Allowables

The detailed techniques presented here are based on particular models for the vapor phase (Hayden-O Connell) and for the liquid phase (UNIQUAC). However, our discussion of these techniques is sufficiently general to allow the use of other models, whenever the user prefers to do so. 

Unfortunately, good binary data are often not available, and no model, including the modified UNIQUAC equation, is entirely adequate. Therefore, we require a calculation method which allows utilization of some ternary data in the parameter estimation such that the ternary system is well represented. A method toward that end is described in the next section. 

There is justification for allowing t to increase beyond 1, and in many particular applications this may be desirable. Here a more conservative approach is used to reduce the chance of unstable iterations. 

An additional option allows the user to fit data for binary mixtures where one of the components is noncondensable. The mixture is treated as an ideal dilute solution. The solute... 

PRCG cols 21-30 the maximum allowable change in any of the parameters when LMP = 1, default value is 1000. Limiting the change in the parameters prevents totally unreasonable values from being attained in the first several iterations when poor initial estimates are used. A value of PRCG equal to the magnitude of that anticipated for the parameters is usually appropriate. 

FLASH determines the equilibrium vapor and liquid compositions resultinq from either an isothermal or adiabatic equilibrium flash vaporization for a mixture of N components (N 20). The subroutine allows for presence of separate vapor and liquid feed streams for adaption to countercurrent staged processes. 

NORMALIZE ACCELERATED COMPOSITIONS ITO ALLOW FOR XRCIl OP XECl) SET... 

Once the flowsheet structure has been defined, a simulation of the process can be carried out. A simulation is a mathematical model of the process which attempts to predict how the process would behave if it was constructed (see Fig. 1.1b). Having created a model of the process, we assume the flow rates, compositions, temperatures, and pressures of the feeds. The simulation model then predicts the flow rates, compositions, temperatures, and pressures of the products. It also allows the individual items of equipment in the process to be sized and predicts how much raw material is being used, how much energy is being consumed, etc. The performance of the design can then be evaluated. 

Having made a choice of the reaction path, we need to choose a reactor type and make some assessment of the conditions in the reactor. This allows assessment of reactor performance for the chosen reaction path in order for the design to proceed. 

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 ... 

Figure 2.4 Reaction and separation in sulfuric Eicid manufacture allow effectively complete conversion despite reversibility of the reaction.

Allow vaporization of liquid in the reactor so that it can be condensed and refluxed back to the reactor as a means of removing the heat of reaction... 

Allow vaporization of one of the components in a reversible reaction in order that removal increases maximum conversion. 

Most processes are catalyzed where catalysts for the reaction are known. The choice of catalyst is crucially important. Catalysts increase the rate of reaction but are unchanged in quantity and chemical composition at the end of the reaction. If the catalyst is used to accelerate a reversible reaction, it does not by itself alter the position of the equilibrium. When systems of multiple reactions are involved, the catalyst may have different effects on the rates of the different reactions. This allows catalysts to be developed which increase the rate of the desired reactions relative to the undesired reactions. Hence the choice of catalyst can have a major influence on selectivity. 

Tubular reactors, as previously stated, are also advantageous for high-pressure reactions where smaller-diameter cylindrical vessels can be used to allow thinner vessel walls. Tubular reactors should be avoided when carrying out multiphase reactions, since it is often difficult to achieve good mixing between phases. 

Generally speaking, temperature control in fixed beds is difficult because heat loads vary through the bed. Also, in exothermic reactors, the temperature in the catalyst can become locally excessive. Such hot spots can cause the onset of undesired reactions or catalyst degradation. In tubular devices such as shown in Fig. 2.6a and b, the smaller the diameter of tube, the better is the temperature control. Temperature-control problems also can be overcome by using a mixture of catalyst and inert solid to effectively dilute the catalyst. Varying this mixture allows the rate of reaction in different parts of the bed to be controlled more easily. 

Figure 2.8 shows the essential features of a refinery catalytic cracker. This particular reaction is accompanied hy the deposition of carhon on the surface of the catalyst. The fiuidized-hed reactor allows the catalyst to he withdrawn continuously and circulated to a fiuidized regenerator, where the carhon is burnt ofi" in an air stream, allowing regenerated catalyst to he returned to the cracker. 

Figure 2.8 A fluidized-bed reactor allows the catalyst to be continuously withdrawn and regenerated as with the refinery catalytic cracker.

Figure 3.3 shows a simple type of classifier. In this device, a large tank is subdivided into several sections. A size range of solid particles suspended in vapor or liquid enters the tank. The larger, faster-settling particles settle to the bottom close to the entrance, and the slower-settling particles settle to the bottom close to the exit. The vertical baffles in the tank allow the collection of several fractions. 

When used to separate solid-solid mixtures, the material is ground to a particle size small enough to liberate particles of the chemical species to be recovered. The mixture of solid particles is then dispersed in the flotation medium, which is usually water. Gas bubbles become attached to the solid particles, thereby allowing them to float to the surface of the liquid. The solid partices are collected from the surface by an overflow weir or mechanical scraper. The separation of the solid particles depends on the different species having different surface properties such that one species is preferentially attached to the bubbles. A number of chemicals are added to the flotation medium to meet the various requirements of the flotation process ... 

Separation of low-molecular-weight materials. Low-molecular-weight materials are distilled at high pressure to increase their condensing temperature and to allow, if possible, the use of cooling water or air cooling in the column condenser. Very low... 

If distillation is the choice of separator, then some preliminary selection of the major design variables must be made to allow the design to proceed. The first decision is operating pressure. As pressure is raised,... 

However, factors such as this should not he allowed to dictate design options at the early stages of flowsheet design because preheating the cold feed hy heat integration with the rest of the process might be possible. 

Again, in practice, there is likely to be a trace of chlorine in the reactor effluent. This can be recycled to the reactor with the unreacted decane or allowed to leave with the hydrogen chloride byproduct (providing this meets with the byproduct specification). 

The reactor effluent is thus likely to contain hydrogen, methane, benzene, toluene, and diphenyl. Because of the large differences in volatility of these components, it seems likely that partial condensation will allow the effluent to be split into a vapor stream containing predominantly hydrogen and methane and a liquid stream containing predominantly benzene, toluene, and diphenyl. 

Allow the use of standardized multipurpose equipment for the production of a variety of products from the same plant. 

Allow product integrity. Each batch of product can be clearly identified in terms of the feeds involved and conditions of processing. This is particularly important in industries such as pharmaceuticals and foodstufls. 

The reactor now becomes batch, requiring the reaction to be completed before the separation can take place. Figure 4.14 shows the time-event chart for a repeated batch cycle. Note in Fig. 4.14 that there is a small overlap between the process steps. This is to allow for the fact that emptying of one step and filling of the following step occur at the same time. 

If the problem in the absence of significant constraints can be decoupled in this way, there must be some mechanism which allows this, and that mechanism should be explored. 

Whether heat integration is restricted to the separation system or allowed with the rest of the process, integration always benefits from colder reboiler streams and hotter condenser streams. This point is dealt with in more general terms in Chap. 12. In addition, when column pressures are allowed to vary, columns with smaller temperature differences are easier to integrate, since smaller changes in pressure are required to achieve suitable integration. This second point is explained in more detail in Chap. 14. 

In addition, one other feature of the prefractionator arrangement is important in reducing mixing effects. Losses occur in distillation operations due to mismatches between the composition of the column feed and the composition on the feed tray. Because the prefractionator distributes component B top and bottom, this allows greater freedom to match the feed composition with one of the trays in the column to reduce mixing losses at the feed tray. 

---