低碳烷烃脱氢Pt系催化剂的研究进展

低碳烷烃脱氢Pt系催化剂由于活性较高且对环境友好等优点而被广泛研究。从催化剂的助剂、载体以及制备方法三个方面,综述了近五年的低碳烷烃脱氢Pt系催化剂的研究进展,并对Pt系催化剂未来的研究方向进行了展望。     

低碳烷烃催化脱氢催化剂的专利概况及Pt系催化剂发展路线

介绍了低碳烷烃催化脱氢领域Pt系催化剂和Cr系催化剂的专利概况,重点分析了UOP、BASF、中国石化、法国石油研究院和康菲石油等跨国石油公司的Pt系催化剂的发展路线,以期给研发方向提供启示。同时指出国内公司也应及时跟踪该领域的最新研究进展,做好专利布局。     

铂系低碳烷烃脱氢催化剂研究进展

综述了近年来国内外铂系低碳烷烃脱氢催化剂的技术现状与研究进展。首先从热力学角度论述了低碳烷烃脱氢反应与相关副反应的反应机理,随后分别从活性位点性能与催化脱氢的关系,氧化铝、分子筛等载体的作用,以及锡、碱金属、碱土金属、过渡金属等助剂改性对催化剂的影响等3个方面分析了铂系低碳烷烃脱氢催化剂的优势与存在的问题,进而探究了铂系脱氢催化剂的失活原因。最后对铂系脱氢催化剂的研究前景做了展望,提出该系列催化剂的主要发展方向包括降低贵金属铂的负载量、提高催化剂的稳定性、减少积炭副反应等。     

一种低碳烷烃脱氢催化剂及其制备方法

<正>申请号:201610252805.4申请日:2016-04-22申请人:中国石油化工股份有限公司;中国石油化工股份有限公司抚顺石油化工研究院本发明公开了一种低碳烷烃脱氢催化剂及其制备方法。该催化剂具有如下性质:以多级孔ZSM-5分子筛和氧化铝为载体,Pt为活性组分,Sn和Na为助剂。低碳烷烃脱氢催化剂的制备方法,包括如下内容:(1)制备多级孔ZSM?5分子筛,然后进行铵处理;(2)将上述多级孔ZSM?5分子筛与氧化铝、田菁粉和稀硝酸溶液混合,经过打浆、混捏、挤条后,     

硼基材料催化低碳烷烃氧化脱氢制烯烃研究进展

以氮化硼为代表的硼基材料在低碳烷烃氧化脱氢反应中显示出高的催化活性和优异的烯烃选择性,已在国际上形成新的研究热点。本文主要综述了近年来硼基材料催化低碳烷烃氧化脱氢的研究进展,阐述了不同硼基催化剂（h-BN、SiB₆、BC₄、硼单质等）对氧化脱氢烯烃选择性的影响,结合多种谱学（IR、XPS、NMR、SVUV-PIMS等）、动力学（分压、同位素效应、同位素标记等）证据和理论计算,探讨了硼基催化剂表面三配位的硼氧物种（B—OH/B—O）是引发烷烃氧化脱氢生成烯烃的活性位,主要遵循表面和气相自由基反应机理。总结了硼基催化材料氧化脱氢中存在的机遇和挑战,提升烯烃选择性是材料设计合成的主要方向,并提出后续硼基催化材料理性设计和实际应用的一些参考建议。     

长链烷烃（n-C10~13）脱氢制单烯烃催化剂的研究Ⅰ.氧化铝载体孔结构对催化剂性能的影响

通过n-C_10～13烷烃脱氢反应考察了氧化铝载体孔结构对长链烷烃脱氢催化剂性能的影响,结果表明,氧化铝载体的总孔容对催化剂影响不大,而有效孔容（孔径分布）影响催化剂的反应性能。小孔对载体的比表面积起主要作用,并影响催化剂的Pt分散度;大孔为催化剂金属位的积炭迁移提供有效空间。Pt与载体的强相互作用对提高催化剂的活性和稳定性有利。     

