Catalytic CO₂ methanation technology can be improved by process intensification, i.e. enabling higher energy efficiency and process sustainability. Here, thin-film composite membranes (TFCM) were developed for in-situ water removal in a catalytic membrane reactor (CMR) for the Sabatier process. The selective separation layer (1.4 μm-thick) of the composite membrane is made of the polyimide 6FDA-6FpDA, a glassy polyimide, which exhibits high permeability and selectivity together with stable function at unprecedented high temperatures (>200 °C), compared to polyimides reported until now (90 °C), thus matching the temperature range of Sabatier reactors. Remarkably, TFCM developed in this work, allow to extract an outstanding amount of water up to 1 m³/(m²·h·bar) at 260 °C. TFCM was implemented for the water removal from the methanation reaction in a CMR operated at 260 °C and using Ni-Todorokite as catalyst. The TFCM-mediated water-extraction enabled to raise both catalytic stability and activity during CMR operation. CO₂ conversion stability was greatly improved exhibiting a conversion value of 72 % during the course of the reaction (21 % increase in CO₂ conversion), with a water removal of 12.5 % and specific flux of ∼100 g·h⁻¹ m⁻².

催化CO ₂甲烷化技术可以通过工艺强化来改进，即实现更高的能源效率和工艺可持续性。在这里，薄膜复合膜 (TFCM) 被开发用于在催化膜反应器 (CMR) 中用于 Sabatier 工艺的原位除水。复合膜的选择性分离层（1.4 μm 厚）由聚酰亚胺 6FDA-6FpDA 制成，这是一种玻璃状聚酰亚胺，具有高渗透性和选择性以及在前所未有的高温（> 200 °C）下的稳定功能，与迄今为止报道的聚酰亚胺 (90 °C)，因此与 Sabatier 反应器的温度范围相匹配。值得注意的是，在这项工作中开发的 TFCM 可以提取高达 1 m 的大量水³ /(m ² ·h·bar) 在 260 °C。TFCM 用于在 260 °C 下操作并使用 Ni-Todorokite 作为催化剂的 CMR 中从甲烷化反应中去除水。TFCM 介导的水提取能够在 CMR 操作期间提高催化稳定性和活性。CO ₂转化稳定性大大提高，在反应过程中表现出 72 % 的转化值（CO ₂转化率增加 21 % ），水去除率为 12.5 %，比通量为~100 g·h ^-1 m ^{- 2} .