Linking up pressure, chemical potential and thermal gradients.

Petroleum reservoirs are remarkable illustrations of the impact of a thermal gradient on fluid pressure and composition. This topic has been extensively studied during the last decades to build tools that are required by reservoir engineers to populate their models. However, one can get only a very limited number of representative samples from a given reservoir and assessing connectivity between all sampling points is often a key issue. In some extreme cases, the whole reservoir fluid properties must be derived from a single point to define the field development plan. To do so, available models are usually not satisfactory as they need too many parameters and so cannot be considered as predictive tools. We propose in this work a comprehensive approach based on the irreversible thermodynamics principles to derive the relationships between pressure, chemical potentials and thermal gradients in porous media. It appears that there is no need for additional assumptions, it is just a matter of a making the right choices along theoretical developments. One of the most important steps is to express the full pressure gradient. As a final result, we obtain the chemical potential gradients for all components of the mixtures that can be easily translated in term of compositions through Equation of State modelling. The most important features of the final expressions are: i) the species relative separation in a thermal field is sensitive to the relative diffusion coefficients at stationary state. In porous media, the separation is sensitive to the permeability when the overall mobility is similar to diffusive mobility; ii) the magnitude of the separation depends on the residual entropy of the species; iii) the separation is not simply balanced by the average residual entropy. The balance is modified by the relative diffusion mobility of the components; iv) in low permeability porous media, the thermal gradient induces a pressure gradient proportional to the fluid residual entropy. As a validation, the proposed approach has been applied on a reservoir fluid subjected to a geothermal gradient and compared with non-equilibrium molecular dynamics simulation results at the stationary state.

Thermodiffusion in multicomponent n-alkane mixtures.

Compositional grading within a mixture has a strong impact on the evaluation of the pre-exploitation distribution of hydrocarbons in underground layers and sediments. Thermodiffusion, which leads to a partial diffusive separation of species in a mixture due to the geothermal gradient, is thought to play an important role in determining the distribution of species in a reservoir. However, despite recent progress, thermodiffusion is still difficult to measure and model in multicomponent mixtures. In this work, we report on experimental investigations of the thermodiffusion of multicomponent n-alkane mixtures at pressure above 30 MPa. The experiments have been conducted in space onboard the Shi Jian 10 spacecraft so as to isolate the studied phenomena from convection. For the two exploitable cells, containing a ternary liquid mixture and a condensate gas, measurements have shown that the lightest and heaviest species had a tendency to migrate, relatively to the rest of the species, to the hot and cold region, respectively. These trends have been confirmed by molecular dynamics simulations. The measured condensate gas data have been used to quantify the influence of thermodiffusion on the initial fluid distribution of an idealised one dimension reservoir. The results obtained indicate that thermodiffusion tends to noticeably counteract the influence of gravitational segregation on the vertical distribution of species, which could result in an unstable fluid column. This confirms that, in oil and gas reservoirs, the availability of thermodiffusion data for multicomponent mixtures is crucial for a correct evaluation of the initial state fluid distribution.

Nonisothermal gravitational segregation by molecular dynamics simulations.

In this work, a molecular dynamics algorithm is proposed to study the transient and the stationary state of gravitational segregation in simple fluid mixtures. Both isothermal and stable nonisothermal (where thermodiffusion occurs) cases have been studied. This approach is applied extensively on a simple fluid model: Lennard-Jones mixtures composed of species differing only in their masses. First, using isothermal binary equimolar mixtures, it is shown that the molecular dynamics simulations provide stationary results consistent with the thermodynamic modeling in various thermodynamic conditions and for different gravity fields. Next, in stable nonisothermal mixtures heated from below, it is shown that the gravitational segregation and the thermodiffusion process (Soret effect) have an opposite effect on the concentration profiles along the fluid column. Then, molecular dynamics simulations are performed on ternary and ten-component mixtures. For these multicomponent nonisothermal mixtures, results obtained emphasize the fact that the way the thermodiffusion is estimated should be done with care. In addition, for all nonisothermal configurations, the simulation results confirm that the thermodiffusion may have a non-negligible influence on the concentration profile in a petroleum reservoir. Finally, by analyzing the transient behavior during the molecular dynamics simulations, it is shown that the dynamic of the gravitational segregation is unambiguously controlled by the mass diffusion.

Molecular dynamics comparative study of Lennard-Jones -6 and exponential -6 potentials: application to real simple fluids (viscosity and pressure).

In this work, using molecular dynamics simulation, the viscosity (dynamic property) and the pressure (static property) of spherical fluid particles interacting through Lennard-Jones -6 and exponential -6 potentials are computed. Simulations are performed for going from 10 to 20 for the Lennard-Jones potential and from 12 to 22 for the exponential one. Six different thermodynamic states are tested that cover a large range of conditions, from sub- to supercritical temperature and from low to high density. To compare in a consistent manner the results for the various potentials tested, the simulations are carried out for the same set of reduced thermodynamic conditions (using the critical point). It is found that a perfect corresponding-states formulation is not possible between these potentials. Then, these potentials are applied on real simple fluids (argon, oxygen, nitrogen, methane, ethane, and one mixture, air) and the calculated viscosity and pressure values are compared with reference values. It appears that, using the appropriate , both potential families lead to a good accuracy in pressure and viscosity using the same set of molecular parameters for both properties, the average absolute deviations being always lower than 5% for the studied states. In addition, it is shown that the exponential potential results do not outperform the Lennard-Jones ones. Furthermore, for all compounds except for methane, the best results are obtained for the Lennard-Jones 12-6 and the exponential 14-6 potentials. This result partly explains why, despite no theoretical background, the Lennard-Jones 12-6 potential is so widely used. Finally, it is shown that a van der Waals one-fluid model performs extremely well for the studied mixture (air).