Directing two-dimensional molecular crystallization using guest templates

The use of a coronene guest template directs the formation of a 2D Kagomé network in preference to alternative close packed and parallel hydrogen-bonded structures of tetracarboxylic acid tectons self-assembled from solution on a graphite surface.     

Acknowledgement of Reviewers for 2021

Transport in Porous Media -     

Elliptic Regions and Stable Solutions for Three-Phase flow in Porous Media

In the limit of zero capillary pressure, solutions to the equations governing three-phase flow, obtained using common empirical relative permeability models, exhibit complex wavespeeds for certain saturation values (elliptic regions) that result in unstable and non-unique solutions. We analyze a simple but physically realizable pore-scale model: a bundle of cylindrical capillary tubes, to investigate whether the presence of these elliptic regions is an artifact of using unphysical relative permeabilities. Without gravity, the model does not yield elliptic regions unless the most non-wetting phase is the most viscous and the most wetting phase is the least viscous. With gravity, the model yields elliptic regions for any combination of viscosities, and these regions occupy a significant fraction of the saturation space. We then present converged, stable numerical solutions for one-dimensional flow, which include capillary pressure. These demonstrate that, even when capillary forces are small relative to viscous forces, they have a significant effect on solutions which cross or enter the elliptic region. We conclude that elliptic regions can occur for a physically realizable model of a porous medium, and that capillary pressure should be included explicitly in three-phase numerical simulators to obtain stable, physically meaningful solutions which reproduce the correct sequence of saturation changes.     

The Effect of Wettability on Three-Phase Relative Permeability

We study three-phase flow in water-wet, oil-wet, and fractionally-wet sandpacks. We use CT scanning to measure directly the oil and water relative permeabilites for three-phase gravity drainage. In an analogue experiment, we measure pressure gradients in the gas phase to determine the gas relative permeability. Thus we find all three relative permeabilities as a function of saturation. We find that the gas relative permeability is approximately half as much in a oil-wet medium than in an water-wet medium at the same gas saturation. The water relative permeability in the water-wet medium and the oil relative permeability in the oil-wet medium are similar. In the water-wet medium the oil relative permeability scales as k _roS _o ⁴ for S _o>S _or, where S _or is the waterflood residual oil saturation. With octane as the oil phase, k _roS _o ² for S _o<S _or, while with decane as the oil phase, k _ro falls sharply for S _o<S _or. The water relative permeability in the oil-wet medium resembles the oil relative permeability in the water-wet medium for a non-spreading oil such as decane. These observations can be explained in terms of wetting, spreading, and the pore scale configurations of fluid.     

An Experimental Study of Three-Phase Trapping in Sand Packs

The trapped saturations of oil and gas are measured as functions of initial oil and gas saturation in water-wet sand packs. Analogue fluids—water, octane and air—are used at ambient conditions. Starting with a sand-pack column which has been saturated with brine, oil (octane) is injected with the column horizontal until irreducible water saturation is reached. The column is then positioned vertically and air is allowed to enter from the top of the column, while oil is allowed to drain under gravity for varying lengths of time. At this point, the column may be sliced and the fluids analyzed by gas chromatography to obtain the initial saturations. Alternatively, brine is injected through the bottom of the vertical column to trap oil and gas, before slicing the columns and measuring the trapped or residual saturations by gas chromatography and mass balance. The experiments show that in three-phase flow, the total trapped saturations of oil and gas are considerably higher than the trapped saturations reported in the literature for two-phase systems. It is found that the residual saturation of oil and gas combined could be as high as 23 %, as opposed to a maximum two-phase residual of only 14 %. For very high initial gas saturations, the residual gas saturation, up to 17 %, was also higher than for two-phase displacement. These observations are explained in terms of the competition between piston-like displacement and snap-off. It is also observed that less oil is always trapped in three-phase flow than in two-phase displacement, and the difference depends on the amount of gas present. For low and intermediate initial gas saturations, the trapped gas saturation rises linearly with initial saturation, followed by a constant residual, as seen in two-phase displacements. However, at very high initial gas saturations, the residual saturation rises again.     

Ingwer-Verf?lschung

Ohne Zusammenfassung     

Dual side-reactions limit the utility of a key polymer therapeutic precursor

In contrast to literature reports, the activated polyacid poly(methacryloxysuccinimide) reacts with nucleophiles to give, initially, a high proportion of ring-opened residues. This copolymer then reacts intramolecularly to form a polymer with a high fraction of glutarimide residues. These side reactions occur to such an extent as to preclude the use of poly(methacryloxysuccinimide) as a precursor to polymethacrylamides.     

Highly efficient one-pot C-, N- and O-acylation of indolin-2-one analogs

A highly efficient one-pot multiple acylation at chemically non-equivalent sites on indolin-2-one and related motifs using 4-(N,N-dimethylamino)pyridine as a catalyst is described. This procedure gives extremely facile entry to highly desired 3-acyl-2-hydroxy-indole synthons among other derivatives.     

Pore-Scale Imaging and Analysis of Wettability Order,Trapping and Displacement in Three-Phase Flow in Porous Media with Various Wettabilities

Three-phase flow in porous media is encountered in many applications including subsurface carbon dioxide storage, enhanced oil recovery, groundwater remediation and the design of microfluidic devices. However, the pore-scale physics that controls three-phase flow under capillary dominated conditions is still not fully understood. Recent advances in three-dimensional pore-scale imaging have provided new insights into three-phase flow. Based on these findings, this paper describes the key pore-scale processes that control flow and trapping in a three-phase system, namely wettability order, spreading and wetting layers, and double/multiple displacement events. We show that in a porous medium containing water, oil and gas, the behaviour is controlled by wettability, which can either be water-wet, weakly oil-wet or strongly oil-wet, and by gas–oil miscibility. We provide evidence that, for the same wettability state, the three-phase pore-scale events are different under near-miscible conditions—where the gas–oil interfacial tension is ≤?1 mN/m—compared to immiscible conditions. In a water-wet system, at immiscible conditions, water is the most-wetting phase residing in the corners of the pore space, gas is the most non-wetting phase occupying the centres, while oil is the intermediate-wet phase spreading in layers sandwiched between water and gas. This fluid configuration allows for double capillary trapping, which can result in more gas trapping than for two-phase flow. At near-miscible conditions, oil and gas appear to become neutrally wetting to each other, preventing oil from spreading in layers; instead, gas and oil compete to occupy the centre of the larger pores, while water remains connected in wetting layers in the corners. This allows for the rapid production of oil since it is no longer confined to movement in thin layers. In a weakly oil-wet system, at immiscible conditions, the wettability order is oil–water–gas, from most to least wetting, promoting capillary trapping of gas in the pore centres by oil and water during water-alternating-gas injection. This wettability order is altered under near-miscible conditions as gas becomes the intermediate-wet phase, spreading in layers between water in the centres and oil in the corners. This fluid configuration allows for a high oil recovery factor while restricting gas flow in the reservoir. Moreover, we show evidence of the predicted, but hitherto not reported, wettability order in strongly oil-wet systems at immiscible conditions, oil–gas–water, from most to least wetting. At these conditions, gas progresses through the pore space in disconnected clusters by double and multiple displacements; therefore, the injection of large amounts of water to disconnect the gas phase is unnecessary. We place the analysis in a practical context by discussing implications for carbon dioxide storage combined with enhanced oil recovery before suggesting topics for future work.