C.C.R.S. Rossi

Phase stability analysis of liquid-liquid equilibrium with stochastic methods

Minimization of Gibbs free energy using activity coefficient models and nonlinear equation solution techniques is commonly applied to phase stability problems. However, when conventional techniques, such as the Newton-Raphson method, are employed, serious convergence problems may arise. Due to the existence of multiple solutions, several problems can be found in modeling liquid-liquid equilibrium of multicomponent systems, which are highly dependent on the initial guess. In this work phase stability analysis of liquid-liquid equilibrium is investigated using the NRTL model. For this purpose, two distinct stochastic numerical algorithms are employed to minimize the tangent plane distance of Gibbs free energy: a subdivision algorithm that can find all roots of nonlinear equations for liquid-liquid stability analysis and the Simulated Annealing method. Results obtained in this work for the two stochastic algorithms are compared with those of the Interval Newton method from the literature. Several different binary and multicomponent systems from the literature were successfully investigated.

Simultaneous calculation of chemical and phase equilibria using convexity analysis

Chemical and phase equilibria were considered for closed multicomponent reactive systems at: (a) constant pressure and temperature; (b) constant pressure and enthalpy. Equilibrium at constant P and T was found by minimization of G, while equilibrium at constant P and H was found by maximization of S or minimization of −S, all with respect to the number of moles of each component in each phase. Both cases could be handled as optimization problems, satisfying the restrictions imposed by mole or atom balances, and non-negativity of number of moles. Convexity analyses were carried out, and the conditions were found in order to guarantee global minimum, for one liquid phase, one gas phase, and a number of solid phases. The minimum point was then found either by analytical methods or by direct minimization methods. These strategies were tested for a number of cases, with good results.

Parameter estimation and thermodynamic model fitting for components in mixtures for bio-diesel production.

In the search of clean, sustainable and renewable energy sources, at present the use of bio-diesel from vegetable oils is one of the possibilities being considered. The knowledge of phase equilibrium in mixtures found in the bio-diesel production is essential for the correct design and operation of the process. However, there is still a lack of information about the parameter values for the models used to describe the phase equilibrium, which could lead to incorrect design of the reactors and the separation processes, and to low efficiency caused by low mass transfer due to the presence of heterogeneous mixtures. In this study, two algorithms are described for the model fitting and parameter estimation, which were used to estimate the values of the parameters in the UNIQUAC and NRTL model for a mixture of vegetable oils and bio-diesel. One of the algorithms uses the Simulated Annealing (SA) method, to find good initial estimates, without any previous knowledge of the parameters. Another algorithm uses Successive Quadratic Programming, using the estimates calculated in the SA algorithm to refine these estimates. In both algorithms, the criterion for fitting is the minimization of the square of the difference between calculated and experimental values. In both algorithms, the equilibrium is calculated using the direct global minimization of the Gibbs free energy with respect to the number of moles of each component, at constant T and P, for a given set of model parameters. The results obtained were able to correctly reproduce the experimental values of phase equilibrium composition.

Theoretical and Empirical Studies on the Catalytic Partial Oxidation of Methane Promoted by FeY and Fe(piperazine)Y Complexes (Y = Y-zeolite)

In this study, we synthesized and characterized zeolite-encapsulated Fe(III) complexes containing piperazine-derived ligands. The catalytic activity of these complexes was tested in the partial oxidation of methane to methanol using O2 as a low-pressure oxidant. Values for methane conversion of up to 1.2% with methanol selectivity of up to 6.7% were obtained. The experimental data were compared with thermodynamic simulation results for the reaction that takes place as a basic principle, the minimization of Gibbs free energy.