CN1130101A - C6-15链烷烃的脱氢催化剂 - Google Patents

C6-15链烷烃的脱氢催化剂 Download PDF

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CN1130101A
CN1130101A CN95120276A CN95120276A CN1130101A CN 1130101 A CN1130101 A CN 1130101A CN 95120276 A CN95120276 A CN 95120276A CN 95120276 A CN95120276 A CN 95120276A CN 1130101 A CN1130101 A CN 1130101A
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H·兰辛克·罗特格林克
T·塔克
R·布兰德
P·潘斯特
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Abstract

本发明涉及C6-15链烷烃的脱氢催化剂，其中含有载体、至少一种铂族组分、至少一种选自锡、锗和铅的助催化剂以及至少一种附加改性剂。该附加改性剂含有至少一种碱土金属。本发明催化性的稳定剂与常规应用碱金属而产生的催化剂稳定性相比要高得多。

Description

C6-15链烷烃的脱氢催化剂
本发明涉及C6-15链烷烃的脱氢催化剂。
烃类尤其是链烷烃的脱氢过程可以工业规模进行。脱氢产物可用于生产多种化合物如洗涤剂、石油组分及药品。C6-15正构链烷烃的脱氢能够产生相应的单烯，这对于生产洗涤剂特别重要。单烯可被用于烷基化芳香化合物如苯以便制备相应的线性烷基苯。
链烷烃的脱氢过程借助在脱氢条件下适宜的催化剂完成。链烷烃可以在固定床、流化床或移动床中与催化剂接触。以选用固定床催化剂体系为佳。在本文中，待脱氢的反应物首先被预热至所需反应温度，随后通过固定床催化剂。烃的脱氢过程以在气相中进行为佳。所需温度范围在300—900℃之间。
用于工业规模脱氢过程的催化剂含铂和氧化铝载体。催化剂通常还含有多种助催化剂例如锡和/或铟。正构链烷烃的脱氢目的是生产直链单烯。因此，应该避免能够产生异构烯烃、异构链烷烃或烷基化芳烃的副反应或后续反应。实际上，通过以适当方式添加改善催化剂活性的碱金属可以抑制这些不需要反应的发生。
举例来说，U.S.专利4,486,547要求保护一种含有铂族组分、锡组分、钢组分、碱金属或碱土金属组分以及多孔载体的催化剂组合物。在其实施例中，仅描述了含有碱金属锂的催化剂。
由于附带的铟组分，U.S.—PS4486547中的催化剂体系与不含铟的可类比的催化剂相比具有更稳定的催化活性。然而，为了将这类催化剂体系投入工业应用，仍需对其催化活性尤其是长期稳定性进行进一步改进。
因此，本发明目的在于提供一种用于正构链烷烃脱氢过程的催化剂体系，其特征在于与已知催化剂体系相比其催化活性的长期稳定性得到进一步改善。
本发明的目的可通过C6-15链烷烃的脱氢催化剂实现，该催化剂含有无机载体、0.01—5％(重)至少一种铂族金属、0.01—5％(重)至少一种作为助催化剂的单质锡、锗或铅和至少一种附加改性剂金属。
催化剂的特征在于附加改性剂金属为占最终催化剂重量0.01—20％的碱土金属。
出人意料的是可以通过将绝对地仅被用作先有技术改性剂的碱金属换成至少一种碱土金属可以显著地增强催化剂稳定性。优选的碱土金属为镁。
本发明催化剂载体的孔体积为0.5—3毫升/克之间，根据DIN66132氮吸附法测定的比表面积为至少5平方米/克。在脱氢条件下，它具备充足的耐热性。适宜的载体材料包括所有已被用于先有技术脱氢催化剂的物质如活性炭、氧化硅、碳化硅、陶土和各类硅酸盐。特别适用的耐热性无机氧化物有如氧化铝、二氧化钛、二氧化锆、氧化铬等。优选采用来自晶相过渡系列的氧化铝如η或γ—氧化铝作为载体。
