Thermophysical property prediction of biodiesel mixtures at extreme conditions using molecular dynamics simulation

Liquid biofuels such as biodiesel are playing an increasing role in renewable energy utilisation, but accu-rate predictions of fuel properties at extreme conditions remain challenging. In this study, molecular dynamics (MD) simulation with classical force field is performed to obtain the thermophysical properties of biodiesel over extended ranges of temperatures and pressures. The predicted properties include the critical temperature, critical density, critical pressure, surface tension, viscosity, thermal conductivity and diffusion coefficient. The specific MD setup for fuel thermophysical property prediction is examined. It is observed that the long-range dispersion interaction is essential to accurately predicting the surface tension, and averaging over a sufficient number of independent replication simulations is required to eliminate the statistical error when using the Green-Kubo method for viscosity calculation. The reliability of MD approach is validated against experimental data at normal temperature and pressure. The equilib-rium MD simulation has an advantage over nonequilibrium MD simulation when building databases of fuel properties. Moreover, the properties of biodiesel are compared with conventional diesel to elucidate the effects of fuel composition and molecular structure of the fuel surrogates on fuel thermophysical properties. For biodiesel utilisation, higher values of critical temperature, surface tension and viscosity, lower diffusivity together with the increased aggregation tendency in bath gas indicate the needs of fur-ther optimisation of injection system to achieve the desired mixing in combustion applications.CO 2022 The Author(s). Published by Elsevier B.V.

Automated summary

This study uses molecular dynamics simulation to predict the thermophysical properties of biodiesel under different temperatures and pressures. The predicted properties include critical temperature, critical density, critical pressure, surface tension, viscosity, thermal conductivity, and diffusion coefficient. The study finds that long-range dispersion interaction is essential for predicting surface tension accurately, and averaging over a sufficient number of independent replication simulations is necessary to eliminate statistical errors in viscosity calculation. The reliability of the molecular dynamics approach is validated against experimental data. Additionally, the study compares the properties of biodiesel with conventional diesel, revealing higher values of critical temperature, surface tension, and viscosity, as well as lower diffusion, indicating the need for further optimization of injection systems for desired combustion mixing.