Tackling irreversible catalyst deactivation: knowledge-driven design and operation of dynamic responsive methanation catalysts

解决不可逆催化剂失活：动态响应甲烷化催化剂的知识驱动设计和操作

• 批准号: 406911435
• 负责人: Professorin Dr. Tanja Franken
• 金额: --
• 依托单位: Lehrstuhl für Chemische Reaktionstechnik (CRT)
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/406911435?language=en
• 关键词: Tackling; irreversible; catalyst; deactivation; knowledge

The general objective of this project is to enable a holistic, fundamental yet mathematically manageable description of the methanation reaction under transient and potentially deactivating conditions taking forced changes of the catalyst into account. This objective is pursued for two different catalyst systems, the SPP’s industrial methanation reference catalyst (IMRC) and a novel dynamic responsive methanation (DRM) catalyst which holds potential to overcome irreversible deactivation of conventional Ni-based CO2 methanation catalysts. Therefore, this project combines synthesis, characterization and exploration of a spinel based DRM catalyst. Enabled by optimized reducibility of the material, the DRM catalyst developed in this project responds to externally applied forced changes by formation and reintegration of active Ni particles.Methods and results obtained in funding phase I for the SPP’s Ni/Al2O3 based IMRC will be extended for the DRM catalyst in phase II. For this, two dedicated experimental set-ups for spatially-resolved DRIFTS (SRD) operando analysis of species adsorbed on the catalyst surfaces as well as a dedicated kinetic set-up (KIN reactor) from phase I are utilized to validate and explore dynamic models that consider the change of active sites (deactivating or activating) during transient reaction conditions. A novel DRM catalyst will be synthetized and catalytically investigated in a catalytic performance (PER) test reactor which allows for the realization of highly transient reaction conditions by fast changes of applied gas mixtures. A thorough characterization of an ideal DRM catalyst by ex situ, in situ and operando methods within this consortium and in cooperation with further SPP2080 consortia allows to establish a solid state kinetic model, which can be integrated into the reaction kinetic model. This way, kinetic models of different complexity are established, including steady-state kinetic models, extensions of the latter for including mechanisms to describe catalyst deactivation and regeneration as well as dynamic kinetic models considering surface coverages for describing the reaction under transient conditions. On this model basis, optimization methods will be developed that reveal optimal operation policies to enable both, high methane yields and long term catalyst operation.The close collaboration of experts within this project consortium covering the areas “operando/spectroscopy” (A), ”kinetic modelling” (C), ”targeted material design” (D) and ”reactor concepts” (E) not only contributes to the description and understanding of catalysts under dynamic operation, but also contributes to a novel approach to exploit unwanted transients to enable enhanced long term performance of catalysts.

该项目的总体目标是在考虑催化剂的强制变化的情况下，对瞬态和潜在失活条件下的甲烷化反应进行整体、基本且数学上可管理的描述。这一目标是通过两种不同的催化剂系统实现的，即 SPP 的工业甲烷化参考催化剂 (IMRC) 和新型动态响应甲烷化 (DRM) 催化剂，该催化剂具有克服传统镍基 CO2 甲烷化催化剂不可逆失活的潜力。因此，该项目结合了基于尖晶石的 DRM 催化剂的合成、表征和探索。通过优化材料的还原性，该项目开发的 DRM 催化剂通过活性镍颗粒的形成和重新整合来响应外部施加的强制变化。在 SPP 基于 Ni/Al2O3 的 IMRC 的第一阶段资助中获得的方法和结果将扩展到第二阶段的 DRM 催化剂。为此，利用两个专用实验装置对催化剂表面吸附的物质进行空间分辨漂移（SRD）操作分析，以及第一阶段的专用动力学装置（KIN反应器）来验证和探索考虑瞬态反应条件下活性位点（失活或活化）变化的动态模型。新型 DRM 催化剂将在催化性能 (PER) 测试反应器中合成和催化研究，该反应器允许通过快速改变所应用的气体混合物来实现高度瞬态反应条件。该联盟内通过异位、原位和操作方法以及与其他 SPP2080 联盟的合作对理想 DRM 催化剂进行了彻底的表征，可以建立一个固态动力学模型，该模型可以集成到反应动力学模型中。这样，就建立了不同复杂性的动力学模型，包括稳态动力学模型、后者的扩展，包括描述催化剂失活和再生的机制，以及考虑表面覆盖的动态动力学模型，用于描述瞬态条件下的反应。在此模型的基础上，将开发优化方法，揭示最佳运行策略，以实现高甲烷产率和长期催化剂运行。该项目联盟内的专家密切合作，涵盖“操作/光谱学”(A)、“动力学建模”(C)、“目标材料设计”(D)和“反应器概念”(E)等领域，不仅有助于描述和理解动态运行下的催化剂， 而且还有助于开发一种利用不需要的瞬态来增强催化剂的长期性能的新方法。