CN1011859B - 用于通过氧化反应破坏氢化物的催化剂及其应用 - Google Patents

用于通过氧化反应破坏氢化物的催化剂及其应用

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CN1011859B
CN1011859B CN89102510A CN89102510A CN1011859B CN 1011859 B CN1011859 B CN 1011859B CN 89102510 A CN89102510 A CN 89102510A CN 89102510 A CN89102510 A CN 89102510A CN 1011859 B CN1011859 B CN 1011859B
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简马克·西雷索尔
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

本发明是关于用于破坏毒性流体的催化剂及其应用。用该催化剂可去除从外延炉或CVD气相沉积容器中产生的残留气中的硅烷、磷化氢、胂等氢化物。在其应用过程中使这些化合物与含有反应剂如氧化铜和反应促进剂如二氧化锰的固体氧化催化剂接触,挥发性氢化物先吸附在催化剂表面,然后在促进剂作用下与反应剂反应,生成惰性物质。为此,含氢化物的流体应以小于或等于60hr-1(每小时体积流速)的流速,通过填满氧化催化剂的吸附柱进行处理。

Description

本发明是关于用于通过氧化反应破坏残留气如在外延炉或CVD气相化学沉积容器中产生的气体中的氢化物的催化剂及其应用,在其应用过程中使残留气与含有反应剂和反应促进剂的固体氧化催化剂接触。
像硅烷、磷化氢、胂、乙硼烷这样的挥发性氢化物是现在大量用于电子工业的化学气体。例如在VLST型集成电路生产的各步骤中,将硅烷作为一种硅源,应用于电子工业中。在外延炉或CVD容器中的化学反应总是不完全的,常常在反应器出口处发现一定数量的、具有危害性的反应气体。
由日本专利申请№61-90726可知,处理含硅化合物的残气的方法是:使该气体以10-20,000hr-1,最好50-10,000hr-1的比气速,通过由氧化铜和/或氧化锌组成固体相。
用该专利申请择优提到的几种组合物进行的各种试验表明,这些组合物破坏上述混合气的能力相当低。确实,根据该专利申请,其破坏程度为,比粘度约860hr-1时每kg催化剂破坏60-70升硅烷。若将比粘度降低到10-100hr-1,预计1kg催化剂的破坏能力应有所增加。但所提到的结果表明,当混合物的比粘度减少时,该60-70kg的破坏能力不但没有被保持住,反而大大降低了。这使人们对现有技术催化剂很不感兴趣。
本发明的目的是提供一种用于破坏残留气中氢化物的固体催化剂及其应用。与此类型的已知催化剂相比,明显改进了其破坏能力。
本发明方法的特征是上述固体催化剂含有10-50wt%氧化铜CuO反应剂和50-90wt%二氧化锰MnO2反应促进剂,使残留气中的氢化物吸附在催化剂表面,在反应促进剂作用下与反应剂反应生成惰性氧化物。使通过催化剂的残留气流量与催化剂的用量相适应,以使残留气中所有的氢化物基本上氧化。
固体催化剂最好含有10-30wt%的CuO和70-90wt%的MnO2,此外,还可含有相对总重量计值到30%的、选自Al2O3、ZnO、SiO2、MnCO3和它们的混合物的另一种成份。
除了待破坏氢化物外,残留气中一般还含有氢和一种惰性气体,最好是选自氮、氩、氦等的惰性气体。混合气的比气速一般为1-1000hr-1,最好为10-600hr-1。一般观察到破坏氢化物的氧化温度应保持在低于500℃,最好低于100℃。
当惰性气体为氢时,氧化温度最好保持在低于70℃。在某些情况下,也可能希望将该温度保持在低于室温。这时,在装有氧化催化剂的催化床周围,利用冷却流体进行冷却。
此催化床最好装在管式密封容器内,根据本发明的一个特征,该密封容器内有多个管子,管内填满氧化催化剂,并排安装在该容器内。
如果需要冷却催化剂,以将温度保持在预定值,尤其是如果要使温度保持在低于或接近室温时,可使冷却流体如水、油、低温液体、冷气等等在管子之间循环。
