For example

Activity-coefficient data at infinite dilution often provide an excellent method for obtaining binary parameters as shown, for example, by Eclcert and Schreiber (1971) and by Nicolaides and Eckert (1978). Unfortunately, such data are rare. 

An adequate prediction of multicomponent vapor-liquid equilibria requires an accurate description of the phase equilibria for the binary systems. We have reduced a large body of binary data including a variety of systems containing, for example, alcohols, ethers, ketones, organic acids, water, and hydrocarbons with the UNIQUAC equation. Experience has shown it to do as well as any of the other common models. V7hen all types of mixtures are considered, including partially miscible systems, the... 

For many liquid mixtures. Equation (19) can be used to provide a crude estimate of excess enthalpy. A much better estimate is obtained if the UNIQUAC parameters are considered temperature-dependent. For example, suppose Equations (4-9) and (4-10) are modified to = + k /t... 

Unfortunately, many commonly used methods for parameter estimation give only estimates for the parameters and no measures of their uncertainty. This is usually accomplished by calculation of the dependent variable at each experimental point, summation of the squared differences between the calculated and measured values, and adjustment of parameters to minimize this sum. Such methods routinely ignore errors in the measured independent variables. For example, in vapor-liquid equilibrium data reduction, errors in the liquid-phase mole fraction and temperature measurements are often assumed to be absent. The total pressure is calculated as a function of the estimated parameters, the measured temperature, and the measured liquid-phase mole fraction. 

It is important to stress that unnecessary thermodynamic function evaluations must be avoided in equilibrium separation calculations. Thus, for example, in an adiabatic vapor-liquid flash, no attempt should be made iteratively to correct compositions (and K s) at current estimates of T and a before proceeding with the Newton-Raphson iteration. Similarly, in liquid-liquid separations, iterations on phase compositions at the current estimate of phase ratio (a)r or at some estimate of the conjugate phase composition, are almost always counterproductive. Each thermodynamic function evaluation (set of K ) should be used to improve estimates of all variables in the system. 

Convergence is usually accomplished in 2 to 4 iterations. For example, an average of 2.6 iterations was required for 9 bubble-point-temperature calculations over the complete composition range for the azeotropic system ehtanol-ethyl acetate. Standard initial estimates were used. Figure 1 shows results for the incipient vapor-phase compositions together with the experimental data of Murti and van Winkle (1958). For this case, calculated bubble-point temperatures were never more than 0.4 K from observed values. 

The convergence rate depends somewhat on the problem and on the initial estimates used. For mixtures that are not extremely wide-boiling, convergence is usually accomplished in three or four iterations,t even in the presence of relatively strong liquid-phase nonidealities. For example, cases 1 through 4 in Table 1 are typical of relatively close-boiling mixtures the latter three exhibit significant liquid-phase nonidealities. 

The program storage requirements will depend somewhat on the computer and FORTRAN compiler involved. The execution times can be corrected approximately to those for other computer systems by use of factors based upon bench-mark programs representative of floating point manipulations. For example, execution times on a CDC 6600 would be less by a factor of roughly 4 than those given in the tcible and on a CDC 7600 less by a factor of roughly 24. 

The synthesis of the correct structure and the optimization of parameters in the design of the reaction and separation systems are often the single most important tasks of process design. Usually there are many options, and it is impossible to fully evaluate them unless a complete design is furnished for the outer layers of the onion. For example, it is not possible to assess which is better. 

If inert material is to be added, then ease of separation is an important consideration. For example, steam is added as an inert to hydrocarbon cracking reactions and is an attractive material in this respect because it is easily separated from the hydrocarbon components by condensation. If the reaction does not involve any change in the number of moles, inert material has no effect on equilibrium conversion. 

Another way to keep the concentration of PRODUCT low is to remove the product as the reaction progresses, e.g., by intermediate separation followed by further reaction. For example, in a reaction system such as Eq. (2.18), intermediate separation of the PRODUCT followed by further reaction maintains a low concentration of PRODUCT as the reaction progresses. Such intermediate separation is most appropriate when separation of the product from the reactants is straightforward. 

