Two-phase flow in heterogeneous porous media II: Numerical experiments for flow perpendicular to a stratified system

In this work, we make use of numerical experiments to explore our original theoretical analysis of two-phase flow in heterogeneous porous media (Quintard and Whitaker, 1988). The calculations were carried out with a two-region model of a stratified system, and the parameters were chosen be consistent with practical problems associated with groundwater flows and petroleum reservoir recovery processes. The comparison between theory (the large-scaled averaged equations) and experiment (numerical solution of the local volume averaged equations) has allowed us to identify conditions for which the quasi-static theory is acceptable and conditions for which a dynamic theory must be used. Byquasi-static we mean the following: (1) The local capillary pressure,everywhere in the averaging volume, can be set equal to the large-scale capillary pressure evaluated at the centroid of the averaging volume and (2) the large-scale capillary pressure is given by the difference between the large-scale pressures in the two immiscible phases, and is therefore independent of gravitational effects, flow effects and transient effects. Bydynamic, we simply mean a significant departure from the quasi-static condition, thus dynamic effects can be associated with gravitational effects, flow effects and transient effects. To be more precise about the quasi-static condition we need to refer to the relation between the local capillary pressure and the large-scale capillary pressure derived in Part I (Quintard and Whitaker, 1990). Herep _c ¦_y represents the local capillary pressure evaluated at a positiony relative to the centroid of the large-scale averaging volume, and {p _c }¦_x represents the large-scale capillary pressure evaluated at the centroid.In addition to{p _c } ^c being evaluated at the centroid, all averaged terms on the right-hand side of Equation (1) are evaluated at the centroid. We can now write the equations describing the quasi-static condition as , , This means that the fluids within an averaging volume are distributed according to the capillary pressure-saturation relationwith the capillary pressure held constant. It also means that the large-scale capillary pressure is devoid of any dynamic effects. Both of these conditions represent approximations (see Section 6 in Part I) and one of our main objectives in this paper is to learn something about the efficacy of these approximations. As a secondary objective we want to explore the influence of dynamic effects in terms of our original theory. In that development only the first four terms on the right hand side of Equation (1) appeared in the representation for the local capillary pressure. However, those terms will provide an indication of the influence of dynamic effects on the large-scale capillary pressure and the large-scale permeability tensor, and that information provides valuable guidance for future studies based on the theory presented in Part I.Roman Letters A scalar that maps {}*/t onto - A scalar that maps {}*/t onto - A interfacial area between the -region and the -region contained within, m² - A interfacial area between the -region and the -region contained within, m² - A interfacial area between the -region and the -region contained within, m² - a vector that maps ({}*/t) onto , m - a vector that maps ({}*/t) onto , m - b vector that maps ({p}– g) onto , m - b vector that maps ({p}– g) onto , m - B second order tensor that maps ({p}– g) onto , m² - B second order tensor that maps ({p}– g) onto , m² - c vector that maps ({}*/t) onto , m - c vector that maps ({}*/t) onto , m - C second order tensor that maps ({}*/t) onto , m² - C second order tensor that maps ({}*/t) onto . m² - D third order tensor that maps ( ) onto , m - D third order tensor that maps ( ) onto , m - D second order tensor that maps ( ) onto , m² - D second order tensor that maps ( ) onto , m² - E third order tensor that maps () onto , m - E third order tensor that maps () onto , m - E second order tensor that maps () onto - E second order tensor that maps () onto - p _c =(), capillary pressure relationship in the-region - p _c =(), capillary pressure relationship in the-region - g gravitational vector, m/s² - largest of either or - - - i unit base vector in thex-direction - I unit tensor - K local volume-averaged-phase permeability, m² - K local volume-averaged-phase