DISTILLATION 9.1 INTRODUCTION The method of separating the components from a solution depending on its distribution between a liquid phase and vapour phase is termed distillation. This is applied to mixtures which distribute in both the phases. This can also be defined as an operation in which a liquid or vapour mixture of two or more components is separated into its component fractions of desired purity, by the application of heat. Thus, in this process, a vapour is obtained from a boiling mixture which will be richer in components that have lower boiling points. 9.2 VAPOUR LIQUID EQUILIBRIA (VLE) The vapour liquid equilibrium data is the basis for design of distillation operation equipments. 9.2.1 Constant Pressure Equilibria A typical VLE at constant pressure is shown in Fig. 9.1. The upper curve is the dew point curve which provides the relationship between temperature and mole fraction of the more volatile component in vapour phase (y) and the lower curve is the bubble point curve which gives the relationship between the temperature and mole fraction of the more volatile component in liquid phase (x) at a particular pressure. The horizontal tie lines CD, EF and GH at different temperatures provide equilibrium compositions of liquid and vapour phase at each temperature. Any mixture lying on the lower (bubble point) curve will be a saturated liquid and the mixture lying on the upper (dew point) curve will be a saturated vapour. A mixture located in between the two 2372838 Mass Transfer—Theory and Practice BPofB — BP ofA 0 1.0 x y¥—> Fig. 9.1 VLE diagram at constant pressure. curves, say K, will be a two-phase mixture of liquid and vapour with compositions C and D in liquid phase and vapour phase respectively. Their relative amounts are given by moles of C_ Length of line KD moles of D- Length of line KC Consider a mixture at point M. It is only a liquid. If it is kept inside a cylinder fitted with a frictionless piston and heated, its temperature will increase till it reaches ‘E’ when it will become a saturated liquid. The vapour in equilibrium with it will have a composition of F. As heating is further continued, more vapourization takes place, the liquid phase composition will move towards G and the associated vapour will have a composition of H. The effective composition of the entire mass comprising both liquid and vapour continues to remain at M. Finally, when the last droplet of liquid as indicated at point ‘I’ is vapourized, the vapour generated would have a composition of ‘J’. Further application of heat results in superheating of the vapour. During the entire operation, the pressure is kept constant. 9.2.2 Effect of Pressure As pressure is increased, the boiling points of components increase and the looped curves become more and more narrow. As the critical pressure is exceeded for one of the components, there is no longer a distinction between vapour and liquid for that component, and for mixtures the looped curves are, therefore, shorter as depicted in Fig. 9.2, for case (C). Distillation is possible only in the region where a looped curve exists. It is also clear that relative volatility, a, also changes in such cases.Distillation 239 | A 0 1.0 xy— Fig. 9.2. Effect of pressure on VLE. 9.2.3 Constant Temperature Equilibria A typical VLE at constant temperature is shown in Fig. 9.3. T: Constant Bubble point curve Liquid VP of A p—— VP of B 0 x%y—— 1.0 Fig. 9.3 VLE at constant temperature. As in the case of constant temperature equilibria, lines CD, EF and GH are tie lines indicating the equilibrium compositions of liquid and vapour phase at various pressures. A liquid defined at point M is a liquid below its bubble point and as the Pressure is reduced at constant temperature, at point ‘N’ on the upper (bubble point) curve, a saturated liquid is obtained. As the pressure is brought down, further, at point Q on the lower (dew point) curve, a saturated vapour forms and a further reduction in pressure gives a fully superheated vapour as defined by R.240 Mass Transfer—Theory and Practice 9.3 RELATIVE VOLATILITY (a) This is defined as the ratio of vapour pressure of more volatile component to that of less volatile component. If P, and Pg are the vapour pressures of A and B respectively, the relative volatility of A with respect to B, 04g is defined as the ratio of vapour pressure of A to that of B. P, ie. Op = y (9.1) Raoult’s law states that when a gas and a liquid are in equilibrium, the partial pressure of A, pa is equal to the product of its vapour pressure, P, at that temperature and its mole fraction x, in the liquid. ie. Pa= Pa-xa (9.2) Similarly, Pp = Pp Xp (9.3) When the gas and liquid behave ideally, Raoult’s law holds good. We know that sum of the partial pressures of components in a gas mixture is equal to the total pressure, Py. The composition of a component y, in gas phase is given by Dalton’s law, Ya =p Pp (9.4) (9.5) Rearranging, we get = %aBXa YA Te xq (Op —D 06) and more simply as ax ¥* Texe@=p on 9.4 COMPUTATION OF VLE DATA (EQUILIBRIUM DATA) The vapour pressure of the components involved is the basis for the computation of VLE data.Distillation 241 From Egs. (9.2) and (9.3), pa = x4 Pa Pp = Xp Pg = (1 ~ Xa) Pp (9.8) For a binary system, Pa + Pp = Pr =X, Pa + (1 — X4) Pp = Pa + Xa (Pa — Po) (9.9) _ (Pp = Pp) “= oP) (9.10) From the vapour pressure data at each temperature, x, can be computed using Eq. (9.10). After computing x4, the partial pressure p, can be estimated by using Eq. (9.2). The mole fraction of A in gas phase, y, is then determined by using Eq. (9.4). Thus, for the whole range of boiling points of components involved, the VLE data can be computed. Whenever or lies in a narrow range, y can be computed by assuming various values of x using Eq. (9.7). 9.5 DEVIATION FROM IDEALITY A mixture whose total pressure is either greater or lesser than that computed using Raoult’s law is said to exhibit either a positive deviation or a negative deviation from ideality. 9.5.1 Positive Deviation from Ideality When the total pressure of a mixture is greater than that for ideal mixtures computed using Raoult’s law, the mixture is said to exhibit positive deviations from ideality and such mixtures are called minimum boiling azeotropes, i.e. at some composition the mixture shows minimum boiling point (at constant pressure) and maximum pressure (at constant temperature) as shown in Figs. 9.4 and 9.5. A typical x-y diagram is also shown in Fig. 9.6. Most of the azeotropic mixtures fall under this category. oO Xx, Y—> 1.0 Fig. 9.4 Minimum boiling azeotrope at constant temperature.242 Mass Transfer—Theory and Practice BP, P: Constant vapour yvs T. 2 3 8 BP, 3 "A s F xvsT Liquid 0 xy——> 1.0 Fig. 9.5 Minimum boiling azeotrope at constant pressure. 1.0 P: Constant 0 x——> 1.0 Fig. 9.6 VLE of minimum boiling azeotrope. 9.5.2 Negative Deviations from Ideality When the total pressure of a system is less than the ideal value as computed using Raoult’s law, the system is said to deviate negatively. Such systems are very rare and they are also called maximum boiling azeotropes, i.e. at some composition the mixture shows maximum boiling point. Typical P-x-y, T-x-y and x-y diagrams are shown in Figs. 9.7, 9.8 and 9.9. 9.6 TYPES OF DISTILLATION COLUMNS Based on the nature of operation, distillation columns have been classified as batch and continuous columns as shown in Fig. 9.10. 