Molecular dynamics simulations of aqueous urea solutions: Study of dimer stability and solution structure, and calculation of the total nitrogen radial distribution function GN(r

Molecular dynamics simulations have been performed in order to study the structure of two molal urea solutions in D2O. Several initial dimer configurations were considered for an adequate sampling of phase space. Eventually all of them appeared to be unstable, when system size and periodic boundary conditions are chosen properly, even after a very careful equilibration. The total nitrogen scattering function GN(r), calculated from these simulations, is in good agreement with neutron scattering experiments when both intra- and intermolecular correlations are considered and the experimental truncation ripples are introduced by a Fourier transform of GN(r) back and forth. The simple pair potential model that we used gives results in good agreement with experiments and with a much more involved potential model, recently described in the literature [J. Chem. Phys. 95, 8419 (1991)]

From wave function to crystal morphology: application to urea and alpha-glycine

In this paper the relation between the molecular electron density distribution and the crystal growth morphology is investigated. Accurate charge densities derived from ab initio quantum chemical calculations were partitioned into multipole moments, to calculate the electrostatic contribution to the intermolecular interaction energy. For urea and alpha-glycine the F-faces or connected nets were determined according to the Hartman-Perdok PBC theory. From attachment energy and critical Ising temperature calculations, theoretical growth forms were constructed using different atom-atom potential models. These were compared to the Donnay-Harker model, equilibrium form and experimental growth forms. In the case of alpha-glycine, the theoretical growth forms are in good agreement with crystals grown from aqueous solution. Crystals obtained by sublimation seem to show some faces which are not F-faces sensu stricto

Micro-computed tomography pore-scale study of flow in porous media: Effect of voxel resolution

A fundamental understanding of flow in porous media at the pore-scale is necessary to be able to upscale average displacement processes from core to reservoir scale. The study of fluid flow in porous media at the pore-scale consists of two key procedures: Imaging - reconstruction of three-dimensional (3D) pore space images; and modelling such as with single and two-phase flow simulations with Lattice-Boltzmann (LB) or Pore-Network (PN) Modelling. Here we analyse pore-scale results to predict petrophysical properties such as porosity, single-phase permeability and multi-phase properties at different length scales. The fundamental issue is to understand the image resolution dependency of transport properties, in order to up-scale the flow physics from pore to core scale. In this work, we use a high resolution micro-computed tomography (micro-CT) scanner to image and reconstruct three dimensional pore-scale images of five sandstones (Bentheimer, Berea, Clashach, Doddington and Stainton) and five complex carbonates (Ketton, Estaillades, Middle Eastern sample 3, Middle Eastern sample 5 and Indiana Limestone 1) at four different voxel resolutions (4.4 µm, 6.2 µm, 8.3 µm and 10.2 µm), scanning the same physical field of view. Implementing three phase segmentation (macro-pore phase, intermediate phase and grain phase) on pore-scale images helps to understand the importance of connected macro-porosity in the fluid flow for the samples studied. We then compute the petrophysical properties for all the samples using PN and LB simulations in order to study the influence of voxel resolution on petrophysical properties. We then introduce a numerical coarsening scheme which is used to coarsen a high voxel resolution image (4.4 µm) to lower resolutions (6.2 µm, 8.3 µm and 10.2 µm) and study the impact of coarsening data on macroscopic and multi-phase properties. Numerical coarsening of high resolution data is found to be superior to using a lower resolution scan because it avoids the problem of partial volume effects and reduces the scaling effect by preserving the pore-space properties influencing the transport properties. This is evidently compared in this study by predicting several pore network properties such as number of pores and throats, average pore and throat radius and coordination number for both scan based analysis and numerical coarsened data

Pore-Scale Modeling of Drainage Displacement Patterns in Association With Geological Sequestration of CO2

©2020. The Authors. We investigate the immiscible displacement (drainage) of a wetting fluid in a porous medium by a nonwetting fluid using multi–graphics processing unit (GPU) lattice Boltzmann simulations with the aim of better understanding the pore-scale processes involved in the geological sequestration of CO2. Correctly resolving the dynamics involved in multiphase flow in permeable media is of paramount importance for any numerical scheme. Generally, the average fluid flow is assumed to be at low Reynolds numbers Reav. Hence, by neglecting inertial effects, this immiscible displacement should be characterized by just two dimensionless numbers, namely, the capillary number Caav and the viscosity ratio, which quantify the ratio of the relevant forces, that is, the viscous and capillary forces. Our investigation reveals that inertial effects cannot be neglected in the range of typical capillary numbers associated with multiphase flow in permeable media. Even as the average Caav and Reav decrease away from the injection point, inertial effects remain important over a transient amount of time during abrupt Haines jumps, when the nonwetting phase passes from a narrow restriction to a wider pore space. The local Rel at the jump sites is orders of magnitude higher than the average Reav, with the local dynamics being decoupled from the externally imposed flow rate. Therefore, a full Navier-Stokes solver should be used for investigating pore-scale displacement processes. Using the Ohnesorge number to restrict the parameter selection process is essential, as this dimensionless number links Caav and Reav and reflects the thermophysical properties of a given system under investigation

Investigation of viscous coupling effects in three-phase flow by lattice Boltzmann direct simulation and machine learning technique

