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**INDUSTRIAL AND ENGINEERING CHEMISTRY
**

LITERATURE CITED (10) (11) (12) (13)

87 1

Baylis, W. S., U. S. Patent 1,776,990 (Sept. 30, 1930). Davidson, R. C., Ewing, F. J., and Shute, R. S., Nutl. Petroleum

News, 35, No. 27 R,318 (1943). Ewing, F . J., U. S. Patent 2,410,436 (Nov. 5, 1946). Ewing, F. J., Secor, R.B., and Warner, J. G., Ibid., 2,391,312 (Dec. 18, 1945) Glaeser, R., Compt. rend., 222, 1241 (1946). IND. ENG* C H E & f s i 2148 (1948); 413 1485 ( 1949) Grim, R. E., J. Geol., 50, 225 (1942). Hauser, E. A., Chem. Rev., 37, 287 (1945). Hofmann, U., and Bilke, VV., Kolloid-Z., 77, 238 (1936).

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Hofmann, U., Endell, K., and Wilm, D., 2. Krist., 86,340 (1933). Marshall, C. E., Ibid., 91, 433 (1935). Prutzman, P.W., U. S. Patent 1,397,113 (Nov. 15, 1921). Ross, C. S., and Hendricks, S. B., U . S . Geol. Survey, Profess.

Grenal’l

.

401

Paper 205B (1945). (14) Shankland, R. U., and Schmitkons, G. E., Proc. Am. Petroleum Inst., 27, 111, 57 (1947). (15) Thomas, C. L., IND. ENG. CHEM., 41, 2564 (1949). (16) Van Horn, L., U. S. Patent 2,391,050 (Dec. 18, 1945). (17) Whitmore, F. C., IND. ENG.CHEM.,26, 94 (1934); J . Am. Chem. Soc., 54, 3274 (1932).

RECEIVED June 2, 1949.

**Calculation of Minimum Reflux in Distillation Columns
**

Three methods for calculatR . N. SHIRAS volatility rates are valid. It Shell ~~~~l~~~~~~ company, sari ~ r a n c i s c o ,calif, is also suitable as an approxiing minimum reflux rates in distillation columns fracmate method for all column tionating multicomponent D. N. HANSON AND C. H. GIBSON design problems which normixtures are presented and mally occur. The third Unicersity o f Caltlfornia, Berkeley, CalV. evaluated. The first method method is an adaptation of is based on some overlooked the Thiele and Geddes plateequations originally published in 1932. It is very simple, by-plate method of calculating finite plate columns. I t is but is rigorous for only a restricted class of separations. completely general, since with it variable overflow and The second method is an extension and elaboration of a variable volatility ratios can be taken into account, and method recently published by Underwood. This ‘ @ functhere are no restrictions as to the type of separation. I t is tion” method is fairly rapid and is exact for all separations recommended as a tool in distillation research but is too for which the postulates of constant overflow and constant laborious for plant design work.

a ?

HE calculation of minimum reflux is important both as an initial step in the design of distillation columns and as a correlating property in research on distillation calculations. In binary systems, methods for the rigorous calculation of this quantity have been well defined (5, 13) although some of the more useful equations appear to have gained less attention than they deserve. For multicomponent systems, both approximate niethods and an exact method have been proposed. The available rigorous method for multicomponent systems (2, 7 ) is quite tedious and can hardly be justified even in application to unusual design problems or to research in distillation calculations O f the proposed approximate methods (1, 4-6, 9, 11-18), the best is the method introduced by Underwood ( 1 1 , l a ) which is quite accurate and is, in addition, rapid in calculation. I t is thus adequate for most design purposes. In a recent paper Cnderwood has shown that this method is accurate not only for sharp separations between adjacent keys but also for cases where the separation is not sharp and where one or more components lie between the keys in volatility. Actually, Underwood’s equations are exact for any multicomponent system for which the assumptions of constant molal flows and constant relative volatility are valid. Further equations are presented here which facilitate the exact solution of a multicomponent system by Undei wood’s equations. When this elaborated Vnderwood method is not exact and a precise evaluation of minimum reflux is required, there is also a new rigorous method which, although time-consuming, is less tedious than that proposed by Jenny ( 7 ) and by Brown and Holcomb ( 8 ) . This new method consists of an adaptation of the finite plate method of Thiele and Geddes (IO) to the calculation for infinite plates (minimum reflux). For the calculation of minimum reflux, all multicomponent

