CN1468150A - 通过可控无电沉积获得的且含铂族金属的载附催化剂 - Google Patents

通过可控无电沉积获得的且含铂族金属的载附催化剂 Download PDF

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CN1468150A
CN1468150A CNA018167616A CN01816761A CN1468150A CN 1468150 A CN1468150 A CN 1468150A CN A018167616 A CNA018167616 A CN A018167616A CN 01816761 A CN01816761 A CN 01816761A CN 1468150 A CN1468150 A CN 1468150A
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T·巴茨
H·尤尼克
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Abstract

本发明涉及一种含有铂族金属的载附的催化剂。所述催化剂可以通过使来自沉积溶液的至少一种铂族金属进行可控无电沉积获得，所述沉积溶液包含：i)至少一种均匀溶解的铂族金属化合物，ii)还原剂，和iii)至少一种控制剂，选自铌、钽、钼、钨和钒的同多酸和杂多酸或其盐。本发明还步及一种使用通过可控无电沉积制备的催化剂氢化无机或有机化合物的方法，特别是用于直接合成过氧化氢。

Description

通过可控无电沉积获得的且含铂族金属的载附催化剂
本发明涉及一种载附的铂族金属催化剂，涉及一种通过可控无电沉积制备该催化剂的方法，和涉及一种使用该催化剂氢化无机和有机化合物、特别是用于直接合成过氧化氢的方法。
载附的铂族金属催化剂应用于许多化学工艺中，特别是用于氢化无机和有机化合物，并在其中具有重要的技术意义。经过深入研究的反应是称为从分子氧和氢直接合成过氧化氢的反应。已经致力于发现对于该反应和其它氢化反应具有高活性和选择性的催化剂。
US 6,168,775描述了用于直接合成过氧化氢的贵金属催化剂。贵金属盐溶液与摩尔质量为300-8000道尔顿的离子性控制聚合物(例如聚丙烯酸酯)的溶液混合，并在用该溶液浸渍载体之前或之后用氢气还原。以此方式获得的催化剂据说在使贵金属细分散在载体上和在表面上优先形成具有110和/或220晶面的晶体方面是突出的。
许多金属可以通过无电沉积施用在载体上，无电沉积也称为自催化沉积。例如，EP-A-0 875 235描述了一种制备载附催化剂的方法，其中多孔载体用催化活性金属的盐与还原剂的溶液处理，以此方式实现催化活性金属的无电沉积。
WO 00/59635描述了一种制备在金属载体上的铂族金属催化剂的方法，其中金属以离散的颗粒形式沉积。沉积从含水介质进行，在该含水介质中，铂族金属以配合物形式存在，并具有大于4的pH。
本发明的目的是进一步改进现有铂族金属催化剂的活性和/或选择性，使得由该催化剂催化的反应的时空产率提高。此外，铂族金属应该牢固地固定在载体上，使得也可以达到在机械应力下长的连续开工期限。
我们已经发现该目的通过一种载附的铂族金属催化剂来实现，该催化剂通过使来自沉积溶液的至少一种铂族金属进行可控无电沉积来获得，所述沉积溶液包含以下组分：
i)至少一种均匀溶解的铂族金属化合物，
ii)还原剂，和
iii)至少一种控制剂，选自铌、钽、钼、钨和钒的同多酸和杂多酸或其盐。