丁烷脱氢工艺及催化剂研究进展

C₄烯烃作为石油化工和聚合物行业的基础原料被广泛用于合成橡胶、塑料和特种燃料等的生产。由低碳烷烃向C₄烯烃的转化,不仅可以有效缓解我国低碳烯烃紧缺的难题,而且可以大大提升低碳烷烃的附加值。综述近年来国内外丁烷催化脱氢的技术现状与研究进展,重点论述正丁烷脱氢反应的机理、催化剂活性组分、载体及助剂对催化脱氢性能的影响,概述脱氢催化剂的失活原因,并对丁烷脱氢催化剂的研究前景进行展望。     

低碳烷烃选择性氧化高分散活性位催化剂的研究进展

石油资源的过渡消耗导致化工原料短缺危机,低碳烷烃选择性氧化可以有效缓解危机并降低化工原料成本。高分散活性位催化剂在低碳烷烃选择性氧化反应中具有特殊催化作用和广阔的应用前景,在石油化工行业发展中具有巨大的潜能。基于国内外研究者在高分散活性位催化剂用于低碳烷烃选择性氧化领域的研究工作,介绍高分散活性位催化剂的制备方法,总结低碳烷烃选择性氧化高分散活性位催化剂体系,分析低碳烷烃选择性氧化反应机理。重点评述钒基、钼基和铁基高分散活性位催化剂用于低碳烷烃选择性氧化反应的催化性能及反应机理。并对高分散活性位催化剂在低碳烷烃选择性氧化中存在的问题、发展趋势和应用前景进行总结和展望。     

低碳烷烃循环流化床脱氢工艺条件优化

针对PBD型脱氢催化剂,采用循环流化床中试装置对低碳烷烃(丙烷、异丁烷、正丁烷)单独脱氢以及不同配比混合低碳烷烃进行了较为系统的工艺条件优化研究。结果表明,反应温度和空速对低碳烷烃脱氢过程的影响至关重要,不同脱氢原料具有不同的适宜操作工况,其中丙烷脱氢在600℃和1 700 h~(-1)条件下,转化率为39%,丙烯收率达33%;异丁烷脱氢在580℃和1 700 h~(-1)条件下,转化率为48%,异丁烯收率为45%;正丁烷脱氢在580℃和1 700 h~(-1)条件下,转化率为40%,丁烯收率高达32%。PBD型催化剂对于不同配比混合低碳烷烃具有较高的催化活性。最终获得的不同脱氢原料适宜的操作工况下,可以为循环流化床低碳烷烃脱氢装置的工程设计与放大和工业装置的生产调优提供基础数据与理论支持。     

低碳烷烃催化转化制取低碳烯烃反应工艺的研究进展

低碳烷烃催化转化制取低碳烯烃可以大大提高低碳烷烃的附加值,因此,受到石油化工和催化领域的广泛关注。对近年来国内外有关低碳烷烃选择氧化制烯烃、低碳烷烃催化裂解制烯烃以及低碳烷烃催化脱氢制烯烃等催化反应过程的催化剂体系、反应工艺流程和催化反应器的设计等方面的研究进展进行评述,并对该领域的研究发展方向作了展望。     

Alkane metathesis by tandem alkane-dehydrogenation-olefin-metathesis catalysis and related chemistry

