Abstract This paper presents simulations of discharges from pressure vessels that consistently account for non-ideal fluid behavior in all the required thermodynamic properties and individually considers all the chemical components present. The underlying assumption is that phase equilibrium occurs instantaneously inside the vessel and, thus, the dynamics of the fluid in the vessel comprises a sequence of equilibrium states. The formulation leads to a system of differential-algebraic equations in which the component mass balances and the energy balance are ordinary differential equations. The algebraic equations account for the phase equilibrium conditions inside the vessel and at the discharge point, and for sound speed calculations. The simulator allows detailed predictions of the condition inside the vessel and at the discharge point as a function of time, including the flow rate and composition of the discharge. The paper presents conceptual applications of the simulator to predict the effect of leaks from vessels containing mixtures of light gases and/or hydrocarbons and comparisons to experimental data.

Abstract The correlation of thermodynamic properties of nonaqueous electrolyte solutions is relevant to design and operation of many chemical processes, as in fertilizer production and the pharmaceutical industry. In this work, the Q-electrolattice equation of state (EOS) is used to model vapor pressure, mean ionic activity coefficient, osmotic coefficient, and liquid density of sixteen methanol and ten ethanol solutions containing single strong 1:1 and 2:1 salts. The Q-electrolattice comprises the lattice-based Mattedi-Tavares-Castier (MTC) EOS, the Born term and the explicit MSA term. The model requires two adjustable parameters per ion, namely the ionic diameter and the solvent-ion interaction energy. Predictions of osmotic coefficient at 298.15 K and liquid density at different temperatures are also presented.

This work compares two strategies to fit parameters of equations of state in parallel computers, emphasizing solutions that require few changes to existing sequential programs. One strategy uses the conventional Nelder-Mead algorithm coupled with parallel objective function evaluation (SSPO). The other strategy uses a parallel Nelder-Mead algorithm coupled with sequential objective function evaluation (PSSO). The PSSO strategy, which executes parallel one-dimensional searches during each iteration, is simpler to implement and converged to parameter sets with objective functions smaller than those obtained by the SSPO strategy. The SSPO strategy produced speedups consistent with the number of processes used and is more suitable when many processors are available. Both strategies are potentially useful and choosing between them is a matter of convenience, depending on the problem at hand. With parallel computers increasingly available, the easy implementation and convenience of these two strategies should appeal to developers and users of thermodynamic models.

This article proposes a new procedure to compute solid-liquid equilibrium in electrolyte systems that may form pure solid phases at a given temperature, pressure, and global composition. The procedure combines three sub-procedures: phase stability test, minimization of the Gibbs free energy with a stoichiometric formulation of the salt-forming reactions to compute phase splitting, and a phase elimination test. After the phase splitting calculation for a system configuration that has a certain number of phases, the phase stability test establishes whether including an additional phase will reduce the Gibbs free energy further. The criteria used for phase stability may lead, in some cases, to the premature inclusion of phases that should be absent from the final solution but, if this happens, the phase elimination sub-procedure removes them. It is possible to use the procedure with several excess Gibbs free energy models for liquid phase behavior. The procedure has proven to be reliable and fast and the results are in good agreement with literature data.

The procedure presented by Cabral et al. (2003) was used to predict the adsorption of multicomponent mixtures of methane, ethane, propane, and n-butane adsorbed on Silicalite S-115 at 300 K. The methodology employed uses the algorithm of molecular simulation for the grand canonical ensemble as an equation of state for the adsorbed phase. The adsorbent surface is modeled as a two-dimensional lattice in which solid heterogeneity is represented by of two kinds of sites with different adsorption energies. In all cases presented, the simulations described well the adsorption characteristics of the systems.

The dynamics of flash drums is simulated using a formulation adequate for phase modeling with equations of state (EOS). The energy and mass balances are written as differential equations for the internal energy and the number of moles of each species. The algebraic equations of the model, solved at each time step, are those of a flash with specified internal energy, volume and mole numbers (UVN flash). A new aspect of our dynamic simulations is the use of direct iterations in phase volumes (instead of pressure) for solving the algebraic equations. It was also found that an iterative procedure previously suggested in the literature for UVN flashes becomes unreliable close to phase boundaries and a new alternative is proposed. Another unusual aspect of this work is that the model expressions, including the physical properties and their analytical derivatives, were quickly implemented using computer algebra.

A closed vessel is an apparatus with very thick walls, in which propellants under test are burnt. After ignition, gaseous products and heat are produced. The time history of pressures is measured by piezoelectric transducers, and recorded in either an analog or digital way. For the design and simulation of a gun performance, it would be rather important if one could use the thousands of P versus t points generated by a single shot for the estimation of as many as possible ballistic parameters. The present work is devoted to the development of predictive models for the closed vessel, comparing the performance to real experimental data. Using known regression procedures (Maximum Likelihood, for instance), ballistic parameters are fitted and lifetime of the propellant can be predicted. This can be done once such parameters are related to its ageing process, which consists of a loss of volatile components.

