CN101239332A - 蒸汽脱烷基化催化剂的再生方法和装置 - Google Patents

蒸汽脱烷基化催化剂的再生方法和装置 Download PDF

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CN101239332A
CN101239332A CNA2007101800907A CN200710180090A CN101239332A CN 101239332 A CN101239332 A CN 101239332A CN A2007101800907 A CNA2007101800907 A CN A2007101800907A CN 200710180090 A CN200710180090 A CN 200710180090A CN 101239332 A CN101239332 A CN 101239332A
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H·弗里茨
V·格克
M·蓬索
N·舍德尔
U·文宁
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Abstract

本发明描述了用于使具有至少6个碳原子的烃类馏份(C6+馏份)和/或具有至少7个碳原子的烃类馏份(C7+馏份)蒸汽脱烷基化的催化剂材料的再生方法以及用于实施该方法的装置，其中该催化剂材料位于从外部加热的装置中。为了从催化剂表面除去高分子碳而使该催化剂材料在该装置的至少一个区段内再生，使主要由水蒸汽和氢气组成的气体混合物通入该区段，同时将该装置的至少一个其他区段用于烃类馏份的蒸汽脱烷基化。该装置的各区段均具有独立的进料物质输入系统和反应产物输出系统。

Description

蒸汽脱烷基化催化剂的再生方法和装置
技术领域
本发明涉及用于使具有至少6个碳原子的烃类馏份(C6+馏份)和/或具有至少7个碳原子的烃类馏份(C7+馏份)在用于由含烃进料产生烃类的设备内进行蒸汽脱烷基化的催化剂材料的再生方法，其中所述催化剂材料位于从外部加热的装置中。
背景技术
在用于由含烃进料产生烃类的设备内产生由具有不同数量的碳原子及不同分子结构的烃类组成的混合物。将该混合物在用于由含烃进料产生烃类的设备内分离成单独的烃类产物。
取决于各种分离顺序及用于由含烃进料产生烃类的设备的类型，产生具有至少6个碳原子的烃类馏份(C6+馏份)和/或具有至少7个碳原子的烃类馏份(C7+馏份)。这些馏份含有芳烃作为可经济使用的产物，其用作合成许多塑料的起始物质，并用于提高汽油的抗爆值。
为了获得C6+馏份的可经济使用的产物，特别是苯，并实现尽可能最大的产率，根据现有技术采用以下方法。将C6+馏份分离成主要由具有6个碳原子的烃类组成的馏份(C6馏份)及C7+馏份。由C6馏份可以直接分离出可经济使用的产物苯。利用液-液萃取由C7+馏份分离出直链烃，并作为所谓的萃余液进一步加工。由直链烃释放的C7+馏份现在主要含有具有7至8个碳原子的芳烃，并分离成主要由具有7个碳原子的烃类组成的馏份(主要是甲苯)以及主要由具有8个碳原子的烃类组成的馏份(主要是二甲苯)。该主要由具有8个碳原子的烃类组成的馏份作为进料物质输送至用于获得对二甲苯的过程。该主要由具有7个碳原子的烃类组成的馏份作为进料输送至用于氢脱烷基化的过程。
例如WO 2005/071045描述了此类用于氢脱烷基化的方法。在存在催化剂的情况下于400℃至650℃的温度及20巴至40巴的压力下使烃类与氢气接触，其中氢气以烃类的3至6倍摩尔过量存在。在这些条件下，从各种经烷基化的芳烃(例如甲苯)分解掉烷基，从而形成苯及各种烷烃(例如甲烷)。
在烃类的氢脱烷基化期间氢气的消耗对于这些根据现有技术用于获得苯的方法的经济性具有负面影响。
在一个选择性的方法中，对C6+馏份和/或C7+馏份实施蒸汽脱烷基化(例如参见已提交的德国专利申请DE 10 2006 058 528.3或DE 10 2006058 529.1)。在对C6+馏份和/或C7+馏份实施蒸汽脱烷基化时，除了诸如一氧化碳和二氧化碳的反应产物以外，主要产生两种可利用的产物苯和氢气。因此在生产所期望的有价值的产物苯和有价值的副产物氢气的同时仅需要廉价的水蒸汽作为蒸汽脱烷基化的进料物质。