Methods for the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels that are both efficient and economically viable could greatly enhance global security and prosperity. Currently, the major route to convert natural gas and coal to liquids is Fischer-Tropsch catalysis, which is potentially applicable to any source of synthesis gas including biomass and nonconventional fossil carbon sources. The major desired products of Fischer-Tropsch catalysis are n-alkanes that contain 9-19 carbons; they comprise a clean-burning and high combustion quality diesel, jet, and marine fuel. However, Fischer-Tropsch catalysis also results in significant yields of the much less valuable C(3) to C(8)n-alkanes; these are also present in large quantities in oil and gas reserves (natural gas liquids) and can be produced from the direct reduction of carbohydrates. Therefore, methods that could disproportionate medium-weight (C(3)-C(8)) n-alkanes into heavy and light n-alkanes offer great potential value as global demand for fuel increases and petroleum reserves decrease. This Account describes systems that we have developed for alkane metathesis based on the tandem operation of catalysts for alkane dehydrogenation and olefin metathesis. As dehydrogenation catalysts, we used pincer-ligated iridium complexes, and we initially investigated Schrock-type Mo or W alkylidene complexes as olefin metathesis catalysts. The interoperability of the catalysts typically represents a major challenge in tandem catalysis. In our systems, the rate of alkane dehydrogenation generally limits the overall reaction rate, whereas the lifetime of the alkylidene complexes at the relatively high temperatures required to obtain practical dehydrogenation rates (ca. 125 -200 °C) limits the total turnover numbers. Accordingly, we have focused on the development and use of more active dehydrogenation catalysts and more stable olefin-metathesis catalysts. We have used thermally stable solid metal oxides as the olefin-metathesis catalysts. Both the pincer complexes and the alkylidene complexes have been supported on alumina via adsorption through basic para-substituents. This process does not significantly affect catalyst activity, and in some cases it increases both the catalyst lifetime and the compatibility of the co-catalysts. These molecular catalysts are the first systems that effect alkane metathesis with molecular-weight selectivity, particularly for the conversion of C(n)n-alkanes to C(2n-2)n-alkanes plus ethane. This molecular-weight selectivity offers a critical advantage over the few previously reported alkane metathesis systems. We have studied the factors that determine molecular-weight selectivity in depth, including the isomerization of the olefinic intermediates and the regioselectivity of the pincer-iridium catalyst for dehydrogenation at the terminal position of the n-alkane. Our continuing work centers on the development of co-catalysts with improved interoperability, particularly olefin-metathesis catalysts that are more robust at high temperature and dehydrogenation catalysts that are more active at low temperature. We are also designing dehydrogenation catalysts based on metals other than iridium. Our ongoing mechanistic studies are focused on the apparently complex combination of factors that determine molecular-weight selectivity.     

丙烷脱氢制丙烯催化剂研究进展

丙烷作为天然气和页岩气等的重要成分,其高效催化转化不仅具有重要的理论研究意义,而且具有广阔的应用前景.丙烷直接脱氢制丙烯已成为增产丙烯的有效手段.对丙烷脱氢反应的铂基催化剂、铬基催化剂、碳基催化剂以及钒基催化剂进行综述,重点介绍载体及助剂对铂基及铬基催化剂活性和稳定性的影响,并提出目前丙烷脱氢反应催化剂研究的关键问题,...     

Dehydrogenation of C3–C4 paraffin's to corresponding olefins over slit-SAPO-34 supported Pt-Sn-based novel catalyst

The objective of this work is to discuss the performance of Pt-Sn/slit-SAPO-34 novel catalyst for selective C₃–C₄ dehydrogenation to corresponding light olefins. The metallic contents, acidity, active metallic sites and metallic dispersion were determined using a number of physico-chemical techniques as it gives a justification for superior catalytic activity for dehydrogenation reaction. The Pt-Sn/slit-SAPO-34 catalyst was analyzed for dehydrogenation activity under optimized operating conditions; at atmospheric pressure, hydrogen to alkane (feed) molar ratio is 0.2, weight hourly space velocity 5 h^?1 and temperature 585 °C. Around 40% light alkane conversion and above 95% of total olefins selectivity with 94% propene, 92% n-butene and about 84% iso-butene selectivity were achieved over Pt-Sn/slit-SAPO-34 novel catalyst. The catalyst was parametrically characterized over the above said operating conditions and effects of operating conditions on product distribution were discussed. The coke formation was inherently related to catalyst activity in dehydrogenation reaction and related to surface intermetallic ensemble effects; and ultimately the prominent stakeholder in catalyst deactivation. The novel catalysts also showed very good hydrothermal stability in a continuous reaction–regeneration cycles due to silica-based acidic structure of support. The results obtained over Pt-Sn/slit-SAPO-34 novel catalyst were compared with other Pt-Sn-based ZSM-5 and SAPO-34 supported catalysts of similar active metallic content under identical operating conditions.     

Efficient Heterogeneous Dual Catalyst Systems for Alkane Metathesis

A fully heterogeneous and highly efficient dual catalyst system for alkane metathesis (AM) has been developed. The system is comprised of an alumina‐supported iridium pincer catalyst for alkane dehydrogenation/olefin hydrogenation and a second heterogeneous olefin metathesis catalyst. The iridium catalysts bear basic functional groups on the aromatic backbone of the pincer ligand and are strongly adsorbed on Lewis acid sites on alumina. The heterogeneous systems exhibit higher lifetimes and productivities relative to the corresponding homogeneous systems as catalyst/catalyst interactions and bimolecular decomposition reactions are inhibited. Additionally, using a “two‐pot” device, the supported Ir catalysts and metathesis catalysts can be physically separated and run at different temperatures. This system with isolated catalysts shows very high turnover numbers and is selective for the formation of high molecular weight alkanes.     