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separations can be classified under two categories: class 1, separations such that, with infinite plates, all components of the feed are present in both the top product and the bottom product; class 2, separations such that, with infinite plates, some of the components are completely in the top product or completely in the bottom product. Failure to recognize the distinction between these two classes has led to much confused thinking about the so-called pinch points. When there are infinite plates in a rectifying or stripping section, as one proceeds away from the section terminus toward the feed plate, a point will be reached where there are only infinitesimal changes in component concentrations and molal flows for successive plates. Some writers on distillation have called this the “pinch point”; the present authors believe that a better designation is the “point of infinitude.” With binary systems the point of infinitude for both sections occurs at the feedplatc. The same is true of all class 1 separations of which a binary separation is merely a special species. With class 2 separations, for one or both of the sections, the point of infinitude occurs away from the feed plate. I f the top product contains all components of the feed, then the point of infinitude for the rectifying section will be at the feed plate. If not all the components are present in the top product, then the point of infinitude will be at an intermediate point of the rectifying section. In the top product the mathematical concentrations of the vanished heavy components are infinitesimals of the second order; the infinite plates between the top of the column and the point of infinitude build the concentrations of these. heavy components up to infinitesimals of the first order; the infinite plates between the point of infinitude and the feed plate build the concentrations for these components up to the

4V or AL and the compositions of these two portions are the same. ’From the operating equations for the two sections it also follows that: (Lm d)(Kd)w d ( X i l d Lm(Xi)m = Lm 1--. and exact solution for the minimum reflux for separations which belong to class 1. The compositions a t the points of infinitude of the rectifying section and the stripping section. From this there follow some interesting relationships as t o the compositions of the liquid and vapor leaving the feed tray. and 10 are completely grneral. Equation 8 becomes simply These equations have been published by Brown and hlartin (3) and by others. The alpha value used is the alpha value for the key components at the feed plate conditions. and LI = AL.b+l)(xi)’$ (7) F(X& = 4V(Y& + 4L(Xi)+ where A V represents the increment of vapor flow a t the feed tray.(x~)+ V+(Yi)+ + F(xi)F = (v+- v i . (V. at least. 42. (L. due to a pronounced nonideality in the binary system and consequent concavity in the equilibrium curve. as the compositions of the vapor and liquid leaving the feed tray. 61 likewise holds true and one may Underwood’s equation KO. boiling point feed. in which case the values of (Xt)fconstitute a mathematical solution of the flash equation without physical counterpart other than their identity with the values of ( X % ) + . By solving Equation 3 for’(&). In view of this identity of flashed feed compositions with feed plate compositions. it is surprising that they have been so completely ignored in subsequent discussions of minimum reflux. then the more general form. ( Y % ) + (at3)+(K7)+. This may be done even though AV is negative or greater than F .)+(X. Underwood (19)has shown that at the point of infinitude in the rectifying section: If AV is equal to neither zero nor F (usually I). No. but only for two coinponent systems. if the feed is flashed to a degree of vaporization. and AL represents the increment of liquid flow a t the feed tray. For separations of class 1. dew point feed. By over-all heat balance calculations the corresponding top internal reflux or the external reflux can then be obtained. Equations 9 and 10 were published by Underwood in 1932. the composition of this vapor portion of the feed - - - .). for such separations (X$)@ in Equation 5 may be replaced by (Xt). 9. since the points of infinitude for both the rectifying and the stripping sections are a t the feed tray.>the mole fraction of component i in the flashed feed liquid. + Lm (3) This is a modified form of equation No. are given by the familiar equations : is the same as that of the feed plate vapor and the composition of the residual liquid. Theoretically. and by sub= (K. V i . . If they are applied to the two key components whose specified distributions define the separation. ) . which holds for class 1 separations. i : ( X i ) +. In other words.I ( X i ) + = (Xi)++ 1 = (Yd+.). 1 t o 6.l ) ( Y i ) + -t’ ( L i . then they give a simple. analogous to the breakdown of the graphical evaluation of a binary minimum reflux when the rectifying line crosses the equilibrium curve betxeen the feed plate composition and the top product coniposition. are valid for all cases. Thus for any component.872 I N D U S T R I A L AND E N G I N E E R I N G CHEMISTRY Vol. direct. is equal to F . (LG L++. Shortly after the publication of UndeiJvood’s compendium of distillation calculation methods.)+ = stituting the relationships. They represent such a simple method of calculating the minimum reflux. Equation 8. E y u n tiori 5 then becomes: and If L. the total feed can be divided into a vapor portion of amount AV and an equilibrium liquid portion of amount F . Similar considerations apply in the stripping section.1 ( ~ i ) + = L. of infinitude in the stripping section: These equations. lioldirig for any two components of the multicompoiient mixture. d)(Ki). V / equal to AV. then. Fenske ( 5 ) also developed it. A and B. write + . For the special case of A V = F .1 = ( Y i h (Yi)‘$+ 1 L++l(Xi)++l f F(Xi)F f ~’G-l(~’i)+--l = L i ( x i ) + ~++l(xiF ) (+ x~)F + V+(Yi)’$ + + ~ . that of the feed plate liquid. According to Equation 7. from the \$-ell known flash equations. The explanation probably lies in a failure to recognize the distinction between class 1 arid class 2 separations. the liquid leaving the feed tray has %hesame composition as the liquid leaving the plat>eabove the feed tray and the liquid leaving the plate below the feed tray. Seither constancy of reflux nor constancy of alpha values Tras assumed in the derivation of these equations. This entails evaluating the ( X . and the minimum reflux found is the minimum reflux rate at the feed plate. Equations 8. and then applying it to two components. and are presented here merely for convenient reference. in equilibrium with this vapor portion of the feed is the same ac. 60 in Underxood’s old paper (13). Lh. MI[NINIUM REFLUX IN CLASS 1 SEPARATIONS (11) Equation I t is one of the alpha value valiants of the standard single flash equation. respectively. Lj. the method can break down in extreme cases of variable alpha.This is permissible because Equation 7 is true regardless of the sign or magnitude of AT’. must be used. 5 finite values of the feed plate.)+and (K. respectively. this equation transforms to Similarly for the point.

