Steam reforming of n-butanol and tetrahydrofuran: Influence of aliphatic carbon chain and furan ring on coking behaviors

Almost all small organics, in theory, could be potential feedstock for production of hydrogen via steam reforming (SR). Nevertheless, not all organics contain a linear carbon chain like ethanol or acetone. How do ring structure of an organic substrate impacted coking behaviors in SR were explored herein with n-butanol and tetrahydrofuran (THF) as the research objects over Ni/SiO2 catalyst, due to the same carbon number but distinct carbon chains in these two molecules. The results indicated that furan ring in THF lowered reactivity towards SR, as its adsorption on metallic sites was more difficult than n-butanol. The in-situ IR analysis for measuring reaction intermediates suggested that n-butanol and THF involved generation of intermediates with C--O formed via dehydrogenation, CxHy formed via cracking and C--C species that can be further gasified or aggregate to coke. However, more oxygenated intermediates generated in SR of n-butanol than in THF, rendering n-butanol more reactive towards SR. This, however, also formed substantially more coke of aliphatic nature in amorphous form, which led to the coke of thermally unstable and had higher tendency being oxidized. In converse, coke formed from SR of THF was more aromatic, showing less impact on catalytic activity, higher thermal stability, and larger crystal size with more carbon nanotube form of coke. This was closely connected with the ring structures that could dehydrogenated to form the unsaturated ring with capability to involve in Diels-Alder reactions, forming coke of aromatic nature.