本发明还涉及一种氢化分子无机或有机化合物的方法，其中使待氢化的化合物与氢气在根据本发明的催化剂存在下接触。
认为在溶解的同多酸和/或杂多酸存在下使铂族金属无电沉积到载体上能实现更均匀的涂布，即贵金属颗粒的更均匀的分布和在载体上更均匀的粒度，得到改进的活性和/或选择性。涂布的均匀性可以例如在扫描电子显微术和/或X-射线光电发射谱(ESCA)的协助下来研究。
同多酸或杂多酸衍生自元素选自铌、钽、钼、钨和钒的元素，优选衍生自钼、钨和钒，更优选衍生自钨。同多酸是无机多元酸，其构成这些元素的原酸的部分酸酐，且仅仅含有一种中心原子。其实例包括庚钼酸、庚钨酸、十二钨酸、二钒酸、癸钒酸、己铌酸和己钽酸。杂多酸是无机多元酸，它除了这些元素之外还含有其它中心原子，通常是砷、碘、磷、硒、硅或碲。这些杂多酸的实例包括12-钼磷酸、12-钨磷酸、12-钨硅酸和庚钨碘酸。同多酸或杂多酸可以预先形成并加入到沉积溶液中，或者在沉积溶液中从适宜的前体化合物原地形成，同多酸和/或杂多酸的缩合度不是关键的。在沉积溶液的pH下得到的缩合度是适宜的。有用的前体化合物是单体含氧酸，例如是内消旋酸或原酸，或低聚合氧酸，例如所述元素的偏酸或其盐。同多酸和/或杂多酸或其前体化合物的有用的盐特别是碱金属盐，特别是钠盐和钾盐，或铵盐。
适宜的前体化合物的实例包括钨酸钠、偏钒酸铵、钼酸钠等。
在沉积溶液中铂族金属与同多酸和/或杂多酸或其前体化合物之间的摩尔比优选为0.01-5.0，特别是0.1-2.0，按照铂族金属原子与铌、钽、钼、钨和/或钒原子之间的摩尔比计算。
对本发明而言，铂族金属是元素周期表第八过渡族的且不属于铁族的贵金属，即钌、铑、铱、钯、锇和铂。优选钌、铑、钯和铂。特别优选钯和铂。所述铂族金属的组合也是合适的，优选钯和铂的组合，钯和铑的组合，钯和铱的组合，钯、铂和铑的组合，钯、铂和铱的组合。特别优选钯和铂的组合。在与钯的组合中，钯优选构成主要组分。基于铂族金属的总含量计，钯的比例则优选大于40％重量，优选大于60％重量，更优选大于80％重量。
根据本发明的催化剂的催化活性组分也可以包含除铂族金属之外的其它元素作为助催化剂或掺杂剂，它们影响催化剂的活性和/或选择性。这些其它元素优选包括：金属，例如钴、镍、铜、银、金、铬、锰、铼、铝、锡、铅、砷、锑和铋；非金属，例如硼、碳、硅、氮和磷。
用作助催化剂或掺杂剂的额外组分通常是基于铂族金属含量的0.01-20％重量，优选0.1-15％重量，特别是0.5-10％重量。
铂族金属化合物选自铂族金属盐和铂族金属配合物。优选使用铂族金属配合物，特别是其中铂族金属以氧化态+1至+4存在的那些。优选四配位的配合物。特别适宜的是钯(II)配合物，其中钯的配位数是4。
铂族金属配合物可以含有不同的配体。这些配合物可以预先制备或在沉积溶液中原地制备。适宜的带负电荷的配体是例如选自卤化物和假卤化物，例如氯化物、溴化物、碘化物、CN、OCN和SCN，C1-C6-羧酸例如甲酸、乙酸和丙酸及其盐；螯合配体，例如乙二胺四乙酸(EDTA)、次氮基三乙酸、1，2-二氨基环己烷四乙酸及其盐；氨基膦酸，例如次氮基亚甲基膦酸；二酮酸盐类，例如乙酰丙酮酸盐；羟基羧酸，例如乙醇酸、乳酸、酒石酸和葡糖酸，及其盐。电中性配体的实例包括烷基腈类，例如乙腈；胺类，例如氨，伯-、仲-和叔-C1-C6-烷基胺，例如乙基胺、正丙基胺、异丙基胺、正丁基胺、叔丁基胺、己基胺、二甲基胺、二乙基胺、二异丙基胺、二正丁基胺、三甲基胺、三乙基胺、三丙基胺、N，N-二甲基乙基胺、N，N-二甲基异丙基胺、和N，N-二甲基丁基胺，二-、三-、四-和多元胺，例如乙二胺、二亚乙基三胺和三亚乙基四胺，非芳族和芳族环状胺，例如吡咯烷、哌啶、吗啉、哌嗪、吡咯及其正-C1-C6-烷基衍生物，吡啶和菲咯啉，膦类，例如叔C1-C6-烷基-和C6-C12-芳基-膦，特别是三苯基膦，以及硫化物，例如C1-C6-单-和-二烷基硫化物，C6-C12-单-和-二芳基硫化物，以及含氧化合物，二-C1-C6-链烷醇，和酚类，及其醚。
