Distillation enthalpy

The McCabe-Thiele constructions described in Chapter 8 embody rather restrictive tenets. The assumptions of constant molal overflow in distillation and of interphase transfer of solute only in extraction seriously curtail the general utility of the method. Continued use of McCabe-Thiele procedures can be ascribed to the fact that (a) they often represent a fairly good engineering approximation and (b) sufficient thermodynamic data to justify a more accurate approach is often lacking. In the case of distillation, enthalpy-concentration data needed for making stage-to-stage enthalpy balances are often unavailable, while, in the Case of absorption or extraction, complete phase equilibrium data may not be at hand. 

In modern separation design, a significant part of many phase-equilibrium calculations is the mathematical representation of pure-component and mixture enthalpies. Enthalpy estimates are important not only for determination of heat loads, but also for adiabatic flash and distillation computations. Further, mixture enthalpy data, when available, are useful for extending vapor-liquid equilibria to higher (or lower) temperatures, through the Gibbs-Helmholtz equation. ... 

Novolak Resins. In a conventional novolak process, molten phenol is placed into the reactor, foHowed by a precise amount of acid catalyst. The formaldehyde solution is added at a temperature near 90°C and a formaldehyde-to-phenol molar ratio of 0.75 1 to 0.85 1. For safety reasons, slow continuous or stepwise addition of formaldehyde is preferred over adding the entire charge at once. Reaction enthalpy has been reported to be above 80 kj /mol (19 kcal/mol) (29,30). The heat of reaction is removed by refluxing the water combined with the formaldehyde or by using a small amount of a volatile solvent such as toluene. Toluene and xylene are used for azeotropic distillation. FoHowing decantation, the toluene or xylene is returned to the reactor. 

General Properties of Computerized Physical Property System. Flow-sheeting calculations tend to have voracious appetites for physical property estimations. To model a distillation column one may request estimates for chemical potential (or fugacity) and for enthalpies 10,000 or more times. Depending on the complexity of the property methods used, these calculations could represent 80% or more of the computer time requited to do a simulation. The design of the physical property estimation system must therefore be done with extreme care. 

Condition of Feed (q Fine). The q line, which marks the transition from rectifying to stripping operating lines, is determined by mass and enthalpy balances around the feed plate. These balances are detailed in distillation texts (15). 

Computer solutions entail setting up component equiUbrium and component mass and enthalpy balances around each theoretical stage and specifying the required design variables as well as solving the large number of simultaneous equations required. The expHcit solution to these equations remains too complex for present methods. Studies to solve the mathematical problem by algorithm or iterational methods have been successflil and, with a few exceptions, the most complex distillation problems can be solved. 

Distillation columns are controlled by hand or automatically. The parameters that must be controlled are (/) the overall mass balance, (2) the overall enthalpy balance, and (J) the column operating pressure. Modem control systems are designed to control both the static and dynamic column and system variables. For an in-depth discussion, see References 101—104. 

The simplest continuous-distillation process is the adiabatic single-stage equihbrium-flash process pictured in Fig. 13-25. Feed temperature and the pressure drop across the valve are adjusted to vaporize the feed to the desired extent, while the drum provides disengaging space to allow the vapor to separate from the liquid. The expansion across the valve is at constant enthalpy, and this facd can be used to calculate To (or T to give a desired To). 

Availability of large digital computers has made possible rigorous solutions of equilibrium-stage models for multicomponent, multistage distillation-type columns to an exactness limited only by the accuracy of the phase equilibrium and enthalpy data utilized. Time and cost requirements for obtaining such solutions are very low compared with the cost of manual solutions. Methods are available that can accurately solve almost any type of distillation-type problem quickly and efficiently. The material presented here covers, in some... 

Example 4 Calculation of the BP Method Use the BP method with the SRK eqiiation-of-state for K values and enthalpy departures to compute stage temperatures, interstage vapor and hqiiid flow rates and compositions, and rehoiler and condenser duties for the light-hydrocarhon distdlation-coliimn specifications shown in Fig. 13-51 with feed at 260 psia. The specifications are selected to obtain three products, a vapor distillate rich in Cri and C3, a vapor side-stream rich in n-C4, and a bottoms rich in n-C and n-Cg. 

