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For a liquid phase (superscript ) in equilibrium with another liquid phase (superscript "), the equation analogous to Equation (1) is... 

At pressures to a few bars, the vapor phase is at a relatively low density, i.e., on the average, the molecules interact with one another less strongly than do the molecules in the much denser liquid phase. It is therefore a common simplification to assume that all the nonideality in vapor-liquid systems exist in the liquid phase and that the vapor phase can be treated as an ideal gas. This leads to the simple result that the fugacity of component i is given by its partial pressure, i.e. the product of y, the mole fraction of i in the vapor, and P, the total pressure. A somewhat less restrictive simplification is the Lewis fugacity rule which sets the fugacity of i in the vapor mixture proportional to its mole fraction in the vapor phase the constant of proportionality is the fugacity of pure i vapor at the temperature and pressure of the mixture. These simplifications are attractive because they make the calculation of vapor-liquid equilibria much easier the K factors = i i ... 

Multiple sets of binary VLE data may be correlated by continuing with another set of cards starting at part B. The last set of cards must be followed with a blank card to end the program. 

The lack of suitable catalysts is the most common reason preventing the exploitation of novel reaction paths. At the first stage of design, it is impossible to look ahead and see all the consequences of choosing one reaction path or another, but some things are clear even at this stage. Consider the following example. 

Polymerization reactions. There are two broad types of polymerization reactions, those which involve a termination step and those which do not. An example that involves a termination step is free-radical polymerization of an alkene molecule. The polymerization requires a free radical from an initiator compound such as a peroxide. The initiator breaks down to form a free radical (e.g., CH3 or OH), which attaches to a molecule of alkene and in so doing generates another free radical. Consider the polymerization of vinyl chloride from a free-radical initiator R. An initiation step first occurs ... 

In describing reactor performance, selectivity is usually a more meaningful parameter than reactor yield. Reactor yield is based on the reactant fed to the reactor rather than on that which is consumed. Clearly, part of the reactant fed might be material that has been recycled rather than fresh feed. Because of this, reactor yield takes no account of the ability to separate and recycle unconverted raw materials. Reactor yield is only a meaningful parameter when it is not possible for one reason or another to recycle unconverted raw material to the reactor inlet. By constrast, the yield of the overall process is an extremely important parameter when describing the performance of the overall plant, as will be discussed later. 

In the preceding section, the choice of reactor type was made on the basis of which gave the most appropriate concentration profile as the reaction progressed in order to minimize volume for single reactions or maximize selectivity for multiple reactions for a given conversion. However, after making the decision to choose one type of reactor or another, there are still important concentration effects to be considered. 

Single irreversible reactions. An excess of one feed component can force another component toward complete conversion. As an... 

Product removal during reaction. Sometimes the equilibrium conversion can be increased by removing the product (or one of the products) continuously from the reactor as the reaction progresses, e.g., by allowing it to vaporize from a liquid-phase reactor. Another way is to carry out the reaction in stages with intermediate separation of the products. As an example of intermediate separation, consider the production of sulfuric acid as illustrated in Fig. 2.4. Sulfur dioxide is oxidized to sulfur trioxide ... 

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. 

Even if the reactor temperature is controlled within acceptable limits, the reactor effluent may need to be cooled rapidly, or quenched, to stop the reaction quickly to prevent excessive byproduct formation. This quench can be accomplished by indirect heat transfer using conventional heat transfer equipment or by direct heat transfer by mixing with another fluid. A commonly encountered situation is... 

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. 

As pointed out previously, the separation of homogeneous fluid mixtures requires the creation or addition of another phase. The most common method is by repeated vaporization and condensation— distillation. The three principal advantages of distillation are... 

Another variable that needs to be set for distillation is refiux ratio. For a stand-alone distillation column, there is a capital-energy tradeoff, as illustrated in Fig. 3.7. As the refiux ratio is increased from its minimum, the capital cost decreases initially as the number of plates reduces from infinity, but the utility costs increase as more reboiling and condensation are required (see Fig. 3.7). If the capital... 

Another factor that can be important in the design of evaporators is the condition of the feed. If the feed is cold, then the backward-feed arrangement has the advantage that a smaller amount of liquid must be heated to the higher temperatures of the second and first stages. 

Another important class of dryer is the fluidized-bed dryers. Some designs combine spray and fluidized-bed dryers. Choice between dryers is usually based on practicalities such as the materials handling characteristics, product decomposition, product physical form (e.g., if a porous granular material is required), etc. Also, dryer efficiency can be used to compare the performance of different dryer designs. This is usually defined as follows -. 

Rather than send the vapor to one of the separation units described above, a purge can be used. This removes the need for a separator but incurs raw material losses. Not only can these material losses be expensive, but they also can create environmental problems. However, another option is to use a combination of a purge with a separator. 

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. 

As with the case of byproduct losses, another cost needs to be added to the tradeoffs when there is a purge. This is a raw materials efficiency cost due to purge losses. If the PRODUCT formation is constant, this cost can be defined to be ... 

When inerts are present in the recycle, the concentration is another important optimization variable, again influencing operations throughout the process. 