9.6.1 Batch Columns In batch columns, the feed to the column is introduced batchwise and the distillation is carried. When the desired quality is reached or when the desired quantity is distilled out, the operation is stopped and next batch of feed is introduced.Distillation Pa Pressure ——> oe 0 x,y—> 1.0 Fig. 9.7 Maximum boiling azeotrope at constant temperature. yvsT Vapour P: Constant BP, Temperature ——> Liquid 0 xY—> 1.0 Fig. 9.8 Maximum boiling azeotrope at constant pressure. 1.0 P: Constant y 0 x——+ 1.0 Fig. 9.9 VLE of maximum boiling azeotrope. 243244 Mass Transfer—Theory and Practice 9.6.2 Continuous Columns These columns have a continuous feed stream and are capable of handling high throughputs. These are further classified on the basis of, © The nature of the feed they are further processing ¢ Binary columns—Feed has only two components ¢ Multicomponent column—Feed has more than two components © The number of product streams they have Two product streams @ Multi product streams © The use of additional components in distillation @ Extractive distillation—use of solvent ¢ Azeotropic distillation—use of entrainer © The type of columns: ¢ Tray columns—use of sieve plate columns/Bubble cap trays/Valve trays for better vapour—liquid contacting «@ Packed towers—use of packings in columns for better vapour—liquid contacting. Distillation o—I_{ Batch Continuous ot Simple! Flash’ I | Differential Equilibrium ‘Stagewise contact distillation distillation (Tray tower) (Pe Differential contact acked tower) Sieve Bubble Valve tray Cap tray tray Fig. 9.10 Types of distillation and equipments. 9.7 STEAM DISTILLATION Some systems have very high boiling points and some of these substances are unstable at high temperatures. Especially when such systems are completely insoluble with each other, steam distillation can be a useful method such mixtures. of separatingDistillation 245 For example, consider a mixture of hydrocarbon and water which are immiscible. The vapour pressure of either component cannot be influenced by the presence of the other component and each exerts its own vapour pressure at the prevailing temperature. When the sum of the vapour pressures is equal to the total pressure, the mixture boils. With vapour pressure data of the individual components, one can also estimate the temperature at which such distillations take place. Pr= Py + Pp @.11) It is clear from Fig. 9.11, that this type of distillation takes place at a temperature which will be even less than that of the boiling point water. This method suffers from poor efficiency in its operation, as large quantity of water has to be evaporated. However, one can introduce the effectiveness in such operations by © Operating at different total pressures in which case the ratio of vapour pressure of the substances may be more favourable. ¢ Sparging the mixture with superheated steam or other insoluble gas. Insoluble Water (A) compound (B) Pressure Ts BP ofA BP of B Temperature ———> Fig. 9.11 Steam distillation. 9.8 DIFFERENTIAL OR SIMPLE DISTILLATION Consider a feed F containing x; mole fraction of more volatile component fed into a batch still as shown in Fig. 9.12. Let L be the total moles present in the still at any instant, t and x be the mole fraction of more volatile component. Let dL be the moles distilled out. The concentration of vapour in the leaving stream is y*. The moles left behind in the still is (L — dL). During this process the concentration of more volatile component left behind in the still is (x — dx). Total moles of more volatile component present initially is Lx Total moles of more volatile component in distillate is y*dL Total moles of more volatile component in residue is (L — dL) (x - dx)246 Mass Transfer—Theory and Practice Cooling water, out Cooling water, in Distillate Heat Fig. 9.12 Differential distillation. Making a component balance, we