Distillation Process Description

Distillation column, (a) Basic column, (b) Multiple feeds and side streams. 

If the process requirement is to strip a volatile component from a relatively nonvolatile solvent, the rectifying section may be omitted, and the column would then be called a stripping column. 

In some operations, where the top product is required as a vapor, only sufficient liquid is condensed to provide the reflux flow to the column, and the condenser is referred to as a partial condenser. When the liquid is totally condensed, the liquid returned to the column will have the same composition as the top product. In a partial condenser the reflux will be in equilibrium with the vapor leaving the condenser. Virtually pure top and bottom products can be obtained in a single column from a binary feed, but where the feed contains more than two components, only a single pure product can be produced, either from the top or bottom of the column. Several columns will be needed to separate a multicomponent feed into its constituent parts. 

The number of stages required for a given separation will be dependent on the reflux ratio used. 

In an operating column, the effective reflux ratio will be increased by vapor condensed within the column due to heat leakage through the walls. With a well-lagged column, the heat loss will be small, and no allowance is normally made for this increased flow in design calculations. If a column is poorly insulated, changes in the internal reflux due to sudden changes in the external conditions, such as a sudden rainstorm, can have a noticeable effect on the column operation and control. 

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It can be seen from the previous description that the design of both a cold-feed stabilizer and a stabilizer with reflux is a rather complex and involved procedure. Distillation computer simulations are available that can be used to optimize the design of any stabilizer if the properties of the feed stream and desired vapor pressure of the bottoms product are known. Cases should be run of both a cold-feed stabilizer and one with reflux before a selection is made. Because of the large number of calculations required, it is not advisable to use hand calculation techniques to design a distillation process. There is too much opportunity for computational eiToi. 

In this chapter the simulation examples are presented. They are preceded by a short description of simulation tools and the MADONNA program in particular. As seen from the Table of Contents, the examples are organised according to thirteen application areas Batch Reactors, Continuous Tank Reactors, Tubular Reactors, Semi-Continuous Reactors, Mixing Models, Tank Flow Examples, Process Control, Mass Transfer Processes, Distillation Processes, Heat Transfer, Biological Process Examples and Environmental Process Examples. There are aspects of some examples that make them relevant to more than one application area, and this is usually apparent from their titles. Within each section, the examples are listed in order of their degree of difficulty. 

ICFs Commercial Process. In 1960 ICI constructed a concentration plant using this extractive distillation process (18) with a capacity of 16,000 tonnes/ annum of product acid (99.5 wt% HNO3) which has subsequently been extended. A flowsheet is given in Figure 8, and the process description is as follows. 

The modeling of RD processes is illustrated with the heterogenously catalyzed synthesis of methyl acetate and MTBE. The complex character of reactive distillation processes requires a detailed mathematical description of the interaction of mass transfer and chemical reaction and the dynamic column behavior. The most detailed model is based on a rigorous dynamic rate-based approach that takes into account diffusional interactions via the Maxwell-Stefan equations and overall reaction kinetics for the determination of the total conversion. All major influences of the column internals and the periphery can be considered by this approach. 

Even in the first publications concerning the copolymerization theory [11, 12] their authors noticed a certain similarity between the processes of copolymerization and distillation of binary liquid mixtures since both of them are described by the same Lord Rayleigh s equations. The origin of the term azeotropic copolymerization comes just from this similarity, when the copolymer composition coincides with monomer feed composition and does not drift with conversion. Many years later the formal similarity in the mathematical description of copolymerization and distillation processes was used again in [13], the authors of which, for the first time, classified the processes of terpolymerization from the viewpoint of their dynamics. The principles on which such a classification for any monomer number m is based are presented in Sect. 5, where there is also demonstrated how these principles can be used for the copolymerization when m = 3 and m = 4. 

The current process description for the PCAPP includes the use of an as-yet-unspecified EDT for the destruction of an estimated 1,000 leaker or reject projectiles containing distilled (sulfur) mustard agent (HD) or distilled mustard mixed with bis[2-(2-chloroethylthio) ethyl] ether (HT). This description is called Requirement P-1. 