All too often safety and health (and environmental) considerations are left to the final stages of the design. Returning to the hierarchy of design illustrated by the onion diagram in Fig. 1.6, such considerations would add another layer in the diagram outside the utilities layer. This approach leaves much to be desired. 

Flexible membrane. Another method to stop the vapor space breathing to atmosphere is to use a tank with a flexible membrane in the roof, Fig. 9.26. 

Sometimes waste streams can be recycled directly, but between different processes. Waste streams from one process can become the feedstock for another. The scope for such waste exchanges is often not fully realized, since it often means waste being transferred between different companies. 

Another test is the total oxygen demand (TOD) test, which oxidizes the waste in the presence of a catalyst at 900°C in a stream of air. Under these harsh conditions, all the carbon is oxidized to CO2. The oxygen demand is calculated from the difference in oxygen content of the air before and after oxidation. The resulting value of TOD... 

The inability to produce high-quality effluents is one significant disadvantage. Another disadvantage is that anaerobic processes must be maintained at temperatures between 35 and 40°C to get the best performance. If low-temperature waste heat is available from the production process, then this is not a problem. 

Another suspended growth method is the upward-flow anaerobic sludge blanket illustrated in Fig. 11.6a. Here the sludge is contacted by upward flow of the feed at a velocity such that the sludge is not carried out of the top of the digester. 

When viewing effluent treatment methods, it is clear that the basic problem of disposing of waste material safety is, in many cases, not so much solved but moved from one place to another. The fundamental problem is that once waste has been created, it cannot be destroyed. The waste can be concentrated or diluted, its physical or chemical form can be changed, but it cannot be destroyed. 

Another way to relate these principles is to remember that heat integration will always benefit by keeping hot streams hot and cold streams cold. ... 

Let us now consider a few examples for the use of this simple representation. A grand composite curve is shown in Fig. 14.2. The distillation column reboiler and condenser duties are shown separately and are matched against it. Neither of the distillation columns in Fig. 14.2 fits. The column in Fig. 14.2a is clearly across the pinch. The distillation column in Fig. 14.26 does not fit, despite the fact that both reboiler and condenser temperatures are above the pinch. Strictly speaking, it is not appropriately placed, and yet some energy can be saved. By contrast, the distillation shown in Fig. 14.3a fits. The reboiler duty can be supplied by the hot utility. The condenser duty must be integrated with the rest of the process. Another example is shown in Fig. 14.36. This distillation also fits. The reboiler duty must be supplied by integration with the process. Part of the condenser duty must be integrated, but the remainder of the condenser duty can be rejected to the cold utility. 

Another design option that can be considered if a column will not fit is use of an intermediate reboiler or condenser. An intermediate condenser is illustrated in Fig. 14.5. The shape of the box is now altered because the intermediate condenser changes the heat flow through the column. The particular design shown in Fig. 14.5 would require that at least part of the heat rejected from the intermediate condenser be passed to the process. An analogous approach can be used to evaluate the possibilities for use of intermediate reboilers. Flower and Jackson," Kayihan, and Dhole and Linnhofl have presented procedures for the location of intermediate reboilers and condensers. 

Figure 16.10 shows another threshold problem that requires only hot utility. This problem is different in characteristic from the one in Fig. 16.9. Now the minimum temperature difference is in the middle of the problem, causing a pseudopinch. The best strategy to deal with this type of threshold problem is to treat it as a pinched problem. For the problem in Fig. 16.10, the problem is divided into two parts at the pseudopinch, and the pinch design method is followed. The only complication in applying the pinch design method for such problems is that one-half of the problem (the cold end in Fig. 16.10) will not feature the flexibility offered by matching against utility.

The purpose of chemical processes is not to make chemicals The purpose is to make money. However, the profit must he made as part of a sustainable industrial activity which retains the capacity of ecosystems to support industrial activity and life. This means that process waste must be taken to its practical and economic minimum. Relying on methods of waste treatment is usually not adequate, since waste treatment processes tend not so much to solve the waste problem but simply to move it from one place to another. Sustainable industrial activity also means that energy consumption must be taken to its practical and economic minimum. Chemical processes also must not present significant short-term or long-term hazards, either to the operating personnel or to the community. 

Economic tradeoffs. Interactions between the reactor and the rest of the process are extremely important. Reactor conversion is the most significant optimization variable because it tends to influence most operations through the process. Also, when inerts are present in the recycle, the concentration of inerts is another important optimization variable, again influencing operations throughout the process. ... 

There can be an element of maintenance costs that is fixed and an element which is variable. Fixed maintenance costs cover routine maintenance such as regular maintenance on safety valves which must be carried out irrespective of the rate of production. There also can be an element of maintenance costs which is variable. This arises from the fact that certain items of equipment can need more maintenance as the production rate increases. Also, royalties which cover the cost of purchasing another company s process technology may have different bases. Royalties may be a variable cost, since they can sometimes be paid in proportion to the rate of production. Alternatively, the royalty might be a single-sum payment at the beginning of the project. In this case, the single-sum payment will become part of the project s capital investment. As such, it will be included in the annual capital repayment, and this becomes part of the fixed cost. 

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