组成如表2中所示:
表2:
所述缩写表示:
构成100%的物质是未详细说明的中间体和更高沸点的化合物。在反应的废气中不仅有未转化的氯化氢和未完全转化的硅烷,还有多达3重量%的氢气和烃例如甲烷、乙烷、乙烯、丁烷、丁烯。
Claims (3)
1.热裂解直接Müller-Rochow合成中的高沸点残余物的方法,所述方法是在无铝的含有二氧化硅的颗粒的流化床中用氯化氢热裂解直接Müller-Rochow合成中的高沸点残余物以得到硅烷,其中所述无铝的含有二氧化硅的颗粒选自石英、陶瓷和酸洗的煅烧砂,其中二氧化硅的含量为至少90重量%,以及所述颗粒的粒径为50μm-1000μm。
2.根据权利要求1所述的方法,其中通式为RcCl6-cSi2的乙硅烷被裂解,其中c=0-6,R=烷基。
3.根据权利要求1所述的方法,其中所述方法在400-650℃的温度下进行。
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BE526512A (zh) | 1953-02-20 | |||
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US4079071A (en) | 1977-03-28 | 1978-03-14 | Union Carbide Corporation | Synthesis of hydrosilanes from methylchloropolysilanes |
US4393229A (en) | 1982-04-28 | 1983-07-12 | General Electric Company | Redistribution of polysilanes in high boiling residues |
JPS59199519A (ja) * | 1983-04-22 | 1984-11-12 | ゼネラル・エレクトリツク・カンパニイ | 廃ケイ素含有反応塊体を処理してハロシランを製造する方法 |
DE3808071A1 (de) * | 1988-03-11 | 1989-09-21 | Basf Ag | Verfahren zur herstellung von acylierten imidazolen |
DE3829581A1 (de) * | 1988-09-01 | 1990-03-15 | Bayer Ag | Verfahren zur aufarbeitung von hydrolyserueckstaenden aus der organochlorsilansynthese |
US5481052A (en) * | 1992-04-22 | 1996-01-02 | Bp Chemicals Limited | Polymer cracking |
US5292909A (en) * | 1993-07-14 | 1994-03-08 | Dow Corning Corporation | Catalytic conversion of direct process high-boiling component to chlorosilane monomers in the presence of hydrogen chloride and hydrogen |
US5292912A (en) | 1993-07-19 | 1994-03-08 | Dow Corning Corporation | Catalytic conversion of direct process high-boiling component to chlorosilane monomers in the presence of hydrogen chloride |
DE4334015A1 (de) * | 1993-10-06 | 1995-04-13 | Hoechst Ag | Verfahren zur Herstellung von fluorierten Monomeren |
DE4431995A1 (de) | 1994-09-08 | 1996-03-14 | Wacker Chemie Gmbh | Verfahren zur Herstellung von wasserstoffhaltigen Methylchlorsilanen |
US5430168A (en) | 1994-10-27 | 1995-07-04 | Dow Corning Corporation | Alumimum trichloride catalyzed hydrogenation of high-boiling residue from direct process |
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US20100264362A1 (en) * | 2008-07-01 | 2010-10-21 | Yongchae Chee | Method of producing trichlorosilane (TCS) rich Chlorosilane product stably from a fluidized gas phase reactor (FBR) and the structure of the reactor |
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