该载体可以被模铸成球形、丸粒、挤出物或颗粒。还可以采用粉末材料。不过，优选采用直径为1—4毫米的η或γ—氧化铝球粒。
由于载体的高孔隙率，这些球粒的体积密度低于0.5克/厘米3，以0.25—0.4克/厘米3为佳。同样由于其高孔隙率，若体积密度低于0.25克/厘米3，载体便不再具有充分稳定性。而当体积密度高于0.4克/厘米3时，由于其孔隙率低，从而影响了反应物分子接近催化活性组分。
本发明催化剂中适宜的铂族元素为铂、钯、铱、铑、锇或钌或其混合物。不过，以选用铂为佳。铂族组分被细密地分布于整个催化剂内。铂族组分占整个催化剂重量的比例为0.01—约5％。以0.1—3％(重)为佳。
可以在载体制备过程中通过共沉淀或共凝胶引入铂族组分。不过，以通过浸渍载体材料引入铂族组分为佳。为此，选用铂族元素的可分解前体化合物溶液或悬浮液。在铂的情况下，举例来说，可以用其它酸进一步酸化以便保证全部载体颗粒被均匀浸渍的六氯铂酸溶液适用于此目的。其它铂盐如硝酸四胺合铂(II)、氢氧化四胺合铂(II)和氯化四胺合铂(II)也适用作铂前体。
所用的助催化剂可以是单独的或以混合物形式存在的单质锡、锗或铅。不过，以锡为佳。与铂族组分相同，也可以将锡组分均匀地分布在催化剂颗粒上。最终催化剂中锡的重量比为0.01—约5％(重)，以0.1—3.0％(重)为佳。
在载体制备过程中，还可以加入锡组分。不过，借助氯化锡或其它锡盐溶液进行后续浸渍同样是优选的。
按照本发明，所用的改性剂金属是至少一种碱土金属。还可以在载体制备过程中加入碱土金属。不过，以借助可溶性碱土金属化合物进行浸渍方式完成的后续加入过程为佳。最终催化剂中碱土金属的比例在0.01—20％(重)之间。以0.1—10％(重)镁为佳。
铂族组分，助催化剂和碱土金属组分可被同时地或依次分别地以浸渍载体的次序加入。业已证实特别有利的作法是将催化剂中全部组分同时地从一个共同溶液中沉积在催化剂载体或载体材料上。为了制备共同浸渍溶液，四胺合铂(11)盐为适宜的例如铂的前体。若在共同浸渍溶液中使用六氯铂酸时，短时间内便会发生沉淀，这只有借助强无机酸如盐酸或硝酸进行酸化方可抑制。若采用四胺合铂(II)盐作为铂前体，只需添加少量酸便可使共同浸渍溶液长时间保持稳定。
采用一步浸渍法制备的催化剂的特征在于其催化活性在长时期内特别稳定。此外，一步浸渍法还大大简化了制备方法。
该催化剂还含有作为另一种助催化剂的铟。铟尤其对于催化剂的长期稳定性具有积极的影响。优选地通过浸渍将占最终催化剂总重多达5％(重)的可溶性前体与其它组分加入催化剂。
除了上述组分以外，催化剂还可以含有多达5％，以多达2％(重)为佳的硫。硫以适当的形式被加入催化剂之中。硫的适宜来源，举例来说，为硫化氢和硫醇化合物。含硫化合物还可以在载体制备过程中以硫酸盐、亚硫酸盐、硫化物或有机硫化合物的形式被加入。然而，在硫的情况下，同样优选的是用硫与来自共同浸渍溶液的其它催化剂组分涂敷载体。
采用本发明催化剂进行的长期测定结果表明与已知催化剂相比，它具有更好的长期稳定性，这应该归功用作改性剂的碱土金属。除了碱土金属以外，催化剂中还可以含有占最终催化剂重量0.01—20％(重)的碱金属组分。
在将组分施加到载体上后，如此获得的催化剂前体被干燥并在300—700℃下煅烧0.5—24小时。随后在200—700℃下通过采用含氢气体的气相还原法还原烧结催剂。选择还原条件以便使大部分铂族组分被还原为金属。还原过程可以在脱氢反应器内进行也可以在反应器外完成。
正构链烷烃的脱氢过程以在气相中完成为佳。为此，链烷烃被加热至300—900℃，随后进入催化剂区域，在0.08—10兆帕的压力下通过催化剂。LHSV(液体时空速度)以0.1—100小时-1为佳。离开脱氢区域的产物流中主要含有未被转化的链烷烃、氢和单烯。产物流通常被冷却。分离出富氢气相后，得到富烃液相。液体产物混合物可被分离为富含链烷烃馏分和富含烯烃馏分。前者通常再次通过脱氢反应器以便进一步脱氢，后者被用于生产二级和目的产物。另外，全部液体产物均可被用于对苯进行烷基化处理。在此情况下，烯烃与苯反应形成易于与未反应链烷烃分离的线性烷基苯化合物。分离后，链烷烃返回脱氢反应器。液体产物中的二烯烃可在脱氢与烷基化反应器之间被选择性的氢化为单烯。