空心微球氧化铝负载Pt-In催化异丁烷脱氢研究

针对异丁烷脱氢催化剂存在容易烧结与积碳的问题,开发了采用水热法制备的2种不同形貌的Al₂O₃载体,将其负载Pt-In获得的催化剂用于异丁烷脱氢反应中,研究其对异丁烷脱氢催化行为的影响。借助XRD、SEM、TEM、NH₃-TPD、XPS、TG-DTA及低温N₂吸-脱附法对催化剂进行物化性能研究。结果表明:由纳米片构建的多孔空心微球氧化铝负载Pt-In催化剂具有较小的Pt纳米粒子、低的比表面积、强的Pt-In相互作用、高的In³⁺/In⁰比例且缺少强酸位,从而获得优异的异丁烷脱氢性能,其异丁烯选择性和产率高达93.5%和40.3%,同时异丁烷转化率可稳定在43.0%,反应后的金属颗粒无聚集烧结现象,表现出优异的抗烧结和积碳性能。     

Pt-Sn-Li/Al2O3/FeCrAl催化剂的制备、表征和长链烷烃脱氢催化性能

以FeCrAl合金薄片为基体,Pt-Sn-Li/γ-Al₂O₃为活性涂层,制备了Pt-Sn-Li/Al₂O₃/FeCrAl金属基复合载体负载型催化剂。采用XRD、SEM、TPR等手段对催化剂进行了表征,并在微型固定床反应器中考察了不同反应温度、液时空速和氢/烃摩尔比下对长链烷烃脱氢的催化性能。结果表明,将活性浆料直接涂覆于焙烧后的金属薄片上制得的催化剂有良好的结合性能,经超声波振荡后涂层脱落率小于2%。当Pt-Sn-Li/γ-Al₂O₃活性涂层涂覆到FeCrAl金属基体后复合载体Al₂O₃/FeCrAl与活性成分的相互作用明显增强。催化反应性能评价表明,较高的反应温度有利于长链烷烃脱氢过程,但温度过高时将加速催化剂积炭失活。较低的空速有利于十二烷的转化,但进一步减小空速将造成十二烯的选择性明显降低。减小氢/烃摩尔比虽然有利于提高十二烷的转化率,但进一步减小氢/烃摩尔比也将加速催化剂积炭失活。     

GS-10/GS-08乙苯脱氢催化剂在燕山石化的工业应用

报道了GS-10催化剂的性能和GS-10/GS-08组合催化剂在燕山石化苯乙烯工业装置上的应用,应用结果标明GS-10/GS-08催化剂组合具有活性高、选择性好和使用寿命长的特点,工业装置上乙苯转化率在76%左右,苯乙烯选择性保持在95%以上,超过工业试验合同要求值。综合性能优良。     

基于Cu基催化剂的二乙醇胺脱氢工艺的研究进展

基于Cu基催化剂在二乙醇胺脱氢工艺中易氧化、易烧结的研究现状,介绍了二乙醇胺脱氢制备亚氨基二乙酸的机理。探讨了Cu基催化剂载体、助剂及微观形态对催化性能的影响。指出未来二乙醇胺脱氢工艺的发展方向不仅需要选择高效催化剂,生产工艺也应由间歇式反应向连续化反应发展。简单介绍了国内外二乙醇胺脱氢在生产工艺上的发展,最后对Cu基催化剂的改性以及二乙醇胺脱氢的连续化生产工艺提出了新思路。     

异丁烷催化脱氢反应机理与失活动力学研究进展

异丁烯是化工行业重要的基础原料,国内外对异丁烯的需求量逐年递增。仅靠石油催化裂解已无法满足对异丁烯的需求,开展异丁烷脱氢制异丁烯工艺的研究备受关注。综述Cr系异丁烷脱氢催化剂的研究进展,探讨Cr系催化剂的活性中心以及发生在活性中心上的多种反应机理和相应的动力学模型,详述催化剂的失活机理,总结积炭的形成过程,指出Cr系异丁烷催化脱氢反应和失活机理以及相关动力学方面研究的不足,并对未来研究前景进行展望。