Liu Ziyang, Bai Peng, Xu Benjing, Wu Pingping, Wu Hao, Sun Haoran, Li Junji, Yan Zifeng
State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao, 266580, China.
Dalton Trans. 2025 Mar 4;54(10):4255-4266. doi: 10.1039/d4dt03391d.
In the utilisation of most oxide-based propane dehydrogenation (PDH) catalysts, each reaction-regeneration cycle necessitates both coke combustion and hydrogen reduction to achieve complete regeneration of the catalyst. However, the need for hydrogen reduction makes it difficult to use such catalysts in chemical looping oxidative dehydrogenation (CL-ODH) processes. This study prepared a series of CrZrO catalysts with Cr/Zr atomic ratios ranging from 0.02 to 1 using a co-precipitation method. Electron paramagnetic resonance (EPR) analysis revealed that the catalyst surface in its oxidised state is rich in oxygen vacancies. These vacancies created numerous coordinated unsaturated Zr (Zr)-based active sites directly linked to the catalyst's unique catalytic activity. This catalyst was paired with a CuMnO@NaWO oxygen carrier to perform the CL-ODH of propane. The results demonstrated that the catalyst-oxygen carrier coupling system significantly enhanced single-pass propane conversion in the PDH process, increasing the initial propane conversion from 27.2% to 35.9%. The enhanced conversion, along with the observed hydrogen consumption over time, confirmed that the PDH process was coupled with hydrogen oxidation the lattice oxygen of the oxygen carrier. This coupling broke through the thermodynamic equilibrium, thereby significantly improving the single-pass propane conversion. These findings provide valuable insights for designing novel catalyst systems tailored for the CL-ODH of propane.
在大多数基于氧化物的丙烷脱氢(PDH)催化剂的使用中,每个反应 - 再生循环都需要进行焦炭燃烧和氢气还原,以实现催化剂的完全再生。然而,氢气还原的需求使得此类催化剂难以用于化学链氧化脱氢(CL - ODH)过程。本研究采用共沉淀法制备了一系列Cr/Zr原子比在0.02至1之间的CrZrO催化剂。电子顺磁共振(EPR)分析表明,处于氧化态的催化剂表面富含氧空位。这些空位产生了许多与催化剂独特催化活性直接相关的配位不饱和Zr基活性位点。该催化剂与CuMnO@NaWO氧载体配对,用于进行丙烷的CL - ODH。结果表明,催化剂 - 氧载体耦合系统显著提高了PDH过程中丙烷的单程转化率,使初始丙烷转化率从27.2%提高到35.9%。转化率的提高以及观察到的随时间的氢气消耗证实,PDH过程与氧载体的晶格氧的氢氧化反应相耦合。这种耦合突破了热力学平衡,从而显著提高了丙烷的单程转化率。这些发现为设计针对丙烷CL - ODH的新型催化剂系统提供了有价值的见解。