if three components distribute.i. if any. of the two equations: tor for the reference component at the rectifying point of infinitude and its value must be less than that of the smallest azV. Even where these presumptions are not valid. if Equation 16 be solved for those roots which lie between the 01~). of the feed the d ( X & values for all components are readily found. adding Equations 13 and 14 gives: + for all common roots of Equations 13 and 14. I t can be shown. the points of infinitude were remote from the feed plate. there will be three common roots. which are defined as the roots. the values of which lie between the alpha values for those components and only those components which distribute between top and bottom products. Thus the only unknowns in Equation 18 are Lminand the d ( X . ) . When filled out in detail. for the rectifying section. Otherwise by Equation 15 for at least one component. ~ is nothing more than the absorption fac- By this equation and the flash. these roots will also be common roots of Equations 13 and 14.this equation becomes a i . ..(K. and then multiplies the numerator and the denominator by a*. roots of Equation 14. Thus. Each such appropriate GI root of Equation 16 gives rise to an independent equation of Equation 18 type. performing numerically the summation and subtracting the yield of the top product.May 1950 1% orkers INDUSTRIAL AND ENGINEERING CHEMISTRY The expression L 873 in distillation theory became acutely aware that with the multicomponent separations normally encountered. and Equation 17 or 18 can be solved directly for Lmin. for the nonkey distributing components. and component B.). in this nomenclature for the stripping section.. that if V and VI are the vapor flow rates in the rectifying and stripping sections. Equation 16 can be solved for the Q root lying in value between the alpha values of the key components. it is relativelyrapid and with suitable elaboration it is in fact exact for all separations for which constancy of reflux and constancy of volatility ratios are valid presumptions. and Lg + 1 is then eliminated. when actually it is merely restricted. Now substituting any one of these common roots in Equation 13. by its equivalent. V ( Y ... the separation belongs to class 1 and all components are present in both products. Furthermore. d. and it is for this class of separations that the various approximate methods which have appeared in the literature have been devised. In other words. or intermediate in volatility. ) . A calculation method which presumed identity of feed plate and feed compositions was regarded accordingly as being erroneous. if in addition to the keys two other coinponents distribute. These equations. ) . The crux of the method is the setting up of a set of parameters. as there are components in the top product. following the line of reasoning indicated by Underwood. there will be two common roots. Equation 8 also provides a means of determining the distribution of the components other than the two keys. in its essential features. also provide the means for calculating these d(X& values of the distributing components other than the keys.). Unfortunately in engineering practice the separations normally encountered belong instead to class 2. Thus the number of these simultaneous independent equations is equal to the number . Thus if it be applied to any such component. I f only the two key components distribute. values of those components which are present in both top and bottom products. Q1.. will give the value of the minimum reflux: + Or an alternative form may be used to calculate L. Of these various methods. and another set of parameters. under minimum reflux conditions. respectively. and these common roots of the two equations will be all the and @.. less volatile. directly: Equation 13 has as many roots. -_ _ V(i. etc. the method usually gives good approximate values of minimum reflux adequate for design purposes. Equation 8 can be used for the evaluation of the minimum reflux only when. however. If any other components distribute. Summing this equation componentwise gives: These relationships are valid. the feed plate composition is markedly different from that of the feed and that with infinite plates in both sections. this argument is completely rigorous within the limitations of the presumptions of constant reflux and constant volatility ratios. the best which has been published thus far is that recently presented by Underwood (11. l a ) . wherein he also sketchily indicated the mathematical argument for its validity. USE OF @ FUNCTION. there will be only one common root. if only the two key components defining the separation are present in both products. because of the choice of key components or the volatility relationships of the components. regardless of whether a distributing component other than the keys is more volatile than either key.. It has already been pointed out that the number of roots of Equation 16 applicable to Equation 18 are one less than the total numbel: of distributing components and hence one more than the number of nonkey distributing components. wm contained in Underwood’s recent paper ( I I ) . This least root can be given a physical interpretation. This method. @>. The d(X&values for the keys are given in the problem specifications. a. one obtains: V(K. MIKIMUM REFLUX FOR CLASS 2 SEPARATIONS As has already been brought out. would be negative and would not be physically real. By definition the d(Xi)dfor the light nondistributing components are the same as the F ( X . If in Equation 1 for the rectifying point of infinitude one replaces (&). and are zero for the heavy nondistributing components. i. Furthermore it can be shown that one of these is less in value than the smallest air and the remaining roots must lie successively between adjacent airvalues. then some of the @1 roots for Equation 13 will be identical with certain @. the exact distribution of these components must be established. the value of the minimum reflux. and the values of the d ( X i ) dfound for these components must be used in solving Equation 17 or 18 for L. and again to component A and component B. the value of the absorption factor for the reference component at the point of infinitude which satisfies Equation 15 is that root of Equation 13 which is smaller than the smallest aZT. Since Equation 15 and Equation 13 have the same form. respectively.).