permeability in the-region, m² - K local volume-averaged-phase permeability in the-region, m² - {K } large-scale intrinsic phase average permeability for the-phase, m² - K –{K }, large-scale spatial deviation for the-phase permeability, m² - K –{K }, large-scale spatial deviation for the-phase permeability in the-region, m² - K –{K }, large-scale spatial deviation for the-phase permeability in the-region, m² - K ^* large-scale permeability for the-phase, m² - L characteristic length associated with local volume-averaged quantities, m - characteristic length associated with large-scale averaged quantities, m - I _i i = 1, 2, 3, lattice vectors for a unit cell, m - l characteristic length associated with the-region, m - ; characteristic length associated with the-region, m - l _H characteristic length associated with a local heterogeneity, m - - n unit normal vector pointing from the-region toward the-region (n =–n ) - n unit normal vector pointing from the-region toward the-region (n =–n ) - p pressure in the-phase, N/m² - p local volume-averaged intrinsic phase average pressure in the-phase, N/m² - {p } large-scale intrinsic phase average pressure in the capillary region of the-phase, N/m² - p local volume-averaged intrinsic phase average pressure for the-phase in the-region, N/m² - p local volume-averaged intrinsic phase average pressure for the-phase in the-region, N/m² - p –{p }, large scale spatial deviation for the-phase pressure, N/m² - p –{p }, large scale spatial deviation for the-phase pressure in the-region, N/m² - p –{p }, large scale spatial deviation for the-phase pressure in the-region, N/m² - P _c p –{p }, capillary pressure, N/m² - {p_c}^c large-scale capillary pressure, N/m² - r ₀ radius of the local averaging volume, m - R ₀ radius of the large-scale averaging volume, m - r position vector, m - , m - S /, local volume-averaged saturation for the-phase - S ^* {}*{}*, large-scale average saturation for the-phaset time, s - t time, s - u , m - U , m² - v -phase velocity vector, m/s - v local volume-averaged phase average velocity for the-phase in the-region, m/s - v local volume-averaged phase average velocity for the-phase in the-region, m/s - {v } large-scale intrinsic phase average velocity for the-phase in the capillary region of the-phase, m/s - {v } large-scale phase average velocity for the-phase in the capillary region of the-phase, m/s - v –{v }, large-scale spatial deviation for the-phase velocity, m/s - v –{v }, large-scale spatial deviation for the-phase velocity in the-region, m/s - v –{v }, large-scale spatial deviation for the-phase velocity in the-region, m/s - V local averaging volume, m³ - V volume of the-phase in, m³ - V large-scale averaging volume, m³ - V capillary region for the-phase within, m³ - V capillary region for the-phase within, m³ - V _c intersection of m³ - V volume of the-region within, m³ - V volume of the-region within, m³ - V () capillary region for the-phase within the-region, m³ - V () capillary region for the-phase within the-region, m³ - V () , region in which the-phase is trapped at the irreducible saturation, m³ - y position vector relative to the centroid of the large-scale averaging volume, m Greek Letters local volume-averaged porosity - local volume-averaged volume fraction for the-phase - local volume-averaged volume fraction for the-phase in the-region - local volume-averaged volume fraction for the-phase in the-region - local volume-averaged volume fraction for the-phase in the-region (This is directly related to the irreducible saturation.) - {} large-scale intrinsic phase average volume fraction for the-phase - {} large-scale phase average volume fraction for the-phase - {}* large-scale spatial average volume fraction for the-phase - –{}, large-scale spatial deviation for the-phase volume fraction - –{}, large-scale spatial deviation for the-phase volume fraction in the-region - –{}, large-scale spatial deviation for the-phase volume fraction in the-region - a generic local volume-averaged quantity associated with the-phase - mass density of the-phase, kg/m³ - mass density of the-phase, kg/m³ - viscosity of the-phase, N s/m² - viscosity of the-phase, N s/m² - interfacial tension of the - phase system, N/m - , N/m - , volume fraction of the-phase capillary (active) region - , volume fraction of the-phase capillary (active) region - , volume fraction of the-region ( + =1) - , volume fraction of the-region ( + =1) - {p }– g, N/m³ - {p }– g, N/m³     