特别优选含氮的配体，特别是胺类，更优选氨。铂族金属化合物优选含有具有含氮配体的铂族金属配合物。
沉积溶液的铂族金属含量通常在0.001-2克/升范围内，优选0.1-0.5克/升。
优选的钯配合物是H2PdHal4、M2PdHal4、M2Pd(CN)4、(NH4)2PdHal4、Pd(NH3)4Hal2、Pd(NH3)4(NO3)2和Pd(NH3)4(CN)2，其中M是碱金属，特别是钠或钾，Hal是卤素原子，特别是氯、溴或碘。
优选的其它铂族金属配合物是(NH4)2IrCl6、H2PtCl4、(NH4)2PtCl4、Na2PtCl4和K2PtCl4。
沉积溶液进一步含有至少一种溶解形式的还原剂。有用的还原剂是氧化还原电势低于所用铂族金属化合物的氧化还原电势的任何物质或物质混合物。优选在含水介质中具有标准电势低于+0.5伏特、优选具有标准电势低于0伏特的物质。
适宜的还原剂的实例包括甲酸，或α-羟基羧酸，例如柠檬酸、乳酸、酒石酸，和特别是羧酸的盐，优选碱金属盐、碱土金属盐、铵盐和C1-C10烷基铵盐，磷酸或次磷酸，磷酸或次磷酸的盐，特别是金属盐或碱土金属盐；C1-C10链烷醇，例如甲醇、乙醇和异丙醇；糖类，例如单糖、二糖和低聚糖形式的醛糖和酮糖，特别是葡萄糖、果糖和乳糖；醛类，例如甲醛；硼氢化合物，例如硼氢化物、硼烷、金属硼酸盐和硼烷配合物，例如二硼烷、硼氢化钠和氨基硼烷，特别是三甲基氨基硼烷；肼和烷基肼类，例如甲基肼；连二亚硫酸氢盐和连二亚硫酸盐，特别是连二亚硫酸氢钠和连二亚硫酸氢钾，连二亚硫酸-钠、-钾和-锌；亚硫酸氢盐和亚硫酸盐，特别是亚硫酸氢钠和亚硫酸氢钾，亚硫酸-钠、-钾和-钙；羟基胺和脲，以及它们的混合物。
优选的还原剂是次亚磷酸钠和次亚磷酸钾、甲酸铵、三甲基胺-硼烷、硼氢化钠，连二亚硫酸钠和连二亚硫酸氢钠，以及甲酸铵和次亚磷酸钠的混合物。
一般来说，使用基于铂族金属和所加各组分(例如助催化剂或掺杂剂)的总量计的至少1氧化还原当量的还原剂。优选使用过量的还原剂。特别适宜的是还原剂与铂族金属之间的摩尔比是10∶1至100∶1，更优选20∶1至60∶1，例如约30∶1，约40∶1或约50∶1。
沉积溶液的pH优选大于6。该pH优选在7-14的范围内，特别是8-12。为此，可能必要的是向沉积溶液中加入碱，以便达到所需的pH。这些碱是适合于将含水介质的pH调节到所需值的任何物质或化合物。具体地说，所用的碱是具有配合物稳定性的那些，即具有至少一部分路易斯碱特性。碱优选选自金属氧化物；金属氢氧化物，特别是碱金属氢氧化物，例如氢氧化钠和氢氧化钾；金属碳酸盐，特别是碱金属和碱土金属碳酸盐，例如碳酸锂、碳酸钠、碳酸钾、碳酸镁和碳酸钙；含氮碱，特别是氨，伯胺、仲胺和叔胺，例如前面在含氮配合物配体中描述的那些。同样适宜的是缓冲体系，特别是前面提到的碱、前述碱的盐和/或适宜的酸的那些。特别优选的碱是氨和氢氧化钠溶液。
沉积溶液通常是含水的，即其含有至少10％重量、优选至少30％重量和特别是至少50％重量的水。非水的部分优选选自水混溶性溶剂，如甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、四氢呋喃或二噁烷。