get Lx = y* dL + (L- dL) (x - dx) (9.12) Ls = yt db + bx Lbs sdb + dy, (9.13) (‘s Product of two very small quantities) Then, dL(y* — x) = Ldx (9.14) qt dx LGD (9.15) Integrating between limits xaxp L=F xoxy L=W i di f dx T= *_ 9.16) pL) 0%=9 (9.16) mee f oe (9.17) Wo) OF=H : Equation (9.17) is called Rayleigh’s equation. The right-hand side cannot be integrated as y* is a function of x. Hence, the right-hand side of Eq. (9.17) can be evaluated either graphically or numerically with the help of x-y or VLE data. For systems where the relative volatility lies in a narrow range, we can use Eq. (9.7) which states that ax > + @-DalDistillation 247 Hence, replacing y in terms of Eq. (9.7), we get dx fe 9.18) “| Tie(@-1)a] a-1)x] RHS of Eq. (9.18) = [ ~- 8 . (9.19) [1+(@-1)x] On simplification, =f [1+ (@ -1)x]dx =f Belen 1)x]dx fax-x-ax?+x?] J xfa-l-ax+x] -f (+(@-Dx}dx ptt (@—-Ix]dx © Saxfl@=)=x(@ =D) J G-x)@-D) dx dx 1 A B Bl iccese=ni lis = awal|(4)-()je-e-9 _ A(1 — x) + B(x) _ =p) wey I-99) 1 dx dx ~ aa JE Ja]? Substituting the limits for x as xp and xy, we get 1 =% —plinx Ind - x)]-In(1-x) 1 Xp) _ ype) ]_ 1, = 3e) aa =) aay - naw) (xp) (=xp) [r(22)- w(@=22)]- ay) Xp F (\-xr))_ 1 oy (+m ( G25) =e 7) (1- xw)248 Mass Transfer—Theory and Practice Fd-xp) _ 1 Xp (l- xy) vce Sw I [=] la aa) xw ain Fz e) _ J ol ea | Fl= xp) _ Waxy) - Iino AE WO- xy) as) ol ete xw) (1-xw) F(l- xp) onlin) F) F(.- xp) Fx, ao [w=] wn( Fae) Fre _[ FQ-x-) 7 Wxy | W0-xy) ie. (9.20) Equation (9.20) is very useful in the estimation of the amount of residue (alternatively, the estimation of the quantity to be distilled) in case of systems of constant relative volatility. This is also used in the estimation of relative volatility for such systems. 9.9 EQUILIBRIUM OR FLASH DISTILLATION Consider a feed at a flow rate of F (moles per hour), containing the more volatile component with a composition of Zp and an enthalpy of Hr (per mole of feed) entering a preheater. Let the heat added in the preheater be Q. The mixture then enters a flash chamber where a distillate leaves at a rate of D (moles per hour) with a composition of yp and an enthalpy of Hp (per mole of distillate). The bottoms (residue) leave at a rate of W, with a composition of xy and an enthalpy of Hw (per mole of residue). The entire process is shown in Fig. 9.13 [> istitate vapour D. Yo. Hp Pressure reduction valve L____, Residue liquid é W. Xp Hy Fig. 9.13 Flash distillation.Distillation 249 A total material balance, gives, F=W+D (9.21) A component balance gives, FZp = Wxy + Dyp (9.22) An enthalpy balance gives, FH; + Q = WHy + DHp ie. (He + 2) = WHy +DHp (9.23) From Eqs. (9.21) and (9.22), we get (W + D)Zp= Wxy + Dyp (9.24) W [Zp ~ x] = -DIZp — yo] (9.25) _W _ (2p - yp) D” @—xw) 9.26) Similarly from Eqs. (9.21) and (9.23), we get y [( +2). ty| “D~ (9.27) Dividing Eq. (9.25) by F, we get w D Fee 8) =- Fr ~ yo) 9.28) Let f be the fraction of feed vaporised and subsequently condensed and removed. Hence, (1 — f) is the fraction of feed left behind as residue. (1 -f) Zr - xw) =f On - Zr) (9.29) 2p — xw - fer + f xw= foo - fer Zr -— xw =f Wo - xw) Zp +xw f- D=fo (f-) Yor =p + aW (9.30) So Eq. (9.30) can be called an operating line drawn with a slope of [(f- 1)/f] and simplified as, y=(2}+(S4) 9.31) The feed point is x = y = Zp250 Mass Transfer—Theory and Practice Having seen the principles involved in flash distillation, let us now see how compositions are estimated in a flash distillation operation. 