Wang Jijie, Li Guanna, Li Zelong, Tang Chizhou, Feng Zhaochi, An Hongyu, Liu Hailong, Liu Taifeng, Li Can
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P.R. China.
Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Van Oder Massage 9, 2629 HZ Delft, Netherlands.
Sci Adv. 2017 Oct 6;3(10):e1701290. doi: 10.1126/sciadv.1701290. eCollection 2017 Oct.
Although methanol synthesis via CO hydrogenation has been industrialized, CO hydrogenation to methanol still confronts great obstacles of low methanol selectivity and poor stability, particularly for supported metal catalysts under industrial conditions. We report a binary metal oxide, ZnO-ZrO solid solution catalyst, which can achieve methanol selectivity of up to 86 to 91% with CO single-pass conversion of more than 10% under reaction conditions of 5.0 MPa, 24,000 ml/(g hour), H/CO = 3:1 to 4:1, 320° to 315°C. Experimental and theoretical results indicate that the synergetic effect between Zn and Zr sites results in the excellent performance. The ZnO-ZrO solid solution catalyst shows high stability for at least 500 hours on stream and is also resistant to sintering at higher temperatures. Moreover, no deactivation is observed in the presence of 50 ppm SO or HS in the reaction stream.
尽管通过CO加氢合成甲醇已实现工业化，但CO加氢制甲醇仍面临甲醇选择性低和稳定性差的巨大障碍，特别是在工业条件下的负载型金属催化剂方面。我们报道了一种二元金属氧化物ZnO-ZrO固溶体催化剂，在5.0 MPa、24,000 ml/(g·小时)、H/CO = 3:1至4:1、320°至315°C的反应条件下，该催化剂可实现高达86%至91%的甲醇选择性以及超过10%的CO单程转化率。实验和理论结果表明，Zn和Zr位点之间的协同效应导致了优异的性能。ZnO-ZrO固溶体催化剂在至少500小时的运行中表现出高稳定性，并且在较高温度下也抗烧结。此外，在反应物流中存在50 ppm SO或HS的情况下未观察到失活现象。