下列实施例将更详细地介绍本发明催化剂的制备及其在线性链烷烃脱氢过程的应用。
对比实施例1
采用锂作为改性剂制备常规脱氢催化剂A。载体为体积密度为0.3克/厘米3、孔体积为1.4毫升/克的球形氧化铝。140毫升由0.95克SnCl2·2H2O、1.05克In(NO3)3和6.03克LiNO3组成的水溶液浸渍100克载体。其中还含有1.2％(重)HNO3。浸渍后，干燥载体，并在550℃煅烧1.5小时。用140毫升含有0.4克以H2PtCl6形式存在的铂和1.2％(重)HNO3的水溶液浸渍载体。如此获得的催化剂前体如上所述再次被干燥和煅烧。随后在490℃于合成气流(5％体积H2、95％体积N2)中还原催化剂。最终催化剂含有0.4％(重)铂、0.5％(重)锡、0.4％(重)铟和0.6％(重)锂。
该催化剂以及下列实施例中的催化剂被用于对C10-14链烷烃混合物进行脱氢处理。为此，将10毫升相应的催化剂置于反应器中，在2.3巴的压力和LHSV＝22小时-1的条件下通入含有氢和链烷烃的气体混合物。H2/链烷烃摩尔比为4.7。选择催化剂床层的初始温度以便使液体产物中烯烃含量约为11％(重)。此时温度为453℃。由于催化剂被减活、不得不在试验期间定期地将温度升高。7.5天后，温度升至490℃。液体产物中平均烯烃含量为11.2％(重)。
实施例1
按照与常规催化剂相同的生产方法制备本发明的催化剂B。不过，用相应数量的Mg(NO3)2·6H2O代替LiNO3。最终催化剂含有0.4％(重)铂、0.5％(重)锡、0.4％(重)铟和2.1％(重)镁。
与对比实施例1中的催化剂相同，该催化剂还被用于对C10-14链烷烃混合物进行脱氢处理。该试验中烯烃平均含量为11.8％(重)。仅仅10天后，最终温度便达到490℃。因此，催化剂B比传统催化剂A稳定得多。催化剂B的使用寿命延长了1/3，不过，烯烃的平均浓度比催化剂高约0.6％(重)。
实施例2
通过将来自共同溶液的所有催化剂组分同时施用于催化剂载体上以一步法制备本发明催化剂C。
在此情况下，用140毫升含有0.79克Pt(NH3)4(NO3)2、Mg(NO3)2·6H2O、1.05克In(NO3)3和0.95克SnCl2·2H2O的水溶液浸渍100克对比实施例1的载体材料。该溶液还含有1.2％(重)HNO3。按照对比实施例1所述干燥催化剂前体，煅烧并将其还原。由一步浸渍法制备的催化剂C具有特殊的长期稳定性。22天后，最终温度达到490℃。
实施例3
按照实施例2的方式制备本发明另一种催化剂D，所不同的是未采用铟，该催化剂被用于C10-14链烷烃的脱氢。该试验中平均烯烃含量为10.9％(重)。16天后，催化剂温度达到490℃。该催化剂虽然不含铟，但是与带有铟的常规催化剂A相比却能提供更多的烯烃。
对比实施例2
基于体积密度为0.6克/厘米3、孔体积为0.64毫升/克的氧化铝载体制备对比催化剂E。用溶解在64毫升1.2％(重)HNO3溶液中的0.3克Pt(NH3)4(NO3)2、0.47克In(NO3)3、22.38克Mg(NO3)2·6H2O和0.43克SnCl2·2H2O浸渍100克该载体。在490℃将其干燥、煅烧并还原。金属含量为(％重)Pt：0.18，In：0.18，Sn，0.23，Mg：2.1。
以与对比实施例1完全相同的方式对10毫升(5.93克)这种催化剂进行脱氢试验。与其它实施例相比，该催化剂的Pt含量较低，而这一点恰恰由其较高的体积密度得到补偿。因此，本文列举的每一应用实例中催化活性铂的用量均是相同的。
当初始温度为462℃时，很明显，产物物流中烯烃含量太低，只有4.9％(重)，将其升至481℃并未带来任何改进。造成该催化剂性能不佳的原因在于其孔隙率低，从而使反应物难以接近催化活性组分。