1 Component - IN TOP PRODUCT (EQCATIOX 12) T.2477 was obtained for it by trial and error procedure. Under these circumstances.0. 5 TABLE I. Had @D. and the values found are listed in Table 11. usually there will be no serious error in assuming nondist. TABLE I\-. C o a r ~ o m RECOVERIES :~~ A N D 111xnin1 REFLUX I'. Eq. RECOVERIES Component . D = 2. it is not obvious. of unknown values of Lminand d ( X i ) dand t.0057 or 1%.5 1. The feed is at its boiling point and constant internal molal flows T.0375 O D . Y i ) d 0 050 0.ing nonkey components will also be slightly in error and must be recalculated after dropping as a variable the component or components thus shown to be nondistributing. if a light component.ion of all components a t minimum reflux.0072 2. I f a component is presumed to distribute at minimum reflux.42 90 48. this procedure gives a value of minimum reflux which differs by only a few per cent from the true value.30095 0. At the same time the d(X.0071 0. are more volatile and less volatile than either key.).han -0. An eight-component feed has the composition and volatility ratios relative to component F .II. c70 d(Xi)d 0. shown in Table I.0 0.05 0. For these reasons.1. these presumptions are not valid.he accuracy that may be expected with it.0~000 - 1. In many cases it is obvious which coinponents will distribute at minimum reflux.51212 0. It is desired to calculate the niinimum reflux for the specifications of 90% recovery of component D in the top product and 90al.02268 0. air.02418 0. Compn.G. 18.270 0 025 0 030 0 002 1.ribution of that component.5604 d(.Yi)d air 1. In general. No.0 and 1.44783 0 1185'3 -0. B . and *. will give rise to an impossible value for d(Xi)dfor this component. if this ratio lies betxeen 0.958SZ -0. found for other distribut. E = 1.1237 -0.14684 0.0 1. respectively.D.ionsthus far has been restricted to the calculation of minimum reflux under the postulates of constant reflux and constant volatility ratios.recovery of component F i n the bottom product.5604 O E F = 1.05 2. give correct values for component distributions in class 2 separations.30 0.01 and 0.0166 0.0 0.1462 0. which is still close enough for most practical cases.3776 The simplified method t. and G through the set of four simultaneous linear equations of Equation 18 type. The next step is to substitute the F(X.99 or 0.01 or less t. but that components C.9192 Recovery in TOP Product. The discussion of class 2 separat.5565 and hence in error by 0. and then to solve this equation for either of the @ roots intermediate in value to 2. which in fact does not.05 1. and G do.050 0 094 0. Equation 12 developed for class l separations. it will be greater than its F(Xi). E .)r values ( F = I) and aLI values from Table I into Equation 16 with Vi equal to zero since boiling point feed has been specified. Since each solution of Equation 16 for an appropriate @ root is a trial and error procedure of the same nature as the trial and error solution of the standard single flash equation. Similarly there is no occasion to determine the exact distribut. 