Data on the gas-liquid or vapor-liquid equilibrium for the system at hand. If absorption, stripping, and distillation operations are considered equilibrium-limited processes, which is the usual approach, these data are critical for determining the maximum possible separation. In some cases, the operations are are considerea rate-based (see Sec. 13) but require knowledge of eqmlibrium at the phase interface. Other data required include physical properties such as viscosity and density and thermodynamic properties such as enthalpy. Section 2 deals with sources of such data. 

It is standard practice in chemical laboratories to distill high-boiling-point substances under reduced pressure. Trichloroacetic acid has a standard enthalpy of vaporization of 57.814 kj-mol 1 and a standard entropy of vaporization of 124 J-K 1-mol. Use this information to determine the pressure that one would need to achieve to distill trichloroacetic-acid at 80.°C. 

Himmelbau (1995) or any of the general texts on material and energy balances listed at the end of Chapter 2. The Ponchon-Savarit graphical method used in the design of distillation columns, described in Volume 2, Chapter 11, is a further example of the application of the lever rule, and the use of enthalpy-concentration diagrams. 

Hvoo, Hloo = molar enthalpies of the vapor and liquid at the rectifying pinch D = distillate rate... 

Reactive distillation involves additional degrees of freedom (Mujtaba and Macchietto, 1997). If the controllable parameters remaining to be specified, namely (1) one heat input, and (2) the flow rate of the product (or the reflux ratio), are determined via optimization, all of the values of Vh Lk, Tk, xi h and yik and the enthalpies can be calculated. More than 2 degrees of freedom can be introduced by eliminating some of the prespecified parameters values. 

Temperature-dependent enthalpy changes effect on maximum temperature in macroporous catalysts, 25 303-305 Temperature differential reduction, in distillation columns, 10 153 Temperature error, 24 455—456 Temperature flattening, in heat pipes,... 

The rate of withdrawal of the sidestream is 10 per cent of the column feed rate and the external reflux ratio is 2.5. Using the enthalpy composition method, determine the number of theoretical stages required, and the amounts of bottom product and distillate as percentages of the feed rate. 

As an example, consider the distillation column of Table I with a feed of six components. A, B, C, D, E, F. If one sets the amounts of each of these in the feed, along with the enthalpy of the feed and the column pressure, then four variables remain to be set. In the present problem, one might choose to set the fraction of component C recovered in the top product and the fraction of D recovered in the bottom product. The third variable set would probably be the reflux. The fourth variable, the arbitrary location of the feed stage, would be set during the calculation. 

Whether or not a variable is independent may be more difficult to determine in other cases. For example, a distillation column with a side stripper is shown in Fig. 1. The side stripper in Fig. 1(a) has a reboiler and that in Figure 1 (b) is stripped with steam. Under the program, the liquid side stream which feeds the side stripper must be set. Also, in the column arrangement of Fig. 1(b) the amount and enthalpy of the steam fed must be set, since it constitutes an external feed. For illustration, we assume that the bottom product from the reboiler of the main column has... 

Recovery Constraints Distillation is a primary means of solvent recovery. In a separation process the chosen solvent must be easily distilled from the extracted solute. The relative volatility should be large to ensure easy separation. The enthalpy of vaporization should be low for reduced energy consumption. 

Unfortunately, many of these costs cannot be easily quantified in dollar amounts. However, we must remember that to rank our candidate solvents it is not necessary to know their absolute costs but only a relative cost. Relative cost can be inferred from physical property values. For example, a solvent with a lower enthalpy of vaporization will in general have a lower recovery cost, assuming recovery is done by distillation. A solvent with a higher enthalpy of combustion will have a lower disposal cost, assuming disposal is done by incineration. 

A colleague of yours who works in oceanography bets you that both the solubility as well as the activity coefficient of naphthalene are larger in seawater (35%o salinity) at 25°C than in distilled water at 5°C. Is this not a contradiction How much money do you bet Estimate C and for naphthalene in seawater at 25°C and in distilled water at 5°C. Discuss the result. Assume that the average enthalpy of solution (A wsHh Fig. 5.1) of naphthalene is about 30 kJmol-1 over the ambient temperature range. All other data can be found in Tables 5.3 and 5.7 and in Appendix C. 

All machines have drivers. A distillation column is also a machine, driven by a reboiler. It is the heat duty of the reboiler, supplemented by the heat content (enthalpy) of the feed, that provides the energy to make a split between light and heavy components. A useful example of the importance of the reboiler in distillation comes from the venerable use of sugar cane, in my home state of Louisiana. 

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