在该根据现有技术的方法中，来自各种烃类馏份的烃类与水蒸汽在气相中于固体催化剂上反应。在此，烃类和水蒸汽在诸如管的装置内于固体催化剂上经过，其中催化剂位于该装置的内部，例如管内部。该装置从外部输入蒸汽脱烷基化所需的反应热，例如通过使气态反应副产物一氧化碳和甲烷与空气燃烧。根据现有技术，进料物质的温度对应于反应产物的温度，并且在400℃至600℃的范围内。该装置内部的催化剂材料主要由以下物质组成：多孔载体材料，如γ-Al2O3、镁铝尖晶石和/或Cr2O3，以及位于载体材料表面上的活性组份，如负载量(Beladung)为0.1至1.0重量％的Rh和/或负载量为0.2至2.0重量％的Pd。由蒸汽脱烷基化的气态反应产物在预先压缩之后经过压力交换吸附而将可经济地利用的氢气与诸如一氧化碳、二氧化碳及甲烷的反应副产物分离。
进料物质在催化剂材料的活性催化中心上发生反应时，除了原本的反应产物以外，还形成一定含量的高分子碳化合物，其部分地作为沉积物残留在催化剂材料上。沉积的高分子碳化合物阻碍催化剂表面上用于吸附起始反应物的可能性，从而导致随时间增大地钝化(积炭)。在此，积炭速度的一次近似与气相内的烃类分压呈线性关系。
积炭过程是可逆的。根据现有技术，以几周的间隔通过输入氧气或含氧气体以进行燃烧而由如此积炭的催化剂材料除去沉积物，从而使催化剂材料再生。作为燃烧的替代方案，可以对催化剂材料用由水蒸汽和氢气组成的进料物质进行吹气，从而同样从催化剂材料除去碳沉积物。该方法由于形成局部非常热的位点而需要小心操作(schonender)，因而对催化剂的寿命产生积极影响。用于使催化剂材料再生的两种方法，均必须中止输入烃类馏份，因而中止所期望的有价值的产物苯的生产。所述用于使催化剂材料再生而导致的中止生产会对该方法的运行成本产生负面影响。
发明内容
因此，本发明的目的是提供避免用于使催化剂材料再生而导致的中止生产并且使方法的运行成本最小化的方法以及用于实施该方法的装置。
该目的是通过如下方式解决的：为了从催化剂表面除去高分子碳而使催化剂材料在装置的至少一个区段内再生，将主要由水蒸汽和氢气组成的气体混合物通入该区段，同时将装置的至少一个其他区段用于烃类馏份的蒸汽脱烷基化，其中各个区段均可单独地通入不同的进料物质。
具体实施方式
由于该装置的各个区段中相互独立地流动，总是可以将该装置的一部分用于蒸汽脱烷基化，同时在该装置的一部分内通过通入由水蒸汽和氢气组成的气体混合物而使催化剂材料再生。因此无需为了催化剂材料的再生而中止生产。
有利地，将其中通入主要由水蒸汽和氢气组成的气体混合物以进行再生的区段的产物与用于烃类馏份的蒸汽脱烷基化的区段的产物混合。除了反应产物氢气、一氧化碳、二氧化碳和甲烷以外，还产生已脱烷基化的芳烃和对应的烷烃作为蒸汽脱烷基化的产物。用主要由水蒸汽和氢气组成的气体混合物使催化剂材料再生时，高分子碳沉积物从催化剂表面脱落，从而使产品流中的再生过程重新恢复。在此通过使碳含量高的沉积物气化而特别产成也存在于通常的产品流中的组份一氧化碳、二氧化碳、氢气和甲烷，以及在小范围内的其他低分子烃类。因此，来自该区段的产品流的组成是相似的，并且可以通入一个共同的分离系统，从而将化学计量数过量的用于再生的氢气残留在该设备内。由含碳的高分子沉积物的水蒸汽气化过程额外地产生氢气。
针对性地在用于蒸汽脱烷基化的装置内产生用于再生的氢气，并且在多级压缩过程之后通过压力交换吸附法从主要由氢气、一氧化碳、二氧化碳和甲烷组成的蒸汽脱烷基化的气态反应产物分离出，并且至少部分地应用于催化剂材料的再生。
用于使催化剂材料再生的气体混合物中的水和氢气的含量优选可随时间改变地与该装置的工作条件相匹配。通过使水和氢气的含量随时间可变地与各个区段的各种工作条件(再生或脱烷基化，压力、温度)相匹配，而可以在消耗进料物质少的情况下实现最佳的再生过程。
有利地，在该装置的至少一个区段内进行再生的情况下，使该装置的加热设备的总的热功率与改变的热需求相匹配。在本发明的一个特别优选的实施方案中，在该装置的至少一个区段内进行再生的情况下，局部匹配该装置的加热设备的热功率，其中减小进行再生的区段的范围内的热功率。
在装置方面，所述目的是通过如下方式解决的：将该装置分成至少2个装填有催化剂材料的具有独立的进料输入系统和产物输出系统的区段，从而在这些区段中相互独立地通入进料物质。因此通过相应的控制系统可以选择在哪些区段中通入蒸汽脱烷基化的进料物质并因此用于形成产物，以及在哪些区段中通入主要由水蒸汽和氢气组成的气体混合物而使催化剂材料再生。
装填有催化剂材料的区段有利地包括至少一条管线，优选包括至少一个管线组。
通过本发明能够避免尤其是用于使催化剂材料再生而导致的中止生产，从而使运行成本最小化。在该装置的各个区段中进行独立流动的额外投资成本是低的。

