The drastic rise in shale gas production has encouraged the quest for alternative uses of methane as a chemical feedstock in the manufacturing industry. While two-step syngas routes for methane valorization are deployed commercially, direct one-step routes for methane conversion are attracting much attention. As steam cracking installations have shifted from using oil-based naphtha to shale-based natural gas liquids, production of aromatics has dropped. Methane dehydroaromatization (MDA) is a one-step reaction capable of valorizing methane to hydrogen and benzene. Challenges with the MDA reaction are two-fold: the reaction is thermodynamically limited with low one-pass methane conversion and even the best catalytic systems, Mo/zeolites, suffer rapid deactivation from coking. A catalyst design strategy to improve stability is the use of multifunctional Mo-X/zeolite systems where X is a dopant capable of modulating the stability. In this paper we provide a complete overview of the main Mo-X/zeolite systems used in MDA and critically draw connections among the different types of dopants (X) employed, as a function of the role they play in the reaction/deactivation pathway. We have also dedicated a section to emerging trends with non-Mo based catalysts. The goal of this review article is to establish a basis that will facilitate the identification of useful multifunctional catalytic systems, and recognize gaps in the knowledge of these systems that deserve more attention. Improving MDA systems to the point to which they can be commercially deployed requires a multifaceted approach that combines optimization of the designs of both the catalyst and the reactor configuration. We therefore also provide a brief overview of the most recent advances in process intensification strategies employed with different reactor configurations.

页岩气产量的急剧上升促使人们寻求在制造工业中将甲烷作为化学原料的替代用途。虽然用于甲烷增值的两步合成气路线已在商业上部署，但用于甲烷转化的直接一步路线却引起了广泛关注。随着蒸汽裂化装置从使用油基石脑油转向使用页岩基天然气液体，芳烃的生产已下降。甲烷脱氢芳构化（MDA）是一步反应，能够将甲烷转化为氢和苯。MDA反应的挑战有两个方面：反应在热力学上受到限制，甲烷的单程转化率低，甚至最好的催化体系Mo /沸石也会因焦化而迅速失活。提高稳定性的催化剂设计策略是使用多功能Mo-X /沸石系统，其中X是能够调节稳定性的掺杂剂。在本文中，我们提供了MDA中使用的主要Mo-X /沸石系统的完整概述，并根据它们在反应/失活途径中所起的作用，严格地确定了所使用的不同类型掺杂剂（X）之间的联系。我们还专门介绍了非钼基催化剂的新兴趋势。这篇综述文章的目的是建立一个基础，以便利于识别有用的多功能催化系统，并认识到这些系统的知识空白值得更多关注。将MDA系统改进到可以商业应用的程度需要一种综合了催化剂和反应器构造的设计的多方面方法。因此，我们还简要概述了在不同反应堆配置中采用的工艺强化策略的最新进展。