CN102123803A - 用于催化剂无纺布的金属纤维 - Google Patents

用于催化剂无纺布的金属纤维 Download PDF

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CN102123803A
CN102123803A CN2009801315063A CN200980131506A CN102123803A CN 102123803 A CN102123803 A CN 102123803A CN 2009801315063 A CN2009801315063 A CN 2009801315063A CN 200980131506 A CN200980131506 A CN 200980131506A CN 102123803 A CN102123803 A CN 102123803A
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boron
phosphorus
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乌韦·扬奇
戴维·F·勒普顿
哈拉尔德·曼哈特
斯特凡·福尔贝格
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WC Heraus GmbH and Co KG
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Abstract

本发明涉及一种基于一种或多种元素的金属纤维，这些金属元素包括：铂、钯、铑、钌或铱，该金属纤维含有0-30重量％的一种或多种附加的合金元素，这些合金元素包括：镍、钴、金、铼、钼和钨，本发明的金属纤维具有1-500重量ppm的硼或磷。本发明的特别用于制备一氧化氮或用于制备氢氰酸的无纺布或网由前述类型的纤维构成。为了制备基于贵金属的、具有直至30重量％的附加合金金属的纤维，通过深拉由熔化物制成的纤维，使金属熔点在深拉纤维之前通过添加硼或磷而降低至少400℃，然后再将硼或磷从纤维中去除。