4 B C E G H 7 Recovery in %op Product 730 330 '34 50 2 . components C and G. then the solution of the set of simultaneous equat'ions. From this it is quite evident that components A .01 it may safely be presumed t o be nondistributing.00 RATIOS O F EIGHTTolatility Ratio 10 5 2. The procedure is to determine the apparent d(Xijd value through Equation 12 for each doubtful component. Xormally. although it will not. @E. I n most practical problems of class 2 separations which arise in the petroleum and chemical industries.08353 -0 00615 0.36 10 2.05 2. Recoveries in top product for all the other components were calculated according to Equation 12.09442 0.UES G C . The component recoveries thus found and the resultant mininiuni reflux value are shonm in Table IV. COMPCTATION OF ~ I I S I M REFLUX U~I O E .0.s obtained by Equation 12 gives an adequate approximation of minimum reflux.2477 Recovery in T o p Product.5831 moles reflux per mole feed.01.62417 -0.00925 0. F = 1. To do this necessitated trial and error evaluation of three more @ roots of Equation 16.. commonly.5832 .05 0. COVPONEST FEED Rlok Fiactioii 0.00994 0.? was selected and a value of 1. and H do not distribute.2477 j: D c r E c 100 100 94. @c.1 .0~000 0. Component E lies between the two keys.27000 0. 2 4 7 7 0.05 0.775. The following numerical example illustrates this practical form of the @ function minimum reflux method and t.01 and -0.57758 Lmin = 0.E been evaluated and used in the simplified method instead of @ ' E . P . either because of appreciable departures from ideal solution behavior or.0211 or 3.57755 0 00713 0. it is highly desirable that no superfluous roots be evaluated. * D .IBLE 111.5 1. 18 Coniment Kondistributing Eondistributing From Table I1 Light key From Table I1 Heavy key From Table I1 Nondistributina % 100 100 94 90 50 10 2 d ( .15110 -0.ities can be found by any of the standard methods for solving simultaneous linear equations. preferably the value lying between the (\I values of the keys. but in some cases with components lying relatively close to but outside t8hekeys on a volatility scale. the of the key components.08000 0. the minimum reflus value found would have been 0.2477 d ( X i ) d O Z T .10 0. and as a consequence there is a wide temperature spread in . the use of the values of d ( X i ) dfor the distributing component.9 0.2477 1. namely. t'he component probably does distribute.603 0. since minimum reflux is only a guide for the estimation of design reflux flows.~BLE 11.0 1.F. only one value of Q need be calculated from Equation 16. the minimum reflux is directly calculated by Equation 18.5604 96. the exact value was found by solving for the exact distributions of components C.5776 = 0.01. I f the ratio of this apparent d(Xi)dvalue to the corresponding F(XijFis greater than 1.99 and 0.1511 -0.10 0. 1 . but their volatilities are so close to that of one or the other of the key components that they also distribute.62 are presumed. E. Coinin. if the ratio lies between 1.he unknown quant. E . The remainder of the computation of the minimum reflux is shown in Table I11 from which it appears that the minimuin reflux is 0.hus gave an anwer xhich was in error by only 0. or negative if a heavy component.2477 d ( X i ) d air .01RF3 0.30 0. can still be used to establish which are the distributing components and thus forestall evaluating unnecessary Q roots of Equation 16. complete rigor in its calculation is unnecessary.874 INDUSTRIAL AND ENGINEERING CHEMISTRY COMPOSITION AND VOLATILITY VoI. because the feed embraces too broad a volatility range.1 0 In order to determine the accuracy of this value for the minimum reflux. 42. so obviously it must distribute. the heavy key.4478 0.0= 0.9 0.

