CN1938246A - 用于将氢气氧化的催化剂及烃类脱氢的方法 - Google Patents
用于将氢气氧化的催化剂及烃类脱氢的方法 Download PDFInfo
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Abstract
本发明涉及一种在烃类脱氢方法中用于将氢气氧化的催化剂。所述催化剂负载在α-氧化铝上并且包含基于催化剂总重量为0.01-0.1重量%的铂和0.01-0.1重量%的锡。还公开了一种用于将氢气氧化的方法和一种使用所述催化剂用一体化氧化方法将烃类脱氢的方法。
Description
本发明涉及一种在烃类脱氢方法中用于将氢气氧化的催化剂,其中该催化剂含有负载在α-氧化铝上的基于催化剂总重量为0.01-0.1重量%的铂和0.01-0.1重量%的锡,还涉及用一体化氧化方法使用所述催化剂将氢气氧化的方法以及烃类脱氢的方法。
现有技术描述了多种在脱氢方法中用于将氢气氧化的催化剂和方法。
US-A 4 418 237描述了一种烃类脱氢并在脱氢催化剂上将第一工艺阶段形成的氢气进行选择性氧化的方法。该氧化催化剂包含负载在BET表面积为1-500m2/g的多孔铝载体上的VIII族贵金属和离子半径≥1.35埃的金属阳离子。该贵金属含量为0.001-5重量%。
US-A 4 599 471描述了一种脱氢方法,其中在两个脱氢区之间设置供有富氧水蒸汽的氧化区。该氧化催化剂包含用量为0.01-5重量%的VIII族贵金属和离子半径≥1.35埃的金属或金属阳离子。
EP-A 826 418描述了用于在乙苯脱氢成为苯乙烯中将氢气选择性氧化的氧化催化剂和方法。该催化剂包含负载在氧化铝载体上的0.01-10重量%的铂,其中氧化铝的BET表面积为0.5-6m2/g并且氧化铝的氨吸附量不超过5μmol/g。
EP-A 1 229 011描述了一种乙苯脱氢的方法,其中氧化区并入到两个脱氢阶段之间,并且在其第二脱氢阶段中二氧化碳的生成速率基于第一阶段保持少于2.1。所用的氧化催化剂包含铂、碱金属或碱土金属、锡或铅和/或第4族金属,例如锗。
尽管现有技术中描述了多种具有一体化氧化阶段的烃类脱氢方法,但继续存在改进需求,特别是在一体化氧化方法的选择性和经济性方面。
因此,本发明的目的是找到一种用于将氢气氧化的催化剂,该催化剂具有高选择性和活性并且比现有技术的催化剂更经济。另外,要找到一种改进的将氢气氧化的方法,特别是并入脱氢工艺之中的将氢气氧化的方法。
此目的通过在烃类脱氢方法中用于将氢气氧化的催化剂得以实现,其中该催化剂包含负载在α-氧化铝上的基于催化剂总重量为0.01-0.1重量%的铂和0.01-0.1重量%的锡。
所用铂和锡的重量比有利地为1∶4-1∶0.2,优选重量比为1∶2-1∶0.5,特别是重量比接近于1∶1。
催化剂有利地包含基于催化剂总重量为0.05-0.09重量%的铂和0.05-0.09重量%的锡。
除了铂和锡,如果适宜的话,也可以使用低于2重量%,特别是低于0.5重量%的碱金属化合物和/或碱土金属化合物。当使用碱金属化合物和/或碱土金属化合物时,优选碱金属化合物,特别是钠、钾和/或铯化合物。
氧化铝催化剂特别优选只含有铂和锡。可以存在痕量的碱金属和碱土金属,其数量级相当于市购的氧化铝中典型地存在的化合物或者在成型体制造过程中例如使用硬脂酸镁作压片助剂时引入的化合物的数量级。
包含α-氧化铝的催化剂载体有利地具有的BET表面积为0.5-15m2/g,优选为2-14m2/g,特别优选7-11m2/g。优选使用成型体作为载体。优选的几何体例如为丸、环形丸、球体、圆柱体、星形挤出物或齿轮形挤出物。这些几何体的直径有利的为1-10mm,优选为2-8mm,并且其单个直径能够分布在上述平均直径附近。特别优选的是球体或圆柱体,特别是球体。通常球体具有的平均直径为3-7mm,并且有利的是不超过5重量%的球体其直径小于3mm以及不超过5重量%的球体其直径大于7mm。
催化剂载体优选只含有α-氧化铝。