Description

用于催化剂无纺布的金属纤维
技术领域
本发明涉及用于制备硝酸和氢氰酸的催化剂结构、和用于制备催化剂的基于贵金属的适合的金属纤维、由该金属纤维制成的网和无纺布以及用于制备这种纤维、无纺布和网的方法。
背景技术
文献DE 199 45 742 C1公开了一种金属纤维催化剂本体，其金属纤维通过熔化物提取的方式进行制备。由这种纤维可以凭借纺织技术制造类似的纤维无纺布。这种催化剂材料铂、钯、铑包含在纤维中，或作为附加的纤维存在于织物中。
文献DE 100 00 097 A1公开了用于从细纤维中制备金属纤维的熔化物提取的方法，细纤维的直径小于100μm，熔化物浴温度达到1500℃。
文献DE 197 12 625 A1提供了一种方法，其中，类似的金属纤维通过具有撒播辊的机器铺设在运动的底层上，并且在交叉点上彼此连接在一起。
上述方法为了制备金属纤维、以及由金属纤维制成的网或无纺布所采用的金属具有较高的熔点，因此并不适合，或者至少是难以实现。
文献DE 100 40 591 C1提出了使铂、铱、铑和钌以及类似金属与硼和磷制成合金。
公知的催化剂、特别使铂-铑催化剂的效率，随着时间的持续会降低。
发明内容
本发明的目的在于制备基于贵金属的纤维、网或无纺布。制备方法应该尽可能简单。催化剂应该持久保持高效率。
为了实现上述目的，使金属熔点在纤维处理之前通过硼或磷而锐减，并且使硼或磷在纤维制成之后、或由纤维制成无纺布或网之后又进一步被除掉。
上述目的通过独立权利要求的技术特征得以实现。从属权利要求提供了优选的实施方案。
由此可知，在硼或磷的除掉过程中纤维表面粗糙度增大，并因此以附加的可渗透性使催化剂的效率提高。此外还可以联想到，硼或磷阻止了氧化物的形成，这样的氧化物会导致催化失效而且会阻碍到达催化剂的渗入。
根据本发明，基于贵金属的金属熔点通过硼或磷显著降低，特别降低至少400℃、优选至少500℃，基于贵金属的金属特别是指基于铂的金属族：铂、钯、铑、钌和铱，以及附加的总共直到30重量％的合金元素，这些合金元素包括金属镍、钴、金、铼、钼和钨。对此，优选生成与硼或磷的共晶成分。这种共晶混合物相对于待操作的金属而通常含有1-5重量％之间的硼或磷。
本发明除了共晶混合物以外也能实现。然而低于0.5重量％的硼或磷就会失效，这是因为合金的宽泛的熔点范围会导致显著的偏析。在太高的硼含量或磷含量的情况下，一方面不必要的硼或磷会燃烧，由此带来更多的其它缺点，即，为了去除同样不需要的元素而增多的耗费。因此在高于10重量％的浓度条件下，自然在成分中伴随升高的硼含量或磷含量，在那之前该成分中还没有共晶体，从而产生硼或磷高消耗形式的缺陷以及相对于越来越小的熔点降低的优点，使用于硼或磷去除的耗费上升。
本发明的熔点降低在使用铂、铱以及它们的合金的情况下特别显著。优选采用硼用于熔点的降低，这是因为，采用磷通常必定会要求更高的安全性。
根据本发明，纤维直径在10和200μm之间，优选在50和100μm之间。根据本发明，纤维由熔化物进行的深拉处理、特别是采用熔化物提取的方法，由于硼或磷导致熔化温度降低而节省能量并且节省设备，特别是相对于没有熔点降低情况下的耗费、或相对于用于制造金属丝的耗费。还以文献DE 197 57 093 A1的金属丝铸造方法制成的纤维、或以文献DE 31 36 303 A1的熔化物纺织的方法制成的纤维，这些纤维都可以采用本发明的熔点降低的方法来制造。
根据本发明，除了通过对熔化物的深拉、特别是通过熔化物提取使纤维的制备简化以外，还使用于制造由纤维构成的网或无纺布所需的烧结温度和时间都有所降低，而且不会破坏无纺布的催化性能和机械性能，这是因为硼以及磷在确定利用纤维、无纺布或网之前又进一步被除掉。硼或磷的去除部分地在深拉纤维的过程中以及将纤维烧结成网或无纺布的过程中进行。太高的硼或磷的剩余量会破坏作为催化剂应用的所需性能。特别要确保使硼或磷在纤维烧结成网或无纺布之后，将产物在白炽状态下加热至少几分钟。在该处理步骤中，使材料的强度在降低硼或磷含量的条件下得以增大。可以理解为，硼或磷含量仍然高于由这些元素生成的正常的杂质，特别是1-500重量ppm之间。特别是在硼降低到1-20重量％或磷降低到5-20重量％的情况下，相对于由本发明制成的纤维、网或无纺布的催化作用和机械稳定性不会产生对这些元素的消极影响。
在采用非贵重合金元素或易氧化的铂族金属、诸如铱和钌时，硼或磷的氧化没有在大气条件下进行，而是在温和条件下、例如含H2/H2O的氧化性混合气体条件下进行。当在合金中含有易氧化金属时，这种温和的方法特别有利于预烧结处理。
具体实施方式
接下来，结合实施例对本发明进行详细说明。
通过在铂中添加大约2重量％的硼，使熔点从1770℃降低到790℃。由此简化了由Pt合金、例如PtRh5通过熔化物提取的方法制取纤维的制备过程。Pd的熔点以类似方式通过添加大约3重量％硼(B)的合金而从1555℃降低到1065℃。
由硼合金而成的PtRh5纤维在仅低于共晶体的温度条件(例如750℃)下预烧结。在预烧结过程中，硼氧化，并且大部分变成液态，或生成的氧化硼蒸发。同样产生纤维之间的第一次烧结连接。通过温度范围在1200℃-1400℃(采用火焰)的短时间(几分钟)烧结处理，使无纺布固定烧结在一起。可能残留的氧化硼遗迹可以通过在温水中进行冲洗而去除。
以类似方式，使无纺布由钯合金制成。然而因为Pd-B系统的共晶体以1065℃而显著高于含铂的情况，或者Pd的熔点以1555℃而显著低于含铂的情况，所以在对于预烧结和烧结的温度进行调节时要特别谨慎。然而，适宜的温度通过简单的装载试验以及接下来的金相抛光试验而便于得到。
