Calabrese, Marcella (2025) Towards the development of a safe hydrogen storage process: aqueous formate and bicarbonate solutions. [Tesi di dottorato]

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Abstract

In order to have reliable solutions for energy storage, hydrogen and its carriers are receiving special scientific attention. In recent years, there has been a growing interest in the development of new hydrogen vectors capable of releasing it in near-ambient conditions. One interesting solution is HCOOM formic acid salts (M = Na+, K+, NH4+), prepared through catalytic hydrogenation of bicarbonate ions. This PhD thesis aims to explore this method in depth: H2 storage in aqueous solutions of formates and bicarbonates. This technology could be a practical solution for storing, transporting, and releasing hydrogen safely and cost-effectively. Based on the literature survey, the goal of this dissertation is the identification of stable catalytic systems that can provide relevant reaction rates for the cyclic formate/bicarbonate interconversion in order to meet the requirements of the industrial sector. Finding stable catalytic systems that could achieve high reaction rates for the cyclic interconversion between formate and bicarbonate was the focus of the first year's study. The study started with a comprehensive literature analysis that emphasized the necessity of meeting performance standards in the industrial operations and plants. Palladium (Pd), supported on carbon or metal oxides, was the common and most efficient active phase among the catalysts that were studied. However, the actual use of many of these heterogeneous catalysts is limited since they need to be reactivated on a regular basis. Consequently, extensive experimental work was initiated to find a catalyst capable of sustaining the entire reaction cycle with minimal deactivation, while exploring alternative supports, particularly oxide semiconductors, to enable simpler preparation methods. After the most promising catalyst was chosen, kinetic research was carried out to evaluate its performance in more detail. One of the strenght point of this storage solution is the safety: a comparative risk assessment evaluated the formate/bicarbonate hydrogen storage method against the established standard of compressed hydrogen storage technology. This analysis highlighted significant differences in risk profiles and potential hazards at both laboratory and pilot scales. Subsequently, a collaboration with Saipem SpA led to the development of an industrial scale-up strategy, illustrating the integrated system’s potential and its compatibility with other innovative technologies.

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