Comparison of mass transfer effects in the heterogeneously catalysed hydrogenation of phenyl acetylene in heptane and an ionic liquid

The selective heterogeneous catalytic reduction of phenyl acetylene to styrene over palladium supported on calcium carbonate is reported in both an ionic liquid and a molecular solvent. By using a rotating disc reactor in conjunction with results from a stirred tank reactor it is possible, for the first time, to disentangle the mass transfer contributions in the ionic liquid system. For both heptane and 1-butyl-3-methyl imidazolium bis{(trifluoromethyl)sulfonyl}imide, the reaction in the rotating disc reactor is dominated by reaction in the entrained film on the disc compared with very limited reaction in the bulk liquid. The lower reaction rate obtained in the ionic liquid compared with the organic solvent is shown to be due to the slow transport of the hydrogen dissolved in the liquid. It is clear from the results presented herein that, although the hydrodynamics of similar reactors used for biological treatment of wastewater are well understood, on using a more viscous fluid and higher rotation speeds necessary for fine chemical catalysis these simple relationships breakdown.

A modified commercial DRIFTS cell for kinetically relevant operando studies of heterogeneous catalytic reactions

This paper discusses a number of checks that should be carried out to ensure that the kinetic and spectroscopic measurements made using a DRIFTS cell are meaningful. The observations reported here demonstrate how an appropriately modified commercial DRIFTS cell can provide pertinent kinetic information about both gaseous products and the related surface intermediates. The oxidation of CO with 02 was used as a test to assess the catalyst bed bypass by the reaction mixture. Full CO conversion was obtained after the light-off temperature in the case of the modified cell, contrary to the case of the original cell, for which 80% of the reaction mixture bypassed the catalyst bed. The water-gas shift reaction over a Pt/CeO2 catalyst was used as a model reaction to further characterize the behavior of the cell under reaction conditions. The catalyst bed was shown not to be a dead-zone and was purged in essentially the same time as that needed to purge the cell. The reaction chamber globally operated in a quasi plug-flow mode and the gas composition in the thin catalyst bed appears to be homogeneous when operated under differential conditions. The production of the gas-phase reaction product CO2 could be simultaneously followed both by mass spectrometry and DRIFTS, both techniques leading to identical results. Various IR bands integration methods were discussed to allow a precise and accurate determination of the surface concentration of adsorbates during isotopic exchange. (c) 2008 Elsevier B.V. All rights reserved.

Combining multi-scale geophysical techniques for robust hydro-structural characterisation in catchments underlain by hard rock in post-glacial regions

Accurate conceptual models of groundwater systems are essential for correct interpretation of monitoring data in catchment studies. In surface-water dominated hard rock regions, modern ground and surface water monitoring programmes often have very high resolution chemical, meteorological and hydrological observations but lack an equivalent emphasis on the subsurface environment, the properties of which exert a strong control on flow pathways and interactions with surface waters. The reasons for this disparity are the complexity of the system and the difficulty in accurately characterising the subsurface, except locally at outcrops or in boreholes. This is particularly the case in maritime north-western Europe, where a legacy of glacial activity, combined with large areas underlain by heterogeneous igneous and metamorphic bedrock, make the structure and weathering of bedrock difficult to map or model. Traditional approaches which seek to extrapolate information from borehole to field-scale are of limited application in these environments due to the high degree of spatial heterogeneity. Here we apply an integrative and multi-scale approach, optimising and combining standard geophysical techniques to generate a three-dimensional geological conceptual model of the subsurface in a catchment in NE Ireland. Available airborne LiDAR, electromagnetic and magnetic data sets were analysed for the region. At field-scale surface geophysical methods, including electrical resistivity tomography, seismic refraction, ground penetrating radar and magnetic surveys, were used and combined with field mapping of outcrops and borehole testing. The study demonstrates how combined interpretation of multiple methods at a range of scales produces robust three-dimensional conceptual models and a stronger basis for interpreting groundwater and surface water monitoring data.

Coupling ground and airborne geophysical data with upscaling techniques for regional groundwater modeling of heterogeneous aquifers: Case study of a sedimentary aquifer intruded by volcanic dykes in Northern Ireland

In highly heterogeneous aquifer systems, conceptualization of regional groundwater flow models frequently results in the generalization or negligence of aquifer heterogeneities, both of which may result in erroneous model outputs. The calculation of equivalence related to hydrogeological parameters and applied to upscaling provides a means of accounting for measurement scale information but at regional scale. In this study, the Permo-Triassic Lagan Valley strategic aquifer in Northern Ireland is observed to be heterogeneous, if not discontinuous, due to subvertical trending low-permeability Tertiary dolerite dykes. Interpretation of ground and aerial magnetic surveys produces a deterministic solution to dyke locations. By measuring relative permeabilities of both the dykes and the sedimentary host rock, equivalent directional permeabilities, that determine anisotropy calculated as a function of dyke density, are obtained. This provides parameters for larger scale equivalent blocks, which can be directly imported to numerical groundwater flow models. Different conceptual models with different degrees of upscaling are numerically tested and results compared to regional flow observations. Simulation results show that the upscaled permeabilities from geophysical data allow one to properly account for the observed spatial variations of groundwater flow, without requiring artificial distribution of aquifer properties. It is also found that an intermediate degree of upscaling, between accounting for mapped field-scale dykes and accounting for one regional anisotropy value (maximum upscaling) provides results the closest to the observations at the regional scale.

Biomineralization of Weathered Rock Rinds:Examples from the Lower Afroalpine Zone on Mount Kenya

Rock rinds have been used for half a century to date glacial deposits and recently inroads have been developed to use nuclides to provide absolute ages of weathering rinds in pebble clasts. Although maximum and minimum rind thicknesses have helped to elucidate time since deposition and allowed stratigraphic division of deposits at glacial rank, little has been done to investigate the wealth of mineral degradation, growth of alteration products and biomineralization that occur in these weathered crusts. In some cases the mass of microbe-mineral intergrowth is nearly present on a 50%/50% basis, with the biotic mass intergrown with mineral matter to such an extent that it probably controls pH and redox phenomena that act as accelerators in the weathering process. Assuming weathering time spans of 2 × 10⁶ years or more for a complete cycle, eventual clast decomposition is the end product. Here we present evidence of microbe-clast intergrowth from selected sites of Pleistocene age (~70 ka to 2.0 Ma) in the lower Afroalpine of Mt. Kenya and hypothesize about its role in rock decomposition and fossilization of biotic end-members. © 2013 Copyright Taylor and Francis Group, LLC.