Residue curve maps properties

The transformed variables describe the system composition with or without reaction and sum to unity as do Xi and yi. The condition for azeotropy becomes X, = Y,. Barbosa and Doherty have shown that phase and distillation diagrams constructed using the transformed composition coordinates have the same properties as phase and distillation region diagrams for nonreactive systems and similarly can be used to assist in design feasibility and operability studies [Chem Eng Sci, 43, 529, 1523, and 2377 (1988a,b,c)]. A residue curve map in transformed coordinates for the reactive system methanol-acetic acid-methyl acetate-water is shown in Fig. 13-76. Note that the nonreactive azeotrope between water and methyl acetate has disappeared, while the methyl acetate-methanol azeotrope remains intact. Only... 

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... 

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. 

Residue Curve Maps for Reactive Mixtures 461 Heat-Exchanger Design 474 Materials of Construction 483 Saturated Steam Properties 487 Vapor Pressure of Some Hydrocarbons 489 Vapor Pressure of Some Organic Components 490 Conversion Factors to SI Units 491... 

Peters, M., et al.. Derivation and properties of membrane residue curve maps. Industrial Engineering Chemistry Research, 2006, 45(26) 9080 9087. 

In the preceding sections, the concept of a residue curve map was introduced. While these maps provide information about the separation of a particular mixture via boUing, they also yield some very interesting mathematical and topological behavior. Analysis of the residue curve equation (Equation 2.8) gives insight into the properties of these maps. 

In contrast to other esterifications, a significant extent of reaction can be reached even without a catalyst though the reaction equilibrium constant is approximately one. A compilation of the major physical property data can be found elsewhere [25, 87]. Fig. 10.2 shows the residue curve map in transformed coordinates as introduced by Doherty and coworkers [108] at a pressure of 1.013 bar. Due to a single maximum azeotrope, there are two distillation regions. The concentration profile in a single feed, two product lab-scale column with 45 bubble cap trays is also displayed in Fig. 10.2. The column is fed with a stoichiometric feed of formic acid and methanol and operated at a reflux ratio of 5. Water and the desired methyl formate are recovered at purities of about 97 % molar concentration in the bottoms and at the top, respectively. 

First simulation results on steady state multiplicity of etherification processes were obtained for the MTBE process by Jacobs and Krishna [45] and Nijhuis et al. [78]. These findings attracted considerable interest and triggered further research by others (e. g., [36, 80, 93]). In these papers, a column pressure of 11 bar has been considered, where the process is close to chemical equilibrium. Further, transport processes between vapor, liquid, and catalyst phase as well as transport processes inside the porous catalyst were neglected in a first step. Consequently, the multiplicity is caused by the special properties of the simultaneous phase and reaction equilibrium in such a system and can therefore be explained by means of reactive residue curve maps using oo/< -analysis [34, 35]. A similar type of multiplicity can occur in non-reactive azeotropic distillation [8]. 

Residue curve maps provide a powerful tool to represent relevant properties of the system, particularly those aiming to predict feasible design sequences. In addition, analytical material balances may be represented in a RCM, resulting in constraints to feasible product compositions and convenient operating strategies e.g. direct or... 

The residue curve maps for ternary mixtures having one binary minimum-boiling azeotrope are much more complicated. They are even more compiex when there are multiple azeotropes. See Doherty and Malone (2001) for illustrative figures. Siirola and Barnicki (1997) illustrate residue curves for a variety of systems. Complex properties of the residue maps are analyzed in detail in Doherty and Perkins (1978) and Van Dongen and Doherty (1984). 

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