Distillation column thermodynamic analysis

Reliable thermodynamic data are essential for the accurate design or analysis of distillation columns. Failure of equipment to perform at specified levels is often attributable, at least in part, to the lack of such data. 

The analysis presented in this chapter is an example of how the principles of thermodynamics can be applied to establish efficiencies in separation units. We have shown how exergy analysis or, equivalently, lost work or availability analysis can be used to pinpoint inefficiencies in a distillation column, which in this case were the temperature-driving forces in the condenser and the reboiler. The data necessary for this analysis can easily be obtained from commonly used flow sheeters, and minimal extra effort is required to compute thermodynamic (exergetic) efficiencies of various process steps. The use of hybrid distillation has the potential to reduce column inefficiencies and reduce the number of trays. We note that for smaller propane-propene separation facilities (less than 5000bbl/day [10]), novel technologies such as adsorption and reactive distillation can be used. 

Today, there is an increasing interest in the theoretical study and the practical application of integrated reactive separation processes such as reactive distillation columns [1-3] or membrane-assisted reactors [37]. However, to date there is no general method available for designing such processes. For practical applications, it is important to be able to evaluate quickly whether a certain reactive separation process is a suitable candidate to reach certain targets. Therefore, feasibility analysis tools being based on minimal thermodynamic and kinetic information of the considered system are valuable. 

Example 4.9 Entropy production in separation process Distillation Distillation columns generally operate far from their thermodynamically optimum conditions. In absorption, desorption, membrane separation, and rectification, the major irreversibility is due to mass transfer. The analysis of a sieve tray distillation column reveals that the irreversibility on the tray is mostly due to bubble-liquid interaction on the tray, and mass transfer is the largest contributor to the irreversibility. 

Hydraulic analysis of the Aspen Plus simulator produces thermodynamic ideal minimum flow and actual flow curves for rigorous distillation column simulations. These types of calculations are performed for RADFRAC columns. Using the input summary given in problem 4.48 construct the stage-flow curves. Assess the thermodynamic performance of the column. 

Thermodynamic cost analysis relates the thermodynamic limits of separation systems to finite rate processes, and considers the environmental impact through the depletion of natural resources within the exergy loss concept. Still, economic analysis and thermodynamic analysis approaches may not be parallel. For example, it is estimated that a diabatic column has a lower exergy loss (39%) than that of adiabatic distillation however, this may not lead to a gain in the economic sense, yet it is certainly a gain in the thermodynamic sense. The minimization of entropy production is not always an economic criterion sometimes, existing separation equipment may be modified for an even distribution of forces or an even distribution of entropy production. Thermodynamic analysis requires careful interpretation and application. 

Example 5.15 Retrofits of distillation columns by thermodynamic analysis The synthesis of methanol takes place in a tube reactor in section 3 in the methanol plant shown in Figure 5.7. The reactor outlet is flashed at 45°C and 75 bar, and the liquid product (stream 407) containing 73.45 mol% of methanol is fed into the separation section (see Figure 5.8), where the methanol is purified. Stream 407 and the makeup water are the feed streams to the section. Table 5.2 shows the properties and compositions of the streams in section 3. The converged simulations are obtained from the Redlich-Kwong-Soave method to estimate the vapor properties, while the activity coefficient... 

Pinch analysis is a thermodynamically based method for the design of heat and power systems. The method of pinch analysis groups the heat sources and sinks of the process streams into temperature intervals, where it is possible to transfer heat in each interval from heat sources to heat sinks [3], The grand composite curve can be used to provide an interface between the distillation column and the utility system. If a number of different utilities are available, the grand composite curve can be used to determine the relative amount of each utility needed. 

Example 5.9 Retrofits of distillation columns by thermodynamic analysis... 

An entropy effect leading to energy dissipation or exergy loss either within or through the boundary of a system is unavoidable in every irreversible system. Thermodynamic analysis determines the net enthalpy deficits and exergy losses due to irreversibility at each stage of a distillation column by combining the first and second laws of... 

Demirel, Y., Retrofit of distillation columns using thermodynamic analysis, Sep. Sci. Technol.,41 (2006)791. 

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