α-氧化铝载体可以通过本领域技术人员熟知的所有方法来制备。通过加入水,如果适宜的话加入助剂例如石墨、硬脂酸镁、马铃薯淀粉或硝酸,在柱塞式挤出机或优选在连续操作挤出机中将氧化铝水合物(假勃姆石)粉末和如果适宜的话γ-氧化铝粉末混合并成型而有利地制备圆柱形成型体。如果适宜的话,成形体在挤出过程中也可被切成段。挤出物有利地在100-180℃的温度下干燥,并通常在400-800℃下优选在带状煅烧炉中煅烧0.5-5小时。接着将其在旋转管式炉、竖式炉或马弗炉中有利地在1000-1200℃温度下进行最后的煅烧。作为另一可供选择的方案,从含假勃姆石的成型体开始的煅烧也可以有利地用分步或连续的升高温度曲线在单一装置中进行,例如在马弗炉中进行。载体的机械性能和孔结构受假勃姆石与γ-Al2O3之比的影响。作为另一可供选择的方案,例如如EP-A 1 068 009中所述,成型也可以通过压片来进行。就压片而言,优选的实施方案包括如US-A 6 518 220中所述的圆顶环形压片。
催化剂活性组分分通常通过浸渍法施涂。α-氧化铝载体浸渍也可以例如如WO03/092887A1中所述进行。优选采用两步法进行浸渍,其中首先将氧化铝载体用铂化合物溶液浸渍,优选用硝酸铂溶液浸渍,干燥该催化剂并随后将其用锡化合物溶液浸渍,优选用氯化锡(II)溶液浸渍,随后将其干燥并煅烧。
有利的是,本发明催化剂磨耗小于5%。另外,有利的是,本发明催化剂的碎裂硬度超过10N。
催化剂有利地具有壳状轮廓。堆积密度有利地为0.3-2g/cm3,特别是0.6-1.2g/cm3。
本发明催化剂可以有利地用作氧化催化剂。在本发明的氧化方法中,含有氢气和烃的气体混合物与含氧气体在本发明氧化催化剂存在下进行反应。含氧气体优选含有至少80体积%的氧气,更优选为至少90体积%的氧气,特别是至少95体积%的氧气,每种情况均基于在STP下为气态的含氧气体,即不考虑用水蒸汽的任何额外稀释。如果适宜的话,也可以使用空气。通常在400-700℃、特别是在500-650℃的温度以及0.3-10巴、特别是0.4-1巴的压力下进行氧化反应。氧气与氢气的摩尔比通常为0.1∶1-1∶1,优选为0.2∶1-0.6∶1,特别是0.3∶1-0.45∶1。氢气与烃类的摩尔比有利的是0.01∶1-0.5∶1,特别是0.1∶1-0.3∶1。
其中可有利地使用本发明催化剂和本发明氧化方法的方法是烃类脱氢的方法,特别是烷基芳香烃脱氢的方法,特别有利的是乙苯脱氢成为苯乙烯。
脱氢反应有利地在多个串联反应器中进行,其中在两个脱氢反应器之间进行至少一个根据本发明的氧化方法或者将根据本发明的氧化方法并入到至少一个脱氢反应器中。
优选三个脱氢反应器串联排列,其中将本发明的氧化方法并入到流动方向上的第二个反应器中以及如果适宜的话并入到流动方向上的第三个反应器中。每个反应器中氧化催化剂床与脱氢催化剂床的体积比通常为0.1∶1-1∶1,优选为0.15∶1-0.6∶1,特别是0.2∶1-0.4∶1。
在一体化氧化催化剂的情况下,此氧化催化剂优选位于脱氢催化剂上游,即各个反应器中的反应气体首先流过氧化催化剂然后流过脱氢催化剂。优选使用径流反应器,在该反应器中氧化催化剂床和脱氢催化剂床同心排列并且如果适宜的话二者通过圆柱形筛网相互隔开。于是氧化催化剂用作两个同心近似中空的圆柱形床的内床。
烃类脱氢可以通过本领域技术人员熟知的所有方法进行。烷基芳香烃脱氢成为链烯基芳香烃优选用绝热或等温方法进行,特别是用绝热方法进行。通常,反应分布在多个串联的反应器,优选径流反应器(R)中。优选2-4个串联的反应器。每个反应器中设有含脱氢催化剂的固定床。脱氢催化剂通常是含氧化铁的催化剂。这些是本领域技术人员所熟知的并且描述于例如DE-A 101 54 718中。例如,如EP-A 1 027 928或EP-A 423 694中所述,脱氢催化剂(DC)优选使用的形式为实心圆柱体、星形挤出物或齿轮形挤出物。特别优选直径(横截面)为大约2-6mm、特别是2.5-4mm的棒状物(实心圆柱体)、直径为3-5mm的星形挤出物或直径为2.5-4mm的齿轮形挤出物。
