Thermochemical performance assessment of solar continuous methane-driven ZnO reduction for co-production of pure zinc and hydrogen-rich syngas

Abstract

Converting renewable solar energy to dispatchable chemical products via solar-driven thermochemical processes is one of the best solutions for long-term solar energy storage and renewable fuel production. This study addresses the performance assessment of continuous methane-driven ZnO reduction, fully powered by renewable solar heat, for co-production of hydrogen-rich syngas and metallic Zn in a solar prototype consuming-bed chemical reactor. On-sun experiments were conducted under continuous ZnO and CH4 co-feeding to assess the effect of key parameters (inlet CH4/ZnO molar ratio: 1–1.5, temperature: 900–1000 °C, and ZnO feeding rate: 0.5–1.5 g/min) in order to maximize syngas and Zn yields, and reactor performance metrics. As a result, a rise in either the CH4/ZnO molar ratio or temperature enhanced the reaction extent but favored solid carbon formation, which downgraded syngas products quality, and consumed more solar energy input. Increasing ZnO feeding rate under a constant ZnO/CH4 molar ratio significantly promoted ZnO + CH4 reaction performance thanks to both hastened ZnO consumption rate (boosting products yield) and reduced solar energy consumption (improving solar conversion efficiency). However, excessively high ZnO feeding rate caused temporal ZnO accumulation in the reactor. Optimal operating conditions for on-sun continuous methane-driven ZnO reduction were identified (at ZnO feeding rate = 1.2 g/min, CH4/ZnO molar ratio = 1.5, and temperature = 950 °C), yielding total syngas yield of 12.3 mmol/gZnO, solid carbon formation down to 0.58 mmol/gZnO, ZnO conversion of 63.0%, methane conversion of 10.6%, energy upgrade factor of 1.08, and solar-to-fuel energy conversion efficiency of 5.3%. High-purity Zn particles with hexagonal morphologies were generated in continuous mode, demonstrating the proposed approach feasibility and reliability for simultaneous methane conversion to syngas and metallic Zn production in a single process.