The momentum transfer across fluid interfaces in multi-phase flow leads to a non-negligible viscous coupling effect. In this study, we use the lattice Boltzmann method (LBM) as a direct simulator to solve the three-phase flow at pore scale. The viscous coupling effects are investigated for various fluid configurations in simple pore geometries with different conditions in terms of saturation, wettability and viscosity ratio. It is found that the viscous coupling effect can be significant for certain configurations. A parametric modification factor for conventional three-phase conductance model is then proposed to estimate the viscous coupling effect. The modification factor as a function of viscosity ratios can be easily incorporated into existing pore network model (PNM) to eliminate errors from viscous coupling effect. Moreover, an elegant approach using machine learning technique is proposed to predict the multi-phase permeability by a trained Artificial Neural Network (ANN) from the direct simulation database. Such data-driven approach can be extended to develop a more sophisticated PNM for a better prediction of transport properties taking account of the viscous coupling effects

Molecular-dynamics simulations of interfaces between water and crystalline urea

Molecular-dynamics simulations of several water-crystalline urea interfaces have been performed. The structure and dynamics of water close to the urea crystal surface are discussed in terms of density profiles, positional and orientational distribution functions, and diffusion coefficients. The water structure close to the interface is strongly determined by the structure of the crystal surface: the (001) and (111) interfaces reveal strong adsorption of water while the (110) and () interfaces do so to a lesser extent. Assuming that the growth rate of a specific crystal face decreases with increasing solvent adsorption, the appearance of only (111) on the urea growth form is predicted. We argue that on the other hand the dominance of (110) over (001) cannot be explained using a simple layer growth model

Spatial Characterization of Wetting in Porous Media Using Local Lattice-Boltzmann Simulations

Wettability is one of the critical parameters affecting multiphase flow in porous media. The wettability is determined by the affinity of fluids to the rock surface, which varies due to factors such as mineral heterogeneity, roughness, ageing, and pore-space geometry. It is well known that wettability varies spatially in natural rocks, and it is still generally considered a constant parameter in pore-scale simulation studies. The accuracy of pore-scale simulation of multiphase flow in porous media is undermined by such inadequate wettability models. The advent of in situ visualization techniques, e.g. X-ray imaging and microtomography, enables us to characterize the spatial distribution of wetting more accurately. There are several approaches for such characterization. Most include the construction of a meshed surface of the interface surfaces in a segmented X-ray image and are known to have significant errors arising from insufficient resolution and surface-smoothing algorithms. This work presents a novel approach for spatial determination of wetting properties using local lattice-Boltzmann simulations. The scheme is computationally efficient as the segmented X-ray image is divided into subdomains before conducting the lattice-Boltzmann simulations, enabling fast simulations. To test the proposed method, it was applied to two synthetic cases with known wettability and three datasets of imaged fluid distributions. The wettability map was obtained for all samples using local lattice-Boltzmann calculations on trapped ganglia and optimization on surface affinity parameters. The results were quantitatively compared with a previously developed geometrical contact angle determination method. The two synthetic cases were used to validate the results of the developed workflow, as well as to compare the wettability results with the geometrical analysis method. It is shown that the developed workflow accurately characterizes the wetting state in the synthetic porous media with an acceptable uncertainty and is better to capture extreme wetting conditions. For the three datasets of imaged fluid distributions, our results show that the obtained contact angle distributions are consistent with the geometrical method. However, the obtained contact angle distributions tend to have a narrower span and are considered more realistic compared to the geometrical method. Finally, our results show the potential of the proposed scheme to efficiently obtain wettability maps of porous media using X-ray images of multiphase fluid distributions. The developed workflow can help for more accurate characterization of the wettability map in the porous media using limited experimental data, and hence more accurate digital rock analysis of multiphase flow in porous media

Dissipative Particle Dynamics with energy conservation

Dissipative particle dynamics (DPD) does not conserve energy and this precludes its use in the study of thermal processes in complex fluids. We present here a generalization of DPD that incorporates an internal energy and a temperature variable for each particle. The dissipation induced by the dissipative forces between particles is invested in raising the internal energy of the particles. Thermal conduction occurs by means of (inverse) temperature differences. The model can be viewed as a simplified solver of the fluctuating hydrodynamic equations and opens up the possibility of studying thermal processes in complex fluids with a mesoscopic simulation technique.Comment: 5 page

Transition from oil & gas drilling fluids to geothermal drilling fluids

The harsh downhole conditions encountered in geothermal wells, specifically the high temperatures (HT) together with the toughness of the rock found in many geothermal formations, makes the drilling operation challenging. Drilling in such environments requires specialised drilling fluid formulations that have high thermal stability, good rheological properties, excellent lubricity and low formation damage. Given the wealth of experience in drilling wells in the oil industry, it is tempting to assume that the design of geothermal drilling fluids would be straightforward. However, is this the case? In this literature review, we have attempted to answer the question: “to what degree can developments in oil and gas drilling fluids be transferred to drilling fluids for geothermal wells?” To keep the scope of the review manageable, we have focused on two key aspects of drilling fluid design: rate of penetration (ROP) and HT fluid stability (and maintenance of the desired rheological properties of the fluid at high temperatures). The review has allowed the identification of gaps in both fundamental understanding and in existing technology. Rate of penetration is improved using low viscosity and low-density fluids, and we recommend that foams and aphron systems should be investigated to achieve this (depending on the application pressure). It should be noted, however, that such systems to date have only been studied at relatively low temperatures and the challenge of increasing the thermal stability of the formulation components needs to be addressed. Highly thermally stable polymer systems exist but these are both expensive and not widely available. A systematic study of the impact of copolymer molecular architecture on hydrolytic thermal stability is recommended. A promising solution to both maintaining good rheological properties at high temperature and providing fluid loss control is the use of particulates, especially those in the nano-size range. Additionally, nanocomposite systems show promise in this area and should be investigated. Particle stabilized foams and aphrons are a particularly interesting solution and we recommend that these are studied. It is also recommended to investigate the effect of drilling fluid on long term geothermal well performance