Claims (10)

1、用于使具有至少6个碳原子的烃类馏份(C6+馏份)和/或具有至少7个碳原子的烃类馏份(C7+馏份)在用于由含烃进料产生烃类的设备内进行蒸汽脱烷基化的催化剂材料的再生方法，其中该催化剂材料位于从外部加热的装置中，其特征在于，为了从催化剂表面除去高分子碳而使该催化剂材料在该装置的至少一个区段内再生，使主要由水蒸汽和氢气组成的气体混合物通入该区段，同时将该装置的至少一个其他区段用于烃类馏份的蒸汽脱烷基化，其中各区段均具有独立的进料物质输入系统和反应产物输出系统。
2、根据权利要求1所述的方法，其特征在于，将其中通入主要由水蒸汽和氢气组成的气体混合物以进行再生的区段的产物与用于烃类馏份的蒸汽脱烷基化的区段的产物混合。
3、根据权利要求1或2所述的方法，其特征在于，在用于蒸汽脱烷基化的装置内产生用于再生的氢气。
4、根据权利要求1至3之一所述的方法，其特征在于，在多级压缩过程之后通过压力交换吸附法从主要由氢气、一氧化碳、二氧化碳和甲烷组成的蒸汽脱烷基化的气态反应产物分离出气态氢，并且至少部分地应用于所述催化剂材料的再生。
5、根据权利要求1至3之一所述的方法，其特征在于，用于使所述催化剂材料再生的气体混合物中的水和氢气的含量与所述装置的工作条件相匹配。
6、根据权利要求1至5之一所述的方法，其特征在于，在所述装置的至少一个区段内进行再生的情况下，使所述装置的加热设备的总的热功率随时间改变地与改变的热需求相匹配。
7、根据权利要求1至6之一所述的方法，其特征在于，在所述装置的至少一个区段内进行再生的情况下，局部匹配所述装置的加热设备的热功率，其中减小进行再生的区段的范围内的热功率。
8、适合于使具有至少6个碳原子的烃类馏份(C6+馏份)和/或具有至少7个碳原子的烃类馏份(C7+馏份)蒸汽脱烷基化的装置，该装置从外部加热并装填有固体催化剂材料，其特征在于，将该装置分成至少2个装填有该催化剂材料的具有独立的进料输入系统和产物输出系统的区段，从而在这些区段中相互独立地通入进料物质。
9、根据权利要求8所述的装置，其特征在于，装填有所述催化剂材料的区段包括至少一条管线。
10、根据权利要求8或9所述的装置，其特征在于，装填有所述催化剂材料的区段包括至少一个管线组。
CNA2007101800907A 2007-01-26 2007-12-26 蒸汽脱烷基化催化剂的再生方法和装置 Pending CN101239332A (zh)

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