Qingdao Energy Institute and others have developed high-stability mixed conductor ceramics for hydrogen purification
Compared with the technology of hydrogen production by electrolysis of renewable energy, obtaining fuel hydrogen by purifying industrial by-product hydrogen is a more realistic and inexpensive way to produce hydrogen at this stage, which is conducive to reducing the operating cost of hydrogen fuel cells. The presence of trace CO impurities in fuel hydrogen can quickly poison fuel cell catalysts. Therefore, the development of CO-free hydrogen (CO≦0.2 ppm) preparation technology is an important direction for hydrogen energy research. The dense ceramic membrane with oxygen ion-electron mixed conductivity has 100% selectivity for the transmission of oxygen. The high-temperature water splitting reaction and the industrial by-product hydrogen combustion reaction are coupled on both sides of the ceramic oxygen-permeable membrane reactor, and low-purity hydrogen The combustion can promote the in-situ removal of oxygen generated by water splitting on the other side of the ceramic membrane, which can efficiently promote water splitting and directly obtain CO-free hydrogen, which can be used as a fuel directly in a hydrogen fuel cell.
During the hydrogen production process, the cobalt and iron ions in the ceramic oxygen permeable membrane reported in the previous period are easy to be deeply reduced, showing poor chemical stability. Recently, Jiang Heqing, a researcher at the Qingdao Institute of Bioenergy and Processes, Chinese Academy of Sciences, collaborated with Caro, a professor at the University of Hannover, Germany, to develop a new type of titanium-based two-phase mixed conductor oxygen permeable membrane. Compared with the chemically unstable iron-based dual-phase membrane, the titanium-based dual-phase membrane material still maintains the original phase structure and microscopic morphology after 100 hours of treatment in an atmosphere containing water vapor and high concentration hydrogen, and exhibits excellent resistance to reduction stability. The two-phase oxygen permeable membrane has good oxygen permeability under a reducing atmosphere, and can be used as a membrane reactor in a hydrogen purification preparation process. Driven by the low-purity hydrogen combustion reaction, CO-free hydrogen can be efficiently obtained on the water splitting reaction side of the membrane reactor. Experimental results show that the titanium-based two-phase membrane can operate stably for a long time, and the membrane material exhibits good stability under actual chemical reaction conditions, and its hydrogen production rate is 0.25 m3 h-1 m-2.
This research solved the problem of poor stability of ceramic membrane materials in a reducing atmosphere and promoted the development of ceramic membrane hydrogen production technology. Related research results were published on "German Applied Chemistry" (Angew. Chem. Int. Ed. 2021, 60, 5204-5208) with the title Hydrogen purification through a highly stable dual-phase oxygen permeable membrane. The research work was supported by the National Natural Science Foundation of China, the Innovation Fund of the Key Laboratory of Biofuels of the Chinese Academy of Sciences and the Dalian Institute of Chemical Physics (Dalian Institute of Chemical Physics)-Qingdao Institute of Energy Convergence Fund of the Chinese Academy of Sciences.
Hydrogen production in a new titanium-based oxygen-permeable membrane reactor; comparison of material stability between titanium-based dual-phase membrane and iron-based dual-phase membrane
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