Polyethylbenzenes (diethylbenzene, triethylbenzene, etc.) are also formed as unwanted byproducts through reversible reactions in series with respect to ethylbenzene but parallel with respect to ethylene. For example,... 

Very often the choice is not available. For example, if reactor temperature is above the critical temperature of the chemical species, then the reactor must be gas phase. Even if the temperature can be lowered below critical, an extremely high pressure may be required to operate in the liquid phase. 

Fixed-bed noncatalytic reactors. Fixed-bed reactors can be used to react a gas and a solid. For example, hydrogen sulfide can be removed from fuel gases by reaction with ferric oxide ... 

For example, hydrogen sulfide and carbon dioxide can be removed from natural gas by reaction with monoethanolamine in an absorber according to the following reactions ... 

This might he worthwhile if the FEED-BYPRODUCT separation is expensive. To use a purge, the FEED and BYPRODUCT must be adjacent to each other in order of volatility (assuming distillation is used as the means of separation). Of course, care should be taken to ensure that the resulting increase in concentration of BYPRODUCT in the reactor does not have an adverse effect on reactor performance. Too much BYPRODUCT might, for example, cause a deterioration in the performance of the catalyst. 

Fl9 4.14 Time-event chart for a repeated batch cycle for Example 4.5. 

Can the byproduct be subjected to further reaction and its value upgraded For example, most organic chlorination reactions produce hydrogen chloride as a byproduct. If this cannot be sold, it... 

Figure 5.3 The direct eind indirect sequence for Example 5.2. 

Figure 5.4 The sequence with the lowest total vapor flow for Example 5.3.

So far it has been assumed that any hot stream could, in principle, be matched with any cold stream, providing there is feasible temperature diflerence between the two. Often, however, practical constraints prevent this. For example, it might be the case that if two... 

Figure 6.20 Temperature-interval heat balances for Example 6.1.

Find a way to overcome the constraint while still maintaining the areas. This is often possible by using indirect heat transfer between the two areas. The simplest option is via the existing utility system. For example, rather than have a direct match between two streams, one can perhaps generate steam to be fed into the steam mains and the other use steam from the same mains. The utility system then acts as a buffer between the two areas. Another possibility might be to use a heat transfer medium such as a hot oil which circulates between the two streams being matched. To maintain operational independence, a standby heater and cooler supplied by utilities is needed in the hot oil circuit such that if either area is not operational, utilities could substitute heat recovery for short periods. 

Figure 6.35 Alternative combined heat and power schemes for Example 6.4.

Figure 6.40 A two-level refrigeration system for Example 6.6 with heat rejection to cooling water.

A path is a sequence of distinct lines which are connected to each other. For example, in Fig. 7.1a, AECGD is a path. A graph forms a single component if any two points are joined by a path. Thus Fig. 7.16 has two components and Fig. 7.1a has only one. 

A loop is a path which begins and ends at the same point, such as CGDHC in Fig. 7.1a. If two loops have a line in common, they can be linked to form a third loop by deleting the common line. In Fig. 7.1a, for example, BGCEB and CGDHC can be linked to give BGDHCEB. In this case, this last loop is said to be dependent on the other two. 

Figure 7.6 The enthalpy interval stream population for Example 7.2.

Figure 7.11 Optimization of the capital/energy tradeoff for Example 7.5.

Figure 8.8 Time-event chart for Example 4.4 with two reactors in parallel.

The first major hazard in process plants is fire, which is usually regarded as having a disaster potential lower than both explosion or toxic release. However, fire is still a major hazard and can, under the worst conditions, approach explosion in its disaster potential. It may, for example, give rise to toxic fumes. Let us start by examining the important factors in assessing fire as a hazard. 

Some operations need to be carried out at low temperature, which requires refrigeration. The refrigeration fluid might, for example, be propylene and present a major hazard. Operation of the process at a... 

Relief systems are expensive and introduce considerable environmental problems. Sometimes it is possibly to dispense with relief valves and all that comes after them by using stronger vessels, strong enough to withstand the highest pressures that can be reached. For example, if the vessel can withstand the pump delivery pressure, then a relief valve for overpressurization by the pump may not be needed. However, there may still be a need for a small relief device to guard against overpressurization in the event of a fire. It may be possible to avoid the need for a relief valve on a distillation column... 

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