9.9.1 Steps There are two methods available to estimate the composition of products. They are explained in detail below. Case I When the equilibrium data and the quantity of either the distillate or the residue and feed are available, the following procedure shall be adopted: © Draw the equilibrium curve © Draw the diagonal (x = y line) © Locate feed point corresponding to xp on the diagonal (xp = yp = w * Draw the operating line with a slope of [-$] © The intersection of this line with equilibrium curve gives xw and yp as shown in Fig. 9.14. Case II When the enthalpy-concentration data (H, vs x and Hg vs y) and heat added Q are available, the following procedure shall be adopted. ¢ Plot the enthalpy concentration data and also equilibrium curve below it. * Locate the feed point corresponding to F (Zp, Hr + O/F) © Draw a line by trial and error, passing through F such that it will be a tie line. © The points of intersection of this line (drawn by trial and error) with enthalpy-concentration curves gives the enthalpy and concentration of both the distillate and the residue. Figures (9.14) and (9.15) represent the procedures followed to determine the product concentrations for case I and case II respectively. LZ > 17] Xw 2 x Fig. 9.14 Estimation of composition of products in flash distillation.Distillation 251 r \ Ho} Hevsy He + QUE Hy vs x 4 |) = 0 iu 1 Slope = -WID — Fig. 9.15 Enthalpy-concentration diagram. 9.10 MULTICOMPONENT SIMPLE DISTILLATION Let us consider a multicomponent mixture fed to a still. The distillate and the residue left behind will also be multicomponent mixtures. For our analysis, let us consider a three-component system wherein a remains fairly constant. Modified Rayleigh’s equation can be applied for material balance, Fp Fry |" w| Wry. 4 l = wl ae (9.32) Frea |_| Fence |“ wl | 7 wl ae 9:33) Fx, Fipe |" Similarly, n| Wien | =In [me | (9.34) Here, BP, < BPs < BPc, where BP is the boiling point. We also know that xwa + Xwe + Xwe = 1.0 (9.35) In a typical feed mixture, the values of F, xp4, Xpg and xpc are known. The unknown quantities will be W, D, xwa, xws and xwc. To solve such problems one252 Mass Transfer—Theory and Practice has to assume W. By substituting in the first three equations, a relationship between Xa, Xwp and xc is obtained. Then it can be solved and checked for the validity of assumed value of W using Eq. (9.35). If Eq. (9.35) is satisfied, the assumed value of W is correct. If not, a new value for W is assumed and the above calculations are repeated till Eq. (9.35) is satisfied. Subsequently using the total material balance equation, D can be calculated and then the mole fraction of each component in the distillate phase (vapour phase) can be evaluated by making a component balance. However, in cases where a varies significantly, the Rayleigh’s equation of the x form inZ- = j 4 has to be used taking two components at a time. Here also Wed (y-x) one has to assume W and suitably estimate xy. The values of xy will have to be determined for all the components and finally checked using Eq. (9.35). If Eq. (9.35) is not satisfied, one has to make a fresh assumption of W and has to proceed till Eq. (9.35) is satisfied. 9.11 MULTICOMPONENT FLASH DISTILLATION At low pressures almost all systems behave ideally. As flash distillation occurs generally at low pressures, ideal behaviour can be expected and Raoult’s law is applicable, Hence, the equilibrium relationship for any component may be expressed as yi = mi (9.36) where m; = vapour pressure of component/total pressure. The suffix i denotes the component. ie. Yip = my (XW) (9.37) _W _ (yp ~-2p) We know that —>=Go—7-) [from Eq, (9.26)] . W _ Vip ~ 4p) o D> ir %w) (9.38) = Lio 7 i | [ee (9.39) or (9.40) (9.41)Distillation 253 Yiv = Zig reg] (9.42) mw = ae 9.43) aad m+ iD ¥i, pis evaluated using Eq. (9.42) and x; is evaluated using Eq. (9.43) by assuming (WID) value and finally checked for its validity by using Ex,w= 10; Ey, p= 10 9.11.1 Steps Involved From vapour pressure, determine m for each component. © Assume W/D value and determine x;y and y;,p © Check whether Zx;, w and Ly, p are 1.0. © If they are 1.0, then the assumed W/D ratio is correct. © If not, assume a new value for W/D and ensure that Ex, w = 1.0; Zyjp = 1.0 are satisfied. 