实施例：
将5kg的以惯用方式预熔融的PtRh5合金在浇铸之后轧制成一根直径为10mm的金属棒，以大约30mm的长度切割成段。然后，使各段金属棒在氧化锆坩埚中于氩气罩环境中慢慢进行电感加热，其中，在熔化物中添加与Pt-B共晶体相对应的2.1重量％的硼颗粒。经过短时间的熔化之后，注意避免使熔化物加热超过1000℃，从而使硼和坩埚的氧化锆之间产生反应的危险降低到最小。这样制成的合金在铜铸模中铸造成约20mm×20mm×120mm的锭。
由含硼的PtRh5合金预先加工而成的锭在氧化锆坩埚中、于熔化物提取装置(参见DE 199 45 742 C1说明书中，第2栏，第40行起)中、在氩保护气环境下进行熔化，其中，熔化浴的温度保持在820-860℃的范围。用于制备由不含硼的PtRh5合金构成的纤维的对比试验是在合金的较高熔化温度条件下进行(液相线大约1820℃)的，由此导致熔化坩埚的损坏。提取过程根据预先的试验进行设定，即，由PtRh5-B合金生成2.6kg的纤维，纤维直径为50-60μm，平均长度为5mm。
类似于DE 197 12 625 A1所公开的方法，使纤维在一层由氧化铝构成的平面底层上以400mm×800mm的尺寸散开，直到纤维的表面重量到达1500g/m2。
将这样铺设的无纺布于底层上导入到大气环境下的箱式炉中，加热到750℃，并在该温度条件下保持5分钟。硼从纤维渗出、在PtRh合金表面上氧化、并形成氧化硼，氧化硼在该温度条件下是液态的(熔点450℃)。使具有预烧结的无纺布的底层从热炉中去除，并且冷却到室温。冷却后，使氧化硼在温水中溶解，由此使无纺布从底层脱离。
通过预烧结处理已经产生足够的机械强度，从而使无纺布挂有铂丝。然而，在这个阶段中，无纺布仍然十分脆弱，而且必须谨慎处理。用氢氧焰将无纺布加热到白炽状态(估计大约1200℃)，并且保持2-3分钟。在该处理之后，使强度显著提高。强度这样进行测试，即，将无纺布圆片坯料(直径95mm)在周边固定夹住，然后用钢半球(直径40mm)进行压入，直到无纺布断裂。达到的最大力测得为95N。与此相比，对两块无纺布进行测量，这两块无纺布通过铺设和烧结处理由深拉的PtRh5丝制成，并且同样具有1500g/mm2的表面重量。第一块无纺布在1640℃条件下于热炉中烧结10分钟，并且具有10N的抗压强度。第二块无纺布在1350℃条件下于热炉中烧结12小时，并且具有85N的抗压强度。本发明的无纺布可以毫无问题地进行操作。PtRh5合金的含硼量减少到＜0.001％。这种无纺布具有91％的孔隙度。
由表面重量为1500g/m2的无纺布冲压出4块直径分别为62mm的圆片坯料。在从氨氧化到一氧化氮的测试反应器中，这些圆片坯料在负载为每平方米每天22.4吨(t N/m2/d)氮、压力为3.5bar、以及温度为860℃的条件下进行试验。为了进行比较，在并列的反应器中，对10种惯用的催化剂网进行测试，这些催化剂网通过编织76μm丝线而由PtRh5制成，其各自的表面重量为600g/m2。
无纺布的压力损失比那些网高1.4倍，即，一氧化二氮在生产气体中的浓度在无纺布和网中的比较。无纺布的氧化效率在测试条件下为96.2％，而且在总的126.0小时的测试时间上都保持在这个水平上。而网的氧化效率在测试的开始为96％，但随着测试时间的持续而降低到95.5％。
权利要求书(按照条约第19条的修改)
1.一种由金属纤维构成的无纺布或网，所述金属纤维基于一种或多种元素，这些金属元素包括：铂、钯、铑、钌或铱，所述金属纤维含有0-30重量％的一种或多种附加的合金元素，这些合金元素包括：镍、钴、金、铼、钼和钨，其特征在于，所述金属纤维具有1-500重量ppm的硼或磷。
2.由权利要求1所述的网或无纺布制备一氧化氮或制备氢氰酸的用途。
3.采用直至30重量％的附加合金金属、通过深拉由熔化物制成的基于贵金属的纤维而制备纤维的方法，其中，使金属的熔点在深拉纤维之前通过添加硼或磷而降低至少400℃，然后再将硼或磷从纤维中去除，
其特征在于，将纤维烧结成无纺布或网。
4.根据权利要求3所述的方法，其特征在于，使硼或磷在保护气的环境中与金属混合。
5.根据权利要求4所述的方法，其特征在于，将硼或磷以热氧化物的形式去除。

Claims (7)

1.一种基于一种或多种元素的金属纤维，这些金属元素包括：铂、钯、铑、钌或铱，所述金属纤维含有0-30重量％的一种或多种附加的合金元素，这些合金元素包括：镍、钴、金、铼、钼和钨，其特征在于，所述金属纤维具有1-500重量ppm的硼或磷。
2.由权利要求1所述的纤维构成的无纺布或网。
3.根据权利要求1所述的纤维的用途，特别是作为网或无纺布根据权利要求5用于制备一氧化氮或用于制备氢氰酸。
4.采用直至30重量％的附加合金金属、通过深拉由熔化物制成的基于贵金属的纤维而制备纤维的方法，其特征在于，使金属的熔点在深拉纤维之前通过添加硼或磷而降低至少400℃，然后再将硼或磷从纤维中去除。
5.根据权利要求4所述的方法，其特征在于，使硼或磷在保护气的环境中与金属混合。
6.根据权利要求4或5所述的方法，其特征在于，将纤维烧结成无纺布或网。
7.根据权利要求4至6中任意一项所述的方法，其特征在于，将硼或磷以热氧化物的形式去除。
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