Deposition of colloidal asphaltene in capillary flow: Experiments and mesoscopic simulations

The aggregation and deposition of colloidal asphaltene in reservoir rock is a significant problem in the oil industry. To obtain a fundamental understanding of this phenomenon, we have studied the deposition and aggregation of colloidal asphaltene in capillary flow by experiment and simulation. For the simulation, we have used the stochastic rotation dynamics (SRD) method, in which the solvent hydrodynamic emerges from the collisions between the solvent particles, while the Brownian motion emerges naturally from the interactions between the colloidal asphaltene particles and the solvent. The asphaltene colloids interact through a screened Coulomb potential. We vary the well depth ecc and the flow rate v to obtain Peflow » 1 (hydrodynamic interactions dominate) and Re « 1 (Stokes flow). In the simulations, we impose a pressure drop over the capillary length and measure the corresponding solvent flow rate. We observe that the transient solvent flow rate decreases when the asphaltene particles become more sticky . For a well depth ecc = 2kBT, a monolayer deposits on the capillary wall. With an increasing well depth, the capillary becomes totally blocked. The clogging is transient for ecc = 5kBT, but appears to be permanent for ecc = 10-20kBT. We compare our simulation results with flow experiments in glass capillaries, where we use extracted asphaltenes in toluene, reprecipitated with n-heptane. In the experiments, the dynamics of asphaltene precipitation and deposition were monitored in a slot capillary using optical microscopy under flow conditions similar to those used in the simulation. Maintaining a constant flow rate of 5 µL min-1, we found that the pressure drop across the capillary first increased slowly, followed by a sharp increase, corresponding to a complete local blockage of the capillary. Doubling the flow rate to 10 µL min-1, we observe that the initial deposition occurs faster but the deposits are subsequently entrained by the flow. We calculate the change in the dimensionless permeability as a function of time for both experiment and simulation. By matching the experimental and simulation results, we obtain information about (1) the interaction potential well depth for the particular asphaltenes used in the experiments and (2) the flow conditions associated with the asphaltene deposition process. © 2008 American Chemical Society

Mechanical Properties of End-crosslinked Entangled Polymer Networks using Sliplink Brownian Dynamics Simulations

The mechanical properties of a polymeric network containing both crosslinks and sliplinks (entanglements) are studied using a multi-chain Brownian dynamics simulation. We coarse-grain at the level of chain segments connecting consecutive nodes (cross- or sliplinks), with particular attention to the Gaussian statistics of the network. Affine displacement of nodes is not imposed: their displacement as well as sliding of monomers through sliplinks is governed by force balances. The simulation results of stress in uniaxial extension and the full stress tensor in simple shear including the (non-zero) second normal stress difference are presented for monodisperse chains with up to 18 entanglements between two crosslinks. The cases of two different force laws of the subchains (Gaussian chains and chains with finite extensibility) for two different numbers of monomers in a subchain (no = 50 and no = 100) are examined. It is shown that the additivity assumption of slip- and crosslink contribution holds for sufficiently long chains with two or more entanglements, and that it can be used to construct the strain response of a network of infinitely long chains. An important consequence is that the contribution of sliplinks to the small-strain shear modulus is about ⅔ of the contribution of a crosslink

New hydraulic insights into rapid sand filter bed backwashing using the Carman–Kozeny model

Fluid flow through a bed of solid particles is an important process that occurs in full-scale water treatment operations. The Carman–Kozeny model remains highly popular for estimating the resistance across the bed. It is common practice to use particle shape factors in fixed bed state to match the predicted drag coefficient with experimentally obtained drag coefficients. In fluidised state, however, where the same particles are considered, this particle shape factor is usually simply omitted from the model without providing appropriate reasoning. In this research, it is shown that a shape factor is not a constant particle property but is dependent on the fluid properties as well. This dynamic shape factor for irregularly shaped grains increases from approximately 0.6 to 1.0 in fluidised state. We found that unstable packed beds in moderate up-flow conditions are pseudo-fixed and in a setting state. This results in a decreasing bed voidage and simultaneously in a decreasing drag coefficient, which seems quite contradictory. This can be explained by the collapse of local channels in the bed, leading to a more uniform flow distribution through the bed and improving the available surface for flow-through. Our experimental measurements show that the drag coefficient decreases considerably in the laminar and transition regions. This is most likely caused by particle orientation, realignment and rearrangement in particles’ packing position. A thorough hydraulic analysis shows that up-flow filtration in rapid sand filters under backwash conditions causes the particle bed to collapse almost imperceptibly. In addition, an improved expression of the drag coefficient demonstrated that the Carman–Kozeny model constant, however often assumed to be constant, is in fact not constant for increasing flow rates. Furthermore, we propose a new pseudo-3D image analysis for particles with an irregular shape. In this way, we can explain the successful method using optimisation of the extended terminal sub-fluidisation wash (ETSW) filter backwashing procedure, in which turbidity and peaks in the number of particles are reduced with a positive effect on water quality