For the problem given by Brown and Holcomb ( 2 ) both procedures gave the same alpha values within the accuracy to which their equilibrium constant charts could be read. unfortunately usual. and an alpha value between the keys of 2. in the rectifying section these are the components heavier than the heavy key and in the stripping section. which is equal to (Ki)R. Two examples of class 2 sepal ations employing variable alpha values which have been reported in the literature (2. On the whole. The respective minimum reflux values were found to be 0. The minimum reflux is then found by Equation 18. There are various criteria which can be used for arriving a t the feed tray temperature. The Thiele and Geddes approach does not require pre-estimation of component distributions and with it the computation time does not mount impossibly with an increase in distributing components.1 to plate n in the stripping section according With finite plate and reflux calculations.66. Moreover. the starting and d (Yi)m/(Xi)b. Considerable research in comparisons of the results of this approximate method with precise values obtained by laborious exact calculations for a wide variety of cases is needed to delineate the trustworthiness of the approximate @ function method. the apparent vaporization of the feed.in passing from the stripping section to the rectifying section must be estimated. Even as outlined by Brown and Holcomb ( 2 )or in the modified version of Jenny ( 7 ) . I t will be recalled that in a Thiele and Geddes type calculation one proceeds from plate n 1 to plate n in the rectifying section according to the recursion equation: + and from plate n to the equation: . Its use is recommended for all ordinary plant design problems involving class 2 separations. In these computations variation in reflux flow can be taken into account by a running heat balance in the usual manner for Lewis and Matheson type calculations. and adjustments are made in the quantities added at the points of infinitude (or equivalently part way toward the feed plate) until the concentration of each nondistributing component in the feed plate vapor is the same when the composition of the feed plate vapor is calculated from either point of infinitude. I n applying the function to class 2 separations involving variable alpha values and variable molal flows throughout the column. The second procedure gave a temperature of 180" F.54 and 0. These alpha values are then used to evaluate component distributions by Equation 12 and one @ root of Equation 16. ( X 6 ) m / ( X J at the rectifying and stripping points of infinitude. After this balance for the nondistributing components has been achieved. and from this evidence a new estimate is made of the minimum reflux and the whole process is repeated until all components are in agreement. compared to their value of 0. For these. employing feed vapor and liquid compositions for feed plate compositions. I n the adapted Thiele and Geddes technique for infinite plate minimum reflux calculations. alpha values are found for all the components at an estimated feed plate temperature. the nature and degree of unbalance for the two key components is observed.and for the stripping section is the ratio (Y<)R/(Xi)*. it has the advantage of being fairly rapid to perform. V f . For the problem given by Jenny ( 7 ) .May 1950 INDUSTRIAL A N D ENGINEERING CHEMISTRY 875 * d the column.09. If the added complication be present.elms 2 separations for which the simplifying assumptions of constant reflux and constant volatility ratios are not valid is necessarily tedious because a certain amount of trial and error plate-by-plate calculation cannot be avoided. the components lighter than the light key. this procedure is quite laborious. since these distributions must also be established for each reflux estimate. tbe compositions and magnitudes of the vapors at the two