实践中观察到该密封容器应由1-30个管,最好10-20个管彼此并排,相互平行安装,以达到最好效果。本发明也是关于利用氧化破坏氢化物的催化剂,其特征为该催化剂含有10-50wt%氧化铜CuO和50-90wt%二氧化锰MnO2
催化剂最好含有10-30wt%的CuO和70-90wt%的MnO2,也可另外含有直到30wt%的、选自Al2O3、ZnO、SiO2、Cr2O3和/或MnCO3的一种成份。
出乎意料是,上面提供的固体催化剂能在比气速小于或等于60hr-1时,以30-60升/公斤的破坏能力,去除残留气中的氢化物。
借助下述非限定性实例,并结合附图,可更好地理解本发明。
图1为本发明实现去除氢化物方法的装置示意图。
图2为实现本发明方法的择优氧化密封容器的剖视图。
图1中,一个外延反应器或CVD密封容器(需要的话)通过泵3,由管道2与完成本发明方法的密封容器的下方入口连接。在此密封容器内产生的气体通过管道7排出。密封容器4可含有反混合剂5,其上为催化剂床6,其中装有适量CuO和MnO2的混合物,该混合物中随意加有选自Al2O、ZnO、SiO2、Cr2O3、MnCO3的一种成份。
图2是一择优密封容器,如图1中的密封容器4的剖视图。该容器能实现本发明方法,尤其是在需要通过冷却方式将温度维持在接近或低于室温的情况下。该密封容器包括:一进气口和一出气口17、18(或反之也可),各与封盖15、16构成一个整体,安装在壳体31上。壳体内装有多个管道19、20、21、22、23,管内填装催化床组份24,组份要装满到管子两端,并用适宜部件封住 两端。管封之间,由空间25、26、27、28、29、30分成多个空腔,每个空腔的大小取决于系统的预定效率和必要时,在空腔25、26、27、28、29、30内循环的冷却流体的冷却效率。
流体循环最好从下方入口32流向上方出口33(逆流循环)。
实例1-8
下面实例1-8是比较例,是在同一条件下完成的,全部参数都一样。按照下表变动催化剂组成,但保持催化剂用量相同。
对于实例1-6的催化剂,经管2,从密封容器4下方入口送入含有10%硅烷SiH4和90%氮气的混合气,比气速为30hr-1,密封容器4的柱直径为4Cm,有效高度17Cm。
在实例7中,残留气由3%硅烷SiH4和97%氮组成,比气速为34hr-1,将残留气输入到直径8Cm,有效高度15Cm的柱内。
在实例8中,残留气由5%硅烷和95%氮组成,比气速为170hr-1,将残留气输入到直径3Cm,有效高度10Cm的柱内。
表1列出各种具体组成的催化剂。表2列出观察到的催化床内的最高温度和这些催化剂的破坏能力。
如表2所示,用反应剂1、2和4(按现有技术)得到的结果不好,与从上述日本专利申请预期的结果相反。反应剂3和6对硅烷无破坏作用。
另一方面,本发明的反应剂5和7的破坏能力,至少比以上现有技术实例1、2和4中反应剂的破坏能力高10倍。
实例8表明,在例5和7的条件下,由于CuO/MnO2之比太高,比气速太快,反应剂8的破坏能力明显低于该两例中反应剂的破坏能力。
上述各例中,硅烷破坏后得到的惰性氧化物基本上是二氧化硅。在磷化氢和胂的情况下,氧化物质基本上分别是P2O5和As2O3
表1
试剂    组成
(催化剂)    (按重量计)
1 CuO 31%,Al2O32%,ZnO 67%
2    CuO    33%,ZnO    67%
3 CuO 68%,SiO232%
4 CuO 38%,Cr2O337%,MnO22%,
SiO223%
5 CuO 22%,MnO278%
6 CuO 28%,Mn2O372%
7 CuO 13%,MnO257%,Co3Mn 30%
8 CuO 41%,MnO217%,SiO228%,
Carbonate    14    %
表2
试剂    密度    催化床最高温度    破坏能力
(催化剂)
1    1.3g/ml    64℃    3.78l/kg
2    1.16g/ml    52℃    4.24l/kg
3    1.2g/ml    -    无破坏性
4    1.49g/ml    44℃    3.65l/kg
5    0.89g/ml    88℃    53.02l/kg
6    0.9g/ml    -    无破坏性
7    1.18g/ml    42℃    41.0l/kg
8    0.9g/ml    60℃    12.6l/kg