Claims (13)

1.一种含有无机载体、0.01-5％(重)至少一种铂族金属、0.01-5％(重)至少一种作为助催化剂的元素锡、锗和铅与至少一种附加改性剂的C6-15链烷烃脱氢催化剂，其特征在于附加改性剂为至少一种占最终催化剂重量0.01-20％(重)的碱土金属。
2.按照权利要求1的催化剂，其特征在于镁被用作附加改进剂。
3.按照权利要求1—2中任一项的催化剂，其特征在于铂族元素为铂。
4.按照权利要求1—3中任一项的催化剂，其特征在于助催化剂为锡。
5.按照权利要求1—4中任一项的催化剂，其特征在于催化剂还含有多达5％(重)铟。
6.按照权利要求1—5中任一项的催化剂，其特征在于催化剂还含有多达5％(重)硫。
7.一种含有无机载体、0.01—5％(重)至少一种铂族金属、0.01—5％(重)至少一种作为助催化剂的元素锡、锗和铅与至少一种附加改性剂的C6-15链烷烃脱氢催化剂，可以通过下列方法获得：向载体材料中同时添加来自共同浸渍溶液的铂族金属可溶性前体、助催化剂和改性剂，干燥载体，在300—700℃下煅烧，随后在200—700℃下于含氢气体中进行还原，其中被用作改性剂的为占最终催化剂重量0.01—20％(重)的至少一种碱土金属。
8.按照权利要求7的催化剂，其特征在于多达5％(重)钢被用作另一助催化剂。
9.按照权利要求7或8的催化剂，其特征在于还含有多达5％(重)与其它来自共同浸渍溶液的组分同时被施用在载体材料上的硫。
10.一种含有无机载体、0.01—5％(重)至少一种铂族金属、0.01—5％(重)至少一种用作助催化剂的元素锡、锗和铅以及至少一种附加改性剂的C6-15脱氢催化剂的制备方法，其中向载体同时添加来自共同浸渍溶液的铂族金属可溶性前体、助催化剂和改性剂，干燥载体，在300—700℃下煅烧，随后在200-700℃下于含氢气体中进行还原，其中被用作改性剂的为占最终催化剂重量0.01—20％(重)的至少一种碱金属和/或碱土金属。
11.按照权利要求10的方法，其特征在于共同浸渍溶液还含有可溶性铟前体。
12.按照权利要求10和11中任一项的方法，其特征在于共同浸渍溶液还含有硫可溶性前体。
13.C6-15链烷烃的脱氢方法，其特征在于脱氢过程在权利要求1—7中任一项的催化剂上进行。
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