points of infinitude are computed by Equations 1 and 2 and to these are added very small amounts of the missing nondistributing components. EXACT CALCULATION OF MINIMUM REFLUX WITH VARIABLE REFLUX AND EQUILIBRIUM CONST4NTS (K VALUES) + *' The exact calculation of minimum reflux for those . alternatively. For evaluation of these ratios Equations 3 and 2 are rearranged to the forms: . compared to Jenny's value of approximately 0. Probably such a research program would show that the biggest sources of error were poor estimates of the feed plate temperature and of the change in vapor flow rate a t the feed plate. the authors do not feel this extra labor to be warranted. for ordinary petroleum feed streams. Moreover. cases there is no rapid method of precise evaluation of the minimum reflux.57. the temperature a t which the K values of the two keg components are equally distant from unity. that several components other than the key components are distributing. two of the simplest are an arithmetic mean of the top plate and reboiler temperatures weighted by the molal amounts of top and bottom product and. The concentration ratio plate-by-plate method of Thiele and Geddes (10) for calculatingwith finite plates can be similarly adapted to infinite plates minimum reflux computations. the computation time and labor become prohibitive. the weighting of top and bottom temperatures for obtaining feed plate temperature gave 158" F. 7 ) have been calculated by the approximate @ function method to estimate the degree of inaccuracy in the assumption of constant alpha values. pending confirmation by a research study.67 mole per mole of feed. Alternatively the true feed plate compositions may be calculated for this purpose.02. In order to solve Equation 16. the accuracy obtained with the 0 function method is easily sufficient. The value for the minimum reflux thus found is regarded as the minimum value for the internal reflux to the feed plate The corresponding top internal reflux or the external reflux can then be found by over-all heat balance around the rectifying section. the starting point in which is equal to the rectifying section is the ratio (Xs)L/(Xi)d. since minimum reflux serves primarily as a base point for selecting a design reflux. Both procedures proposed above for estimating feed plate temperature and thus obtaining average alpha values were used in these calculations. This estimate should be made on the basis of the feed plate temperature used for obtaining the alpha values of the components. The approximate minimum reflux found was 0. but the 0 function method may still be used to give good approximate values. l/(Ki)t. and an alpha value betueen the keys of 2. the method should be as dependable or more so than the other approximate methods which have been published and which involve the same or greater uncertainties. I n both problems the accuracy of the minimum reflux calculated by the approximate @ function method with either procedure for obtaining average alpha values is as good as the accuracy of reading the charts of equilbrium constants. This Brown and Holcomb method is simply an adaptation to minimum reflux determination of the method of Lewis and Matheson for calculations of finite plates and reflux. the change in vapor flow rate. The approximate value of the minimum reflux is estimated or computed by one of the available methods. Plate-by-plate calculations of the Lewis and Matheson ( 8 ) type are then made from both points toward the feed plate. With this reflux. points are the concentration ratios.57. but since this entails evaluation of all but one each of the 0 and roots of Equations 13 and 14 and still only leads to an approximate value of the minimum reflux. The recognized technique for such a calculation has been well outlined by Brown and Holcomb ( 2 ) for distribution of the key components only and need merely be summarized here.