9.12 CONTINUOUS RECTIFICATION A schematic sketch of a typical distillation column with a feed stream and a distillate and residue stream is shown in Fig. 9.16 along with its main accessories. 9.12.1 Ponchon-Savarit Method There are two methods by which the design of the continuous fractionator can be established. Let us first consider Ponchon-Savarit method where it requires both enthalpy and concentration data. Envelope I: Condenser section Envelope II: Full distillation unit Envelope III: Enriching/Rectifying section Envelope IV: Stripping/Exhausting section The numbering of plates or trays is accounted from the top to bottom. Suffix denotes the properties of streams leaving a particular plate or tray. Let n and m, denote general plates in the enriching section and stripping section respectively. Let G be the molar flow rate of vapour in enriching section, G the molar flow rate of vapour in stripping section, L the molar flow rate of liquid in enriching254 Mass Transfer—Theory and Practice Distillate, D, Zp, Hp 2) Heat loss t+] 1, M4 n Feed —1}------- I ja ---- ' L, Snes ! x, Yn ' Hin Heme Heat loss ---— Fig. 9.16 Continuous fractionator. section, Z the molar flow rate of liquid in stripping section, Hg the Enthalpy of vapour, H, the Enthalpy of liquid, y the mole fraction of more volatile component in vapour and x the mole fraction of more volatile component in liquid. Let R be the external reflux ratio LoD, Qc the load on condenser, Qz the heat supplied in reboiler and Q, the total heat loss.Distillation Considering envelope I and making a mass balance, A component balance gives Giy, = DZp + Loxo Making an energy balance, we get GiHa, = Loi, + DHp + Oc Qc = G\He, - Lo, - DHp Substituting for G, from Eq. (9.45), we get Qc = [D(R + 1) Hg,] - RDHi, - DHp = D((R + 1)Hg, - RHiy - Hol Considering envelope II and making an energy balance, we have Heat in = Heat out Qp + FH = DHp + WHy + Oc + Heat added in reboiler Qg = DHp + WHw + Qc + Q, - FHr 255 (9.44) (9.45) (9.46) (9.47) (9.48) (9.49) (9.50) (9.51) Now, let us consider envelope III, the enriching section and make mass and energy balance. A total mass balance yields, Gust = Ly + D A component balance gives, GnstYne1 = Lnkn + DZp An energy balance gives, GnstHe,,, = Ln Ht, + Dp + Qc Let Q’ = (Net heat out/Net moles out) = [expe] Then, Eq. (9.54) becomes Gyut Heyy, = LH, + DQ’ Eliminating D from Eq. (9.53) using Eq. (9.52), we get (Gre net) — Lekn = (Gre — LndZr (GneZp — Yneil = Ln(Zp — %n) Ly _ Zp — Ynsi) G, Gut Zp %) where (L,/G,, , 1) is defined as internal reflux ratio. (9.52) (9.53) (9.54) (9.55) (9.56) (9.57) (9.58)256 Mass Transfer—Theory and Practice Similarly, Eqs. (9.52) and (9.56) yield L,_ _ Q' - How) Gai @H,,) ae Equating Eq. (9.58) with Eq. (9.59), we get Ly _ (Zp -Ynsi Gin Zp-%)— Q-H,) (9.60) Equation (9.60) represents a straight line passing through (Hpsir Yuet) At Gastr (Ay Xn) at Ly and (Q’, Zp) at Ap where Ap is called the difference point and it represents Q’: Net heat, out/Net moles, out and Zp: Net moles of more volatile component, out/Net moles, out Let us consider Eq. (9.59). L, _ @Q'-He,.,) Gir (Q"- H,,) Substituting for G,,; in the above expression from Eq. (9.52), we have L,__ Q'-He,,) Gu) @-H,,) (9.61) Cys) _ (O' - Hi,) L, (-Hg,,) D _ (HG, ~ H,) 7" @ 2H, (9.62) 1, _ O'-He,) eS a) (9.63) When n = 0, it indicates the condenser and for n = 0, we get In _ Q'-Ha) D Hg —Hi, (9.64) o= Io = Length of line ApG, ie. R, the external reflux rati re © externa rex D ~ Length of line G,Ly (9.65) as indicated