Claims (15)

1、用于通过氧化反应破坏氢化物的催化剂,其特征在于,该催化剂含有10-50wt%的cuo和50-90wt%的MnO2
2、根据权利要求1所述的催化剂,其特征在于,该催化剂含有10-30wt%cuo和70-90wt%Mno2
3、根据权利要求1或2所述的催化剂,其特征在于该催化剂另外含有直到30wt%的,选自AL2O3、ZnO、SiO2、Cr2O3、MnCO3的一种成份。
4、应用如权利要求1所述的催化剂,其中使残留气与含有反应剂和反应促进剂的固体氧化催化剂接触,然后将基本上破坏掉氢化物的残留气排入大气,其特征在于:上述固体催化剂含有10-50wt%的反应剂氧化铜CuO和50-90wt%的反应促进剂二氧化锰MnO2,残留气中的氢化物吸附在催化剂表面,在反应促进剂作用下与反应剂反应,生成惰性氧化物质,流过催化剂的残留气流量与催化剂用量相适应,以将残留气中的所有氢化物基本上氧化。
5、根据权利要求4所述的用途,其特征在于,所说的固体催化剂含有10-30wt%和70-90wt%MnO2
6、根据权利要求4或5的方法,其特征在于,氧化催化剂中另外含有直到30%(以总重量计)的、选自AL2O3、ZnO、SiO2、Cr2O3、MNCO3的一种成分。
7、根据权利要求4-6中任何一项所述的用途,其特征在于,残留气中含有选自氢和惰性气体的一种气体及待破坏的氢化物。
8、根据权利要求7的用途,其特征在于,惰性气体可选自氮、氩、和氦气。
9、根据权利要求4-8中任何一项所述的用途,其特征在于氧化温度保持低于150℃,最好低于100℃的催化床。
10、根据权利要求4-9中任何一项所述的用途,其特征在于,当惰性气体是氢时,氧化温度维持在基本上不高于室温。
11、根据权利要求9或10所述的用途,其特征在于,在催化床周围提供冷却流体,以将氧化温度维持在预定值以下。
12、根据权利要求4-11中任何一项所述的用途,其特征在于,由氧化催化剂构成的催化床安装在最好是管状的密封容器内。
13、根据权利要求12所述的用途,其特征在于,密封容器内有多个填满氧化催化剂的、并排安装的管子。
14、根据权利要求13所述的用途,其特征在于,在管与管之间提供空间,以使冷却流体如水、油、低温液体、和/或冷气可在其中循环流动。
15、根据权利要求13或14所述的用途,其特征在于,密封容器内有1-30个,最好10-20个彼此平行安装的管子。
CN89102510A 1988-03-30 1989-03-30 用于通过氧化反应破坏氢化物的催化剂及其应用 Expired CN1011859B (zh)

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US4992620A (en) * 1989-11-21 1991-02-12 Phillips Petroleum Company Removal of trialkyl arsines from fluids
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FR2629362A1 (fr) 1989-10-06
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JPH0214718A (ja) 1990-01-18
CN1040514A (zh) 1990-03-21
KR890014163A (ko) 1989-10-23

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