Magnetic resonance imaging of chemical waves in porous media

Magnetic resonance imaging (MRI) provides a powerful tool for the investigation of chemical structures in optically opaque porous media, in which chemical concentration gradients can be visualized, and diffusion and flow properties are simultaneously determined. In this paper we give an overview of the MRI technique and review theory and experiments on the formation of chemical waves in a tubular packed bed reactor upon the addition of a nonlinear chemical reaction. MR images are presented of reaction-diffusion waves propagating in the three-dimensional (3D) network of channels in the reactor, and the 3D structure of stationary concentration patterns formed via the flow-distributed oscillation mechanism is demonstrated to reflect the local hydrodynamics in the packed bed. Possible future directions regarding the influence of heterogeneities on transport and reaction are discussed.     

Fractal patterns of fluid domains for displacement processes in porous media

Percolation invasion displacement of a compressible defender is examined for two cases: when only the smallest accessible site is entered at each step and when all accessible sites less than the size given by a reducing back pressure are entered at each time step. Although the fractions of invading fluid are different, their scaling properties are equivalent. The effect of limited control of a back pressure in a real displacement and the effect of viscosity in a real time displacement are examined. In these cases the scaling properties of a percolation process at breakthrough are removed. As a result, one should expect that realistic displacement models will not have the singular properties usually attributed to percolation processes.     

Quantitative magnetic resonance flow and diffusion imaging in porous media

Quantitative flow and diffusion measurements have been made for water in model porous media, using magnetic resonance micro-imaging methods. The samples consisted of compacted glass beads of various sizes down to 1 mm diameter. Typical flow and diffusion images exhibited a spatial resolution of 117 μm × 117 μm and velocities in the range 1–2 mm/s. Comparison of volume flow rates calculated from the flow velocity maps with values measured directly yielded good agreement in all cases. There was also good agreement between the mean diffusion coefficient of water calculated from the diffusion maps and the bulk diffusion coefficient for pure water at the same temperature. In addition, the mean diffusion coefficient did not depend on the pore sizes in the bead diameter range of 1–3 mm. Our results also show that partial volume effects can be compensated by appropriate thresholding of the images prior to the final Fourier transformation in the flow-encoding dimension.     

Magnetic resonance visualisation of single- and two-phase flow in porous media.

Three-dimensional MRI and flow visualisation data are presented for single and two-phase flow occurring within packed beds of glass spheres. The initial motivation for this work has been to understand the operation of fixed-bed reactors used in many chemical processing operations; these systems also serve as model porous media in which to investigate the effect of the structure of a pore space on the flow phenomena occurring within it. For the case of single-phase flow, maps of the liquid shear rate components are calculated from which forces on individual spheres within the bed are obtained. The velocity histogram for flow transverse to the direction of superficial flow is exponential in both negative and positive directions. This form of the velocity histogram implies an exponential form for the displacement propagator, in contrast to the Gaussian distribution obtained by pulsed gradient spin echo measurements. This difference arises because the spatially resolved velocity imaging sequence measures only the average velocity within each voxel and is insensitive to the effects of incoherent (diffusive) motion. Visualisations of air-water flow through a sphere pack are also reported and the capability of MRI to yield information on rivulet formation and surface wetting characteristics is illustrated.     

Using NMR displacement imaging to characterize electroosmotic flow in porous media.

Pulsed field gradient nuclear magnetic resonance (PFG-NMR) and NMR imaging were used to study temporal and spatial domains of an electrokinetically-driven mobile phase through open and packed segments of capillaries. Characteristics like velocity distribution and an asymptotic dispersion are contrasted to viscous flow behavior. We show that electroosmotic flow in microchannel geometries can offer a significant performance advantage over the pressure-driven flows at comparable Peclét numbers, indicating that velocity extremes in the pore space of open tubes and packed beds are drastically reduced. An inherent problem of capillary electrochromatography that we finally address is the existence of wall effects when in the general case the surface zeta-potentials of the capillary inner wall and the adsorbent particles are different. Using dynamic NMR microscopy we were able resolve this systematic velocity inequality of the flow pattern which strongly influences axial dispersion and may be responsible for long time-tails of velocity distribution in the mobile phase.     

Magnetic resonance imaging: applications of novel methods in studies of porous media.

