Investigating the behaviour of NaCl brines and hydrocarbons in porous alumina using low-field NMR relaxation and diffusion methods.

The behaviour of multiple fluid phases within a porous medium is hard to predict. NMR measurements offer an excellent tool to probe such systems in a fast and non-invasive way. Such systems can be relevant to hydrocarbon recovery, catalysis, and CO2 and H2 geo-storage, among others. Since electrolyte solutions are always present in subsurface reservoirs, understanding their behaviour within porous media is highly important. In this study, we use NMR relaxation and diffusion methods to investigate the diffusion coefficients and strength of interactions between alumina surfaces and brines at various NaCl concentrations, focusing on the effect of salt concentration on transport and interactions within the porous structure. Furthermore, we study the spontaneous displacement of dodecane, a model hydrocarbon, from the same alumina pellets using the same brine solutions. Results show that brines of lower salinity consistently displace more dodecane in total, after soaking dodecane-saturated pellets in a brine solution for several days. This indicates that increased salt concentrations can reduce wettability towards the aqueous phase in simple metal oxide surfaces and highlights the capabilities of NMR to efficiently study such systems.

Enhancing Hydrogen Production from the Photoreforming of Lignin.

Photoreforming of lignocellulose biomass is widely recognised as a challenging but key technology for producing value-added chemicals and renewable hydrogen (H2 ). In this study, H2 production from photoreforming of organosolv lignin in a neutral aqueous solution was studied over a 0.1 wt % Pt/TiO2 (P25) catalyst with ultraviolet A (UVA) light. The H2 production from the system employing the lignin (~4.8 µmol gcat -1 h-1 ) was comparable to that using hydroxylated/methoxylated aromatic model compounds (i. e., guaiacol and phenol, 4.8-6.6 µmol gcat -1 h-1 ), being significantly lower than that from photoreforming of cellulose (~62.8 µmol gcat -1 h-1 ). Photoreforming of phenol and reaction intermediates catechol, hydroquinone and benzoquinone were studied to probe the mechanism of phenol oxidation under anaerobic photoreforming conditions with strong adsorption and electron transfer reactions lowering H2 production from the intermediates relative to that from phenol. The issues associated with catalyst poisoning and low photoreforming activity of lignins demonstrated in this paper have been mitigated by implementing a process by which the catalyst was cycled through anaerobic and aerobic conditions. This strategy enabled the periodic regeneration of the photocatalyst resulting in a threefold enhancement in H2 production from the photoreforming of lignin.

Phase effects in zirconia catalysed glucose conversion to 5-hydroxy methylfurfural.

5-(hydroxymethyl)furfural (HMF) is a key biomass derived platform chemicals used to produce fuel precursors or additives and value-added chemicals, synthesised by the cascade isomerisation of glucose and subsequent dehydration of reactively formed fructose to HMF over Lewis and Bronsted acid catalysts respectively. Zirconia is a promising catalyst for such reactions; however, the impact of acid properties of different zirconia phases is poorly understood. In this work, we unravel the role of the zirconia crystalline phase in glucose isomerisation and fructose dehydration to HMF. The Lewis acidic monoclinic phase of zirconia is revealed to preferentially facilitate glucose isomerisation, while the nanoparticulate tetragonal phase possesses Brønsted acid sites which favour fructose dehydration. Synergy between both zirconia phases facilitates cascade HMF production, with both catalysts investigated as physical mixtures in batch and flow reactor configurations. Using a physical mixture of only 15 wt% m-ZrO2 with 85 wt% t-ZrO2 in either batch or packed bed reactor configuration is sufficient to reach equilibrium conversion of glucose for subsequent dehydration by the t-ZrO2 component. Under continuous flow, a six-fold increase in HMF production was obtained when operating with a physical mixture of m- and t-ZrO2 compared to that from a single bed of t-ZrO2.