Optimization of the CeO2/CeCl3 cycle by cerium IV oxide reductive dissolution catalysis

•Upgrading of hydrochlorination of CeO2 by adding fluorine under stable form of CaF2.•Ability to reach reaction progress of 100% with fluorinated catalysis.•In-line distillation of produced water provides better kinetic.•CeCl3 hydrolysis done by hot spraying solution coming from hydrochlorination.

While thermochemical cycles can be a way to produce hydrogen, physiochemical studies show that implementing them is often difficult for reactivity reasons. Most of the cycles actually involve solid–gas type systems with limited reactivity due to interface passivation processes. To overcome this difficulty, studies have shown that using the CeO2/CeCl3 pair, in which the cerium undergoes a reversible oxidation–reduction cycle, has enormous potential since it may partially be carried out in aqueous phase by reductive dissolution from cerium oxides (IV) to cerium chloride (III).If the first reaction of the cycle is well known for industrial application, its second and its third reaction still need some investigation. Thus, this article primarily describes the work done on the second reaction to assess the possibility of carrying out cerium reduction in aqueous phase. The extremely positive results have highlighted the possibility of achieving 100% reaction efficiency in systems catalyzed by fluoride ions. Conducting the reaction with in-line distillation of the excess water also helps significantly reduce reaction time which offers good potential for the next stage. A ratio of 8 ml of a 20 w% HCl solution per gram of CeO2 containing 6w% of CaF2 leads to ensure a total reaction in a few minutes at 108.6 °C (boiling temperature of the H2O–HCl azeotrope).The work presented herein also describes a brief feasibility study for the third reaction cycle which could be carried out by spraying the solution from the second reaction, in a hot column whose temperature will be determined by further work. These results have allowed upgrading the first flowsheet proposed in a previous publication.