Thermodynamics residue curve maps

Process synthesis and design of these non-conventional distillation processes proceed in two steps. The first step—process synthesis—is the selection of one or more candidate entrainers along with the computation of thermodynamic properties like residue curve maps that help assess many column features such as the adequate column configuration and the corresponding product cuts sequence. The second step—process design—involves the search for optimal values of batch distillation parameters such as the entrainer amount, reflux ratio, boiler duty and number of stages. The complexity of the second step depends on the solutions obtained at the previous level, because efficiency in azeotropic and extractive distillation is largely determined by the mixture thermodynamic properties that are closely linked to the nature of the entrainer. Hence, we have established a complete set of rules for the selection of feasible entrainers for the separation of non ideal mixtures... 

For the synthesis of heterogeneous batch distillation the liquid-liquid envelope at the decanter temperature is considered in addition to the residue curve map. Therefore, the binary interaction parameters used in predicting liquid-liquid equilibrium are estimated from binary heterogeneous azeotrope or liquid-liquid equilibrium data [8,10], Table 3 shows the calculated purity of original components in each phase split at 25 °C for all heterogeneous azeotropes reported in Table 1. The thermodynamic models and binary coefficients used in the calculation of the liquid-liquid-vapour equilibrium, liquid-liquid equilibrium at 25 °C and the separatrices are reported in Table 2. 

From the thermodynamic information given in Tables 1-3, the residue curve maps are drawn in Fig. 1 for each entrainer and the batch distillation task sequence required to perform the separation of the original components is deduced using published rules [5], The residue curve maps of the ternary... 

The feasibility of separations of nonideal mixtures, as well as the screening of mass-separation agents for breaking azeotropes can be rationalized by means of thermodynamic methods based on residue curve maps. The treatment was extended processes with simultaneous chemical reaction. Two comprehensive books have been published recently by Stichlmair and Frey [10], as well as by Doherty and Malone [11]. 

Table 8.1 describes the steps of the methodology in more detail. The procedure starts with the Problem definition production rate, chemistry, product specifications, safety, health and environmental constraints, physical properties, available technologies. Then, a first evaluation of feasibility is performed by an equilibrium design. This is based on a thermodynamic analysis that includes simultaneous chemical and physical equilibrium (CPE). The investigation can be done directly by computer simulation, or in a more systematic way by building a residue curve map (RCM), as explained in the Appendix A. This step will identify additional thermodynamic experiments necessary to consolidate the design decisions, mainly phase-equilibrium measurements. Limitations set by chemical equilibrium or by thermodynamic boundaries should be analyzed here. 

In the following, the strategy presented before will this time be applied for developing a process for the esterification of lauric acid with methanol. All the thermodynamic data for pure components and binary mixtures are available in Aspen Plus. A residue curve map of the reactive mixture at equilibrium can be computed as described in Appendix A. A useful representation can be done in reduced coordinates defined by Xx = water + add and X2 = add + ester. The diagram displayed... 

We start the chapter by explaining the graphical thermodynamic representations for ternary mixtures known as Residue Curve Maps. The next section deals with the separation of homogeneous azeotropes, where the existence of a distillation boundary is a serious obstacle to separation. Therefore, the choice of the entrainer is essential. We discuss some design issues, as entrainer ratio, optimum energy requirements and finite reflux effects. The following subchapter treats the heterogeneous azeotropic distillation, where liquid-liquid split is a powerful method to overcome the constraint of a distillation boundary. Finally, we will present the combination of distillation with other separation techniques, as extraction or membranes. 

The integration of the equation (9.2) is easy, but in each point the equilibrium constants Kj has to be calculated by a suitable thermodynamic model, as function of pressure, temperature and composition. The trajectory obtained in this way starting with an arbitrary initial concentration describes a residue curve. The assembly of trajectories of liquid composition forms a Residue Curves Map (RCM). 

The conceptual design of distillation systems involving high non-ideal mixtures can be managed nowadays by means of systematic methods. These new methods combine the insight capabilities of graphical thermodynamic tools based on Residue Curve Maps with the power of computer simulation. The main ideas are ... 

FIGURE 4.5 A residue curve map for the diethyl ether/benzene/methanol system generated using the NRTL thermodynamic model at P s 0.825 atm. 

Certain techniques for the application of thermodynamics in separation technology are introduced in Chapter 11, for example, the concept of residue curve maps, a general procedure for the choice of suitable solvents for the separation of azeotropic systems, the verification of model parameters prior to process simulation and the identification of separation problems. 

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