Experimental and numerical insights into heterogeneous liquid-solid behaviour in drinking water softening reactors

Liquid-solid fluidisation is frequently encountered in drinking water treatment processes, for instance in seeded crystallisation softening processes. For modest superficial fluid velocities, liquid–solid fluidisation systems are generally considered to be homogeneous, as reported in literature. However, during fluidisation experiments with calcite grains, open spaces of water can be observed between the fluidised particles, even at relatively low fluid velocities. Moreover, significant heterogeneous particle–fluid patterns are detected at higher fluid velocities. Such heterogeneous behaviour can beneficially or adversely affect the chemical crystallisation efficiency. To obtain information about voids in bulk regions, complementary Computational Fluid Dynamics - Discrete Element Method (CFD-DEM) simulations were performed and compared with the experimental results for validation. Simulations were performed using different water inlet velocities and fractionised calcite granules obtained from full-scale reactors. Here, the results are analysed using the bed height, voidage and pressure drop of the system. Furthermore, images of the experiments and simulations are visually compared for the formation of voids. The simulations showed distinct differences in void fraction in the cross-section of the column. It is shown that throughout the range of considered water velocities, heterogeneous behaviour exists and cannot be neglected. The heterogeneity and onset of fluidisation behaviour obtained from the simulations and experimental observations were compared and found to agree reasonably well

Simulational study of anomalous tracer diffusion in hydrogels

In this article, we analyze different factors that affect the diffusion behavior of small tracer particles (as they are used e.g.in fluorescence correlation spectroscopy (FCS)) in the polymer network of a hydrogel and perform simulations of various simplified models. We observe, that under certain circumstances the attraction of a tracer particle to the polymer network strands might cause subdiffusive behavior on intermediate time scales. In theory, this behavior could be employed to examine the network structure and swelling behavior of weakly crosslinked hydrogels with the help of FCS.Comment: 11 pages, 11 figure

Quantitative imaging of concentrated suspensions under flow

We review recent advances in imaging the flow of concentrated suspensions, focussing on the use of confocal microscopy to obtain time-resolved information on the single-particle level in these systems. After motivating the need for quantitative (confocal) imaging in suspension rheology, we briefly describe the particles, sample environments, microscopy tools and analysis algorithms needed to perform this kind of experiments. The second part of the review focusses on microscopic aspects of the flow of concentrated model hard-sphere-like suspensions, and the relation to non-linear rheological phenomena such as yielding, shear localization, wall slip and shear-induced ordering. Both Brownian and non-Brownian systems will be described. We show how quantitative imaging can improve our understanding of the connection between microscopic dynamics and bulk flow.Comment: Review on imaging hard-sphere suspensions, incl summary of methodology. Submitted for special volume 'High Solid Dispersions' ed. M. Cloitre, Vol. xx of 'Advances and Polymer Science' (Springer, Berlin, 2009); 22 pages, 16 fig

Effects of macromolecular crowding on intracellular diffusion from a single particle perspective

Compared to biochemical reactions taking place in relatively well-defined aqueous solutions in vitro, the corresponding reactions happening in vivo occur in extremely complex environments containing only 60–70% water by volume, with the remainder consisting of an undefined array of bio-molecules. In a biological setting, such extremely complex and volume-occupied solution environments are termed ‘crowded’. Through a range of intermolecular forces and pseudo-forces, this complex background environment may cause biochemical reactions to behave differently to their in vitro counterparts. In this review, we seek to highlight how the complex background environment of the cell can affect the diffusion of substances within it. Engaging the subject from the perspective of a single particle’s motion, we place the focus of our review on two areas: (1) experimental procedures for conducting single particle tracking experiments within cells along with methods for extracting information from these experiments; (2) theoretical factors affecting the translational diffusion of single molecules within crowded two-dimensional membrane and three-dimensional solution environments. We conclude by discussing a number of recent publications relating to intracellular diffusion in light of the reviewed material