In this paper, we demonstrate CO₂ thermochemical reduction to CO in a La_0.9Ca_0.1FeO_3-δ oxygen ion transport membrane reactor. For process intensification, we also show that methane can be used on the sweep side, producing two streams: a CO stream from CO₂ reduction on the feed side, and a syngas stream on the other. We show that surface reactions are the rate-limiting steps for fuel-assisted CO₂ reduction on a flat LCF-91 membrane. To improve productivity, we study how that adding catalytic porous layers can accelerate these steps and hence, increase the CO₂-to-fuel conversion rates. Adding LCF-91 porous layers onto the membrane surface raised the oxygen flux by 1.4X. Secondly, different catalysts (Ce_0.5Zr_0.5O₂ on the feed side and (La_0.6Sr_0.4)_0.95Co_0.2Fe_0.8O₃ on the sweep side) were added onto the porous layers to further accelerate the surface reaction rates. As a result, the oxygen flux was further increased especially at lower temperatures, e.g., at 850°C, oxygen flux was raised by one order of magnitude as compared to the unmodified membrane. Process intensification was tested on the latter membrane configuration, and the syngas produced on the sweep side had a H₂:CO ratio very close to 2, ideal for production of fuels. Carbon species balance showed that higher methane concentration on the sweep side could lead to coke formation. Results also show that the selectivity to CO₂ near the membrane surface is higher than that at the reactor outlet due to the availability of lattice oxygen and the favorable water-gas shift reactions.

在本文中，我们证明了在La _0.9 Ca _0.1 FeO3 _-δ氧离子迁移膜反应器中将CO ₂热化学还原为CO 。对于工艺强化，我们还表明，可以在吹扫侧使用甲烷，产生两股物流：进料侧由CO ₂还原产生的CO物流，另一侧为合成气物流。我们表明，表面反应是在平坦的LCF-91膜上进行燃料辅助的CO ₂还原的限速步骤。为了提高生产率，我们研究了添加催化多孔层如何加速这些步骤，从而提高了CO _2-燃料转化率。将LCF-91多孔层添加到膜表面的氧气通量提高了1.4倍。其次，将不同的催化剂（进料侧的Ce _0.5 Zr _0.5 O ₂和吹扫侧的（La _0.6 Sr _0.4） _0.95 Co _0.2 Fe _0.8 O ₃ ）添加到多孔层上以进一步加速表面反应速率。结果，特别是在较低温度下，例如在850℃下，氧通量进一步增加，与未改性膜相比，氧通量提高了一个数量级。在后一种膜构型上测试了工艺强度，并且在吹扫侧产生的合成气具有H ₂：CO比非常接近2，非常适合生产燃料。碳物质平衡表明，吹扫侧较高的甲烷浓度可能导致焦炭形成。结果还表明，由于晶格氧的存在和有利的水煤气变换反应，膜表面附近对CO ₂的选择性高于反应器出口处的选择性。