所用的载体可以是本领域技术人员公知的任何催化剂载体，是金属的或非金属的。适宜的金属载体例如描述在WO 00/59635中，这里参考其公开内容。非金属载体通常选自无机材料或塑料。
在本文中，术语“无机材料”通常包括非金属无机材料，如天然和合成的矿物、玻璃、陶瓷等。所用的无机材料优选是玻璃。优选由熔融二氧化硅或熔融石英组成的玻璃，以及基于碱金属硅酸盐、碱土金属硅酸盐、硅硼酸盐、硅铝酸盐和硅酸铅的玻璃。进一步优选的载体材料是硼酸盐、磷酸盐、锗酸盐、硫属元素化合物和卤化物玻璃，如由氟化铍制成的材料。
也优选用作载体的无机材料选自陶瓷材料。有用的陶瓷材料可以从金属氧化物、硼化物、氮化物和/或碳化物制备。根据本发明所用的陶瓷材料可以是上釉或未上釉的，结晶或半结晶的。对于根据本发明的方法，优选使用由基本材料制成的陶瓷，所述基本材料选自氧化铝、碳化硅、氮化硅、二氧化锆及其混合物。进一步优选使用含有阳离子的陶瓷，例如在Chelatit、滑石、堇青石、钙长石、富铝红柱石或铯榴石中的情况。进一步优选陶瓷复合材料。
非金属载体通常必须活化。载体的“活化”指在用于支载随后的铂族金属无电沉积的载体表面上形成种子的工艺。这些种子通常含有金属，优选铂族金属，特别是钯。为了将其活化，载体优选用敏化剂的溶液处理，然后用铂族金属盐的溶液处理。有用的敏化剂通常是还原剂，特别优选锡(II)化合物，特别是氯化锡(II)，和钛(III)化合物，任选地与其它还原剂组合。适合作为敏化剂的其它还原剂包括次磷酸的盐。活化描述在例如EP-A-0 875 235中，参考其公开内容。
沉积通常在0-100℃的温度下进行，优选30-100℃，特别是40-85℃。
为了沉积铂族金属，载体例如与完全配好的沉积溶液接触。或者，载体可以先与还原剂和任选含有全部或部分沉积溶液的任选组分的控制剂的溶液接触。铂族金属和其余的任选组分然后在沉积温度或在例如至多30℃的温度下加入。其它选择是使载体与铂族金属化合物和控制剂的溶液接触，然后加入还原剂的溶液。
在根据本发明的方法中，已经证明有利的是在铂族金属沉积在载体上期间通过例如泵抽或搅拌保证充足的沉积溶液的循环。
沉积溶液与载体接触足够长的时间，以实现铂族金属在载体上的无电沉积。必要的反应时间通常是0.5-500分钟，优选1-300分钟，更优选2-60分钟。一般来说，所用的铂族金属的大于70％重量、优选大于80％重量和更优选大于90％重量沉积在载体上。铂族金属通常如此牢固地连接在载体上，从而当在催化反应中使用时不会由于与液体和气体的接触而显著移动。在催化剂中仅仅发现可忽略量的作为控制剂基础的元素。
根据本发明的催化剂适合于有机和无机化合物的氢化，特别是对于有机化合物，例如烯烃，如乙烯、丙烯、乙炔和丁二烯，羰基化合物，例如醛类和酮类，芳族化合物，例如苯，更优选用于氢化氧气来制备过氧化氢。
本发明进一步提供通过使氧气和氢气在液体介质、优选基本上水溶液中与根据本发明的催化剂接触来制备过氧化氢的方法。
适合于合成H2O2的反应器例如描述在EP-A-068 862、EP-A-201 614和EP-A-448 884中。特别优选管式反应器，其中根据本发明的催化剂作为床存在或以圆柱状结构的催化剂单元的形式存在。如前所述，合适的载体形状可以保证对于气体和液体的最佳流动条件。
液相优选在催化剂床中从顶部滴流到底部。气体可以以顺流或以逆流方向进行，优选以顺流方向。