NMR imaging is finding broad applications in nonbiological areas including the study of fluid flow and fluid ingress in porous media. The porous media include at the one end mineral rocks and various building materials through various solid plastic materials to foodstuffs at the other end of the spectrum. The fluids within these various media range from crude oil and water mixtures, and water itself, to a range of organic solvents in plastic materials. This paper is concerned with the flow and ingress of water through Bentheimer sandstone and Ninian reservoir specimens, and also in solid nylon blocks.     

Magnetic resonance in porous media: forty years on

A personal view of the field of magnetic resonance in porous media is presented in which an attempt is made to survey the current status and achievements, to highlight some of the contributions made by my group over the years and, at the end, to try and identify where further effort and growth points may be perceived. All this is done with the knowledge that the first and last sections are certain to be partial, incomplete and wrong, at least in part, and that the middle section describes work carried out by some of the many excellent students, post-doctoral researchers and other colleagues with whom it has been a pleasure to collaborate over a forty year research career.     

Three-dimensional fluid pressure mapping in porous media using magnetic resonance imaging with gas-filled liposomes

This paper presents and demonstrates a method for using magnetic resonance imaging to measure local pressure of a fluid saturating a porous medium. The method is tested both in a static system of packed silica gel and in saturated sintered glass cylinders experiencing fluid flow. The fluid used contains 3% gas in the form of 3-mum average diameter gas filled 1,2-distearoyl-sn-glycero-3-phosphocholine (C18:0, MW: 790.16) liposomes suspended in 5% glycerol and 0.5% Methyl cellulose with water. Preliminary studies at 2.35 T demonstrate relative magnetic resonance signal changes of 20% per bar in bulk fluid for an echo time T(E)=40 ms, and 6-10% in consolidated porous media for T(E)=10 ms, over the range 0.8-1.8 bar for a spatial resolution of 0.1 mm(3) and a temporal resolution of 30 s. The stability of this solution with relation to applied pressure and methods for improving sensitivity are discussed.     

多孔介质中卡森流体的分形分析

研究了非牛顿流体中的卡森流体在多孔介质中的流动特性.基于服从分形分布的弯曲毛细管束模型,运用分形几何理论推导出了该流体在多孔介质中流动的流量、流速、启动压力梯度和有效渗透率的分形解析解.模型中的每一个参数都有明确的物理意义,它将卡森流体在多孔介质中的流动特性与多孔介质的微结构参数有机联系起来.文中给出了卡森流体的流速、启动压力梯度和有效渗透率随着各影响因素的变化趋势,并进行了讨论.所得分形模型可以更深刻地理解卡森流体在多孔介质中流动的内在物理机理. 关键词： 多孔介质 卡森流体 分形     

Direct pore-level modeling of incompressible fluid flow in porous media

We present a dynamic particle-based model for direct pore-level modeling of incompressible viscous fluid flow in disordered porous media. The model is capable of simulating flow directly in three-dimensional high-resolution micro-CT images of rock samples. It is based on moving particle semi-implicit (MPS) method. We modify this technique in order to improve its stability for flow in porous media problems. Using the micro-CT image of a rock sample, the entire medium, i.e., solid and fluid, is discretized into particles. The incompressible Navier–Stokes equations are then solved for each particle using the MPS summations. The model handles highly irregular fluid–solid boundaries effectively. An algorithm to split and merge fluid particles is also introduced. To handle the computational load, we present a parallel version of the model that runs on distributed memory computer clusters. The accuracy of the model is validated against the analytical, numerical, and experimental data available in the literature. The validated model is then used to simulate both unsteady- and steady-state flow of an incompressible fluid directly in a representative elementary volume (REV) size micro-CT image of a naturally-occurring sandstone with 3.398 μm resolution. We analyze the quality and consistency of the predicted flow behavior and calculate absolute permeability using the steady-state flow rate.     