Transport in ordered and disordered porous media II: Generalized volume averaging

In this paper we develop the averaged form of the Stokes equations in terms of weighting functions. The analysis clearly indicates at what point one must choose a media-specific weighting function in order to achieve spatially smoothed transport equations. The form of the weighting function that produces the cellular average is derived, and some important geometrical theorems are presented.Roman Letters A interfacial area of the- interface associated with the local closure problem, m² - A _e area of entrances and exits for the-phase contained within the averaging system, m² - A _p surface area of a particle, m² - d _p 6V _p/A_p, effective particle diameter, m - g gravity vector, m/s² - I unit tensor - K _m permeability tensor for the weighted average form of Darcy's law, m² - L general characteristic length for volume averaged quantities, m - L _p general characteristic length for volume averaged pressure, m - L characteristic length for the porosity, m - L _v characteristic length for the volume averaged velocity, m - l characteristic length (pore scale) for the-phase - l _i i=1, 2, 3 lattice vectors, m - (y) weighting function - m(–y) (y), convolution product weighting function - _v special weighting function associated with the traditional averaging volume - m _v special convolution product weighting function associated with the traditional averaging volume - m _g general convolution product weighting function - m _V unit cell convolution product weighting function - m _C special convolution product weighting function for ordered media which produces the cellular average - m _D special convolution product weighting function for disordered media - m _M master convolution product weighting function for ordered and disordered media - n unit normal vector pointing from the-phase toward the-phase - p pressure in the-phase, N/m² - p_m superficial weighted average pressure, N/m² - p _m intrinsic weighted average pressure, N/m² - p traditional intrinsic volume averaged pressure, N/m² - p p p _m , spatial deviation pressure, N/m² - r ₀ radius of a spherical averaging volume, m - r _m support of the convolution product weighting function, m - r position vector, m - r position vector locating points in the-phase, m - V averaging volume, m³ - V volume of the-phase contained in the averaging volume, m³ - V _cell volume of a unit cell, m³ - V velocity vector in the-phase, m/s - vm superficial weighted average velocity, m/s - v _m intrinsic weighted average velocity, m/s - V volume of the-phase contained in the averaging volume, m³ - V _p volume of a particle, m³ - v traditional superficial volume averaged velocity, m/s - v v p _m spatial deviation velocity, m/s - x position vector locating the centroid of the averaging volume or the convolution product weighting function, m - y position vector relative to the centroid, m - y position vector locating points in the-phase relative to the centroid, m Greek Letters indicator function for the-phase - Dirac distribution associated with the- interface - V /V, volume average porosity - _m m * . weighted average porosity - mass density of the-phase, kg/m³ - viscosity of the-phase, Ns/m² - V /V, volume fraction of the-phase     

Asymmetric catalytic synthesis of the proposed structure of trocheliophorolide B

A concise catalytic asymmetric synthesis of the proposed structure of trocheliophorolide B is reported. The synthetic sequence notably features an asymmetric acetaldehyde alkynylation, a Ru-catalyzed alder-ene reaction, and a Zn-ProPhenol ynone aldol condensation. Comparison with the reported data suggests a misassignment of the natural product structure.     

Transport in ordered and disordered porous media IV: Computer generated porous media for three-dimensional systems

In the method of volume averaging, the difference between ordered and disordered porous media appears at two distinct points in the analysis, i.e. in the process of spatial smoothing and in the closure problem. In theclosure problem, the use of spatially periodic boundary conditions isconsistent with ordered porous media and the fields under consideration when the length-scale constraint,r ₀L is satisfied. For disordered porous media, spatially periodic boundary conditions are an approximation in need of further study.In theprocess of spatial smoothing, average quantities must be removed from area and volume integrals in order to extractlocal transport equations fromnonlocal equations. This leads to a series of geometrical integrals that need to be evaluated. In Part II we indicated that these integrals were constants for ordered porous media provided that the weighting function used in the averaging process contained thecellular average. We also indicated that these integrals were constrained by certain order of magnitude estimates for disordered porous media. In this paper we verify these characteristics of the geometrical integrals, and we examine their values for pseudo-periodic and uniformly random systems through the use of computer generated porous media.