优选经由处于氧气或空气计量点下游的一个或多个中间进料点将氢气加入反应器中。反应气体和反应介质的空塔速度优选在约20-7000m/h的范围内，更优选50-1400m/h。
反应介质优选是水和/或C1-C3链烷醇，特别是水和/或甲醇。当所用的反应介质是水时，可以加入最多20％重量的醇、优选甲醇。当使用含醇的反应介质时，其可以包含最多40％重量、优选最多20％重量和更优选最多5％重量的水。非常特别优选使用水作为唯一的反应介质。为了使过氧化氢对分解稳定，向反应介质中加入酸，其pKa优选小于乙酸、特别是无机酸例如硫酸、磷酸或盐酸的pKa。酸浓度通常是至少10-4摩尔/升，优选10-3至10-1摩尔/升。通常还加入痕量的溴化物或氯化物，其浓度为1-1000ppm，优选5-700ppm，更优选50-600ppm。但是，也可以使用其它稳定剂，例如甲醛。
除了氢气和氧气以外，反应气体还可以含有其它惰性气体，例如氮气或稀有气体，通常具有O2∶H2比例为2∶1至1000∶1。优选使用摩尔比为5∶1至100∶1，特别是20∶1至100∶1。在反应气体中所用的氧气也可以以空气的形式加入反应气体中。
在优选的实施方案中，反应气体进行循环。在这种情况下，在新鲜的气体混合物中的摩尔比在化学计量范围内，优选1.5∶1至0.5∶1。在循环气体中的O2∶H2摩尔比应该为5∶1至1000∶1，优选20∶1至100∶1。反应可以在大气压或在至多200巴的高压下进行。压力优选是10-100巴，特别是10-80巴。反应温度可以为0-80℃，优选在5-60℃、特别是25-55℃。优选选择在反应器中反应气体混合物中的以及循环气体中的反应气体分压，使得在反应条件下的氢气浓度低于最低爆炸极限。
所述方法允许制备氢气含量达到2％重量、优选3-25％重量的过氧化氢溶液。可以通过调节料流按照希望的方式预先选择浓度。长期研究显示，即使在大于40天的操作时间之后，如果有的话，只观察到很少的催化剂活性和选择性降低。
与现有技述公知的催化剂相反，根据本发明制备的催化剂具有优异的催化剂性能。它们在氢化反应中是高活性和高选择性的。该方法还实现了铂族金属颗粒对载体的特别好的粘合，这就是根据本发明制备的催化剂达到特别长的连续开工期限的原因。
下面通过附图和实施例详细说明本发明。
图1显示用本发明催化剂或对比催化剂催化的直接合成过氧化氢的时空产率随时间的变化。
催化剂的制备
实施例1(＝对比例，催化剂B1)：
将来自Ceramtec的2毫米直径的1200克球形滑石载体连续用氢氧化钠水溶液、25％硫酸和蒸馏水洗涤。以此方式预处理的球然后在抽滤器上如下活化：使溶液A(＝5克/升的SnCl2+10毫升/升的浓盐酸)作用3分钟，滤出并用0.5升蒸馏水洗涤后，使溶液B(＝0.2克/升的PdCl2+1毫升/升的浓盐酸)作用3分钟。在重新过滤和用水洗涤后，重复整个过程，最后每次用0.5升蒸馏水洗涤球，共洗涤三次。
将球填充在玻璃管中，并与溶液C(＝70克/升的NH4Cl、23克/升的NH3和30克/升的次亚磷酸钠)混合。通过泵以这样的方式泵抽该溶液，使得仅仅球移动，并形成流化床。同时用作气体分离器的储库用于将该溶液循环回玻璃管的入口。玻璃管也装有夹套，在夹套中填充了加热液体。使该溶液中的温度达到40±0.5℃，在涂布之前通过泵抽循环。然后加入含有2.8毫克六氯铂酸和526毫克四氯钯酸钠的20克水溶液D，开始反应。在1小时后，反应完成。抽出溶液，用水进行冲洗。以此方式制备的催化剂的Pd含量是145毫克/千克，对应于沉积程度为92％。
实施例2(＝催化剂B2)：
