More Than

Comprehensive data collection for more than 6000 binary and multicomponent mixtures at moderate pressures. Data correlation and consistency tests are given for each data set. 

Since the accuracy of experimental data is frequently not high, and since experimental data are hardly ever plentiful, it is important to reduce the available data with care using a suitable statistical method and using a model for the excess Gibbs energy which contains only a minimum of binary parameters. Rarely are experimental data of sufficient quality and quantity to justify more than three binary parameters and, all too often, the data justify no more than two such parameters. When data sources (5) or (6) or (7) are used alone, it is not possible to use a three- (or more)-parameter model without making additional arbitrary assumptions. For typical engineering calculations, therefore, it is desirable to use a two-parameter model such as UNIQUAC. 

In the next three sections we discuss calculation of liquid-liquid equilibria (LLE) for ternary systems and then conclude the chapter with a discussion of LLE for systems containing more than three components. 

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. 

Flash calculations for these mixtures usually require four to eight iterations. Cases 5 and 6 in Table 1 have feeds of this type, including noncondensable components in Case 6. Within the limits of the thermodynamic framework used here, no case has been encountered where FLASH has required more than 12 iterations for satisfactory convergence. 

If the reaction involves more than one feed, the picture becomes more complex. Consider the reaction system from Eq. (2.6) with the corresponding rate equations ... 

When more than one reactant is used, it is often desirable to use an excess of one of the reactants. It is sometimes desirable to feed an inert material to the reactor or to separate the product partway through the reaction before carrying out further reaction. Sometimes it is desirable to recycle unwanted byproducts to the reactor. Let us now examine these cases. 

Another possibility to improve selectivity is to reduce the concentration of monoethanolamine in the reactor by using more than one reactor with intermediate separation of the monoethanolamine. Considering the boiling points of the components given in Table 2.3, then separation by distillation is apparently possible. Unfortunately, repeated distillation operations are likely to be very expensive. Also, there is a market to sell both di- and triethanolamine, even though their value is lower than that of monoethanolamine. Thus, in this case, repeated reaction and separation are probably not justified, and the choice is a single plug-flow reactor. 

The step with the longest time limits the cycle time. Alternatively, if more than one step is carried out in the same equipment, the cycle time is limited by the longest series of steps in the same equipment. The batch cycle time must be at least as long as the longest step. The rest of the equipment other than the limiting step is then idle for some fraction of the batch cycle. 

Clearly, the time chart shown in Fig. 4.14 indicates that individual items of equipment have a poor utilization i.e., they are in use for only a small fraction of the batch cycle time. To improve the equipment utilization, overlap batches as shown in the time-event chart in Fig. 4.15. Here, more than one batch, at difierent processing stages, resides in the process at any given time. Clearly, it is not possible to recycle directly from the separators to the reactor, since the reactor is fed at a time different from that at which the separation is carried out. A storage tank is needed to hold the recycle material. This material is then used to provide part of the feed for the next batch. The final flowsheet for batch operation is shown in Fig. 4.16. Equipment utilization might be improved further by various methods which are considered in Chap. 8 when economic tradeoffs are discussed. 

Distillation Sequencing Using Columns with More than Two Products... 

If the feed is dominated by the middle product (typically more than 50 percent) and the lightest product is present in small quantities (typically less than 5 percent), then the arrangement shown in Fig. 5.106 can be an attractive option. This time the light product must find its way up the column past the sidestream. Again, unless the light product is a small flow and the middle product a high flow, a... 

More than 7.5 MW could be added from a hot utility to the first interval, but the objective is to find the minimum hot and cold utility. Thus from Fig. 6.186, QHmin = 7.5MW and Qcmm = 10MW. This corresponds with the values obtained from the composite curves in Fig. 6.5a. One further important piece of information can be deduced from the cascade in Fig. 6.186. The point where the heat flow goes to zero at T = 145°C corresponds to the pinch. Thus the actual hot and cold stream pinch temperatures are 150 and 140°C. Again, this agrees with the result from the composite curves in Fig. 6.5a. 

Most refrigeration systems are essentially the same as the heat pump cycle shown in Fig. 6.37. Heat is absorbed at low temperature, servicing the process, and rejected at higher temperature either directly to ambient (cooling water or air cooling) or to heat recovery in the process. Heat transfer takes place essentially over latent heat profiles. Such cycles can be much more complex if more than one refrigeration level is involved. 

Calculate the weighted network area Anetwork from Eq. (7.22). When the weighted h values i4>h) vary appreciably, say, by more than one order of magnitude, an improved estimate of Anetwork can be evaluated by linear programming. ... 

These small positive and negative errors partially cancel each other. The result is that capital cost targets predicted by the methods described in this chapter are usually within 5 percent of the final design, providing heat transfer coefficients vary by less than one order of magnitude. If heat transfer coefficients vary by more than one order of magnitude, then a more sophisticated approach can sometimes be justified. ... 

Overall, the accuracy of the capital cost targets is more than good enough for the purposes for which they are used ... 

Merging more than one operation into a single piece of equipment (e.g., feed preheating and reaction in the same vessel), providing these operations are not limiting the cycle time. 

Overlapping hatches i.e., more than one hatch at different processing stages resides in the plant at any given time. 

Short-term exposure. This is the maximum concentration to which workers can be exposed for a period of up to 15 minutes continuously without suffering from (a) intolerable irritation, (b) chronic or irreversible tissue change, or (c) narcosis of sufficient degree to increase accident proneness, impair self-rescue, or materially reduce efficiency, provided that no more than four excursions per day are permitted, with at least 60 minutes between exposure periods, and provided the daily time-weighted value is not exceeded. 

Use an excess of one of the feeds when more than one feed is involved. 

If the problem involves more than one pinch, then between pinches the design should be started from the most constrained pinch. 

Often there is more than one enzyme catalysing the same reaction. 

Covalent. Formed by most of the non-metals and transition metals. This class includes such diverse compounds as methane, CH4 and iron carbonyl hydride, H2Fe(CO)4. In many compounds the hydrogen atoms act as bridges. Where there are more than one hydride sites there is often hydrogen exchange between the sites. Hydrogens may be inside metal clusters. 

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