Abstract The reduction reaction of copper oxide with CH4 is highly exothermic and can be arranged to generate sufficient heat to in-situ calcine calcium carbonate and produce a highly concentrated stream of CO2. This concept is tested at TRL4 in a packed-bed reactor operated close to adiabatic conditions. The impact of the initial solids temperature and the inlet flowrate of the gases is evaluated. A 50/50 (vol.%) mixture of methane and hydrogen (i.e., a possible composition of the PSA-off gas generated in a reforming process) has also been used as reducing gas. The presence of H2 reduces the CuO/CaCO3 proportion required in the bed and promotes the calcination at temperatures lower than 870 °C. The experimental measurements are well predicted by a one-dimensional fixed-bed reactor model, in which the steam methane reforming, water–gas-shift, carbon deposition and carbon gasification reactions are also considered. Different characterization techniques (i.e., SEM, XRD, N2 adsorption, TPR) demonstrate that both commercial CuO- and CaO-based materials show good stability after successive cyclic experiments.

中文翻译：

---

CH4还原氧化铜煅烧碳酸钙的实验测试和模型验证

摘要 氧化铜与 CH4 的还原反应是高度放热的，可以安排产生足够的热量来原位煅烧碳酸钙并产生高浓度的 CO2 流。这个概念在接近绝热条件下运行的填充床反应器中的 TRL4 进行了测试。评估初始固体温度和气体入口流速的影响。甲烷和氢气的 50/50 (vol.%) 混合物（即重整过程中产生的 PSA 废气的可能组成）也已用作还原气体。H2 的存在降低了床中所需的 CuO/CaCO3 比例，并促进了在低于 870 °C 的温度下的煅烧。一维固定床反应器模型很好地预测了实验测量结果，其中蒸汽甲烷重整、水煤气变换、还考虑了碳沉积和碳气化反应。不同的表征技术（即 SEM、XRD、N2 吸附、TPR）表明商业 CuO 和 CaO 基材料在连续循环实验后都表现出良好的稳定性。