重复实施例1的催化剂制备过程，不同的是溶液D另外含有405毫克的钨酸钠。
在从氢气和氧气直接合成过氧化氢中检测催化剂的性能。
实施例3：
向内径为2.1厘米和长度2.00米的夹套反应器中装入催化剂B1。在40℃和50巴压力下，使含5克/升磷酸和120毫克/升溴化氢的水溶液以1.0千克/小时的速率滴流过催化剂床。同时，用气体压缩器以10400升(STP)/小时的速率将3％氢气和97％氧气的混合物从顶部到底部循环通过催化剂床。在两个对于氢气和氧气的质流计的帮助下产生气体混合物。用热导式检测器检测和控制其组成，在该检测器上小股料流作为废气流通过。
该反应生成过氧化氢和水的过程中所消耗的氢气量是从引入的气体总料流和废气料流计算出来的。
离开反应管的产物混合物在分离器中从气体中分离出来，同时仍然处于压力下，并以液体形式从该装置中送出。质量平衡通过总料流与进料流来进行。在液体流出物中的过氧化氢含量通过滴定来确定。
流出物料流的质量、过氧化氢的含量以及氢气的消耗量用于计算基于氢气的选择性。时空转化率(STC)由基于催化剂床体积的每单位时间氢气消耗的摩尔数来确定。
时空产率(STY)由在管式反应器中基于690ml催化剂床体积的每单位时间形成的过氧化氢的量来确定。结果列在下表1中。时空产率随着时间的变化如图1所示。
实施例4：
重复进行实施例3，不同的是使用催化剂B2。由于较高的活性和稍微较好的选择性，该检测得到较高的时空产率(参见表1和图1)。可见，根据本发明的催化剂的STY总是高于对比催化剂的STY。
编号  催化剂  T[℃] 选择性 STC[mol H2/lh] STY[g H2O2/lh] 操作时间
3  B1  50℃ 79％ 3.0-2.7 85-77 90h
4  B2  50℃ 81％ 3.4-3.0 100-85 ＞400h

Claims (12)

1.一种通过使来自沉积溶液的至少一种铂族金属进行可控无电沉积获得的载附的铂族金属催化剂，其中所述沉积溶液包含：
i)至少一种均匀溶解的铂族金属化合物，
ii)还原剂，和
iii)至少一种控制剂，选自铌、钽、钼、钨和钒的同多酸和杂多酸或其盐。
2.根据权利要求1的催化剂，其中所述铂族金属选自钯或者钯和铂的组合。
3.根据权利要求1或2的催化剂，其中所述铂族金属化合物包括具有含氮配体的铂族金属配合物。
4.根据前述任一项权利要求的催化剂，其中所述沉积溶液的pH为8-12。
5.根据前述任一项权利要求的催化剂，其中所述同多酸或杂多酸是在沉积溶液中从单体或低聚含氧酸现场形成的。
6.根据前述任一项权利要求的催化剂，其中所述载体在沉积之前已经被活化。
7.根据权利要求6的催化剂，其中所述载体已经经过处理以便用敏化剂的溶液、然后用铂族金属盐溶液将其活化。
8.根据前述任一项权利要求的催化剂，其中所述载体选自陶瓷材料和玻璃。
9.一种氢化分子无机或有机化合物的方法，其中使待氢化的化合物与氢气在如权利要求1-8任一项所述的催化剂存在下接触。
10.根据权利要求9的用于制备过氧化氢的方法，其中无机化合物是分子氧。
11.根据权利要求10的方法，其中氧气和氢气在液体介质中与催化剂接触。
12.一种制备权利要求1-8任一项所述的催化剂的方法，其中通过无电沉积从沉积溶液将至少一种铂族金属沉积在载体上，所述沉积溶液含有：
i)至少一种均匀溶解的铂族金属化合物，
ii)还原剂，和
iii)至少一种控制剂，选自铌、钽、钼、钨和钒的同多酸和杂多酸或其盐。
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