Wave-induced fluid flow in random porous media: attenuation and dispersion of elastic waves

A detailed analysis of the relationship between elastic waves in inhomogeneous, porous media and the effect of wave-induced fluid flow is presented. Based on the results of the poroelastic first-order statistical smoothing approximation applied to Biot's equations of poroelasticity, a model for elastic wave attenuation and dispersion due to wave-induced fluid flow in 3-D randomly inhomogeneous poroelastic media is developed. Attenuation and dispersion depend on linear combinations of the spatial correlations of the fluctuating poroelastic parameters. The observed frequency dependence is typical for a relaxation phenomenon. Further, the analytic properties of attenuation and dispersion are analyzed. It is shown that the low-frequency asymptote of the attenuation coefficient of a plane compressional wave is proportional to the square of frequency. At high frequencies the attenuation coefficient becomes proportional to the square root of frequency. A comparison with the 1-D theory shows that attenuation is of the same order but slightly larger in 3-D random media. Several modeling choices of the approach including the effect of cross correlations between fluid and solid phase properties are demonstrated. The potential application of the results to real porous materials is discussed.     

Magnetic resonance for fluids in porous media at the University of Bologna

The magnetic resonance in porous media (MRPM) community is now a vast community of scientists from all over the world who recognize magnetic resonance as an instrument of choice for the characterization of pore space and of the distribution, diffusion and flow of fluids inside a vast range of different materials. The MRPM conferences are the occasions in which this community gets together, compares notes and grows. The scene was different in 1990, when this series of conferences was promoted at Bologna. I will go briefly over the history of these events, showing the role played by the University of Bologna and in particular by the intuition, ingenuity and passion of Giulio Cesare Borgia. The MRPM work at Bologna began in the mid-1980s. New correlations were found among parameters from NMR relaxation measurements and oil field parameters such as porosity, permeability to fluid flow, irreducible water saturation, residual oil saturation and pore-system surface-to-volume ratio, and fast algorithms were developed to give the different NMR parameters. Interest in valid interpretation of data led to extensive work also on the inversion of multiexponential relaxation data and the effects of inhomogeneous fields from susceptibility differences on distributions of relaxation times. In the last few years, extensive developments were made of combined magnetic resonance imaging and relaxation measurements in different fields.     

Magnetic resonance imaging of single- and two-phase flow in fixed-bed reactors

Magnetic resonance imaging and flow visualization techniques are increasingly used to study transport processes in chemical and biochemical reactors. Three recent case studies from our own research program are reported, each illustrating quite different applications of magnetic resonance techniques in such applications. First, two-phase flow in a trickle-bed reactor is considered. Images of the steady-state gas-liquid distribution are obtained which yield quantitative measures of liquid holdup and wetting efficiency. Second, a radiofrequency pulse sequence based on that for rapid acquisition with relaxation enhancement is used to perform ultrafast visualization of gas-liquid flow in individual channels within a ceramic monolith. Finally,¹H volume-selective nuclear magnetic resonance spectroscopy is employed to perform an in situ spatially resolved study of the extent of conversion of the liquid-phase esterification reaction of methanol and acetic acid, catalyzed by an acid catalyst (Amberlyst 15 ion exchange resin) in a fixed-bed reactor. In particular, the effect of the superficial flow rate of the feed on conversion is investigated.     

Magnetic resonance diffusion-weighted imaging: quantitative evaluation of age-related changes in healthy liver parenchyma

The purpose of this study was to verify in healthy liver parenchyma the possible influence of age on DwI-related parameters: apparent diffusion coefficient (ADC), perfusion fraction (PF), diffusion and pseudodiffusion coefficient (D and D^?). Forty healthy adult volunteers (age range 26-86 years), divided into four age groups, were prospectively submitted to a breath-hold magnetic resonance diffusion imaging (MR-DwI) (two b values, 0-300 and 0-1000 s/mm²). A smaller cohort of 16 subjects underwent a free-breath multi-b acquisition (16 b values, 0-750 s/mm²). Quantitative analysis was performed by two observers with manually defined regions of interest, on the most homogeneous portion of the right liver lobe. Individual and group statistical analysis of data was performed: ANOVA to establish differences between groups and Pearson correlation coefficient to investigate the association between DwI parameters and age. The mean, S.D. and 95% limits of agreement of ADC values for each age-defined group are reported. ANOVA showed no significant differences between group means (P always >.05). No significant correlation between subjects' age and DwI parameters was established, both in breath-hold and free-breath acquisitions, on the whole range of adopted b values. Our study conducted on healthy liver parenchyma shows that there are no significant differences in ADC, PF, D and D^? of younger or older subjects.