Modeling and Experimental Measurements of Thermodynamic Properties of Natural Gas Mixtures and Their Components

Chemical process design requires mathematical models for predicting thermophysical properties. Those models, called equations of state (EoS), need experimental data for parameter estimation and validation. This work presents a detailed description of a vibrating tube densimeter, which is an alternative technique for measurement of p-ρ-T data in gases at critical conditions. This apparatus can measure fluids in a temperature range of 300 K to 470 K and pressures up to 140 MPa. This work calibrates the vibrating tube using a physical-based methodology with nitrogen, methane and argon measurements. Carbon dioxide and ethane p-ρ-T data validate calibration procedures covering a wide range in density and pressure. The vibrating tube densimeter performs density measurements for nitrogen + methane mixtures for pressures up to 140 MPa. This work also presents a new equation of state (EoS) having a rational form that can describe properties with accuracy comparable to the best multi-parametric equations with less mathematical complexity. This EoS presents the Helmholtz residual energy as a ratio of two polynomial functions in density (no exponential terms in density are included), which can describe the behavior of pure components. The EoS can be transformed to describe other thermophysical properties as pressure, compressibility factor, heat capacity and speed of sound. Also this equation can calculate saturated liquid-vapor properties with 20 times less computational time. This work presents rational EoS for nitrogen, argon and methane applicable in wide ranges of pressure and temperature. Finally, this work proposes a new mixing rule for binary mixtures of gases based upon a quadratic combination of residual Helmholtz energy. This approach divides the energy contribution between interactions of same species and interaction of different species molecules. A rational form is proposed for description of energy interaction between molecules of different species. The mixing rule is applied to nitrogen + methane data