Ionic liquids (IL) have been described as novel environmentally benign solvents because of their remarkable characteristics. Numerous applications of these solvents continue to grow at an exponential rate. In this work, high pressure vapor liquid equilibria for 17 different IL + gas binary systems were modeled at different temperatures with Peng-Robinson (PR) and Soave-Redlich-Kwong (SRK) equations of state, combined with the van der Waals mixing rule with two binary interaction parameters (vdW-2). The experimental data were taken from the literature. The optimum binary interaction parameters were estimated by minimization of an objective function based on the average absolute relative deviation of liquid and vapor phases, using the modified Simplex algorithm. The solubilities of all gases studied in this work decrease as the temperature increases and increase with increasing pressure. The correlated results were highly satisfactory, with average absolute relative deviations of 2.10% and 2.25% for PR-vdW-2 and SRK-vdW-2, respectively.

An optimization problem regarding water removal in the press section of a paper machine is considered in this work. The proposed model tries to minimize a cost function comprising the replacement of the felts in the press section, the cost of energy to operate the press and the cost of energy in the drying section, while satisfying the constraints of water mass balance in the process. The model is classified as a mixed-integer nonlinear program (MINLP) in which the most important decisions are: a) the sequence of paper to produce or when to produce the paper; b) the need to exchange the felts; and c) when to exchange the felts. Numerical examples are presented to illustrate the performance of the model.

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.

In this paper, a new resolution method for the dynamic simulation of a simulated moving bed is presented. A general rate model for each solute and each column is presented for the case of a linear isotherm. A hybrid resolution is developed, in which an analytical solution is used for the solid stationary phase, while the mobile fluid phase concentrations are obtained by numerical resolution. It is illustrated, through a numerical study, that the resolution method is robust. The method is validated by comparison with previously published experimental results. It is also shown that these numerical simulations are obtained much faster than those based on the physical separation process, allowing the use of this resolution method for on-line applications and process control.

The tangent plane criterion has become important for a correct solution evaluation phase and chemical of equilibrium problem. This method, applicable to single and multiphase systems, is mainly used for a single equation of state modeling all phases involved. The present work is mainly concerned with the application of interval analysis methods for global energy minimization in high-pressure phase stability problems. Two approaches are applied: (i) the Gibbs free energy global minimization under conditions of constant temperature and pressure and (ii) the Helmholtz free energy density global minimization under conditions of constant temperature and volume. Five case studies, one ternary and four binary systems, are analyzed in connection with the Peng-Robinson equation of state (PREOS) model. Five more case studies, for the CO2 + trans-2-hexen-1-ol system at high pressures, are used to compare different methods of phase equilibrium calculation with the approach using interval analysis. Finally, a complex system, clove oil + CO2, is analyzed. The results indicate that the interval analysis method is robust and reliable for all the problems studied.

Studies have shown that humankind will experience a water shortage in the coming decades. It is therefore paramount to develop new techniques and models with a view to minimizing the impact of pollution. It is important to predict the environmental impact of new emissions in rivers, especially during periods of drought. Computational fluid dynamics (CFD) has proved to be an invaluable tool to develop models able to analyze in detail particle dispersion in rivers. However, since these models generate grids with thousands (even millions) of points to evaluate velocities and concentrations, they still require powerful machines. In this context, this work contributes by presenting a new three-dimensional model based on CFD techniques specifically developed to be fast, providing a significant improvement in performance. It is able to generate predictions in a couple of hours for a one-thousand-meter long section of river using Pentium IV computers. Commercial CFD packages would require weeks to solve the same problem. Another innovation inb this work is that a half channel with a constant elliptical cross section represents the river, so the Navier Stokes equations were derived for the elliptical system. Experimental data were obtained from REPLAN (PETROBRAS refining unit) on the Atibaia River in São Paulo, Brazil. The results show good agreement with experimental data.

The adsorption of two metal ions, Cr(III) and Cu(II), in single-component and binary systems by Sargassum sp., a brown alga, was studied. Equilibrium batch sorption studies were carried out at 30ºC and pH 3.5. Kinetic tests were done for a binary mixture (chromium + copper) for a contact time of 72 hours to guarantee that equilibrium was reached. The monocomponent equilibrium data obtained were analyzed using the Langmuir and Freundlich isotherms. The binary equilibrium data obtained were described using four Langmuir-type and Freundlich isotherms. The F-test showed a statistically significant fit for all binary isotherm models. The parameters for isotherms of the Langmuir-type were used to determine the affinity of one metal for the biosorbent in the presence of another metal. The chromium ion showed a greater affinity for Sargassum sp. than the copper ion.

Phenylalanine (Phe) and tyrosine (Tyr) are two of the twenty amino acids in proteins; they are classified as aromatic amino acids, because both have a benzene ring in their structures. These amino acids are important in the synthesis of several biologically active amines, such as beta-endorphin, a neurotransmitter. Amino acids can be separated by ion-exchange chromatography. In this case, it is important that fixed-bed adsorber design adequately predict the breakthrough curve. This work presents a mathematical model for both fluid and porous phases. In the solution proposed for this model the liquid-phase concentration inside the particles is solved analytically and is related to the liquid-phase concentration in the bed using Duhamel's theorem. The solution for liquid-phase concentration in the bed is then solved numerically instead of analytically. The basic mass transfer parameters are from the literature. The results from the model are compared with those obtained experimentally using Phe and Tyr diluted in aqueous solutions in a fixed bed of PVP (poly-4-vinylpyridine) resin.

This work presents a model to predict the behavior of velocity, gas holdup and local concentration fields in a pseudo-two-phase gas-liquid column reactor applied for thermal hydrocracking of petroleum heavy fractions. The model is based on the momentum and mass balances for the system, using an Eulerian-Eulerian approach. Using the k-epsilon model,fluid dynamics accounts for both laminar and turbulent flows, with discrete small bubbles (hydrogen) flowing in a continuous pseudohomogeneous liquid phase (oil and catalyst particles). The petroleum is assumed to be a mixture of pseudocomponents, grouped by similar chemical structural properties, and the thermal hydrocracking is taken into account using a kinetic network based on these pseudocomponents.

A model is presented for the description of the concentration behavior of organometallic and sulfurated compounds in hydrodemetallation and hydrodesulfurization catalytic processes, where catalyst effectiveness decreases with time. Due to the complexity of the mixture, an approach based on pseudocomponents was adopted. The system is modeled as an isothermal tubular reactor with axial dispersion, where the gas phase (hydrogen in excess) flows upward concurrently with the liquid phase (heavy oil) while the solid phase (catalyst) stays inside the reactor in an expanded (confined) bed regime. The catalyst particles are very small and are assumed to be uniformly distributed in the reactor. The heavy oil fractions contain organometallics and sulfurated compounds, from which the metals and sulfur are to be removed, the metals as deposits in the catalyst pores and the sulfur as gas products. Simulations were carried out where the concentration profile inside the reactor was calculated for several residence times.

This work presents a model to describe the behavior of the concentration of constituents of heavy fractions from petroleum during the hydrocracking process. An approximation based on pseudocomponents or lumps is adopted due to the complexity of the mixture. The system is modeled as an isothermal tubular reactor with an axial dispersion, where the hydrogen flows upward concurrently with the oil while the solid catalyst particles stay inside the reactor in an expanded bed regime. Simulations are carried out for different values of liquid superficial velocity, reactor length and degree of mixing (Peclet number).