在乙苯脱氢制备苯乙烯中,典型地是通过热交换器(HE)将乙苯(EB)与基于乙苯其有利用量为少于15重量%的水蒸汽(H2O)一起加热至大约500℃,并且恰在进入第一个反应器(R1)前与来自蒸汽过热器(SSH)的过热蒸汽进行混合,从而使得第一个反应器中所需的进口温度通常为600-650℃。进入第一个反应器中脱氢催化床的水蒸汽(全部水蒸汽)与乙苯的质量比有利地为0.7∶1-2.5∶1。优选使用的水蒸汽/乙苯之比为0.75∶1-1.8∶1,特别是0.8∶1-1.5∶1。当供入的氧气被水蒸汽稀释时,水蒸汽/乙苯之比也可以顺着随后反应阶段的方向而增加。该方法优选在减压下操作;典型的反应器压力为300-1000毫巴。液时空速(LHSV)基于包含脱氢催化剂的有效床体积(即:将任何极少有流体通过或没有流体通过的死区域减去了的床体积)通常为0.2-0.7/小时,优选为0.3-0.5/小时并特别是0.35-0.45/小时。优选流体在中空圆柱状催化剂床(径流反应器)中的流动是从内向外流动。
所用氧气(O2)与从在前反应器(R1)排出的氢气之摩尔比通常为0.1∶1-0.6∶1,优选为0.2∶1-0.5∶1,特别是0.3∶1-0.45∶1,以有利地实现在第二反应器(R2)中的氧化催化剂(OC)上有50-150℃、特别是70-130℃的温度升高。氧气可以以空气的形式供入或优选以用水蒸汽(H2O)稀释的富集形式供入以避免爆炸性混合物。所用氧气的浓度不考虑用任何水蒸气稀释的条件基于STP下为气态的含氧气体优选至少为80体积%,特别优选至少为90体积%并且特别是至少95体积%。
在进入第三个反应器(R3)前,将反应混合物通过热交换器(HE)中的过热蒸汽有利地恢复至通常600-650℃的温度。第三个反应器(R3)出口处的压力优选应该不超过700毫巴,特别优选不超过600毫巴并且特别是不超过500毫巴。作为另一可供选择的方案,也可以类似于在R2进口处热导入的方式在R3的进口处设置另一个本发明的氧化催化剂床代替热交换器,类似地加入氧气。
在水蒸汽和液态烃基本冷凝后离开工艺的气体(脱氢气体)中的二氧化碳的比例优选不超过20体积%,更优选不超过15体积%并特别是不超过10体积%。
在第三个反应器后,将产物流冷却并将气态产物和水相分开,并且通过蒸馏将剩余产物流分离为所需产物苯乙烯(ST)、未反应的原料乙苯以及作为副产物的苯、甲苯和高沸点物质。将反应产物混合物后处理之后,未反应的乙苯可以再循环。
取决于操作条件,全部三个反应阶段实现的总转化率为大约60-80%,特别是65-75%。苯乙烯选择性通常为大约95-98%。所形成的副产物主要是甲苯和苯,还有氢气、二氧化碳、一氧化碳、甲烷、乙烷和乙烯。
一个优选实施方案中所用的装置示意性地示于图1。热交换器的数目及其连接以简化形式显示;产物混合物的后处理没有显示。
本发明催化剂的优点在于尽管减少了活性催化剂质量但其具有高选择性。因此与现有技术催化剂相比,贵金属含量的减少提供了极大的经济性优点。
实施例:
A.制备氧化催化剂
通过类似于EP1 068 009B1中载体制备实施例的方法,将γ-氧化铝和假勃姆石的混合物挤出并随后煅烧至BET表面积为7m2/g,来制备实心圆柱形挤出物形式的α-氧化铝载体,该α-氧化铝载体的端面直径为4mm、吸水率为0.38cm3/g以及切削硬度为60N。将225g(250cm3)载体用86ml0.3134g硝酸铂的溶液(铂含量为57.52%)浸渍。两个小时后,在120℃下干燥该浸渍的催化剂载体。随后,将该催化剂用77ml 0.3427g二水合氯化锡(II)的溶液浸渍。接着将该催化剂在120℃下干燥并在500℃下煅烧3小时。
B.氧化催化剂的组成
99.84重量%的α-氧化铝
0.08重量%的铂
0.08重量%的锡
BET表面积为7m2/g
C.乙苯脱氢制成苯乙烯
将434ml如DE-A101 54 718的实施例8中所述的3mm挤出物形式的催化剂放置在具有三个串联的绝缘(绝热)管式反应器的三阶段反应装置的每个反应器中。第一和第三反应阶段的反应器各自装有用于流入气体的预热器。在第二个反应器中,在脱氢催化剂上方安置127ml的氧化催化剂床并通过10cm长的惰性滑石环床将其分隔开。氧化催化剂床完全处在反应器的绝缘(绝热)区域中。恰在氧化催化剂床上方通过喷枪将空气供入来自第一反应阶段的反应混合物中。(仅在实验规模上而不是在工业规模上用氮气稀释比用蒸汽稀释优选。)该装置在不引入空气的条件下逐渐增加载荷运行7天之后,从运行的第8天开始将空气引入第二个反应阶段。条件及第22天运行获得的结果总结于下表中:
反应阶段1的进口温度 | 611℃ |
贵金属催化剂上游反应阶段2的进口温度 | 大约525℃ |
贵金属催化剂下游反应阶段2的进口温度 | 606℃ |