Nomenclature

Roman Letters A interfacial area of the- interface associated with the local closure problem, m² - A _e area of entrances and exits for the-phase contained within the averaging system, m² - a _i i=1, 2, 3 gaussian probability distribution used to locate the position of particles - I unit tensor - L general characteristic length for volume averaged quantities, m - L characteristic length for , m - L characteristic length for , m - characteristic length for the -phase particles, m - ⁰ reference characteristic length for the-phase particles, m - characteristic length for the-phase, m - _i i=1, 2, 3 lattice vectors, m - m convolution product weighting function - m _v special convolution product weighting function associated with the traditional volume average - n _i i=1, 2, 3 integers used to locate the position of particles - n unit normal vector pointing from the-phase toward the-phase - n _e outwardly directed unit normal vector at the entrances and exits of the-phase - r _p position vector locating the centroid of a particle, m - r gaussian probability distribution used to determine the size of a particle, m - r ₀ characteristic length of an averaging region, m - r position vector, m - r _m support of the weighting functionm, m - averaging volume, m³ - V volume of the-phase contained in the averaging volume,, m³ - x positional vector locating the centroid of an averaging volume, m - x ₀ reference position vector associated with the centroid of an averaging volume, m - y position vector locating points relative to the centroid, m - y position vector locating points in the-phase relative to the centroid, m Greek Letters indicator function for the-phase - Dirac distribution associated with the- interface - V /V, volume average porosity - /L, small parameter in the method of spatial homogenization - standard deviation ofa _i - _r standard deviation ofr - _r intrinsic phase average of      

Origin of the Enantioselectivity in Organocatalytic Michael Additions of β‐Ketoamides to α,β‐Unsaturated Carbonyls: A Combined Experimental,Spectroscopic and Theoretical Study

The organocatalytic enantioselective conjugate addition of secondary β‐ketoamides to α,β‐unsaturated carbonyl compounds is reported. Use of bifunctional Takemoto’s thiourea catalyst allows enantiocontrol of the reaction leading either to simple Michael adducts or spirocyclic aminals in up to 99 % ee. The origin of the enantioselectivity has been rationalised based on combined DFT calculations and kinetic analysis. This study provides a deeper understanding of the reaction mechanism, which involves a predominant role of the secondary amide proton, and clarifies the complex interactions occurring between substrates and the catalyst.     

Didecarboxylative Iron‐Catalyzed Bidirectional Aldolization towards Diversity‐Oriented Ketodiol Synthesis

1,3‐Acetonedicarboxylic acid was selectively activated by Fe(acac)₃, providing a synthetic platform for rapid synthesis of keto‐3,3′‐diols. The bidirectional aldol reaction was efficient for challenging aliphatic aldehydes, providing a rapid route to potentially bioactive complex structures.     

Interet de la deuteriation des molecules organostanniques en rmn de 119Sn : I. Acces aux constantes de couplage nJ(SnD) et application a l'etude structurale de vinyl et d'allyletains

The selective deuteration of organotin compounds gives FT ¹¹⁹Sn NMR a new proficiency, since it allows direct access to ⁿJ(SnD) coupling constants. Usually ⁿJ(SnD) is easily apparent for n  1, 2, 3 and sometimes 4 (allyltin compounds). This criterion has been successfully applied for qualitative and subsequently quantitative analysis of vinyltin and allyltin compounds.In the first series, the stereochemistry of alkyne deuterostannation has been easily explored, the assignments of configurations being made directly from ³J(SnD) on the basis of ³J(SnD)_trans > ₃J(SnD)_cis. In the second series, the method appears to be the best tool for simultaneous study of regiochemistry and stereochemistry in the substitution of 3-deutero-5-methyl-2-cyclohexenyl toluene sulphonates by trialkylstannyl anions. The choice between regioisomers was made on the basis of ₂J(SnD) >- ⁴J(SnD).A further aspect of this work is the observation of isotopic effects on ¹¹⁹Sn chemical shifts which were tentatively rationalized considering inductive, steric or hyperconjugative contribution of deuterium.