Sundmacher and Qi (Chapter 5) discuss the role of chemical reaction kinetics on steady-state process behavior. First, they illustrate the importance of reaction kinetics for RD design considering ideal binary reactive mixtures. Then the feasible products of kinetically controlled catalytic distillation processes are analyzed based on residue curve maps. Ideal ternary as well as non-ideal systems are investigated including recent results on reaction systems that exhibit liquid-phase splitting. Recent results on the role of interfadal mass-transfer resistances on the attainable top and bottom products of RD processes are discussed. The third section of this contribution is dedicated to the determination and analysis of chemical reaction rates obtained with heterogeneous catalysts used in RD processes. The use of activity-based rate expressions is recommended for adequate and consistent description of reaction microkinetics. Since particles on the millimeter scale are used as catalysts, internal mass-transport resistances can play an important role in catalytic distillation processes. This is illustrated using the syntheses of the fuel ethers MTBE, TAME, and ETBE as important industrial examples. 

Reactive distillation occurs in multiphase fluid systems, with an important role of the interfacial transport phenomena. It is an inherently multicomponent process with much more complexity than similar binary processes. Multi-component thermodynamic and diffusional coupling in the phases and at the interface is accompanied by complex hydrodynamics and chemical reactions [4, 42, 43]. As a consequence, an adequate process description has to be based on specially developed mathematical models. However, sophisticated RD models are hardly applicable for plant design, model-based control and online process optimization. For such cases, a reasonable model reduction should be applied [44],... 

In the course of this thesis we have covered novel tools and methods that can be used to assist the design of reactive distillation processes (see chapters 5 to 7). A brief description of the highlights of the chapters is given below. 

The separation factors mainly depend on composition and temperature. The correct composition dependence is described with the help of activity coefficients. Following the Clausius-Clapeyron equation presented in Section 2.4.4 the temperature dependence is mainly influenced by the slope of the vapor pressure curves (enthalpy of vaporization) of the components involved. But also the activity coefficients are temperature-dependent following the Gibbs-Helmholtz equation (Eq. (5.26)). This means that besides a correct description of the composition dependence of the activity coefficients also an accurate description of their temperature dependence is required. For distillation processes at moderate pressures, the pressure effect on the activity coefficients (see Example 5.7) can be neglected. To take into account the real vapor phase behavior, equations of state, for example, the virial equation, cubic equations of state, such as the Redlich-Kwong, Soave-Redlich-Kwong (SRK), Peng-Robinson (PR), the association model, and so on, can be applied. 

This chapter extends the geometric description of the distillation process to infinite complex columns and complexes, and then on this basis to develop methods of their calculation. 

A rigorous simulation and optimization of reactive distillation processes usually is based on nonlinear fimctions for a realistic description of the reaction kinetics and the vapor-liquid-equilibrium. Within GAMS models, this description leads to very complex models that often face convergence problems. By using the new so-called external functions, the situation can be improved by transferring calculation procedures to an external module. 

Anhydrous Acetic Acid. In the manufacture of acetic acid by direct oxidation of a petroleum-based feedstock, solvent extraction has been used to separate acetic acid [64-19-7] from the aqueous reaction Hquor containing significant quantities of formic and propionic acids. Isoamyl acetate [123-92-2] is used as solvent to extract nearly all the acetic acid, and some water, from the aqueous feed (236). The extract is then dehydrated by azeotropic distillation using isoamyl acetate as water entrainer (see DISTILLATION, AZEOTROPIC AND EXTRACTIVE). It is claimed that the extraction step in this process affords substantial savings in plant capital investment and operating cost (see Acetic acid and derivatives). A detailed description of various extraction processes is available (237). 

Irreversible processes are mainly appHed for the separation of heavy stable isotopes, where the separation factors of the more reversible methods, eg, distillation, absorption, or chemical exchange, are so low that the diffusion separation methods become economically more attractive. Although appHcation of these processes is presented in terms of isotope separation, the results are equally vaUd for the description of separation processes for any ideal mixture of very similar constituents such as close-cut petroleum fractions, members of a homologous series of organic compounds, isomeric chemical compounds, or biological materials. 

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