and the (Ki). 2i-30 (1940). (1933). CXG. Chem.V. V. with the respective (Yi)+values comput. I n most plnnt design and proc('ss cv:duation work thc @ funrtion ini~thod gives adeynnte :tpproximations of the ininirnum reflux. D . Inst. E . tions of Equation 19 according to the postulated L. 24. M.CHCM. 5 v d u c i n ordinary circuinstnnces. P. G. moles 1. Petroleum Engr. and *' * LITERATURE (2ITLU Bailey. 10. F. V. It is a method suitable for a research calculation program.. A.W.. is satisfied. A. Colburn. sild the (Xi)b values from the first over-all material balance. Petroleum Refiner. This is especially true of the Thiele and Ceddes type and the computation time is largely controlled by the experience. W. Jenny. and Holcomb.. The technique of trial arid error revision of plate teifiperattires and flow quantities for a postulated reflux rate and one separation specification is the same as for ordinary Thiele and Geddes calcula. 25.ifying section. J. D. Petroleum Rehner. NOR1EXCLATURE The number of plates required above the feed plate to effect the disappearance from the calculations of all heavy nondistributing components is estimated and for these plates.J . Engrs. ESG. E.. 35.24. respectively j = general values of parameters. siinilarly for the stripping section.. 3. 1101-6 j1940). 11.. respectively. ( Y e ) + / ( X i ) d . moles vapor flow leaving plate in rectifying section. In t. -4. moles = parameter in equations writ'ten for rectifying section $' = parameter in equations n-ritten for stripping section + Also values for ( Y i ) + / ( X i ) bare found directly by the successive application of Equation 20. Trans.ude either in the rectifying sectioii 0 1 ' i n the stripping section f = top plate I ? = reboiler n = general plate numbering increases up the column f = concentrations either in liquid portion of feed or in vapor portion of feed.. B. Y / X Y = mole fraction in vapor phase X = mole fraction in liquid phase or in total feed F = total feed.25. Progress. 1%. A. moles A . moles T i = vapor portion of feed.482-5 (1932). Underwood. etc. E n g i s .ed from the (Yi)+/(Xi)d ratios and (Xi)d values.. + . = specific components (Y = relative volatility A = increment of flow. IND. Gilliland. A .. J. E. snd ACKNOWLEI)(:lENT The aut. and analytical judgment of the person insking or closely supervising the calculations. These liquid phase concentration ratios are converted $0 feed plate vapor concentration ratios.. Am.i = liquid port'ion of feed. These light and heavy run-out calculations show how many rectifying and stripping plat. Likewise Leviis and AIatheson run-out calculations are made for the light nondistributing components in the stripping section. Fenske. and Matheson. V. and Martin. temperatures are postulated.hors wish t. 1949.. Eng. Isu.. Lewis. and May. B ./(Xt)d are found from successive applicaValues for the (Xi). moles V' = vapor flow leaving plate in stripping section.es are required for practical disappearance of all heavy and all light. moles K = vapor-liquid equilibrium constant. CHEN. 42. cut point.ion specification parameter will usually be the distribution of one of the key componcnts. Inst Chem.. = liquid flow leaving platme in rect.. Engrs. 32.. I n s t . moles T' = L' = liquid flow leaving plate in stripping section. No.. normally the distribution of a second key component.. and Coates.ions. 679-708 (1939). 44.. 27.rations of 6he heavy nondistributing components arc computed in t'he feed plate vapor from the (Yi)+/(Xi)b ratios. G. moles d = top product.L. J. Underwood. but the first trial run will correctly revise these preestimates.he checking of the plate temperature estimates the concent. V. 37.. Chem. G.30-4 (1948) Brown. hfayfield. moles h = bottom product. Although this separat. understanding. but probably too time-consuniing and too demanding of a specialized skill to be of much Subscripts A . G.603-14 (1948). by the equation I. RECEIVED June 21. L. Trans. Inst.. ENG.816 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 35. L.494-8 (1932). 112-58 (1932). The minimum reflux is established by varying the postulated reflux until the second separation specification. R. = specific components i = general component r = reference component on which relative volatilities are based F = tot.c.. Ibid.al feed-(Xi)p refers to mole fraction of i in total feed d = top product b = bottom product + = feed plate m = point of irifinit.tions. Brown. J. nondistributing components. 141-5 (1946). Trans.. Ibid.o thank thc Shpll I>evelopnwnt Company for t. F. . IXD. 635-77 (1939).. Underwood. If variable flow rates and heat balances are also to be considered. and the corresponding concentrations in the rectifying plate liquids are computed until disappearance by Lewis and Matheson type plate-by-plate calculat. and Geddes. n-hen used with X and Y . These numbers of stripping and rectifying plates to be used in the calcuIations w r e already preestimated. From these latter ratios the c o r e sponding component distributions can be found from over-all Inaterial balance equations in the usual manner. CHEM. All plate-by-plate column calculations are tBo quite an extent an a r t which can be learned only by doing. J. Dividing the ( Y i ) + / ( X i ) dinto the ( Y i ) + / ( x i ) bgives tentative values for (Xi)d/(Xi)b ratios for the dist.lic re1e:ise for publication of sections of this paper. R. Z. B . G . That limited group of distillation workers who are already experienced in calculating finite plate fractionating columns in the Thiele and Geddes manner should have little difficulty with this adaptation to minimum reflux problems. 32. molal flow rates (LL and VrL) are postulated. or product purity. it may be any single defining property of the separation such as yield of principle product. 806-25 (1941).ributing components. 259-85 Thiele. Am. et.. for the postulated tray temperatures immediately above the feed tray. Chem. II. Petioleurn (London).. (London). 614-26 (1946). The procedure from here on is the same as for ordinary Thiele and Geddes type calculations.

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