Reflux, enthalpy

If distillate flow is made the dependent variable, it then depends not only on reflux and vapor rates, but also on feed and reflux enthalpies. Composition is so difficult to control under these conditions, that special-purpose computers are often used to compensate for qp and 5. But if distillate flow is made independent of the heat balance, no such measures are necessary. 

Fig. 12. (a) Schematic diagram of cmde unit showing five hot streams leaving the cmde column, and (b) temperature enthalpy diagram for the streams in (a) where A represents the kerosene pumparound B, the gas oil product C, the residuum D, the overhead reflux and E, the cmde. The dashed line is the... 

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. 

Resoles. Like the novolak processes, a typical resole process consists of reaction, dehydration, and finishing. Phenol and formaldehyde solution are added all at once to the reactor at a molar ratio of formaldehyde to phenol of 1.2—3.0 1. Catalyst is added and the pH is checked and adjusted if necessary. The catalyst concentration can range from 1—5% for NaOH, 3—6% for Ba(OH)2, and 6—12% for hexa. A reaction temperature of 80—95°C is used with vacuum-reflux control. The high concentration of water and lower enthalpy compared to novolaks allows better exotherm control. In the reaction phase, the temperature is held at 80—90°C and vacuum-refluxing lasts from 1—3 h as determined in the development phase. SoHd resins and certain hquid resins are dehydrated as quickly as possible to prevent overreacting or gelation. The end point is found by manual determination of a specific hot-plate gel time, which decreases as the polymerization advances. Automation includes on-line viscosity measurement, gc, and gpc. 

Derivatives or rates of change of tray and condenser-reflux drum hquid holdup with respecl to time are sufficiently small compared with total flow rates that these derivatives can be approximated by incremental changes over the previous time step. Derivatives of liquid enthalpy with respect to time eveiywhere can oe approximated in the same way. The derivative of the liquid holdup in the reboiler can likewise be approximated in the same way except when reflux ratios are low. 

Calculate liquid densities, molar tray and condenser-reflux drum holdups, ana hquor and vapor enthalpies. Determine holdup and enthalpy derivatives with respect to time by forward difference approximations. 

Binary minimum reflux so calculated implies feed enthalpy just equal to the above started vapor V and liquid L. Any increase or decrease in that enthalpy must be matehed by inerease or decrease in total heat content of overhead reflux. Note that the Underwood" binary reflux equation essentially computes the flash versus specifi-eation composition relationship along with enthalpy correction. 

The enthalpy of the top product and reflux are zero, as they are both at the base temperature. Both are liquid, and the reflux will be at the same temperature as the product. 

Example 9.2 Apply the enthalpy correction to the prediction of minimum reflux ratio for Example 9.1 to obtain a more accurate estimate of the minimum reflux ratio. 

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. 

To obtain a relation between Ln and Lm, it is necessary to make an enthalpy balance over the feed plate, and to consider what happens when the feed enters the column. If the feed is all in the form of liquid at its boiling point, the reflux Lm overflowing to the plate below will be Ln + F. If however the feed is a liquid at a temperature Tf, that is less than the boiling point, some vapour rising from the plate below will condense to provide sufficient heat to bring the feed liquor to the boiling point. 

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. 

From the enthalpy data and the reflux ratio, the upper pole point M may be located as shown in Figure 11.32. Points F and S are located on the liquid line, and the position of the effective feed, such that F S /F F = 10. NF is joined and extended to cut x = xw at M, the lower pole point. 

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. 

The prior discussion assumes that the feed rate, feed composition, and heat content (enthalpy) are fixed. My purpose in presenting this review of the phase rule is to encourage the routine manipulation of tower operating pressures, in the same sense, and with the same objectives, as adjusting reflux rates. Operators who arbitrarily runs a column, at a fixed tower pressure, discards one-third of the flexibility available to them, to operate the column in the most efficient fashion. And this is true, regardless of whether the objective is to save energy or improve the product split. 

The procedure is outlined in Figure 13.17. The input data are listed above Box 1 and include all external material and enthalpy flows except condenser and reboiler loads, the number of trays, the reflux rate, and the reboiler load. The process is iterative, starting with estimates of temperature and vapor flow rates on each tray and making successive improvements in these values until a convergence criterion on temperatures is satisfied. 

Controlled variables include product compositions (x,y), column temperatures, column pressure, and the levels in the tower and accumulator. Manipulated variables include reflux flow (L), coolant flow (QT), heating medium flow (Qb or V), and product flows (D,B) and the ratios L/D or V/B. Load and disturbance variables include feed flow rate (F), feed composition (2), steam header pressure, feed enthalpy, environmental conditions (e.g., rain, barometric pressure, and ambient temperature), and coolant temperature. These five single loops can theoretically be configured in 120 different combinations, and selecting the right one is a prerequisite to stability and efficiency. 

The key to doing process analysis is the identification of the equations that may be used to achieve zero degrees of freedom. These equations will come from a number of sources, including the balance equations themselves (Equations (1) and (19)), process specifications (such as the purity of output streams and the reflux ratio), physical relations (such as the definition of enthalpy for liquid and vapour streams) and other constraints imposed by the problem. Once a full set of equations has been developed, the equations can be solved, usually with little difficulty, and the desired results obtained. 

The high lipid content of oat starch is reflected in the high value of the transition enthalpy (AHCX) measured for the amylose-lipid complex (Table 15.4). This transition is reversible, and on a rerun greater AHCX, as well as Tcx (endotherm peak temperature), was found.26 When the oat starch was defatted, the endotherm assigned to the amylose-lipid complex disappeared from the DSC thermogram.26 Extraction at room temperature with 1-propanol water (3 lv/v) did not influence the thermogram of the starch, but if the starch was refluxed in the same solvent, a decrease in AH and a complete elimination of the endotherm ascribed to the amylose-lipid complex occurred.28 For oat starches with a lipid content of 1.1-1.7%, it was possible to... 

Mujtaba (1989) used CMH model to simulate the operations considered by Domenech and Enjalbert (1974). Since the overall stage efficiency in the experimental column was 75%, the number of theoretical plates used by Mujtaba was 3. The column was initialised at its total reflux steady state values. Soave-Redlich-Kwong (SRK) model was used for the VLE property calculations. Vapour phase enthalpies were calculated using ideal gas heat capacity values and the liquid phase enthalpies were calculated by subtracting heat of vaporisation from the... 

Only a few modifications of the algorithm were required to make it applicable to absorption and reboiled absorption. The changes were mainly in the handling of the enthalpy and total mass balance equations to accommodate different specification combinations involving the reflux, heat duties, and top and bottom product flow rates. The results of two example problems, one each for absorption and reboiled absorption, are shown in Table II. 

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