The Development of Appropriate Upscaling Procedures

Permeability upscaling should be carried out with careful attention to the nature of rock heterogeneities. While there are many large-scale features which must be taken into account, there are also important heterogeneities at the small-scale. Many sedimentary structures contain laminae at the mm–cm scale, and beds at the m-scale, which give rise to strong contrasts in permeability. We use a 2D model derived from a photo-panel of an aeolian outcrop, along with permeability measurements from a North Sea oil field, to demonstrate the effects of small-scale heterogeneity. This model is similar in size to a typical cell of a reservoir geological model. We take imaginary probe and core plug measurements from the model, average them, and compare these with the effective permeability for the model computed from a finite difference flow calculation. Although this procedure is standard practice, we show that it can lead to biased estimates of the permeabilities used in flow simulation. As an alternative we suggest using models of representative beds, and performing flow simulation to calculate effective permeabilities for both single-phase and two-phase flow.     

Multi-Stage Upscaling: Selection of Suitable Methods

Reservoirs are often composed of an assortment of rock types giving rise to permeability heterogeneities at a variety of length-scales. To predict fluid flow at the full-field scale, it is necessary to be aware of these different types of heterogeneity, to recognise which are likely to have important effects on fluid flow, and to capture them by upscaling. In fact, we may require a series of stages of upscaling to go from small-scales (mm or cm) to a full-field model. When there are two (or more) phases present, we also need to know how these heterogeneities interact with fluid forces (capillary, viscous and gravity). We discuss how these effects may be taken into account by upscaling. This study focusses on the effects of steady-state upscaling for viscous-dominated floods and tests carried out on a range of 2D models are described. Upscaling errors are shown to be reduced slightly by the increase in numerical dispersion at the coarse scale. We select a combination of three different upscaling methods, and apply this approach to a model of a North Sea oil reservoir in a deep marine environment. Six different genetic units (rock types) were identified, including channel sandstone and inter-bedded sandstone and mudstone. These units were modelled using different approaches, depending on the nature of the heterogeneities. Our results show that the importance of small-scale heterogeneity depends on the large-scale distribution of the rock types. Upscaling may not be worthwhile in sparsely distributed genetic units. However, it is important in the dominant rock type, especially if there is good connectivity through the unit between the injector wells (or aquifer) and the producer wells.This revised version was published online in May 2005. In the previous version one of the authors name was missing.     

HPLC–MS Profiling and Structural Identification of [14C]-Diclofenac Metabolites in Mouse Bile

Biliary metabolites present at 6 h post-dose following a single oral dose of [¹⁴C]-diclofenac (10 mg kg^?1) to male bile duct-cannulated C57BL/6 J mice were profiled and identified. Over the 6 h duration of the study ~19.5 % of the administered radioactivity was excreted into the bile as either [¹⁴C]-diclofenac or metabolites. When profiled using HPLC with online radiodetection, the presence of at least 13 radiolabelled components was indicated. These compounds were shown, by consecutive reaction mass spectrometry, to comprise a range of hydroxylated metabolites conjugated to either taurine, glucose and/or glucuronic acid. Both phenolic and acylglucuronide-containing metabolites were observed. The confirmation of the presence of these glucuronide conjugates in mouse bile may have important consequences in the light of emerging theories concerning the role of bacterial glucuronidases for the GI-tract toxicity of NSAIDs such as diclofenac.     

Analysis of Compositional Effects on Global Flow Regimes in CO2 Near-Miscible Displacements in Heterogeneous Systems

Transport in Porous Media - The objective of this paper is developing new methodology for constructing the inflow performance relationships (IPRs) of unconventional reservoirs experiencing...     