反应阶段3的进口温度 | 613℃ |
反应阶段3之后的压力 | 460毫巴(绝对压力) |
LHSV | 0.37/h |
蒸汽/乙苯(EB) | 1.45kg/kg |
贵金属催化剂上游反应阶段2进口处引入的空气 | 59标准l/h |
反应阶段3之后EB的转化率 | 71.0% |
反应阶段3之后苯乙烯的选择性 | 96.6% |
脱氢气体中的CO2含量 | 4.22体积% |
Claims (10)
1.一种在烃类脱氢方法中用于将氢气氧化的催化剂,其中该催化剂包含负载在α-氧化铝上的基于催化剂总重量为0.01-0.1重量%的铂和0.01-0.1重量%的锡。
2.根据权利要求1的催化剂,其中铂和锡的重量比为1∶4-1∶0.2。
3.根据权利要求1或2的催化剂,其中该催化剂包含基于催化剂总重量为0.05-0.09重量%的铂和0.05-0.09重量%的锡。
4.根据权利要求1-3任意一项的催化剂,其中α-氧化铝的BET表面积为0.5-15m2/g。
5.根据权利要求1-4任意一项的催化剂,其中催化剂只包含负载在α-氧化铝上的铂和锡。
6.一种用于将氢气氧化的方法,其中在根据权利要求1-5中任意一项的氧化催化剂存在下,将含有氢气和烃的气体混合物与含氧气体进行反应。
7.根据权利要求6的方法,其中氧气与氢气之比为0.1∶1-1∶1。
8.一种烃类脱氢的方法,其中脱氢反应在多个串联的反应器中进行,并且在两个脱氢反应器之间进行至少一个根据权利要求6或7的氧化方法或者将该氧化方法并入到至少一个脱氢反应器中。
9.根据权利要求8的方法,其中使用三个串联的脱氢反应器,并将根据权利要求6或7的氧化方法并入到流动方向上的第二个脱氢反应器中以及如果适宜的话,并入到流动方向上的第三个脱氢反应器中。
10.根据权利要求8或9所述的方法,其中乙苯脱氢制成苯乙烯。
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CN110013759A (zh) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | 低温催化氧化处理含氢驰放气的装置及方法 |
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DE102005040286A1 (de) | 2005-08-25 | 2007-03-01 | Basf Ag | Mechanisch stabiler Katalysator auf Basis von alpha-Aluminiumoxid |
EP1986982A2 (de) * | 2006-02-15 | 2008-11-05 | Basf Se | Verfahren zur dehydrierung |
CN100372819C (zh) * | 2006-06-22 | 2008-03-05 | 华东理工大学 | 一种氢氧化制苯乙烯的反应方法 |
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CN102247843A (zh) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | 一种用于环烷烃脱氢铂基催化剂稳定性的改进方法 |
CN110013759A (zh) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | 低温催化氧化处理含氢驰放气的装置及方法 |
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CA2558547A1 (en) | 2005-10-20 |
RU2006137946A (ru) | 2008-05-10 |
US20080262281A1 (en) | 2008-10-23 |
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EP1732867A1 (de) | 2006-12-20 |
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