High-Purity Hydrogen Generation via Dehydrogenation of Organic Carriers: A Review on the Catalytic Process

High-purity hydrogen delivery for stationary and mobile applications using fuel cells is a subject of rapidly growing interest. As a consequence, the development of efficient storage technologies and processes for hydrogen supply is of primary importance. Promising hydrogen storage techniques rely on the reversibility and high selectivity of liquid organic hydrogen carriers (LOHCs), for example, methylcyclohexane, decalin, dibenzyltoluene, or dodecahydrocabazole. LOCHS have high gravimetric and volumetric hydrogen density, and they involve low risk and capital investment because they are largely compatible with the current transport infrastructure used for fossil fuels. A further advantage comes from the high purity (close to 100%) of the hydrogen generated by dehydrogenation, suitable to directly feed fuel cells without the need for bulky purification modules. Partial dehydrogenation (PDH) of liquid fuels has recently emerged as a transition technology for hydrogen delivery purposes. The principle is to extract from fossil fuels a small fraction of the available hydrogen, which can be used for fuel cell applications, while the dehydrogenated hydrocarbon mixture maintains suitable properties for its use as fuel. With this technology, the large energy demand of dehydrogenation processes can be satisfied by implementing a heat exchanger between the engine and the dehydrogenation reactor, overcoming one of the main constraints associated with the use of organic liquids as hydrogen carriers. This method qualifies itself as a transition technology toward more electrified transportations, in which the main propulsion is still obtained by fuel combustion, although the electrical utilities or auxiliary propulsion are powered by fuel cells. This paper provides a review of the effort that has been directed toward the utilization of organic liquids as hydrogen carriers, with particular focus on the design of the catalytic dehydrogenation process and on the recent approach of fuel partial dehydrogenation.