Influence of counterion charge on the electrochemistry and impedance of polypyrrole

Polypyrroles doped with multiply charged anions are becoming increasingly important in a wide range of energy, environmental and biomedical applications. The increased counterion charge promotes anion binding and retention and can significantly increase stability and performance. The electrochemical properties of polypyrrole films prepared galvanostatically in Na₂SO₄ (PPySO₄) where found to be similar those of PPyClO₄ prepared in NaClO₄, although there was significantly more anion retention during potential cycling. In contrast, PPyPO₄ films prepared in Na₃PO₄ under the same conditions were over-oxidised and more dense, which is beneficial for corrosion protection and electroanalysis. Paradoxically, the low mobility of SO₄²⁻ counterions results in more facile charging and discharging of the film, as observed with large and polymeric counterions. This can create significant benefits in applications that require fast cycling, such as supercapacitors and high-rate batteries. These conclusions are corroborated by electrochemical impedance measurements in various aqueous electrolytes. Ionic conductivity was dominated by anion transport for both PPyClO₄ and PPySO₄, whilst PPyPO₄ was predominantly a cation conductor.

     

Online analysis of products from a direct ethanol fuel cell

Methodology for the online analysis of the main products from a direct ethanol fuel cell (DEFC) has been developed. The liquid exhaust from the fuel cell is first passed through a conductivity cell to determine the concentration of acetic acid and then CO₂ is extracted into a nitrogen stream for determination with a flow-through infrared-based CO₂ sensor. The other major product, acetaldehyde can be obtained by difference from the current. The continuous measurement of these products allows monitoring of changes in product distributions with time and operating conditions, resulting in a simple online system for rapid evaluation of anode catalysts in DEFCs.     

Infrared optical constants, dielectric constants, molar polarizabilities, transition moments, dipole moment derivatives and Raman spectrum of liquid cyclohexane

Previous studies have been done in this laboratory focusing on the optical properties of several liquid aromatic and aliphatic hydrocarbons in the infrared. The current study reports the infrared and absorption Raman spectra of liquid cyclohexane. Infrared spectra were recorded at 25 °C over a wavenumber range of 7400–490 cm⁻¹. Infrared measurements were taken using transmission cells with pathlengths ranging from 3 to 5000 μm. Raman spectra were recorded between 3700 and 100 cm⁻¹ at 25 °C using a 180° reflection geometry. Ab initio calculations of the vibrational wavenumbers at the B3LYP/6311G level of theory were performed and used to help assign the observed IR and Raman spectra. Extensive assignments of the fundamentals and binary combinations observed in the infrared imaginary molar polarizability spectrum are reported. The imaginary molar polarizability spectrum was curve fitted to separate the intensity from the various transitions and used to determine the transition moments and magnitudes of the derivatives of the dipole moment with respect to the normal coordinates for the fundamentals.     

Direct calculation of ionization energies

The advantages of the propagator formalism, as a direct method of calculating ionization energies, are stressed. The propagator equations are derived for closed-shell systems using an operator method instead of the usual diagrammatic derivations. The equations enable the development of an interpretation of the ionization energies in terms of conceptually simple quantities, such as pair correlation energies and associated relaxation effects, and retain the idea of orbital ionization. Infinite summations appearing in the self-energy terms are replaced by finite expressions involving functions satisfying uncoupled inhomogeneous differential equations. Certain high-order propagator equations are derived, and a connection with the Bethe-Goldstone formulation of pair correlation is made. Several computational procedures are advocated as forming the basis for balanced calculations of atomic and molecular ionization energies.     

Radiative decay ofJ/ψ into γ π+ π−

The radiative decayJ/ψ → γ π⁺ π^? has been studied using the 8.6 millionJ/ψ produced in the DM2 experiment at the DCIe ⁺e^? storage rings at Orsay. The π⁺ π^? mass spectrum shows a cleanf ₂ (1270) signal, and the possible presence of two other states at thef ₂ (1720) andf ₄ (2030) masses. For thef ₂ (1270), the branching ratio BR(J/ψ →γf)xBR(f→π⁺ π^?) is measured to be (7.50±0.30±1.12)×10^?4, and the spin analysis prefers theJ=2 assignment, with helicity parametersx=0.83±0.06 andy=0.01±0.06. The existence of higher mass states is discussed.     

A method for molecular ionization potentials

A new method for one-electron propagator calculations of molecular inization potentials is proposed, using a large matrix technique The results of some trial calculations on molecular nitrogen are given.