Most of the solids used in adsorption processes are heterogeneous and most isotherm models are not derived to use information about the solid structure and energy heterogeneity. A possible alternative is to use molecular simulation techniques, which turn the thermodynamic model more microscopic. Then, starting from information on the solid structure, it is possible to develop appropriate solid models for each type of real system. Therefore, the objective of this work is to use the grand canonical Monte Carlo technique of molecular simulation for correlating pure-component data and predicting adsorption of multicomponent mixtures. To decrease the computational effort, we use a simplified solid model that is represented by a two-dimensional square lattice. The solid heterogeneity is represented by a random distribution of different kinds of sites, characterized by distinct energy levels. The methodology developed by Cabral et al. (2003a) is used here to correlate pure components and for predicting binary mixtures of ethane, ethylene, isobutane, and carbon dioxide on zeolite 13X with good results.

Phase equilibrium calculations for fluids confined inside capillary tubes or porous media are formulated using the isofugacity equations. In this situation, the phase pressures are not equal and it is assumed that they are related by the Laplace equation. With this formulation, existing procedures for phase equilibrium calculations can be readily modified to include capillary effects. In this paper, we review some of the main authors who have studied the behavior of fluids inside porous media and perform bubble- and dew-point calculations for pure components and mixtures, using the Peng-Robinson equation of state to model the coexisting phases and several planar surface tension models. Comparisons with results from the literature indicate that the proposed formulation is adequate for representing phase equilibrium inside capillary tubes.

The behavior of binary mixtures of carbon dioxide+alkanol (1-butanol, 2-butanol, 1-pentanol, or 2-pentanol) at high pressures was modeled using the Stryjek-Vera version of the Peng-Robinson equation of state. Two mixing rules were compared for this purpose: the classical one-fluid van der Waals and the Wong-Sandler mixing rules. In the case of the latter mixing rule, the NRTL model for the excess Gibbs free energy was used. We observed that both mixing rules can reproduce the qualitative aspects of the critical diagrams of these binary mixtures. A comparison of the results shows that there is no clear superiority of one mixing rule over the other in terms of the ability to predict the critical behavior of these mixtures.

Molecular simulation data were used to study the performance of equations of state (EoS) and combining rules usually employed in thermodynamic property calculations. The Monte Carlo method and the Gibbs ensemble technique were used for determining composition and densities of vapor and liquid phases in equilibrium for binary mixtures of Lennard-Jones fluids. Simulation results are compared to data in the literature and to those calculated by the t-PR-LJ EoS. The use of adequate combining rules has been shown to be very important for the satisfactory representation of molecular simulation data.

A modified form of the Hicks and Young algorithm was used with the Mattedi-Tavares-Castier lattice equation of state (MTC lattice EOS) to calculate critical points of binary mixtures that exhibit several types of critical behavior. Several qualitative aspects of the critical curves, such as maxima and minima in critical pressure, and minima in critical temperature, could be predicted using the MTC lattice EOS. These results were in agreement with experimental information available in the literature, illustrating the flexibility of the functional form of the MTC lattice EOS. We observed however that the MTC lattice EOS failed to predict maxima in pressure for two of the studied systems: ethane + ethanol and methane + n-hexane. We also observed that the agreement between the calculated and experimental critical properties was at most semi-quantitative in some examples. Despite these limitations, in many ways similar to those of other EOS in common use when applied to critical point calculations, we can conclude that the MTC lattice EOS has the ability to predict several types of critical curves of complex shape.

In this work, several simulated annealing algorithms presented in the literature as solutions to different problems were compared in the scheduling of multiproduct serial batch plants. A systematic performance study of the original algorithm, based on the Boltzmann statistics, and a recently proposed algorithm, based on the Tsallis statistics, were analyzed for three different annealing schemes. It was observed that performance (defined in terms of the number of configurations) is more sensitive to the annealing scheme than to the statistics used. We also observed that the overall performance of the simulated annealing procedure is very dependent on the parameters of the algorithm and on the kind and size of the problems. For large problems, algorithms based on the Tsallis statistics converged to the global minimum more frequently than those based on the Boltzmann statistics, although they needed a larger number of configurations to obtain the results.

In this work, the Monte Carlo method (MC) was extended to simulate the packing and segregation of particles subjected to a gravitational field and confined inside rigid walls. The method was used in systems containing spheres inside cylinders. The calculation of void fraction profiles in both the axial and radial directions was formulated, and some results are presented. In agreement with experimental data, the simulations show that the packed beds present structural ordering near the cylindrical walls up to a distance of about 4 particle diameters. The simulations also indicate that the presence of the cylindrical wall does not seem to have a strong effect on the gravitational segregation phenomenon.

- A group contribution equation of state recently proposed by the authors is used to calculate the activity of solvents in polymer+solvent solutions. The model is based on the generalized van der Waals theory and combines the Staverman-Guggenheim combinatorial term with an attractive lattice gas expression. The results show that the equation correlates the properties of pure solvents and polymers accurately. Furthermore, the equation satisfactorily represents the vapor-liquid equilibrium of solutions containing polymer and solvents of different polarities.