in Fig. 9:17(a).Distillation 257 Hence, if the reflux ratio R is known, then it will be easy for us to locate Ap point (Zp, 2’). Ly _ Zp ~Ynet) Also, D Ont ~%n) [from Eq. (9.58)] Let us consider envelope IV in the stripping section. A mass balance yields a Ln = Gai + W (9.66) ‘A component balance yields Ln km = GniiYmer + Wey (9.67) Lm %m~ Gms Ym +1 = Wry (9.68) ‘An energy balance yields Lm Hin + Qn = Gnss Hogs + WHw (9.69) Let o”= City 80) (9.70) Tn Ht, ~ Gms He,,, = WO" (9.71) Eliminating W from Eqs. (9.66) and (9.68), we get Lm msi = *w) 9.72) A a) eo”) Similarly eliminating W from Eqs. (9.66) and (9.71), we have L, — Honus ~ 2") Gea i, =O) (9.73) Hence from Eqs. (9.72) and (9.73), we get Ly Om — Xw) _ (Hoy, ~ 2") Ga” Om iy) 7 Gh, =O") 0.74) G, £m =1 ( a } Got Gt m+ Hence, rearrangement of Eq. (9.74) using Eq. (9.66) gives From Eq. (9.66), we have W_ _ Oma -4w) Gre nm ~Xw) (9.75)258 Mass Transfer—Theory and Practice Ey Begs = 2") __Ymes = XW W He, —4,) Om =n) (9.76) Equation (9.76) represents a line passing through (xy, Q”), (mw Hr,) and (mss Hg,,,,) where Q” represents net heat out /Net moles out and xy denotes moles of A out/net moles out. Now let us consider the fractionator as single unit and make mass and energy balances; Total mass balance gives F=D+W (9.77) ‘A component balance gives FZp = Dyp + Wx (9.78) An enthalpy balance gives F- Hr= (DQ + WQ”) (9.79) (Neglecting Q;, the heat loss) Eliminating F from Eqs. (9.77), (9.78) and (9.79) we get D _@r-xw) _ (Hr-0") W @p-Zp) (@-H;) (9.80) Equation (9.80) represents a line passing through (Zp, Q’), (Zp, Hp) and (xy, Q”) In other words, F=Ap + dy (9.81) The schematic representation of enthalpy concentration and distribution diagrams for determination of number of stages for a total condensation of distillate vapour is shown in Fig. 9.17(a). Steps involved 1. Draw H vs x, y diagram and the equilibrium curve. 2. Locate zp, yp and xw in both the diagrams and draw vertical lines from zp in positive y-axis direction and from xy in the negative y-axis direction. 3. Locate F(xp, Hr) in the H-x, y diagram. an eaae 5 . (Q’- Ha) 4. Obtain Q’ using the given reflux ratio, R = aH) where Hg,, Hi, indicate the enthalpy of vapour and liquid correspond to the distillate composition for a total condensation. 5. In cases where the reflux ratio is not given, an optimum reflux ranging from 1.5 to 2 times the minimum reflux can be chosen. 6. To determine the minimum reflux, several lines can be drawn through the feed point F in the entire range of x and projected downwards from both H vs x and H vs y curves to the x-y diagram as shown in Fig. 9.17(b) and one such horizontal line in x-y diagram will be a tie line. This line is extended to cut the vertical line drawn at zp and this intersection point corresponds to the value of Q’ at minimum reflux and the value of R estimated is Riin-Distillation 259 40 (Zp, @) = = WI Yo 1.0 08 5 ! Aw Ln 0.6 4 %w @) Slope Gaet 04-4 0.2 + Oo mw 02 04 06 os = % 1.0 x— Fig. 9.17(a) Determination of number of stages by Ponchon-Savarit method.Mass Transfer—Theory and Practice 260 —— Proper tie line ~ Improper tie line Fig. 9.17(b) Determination of minimum reflux in Ponchon-Savarit method.10. 11. Distillation 261 Locate Ap (yp, Q’) using the Hg,, Hy, and reflux ratio. Join Ap with F and project it to cut the vertical line at xy and that point is Ay. Draw arbitrarily several lines both from Ap and Aw to cut both the curves. The values taken from H vs y give y’ and the line from H vs x gives x’ For each line drawn we will have a set of x’ and y’ values with which we can construct the operating line in the distribution diagram for both enriching and stripping sections. Draw the equilibrium curve and plot x’, y’ data obtained from step (9). By stepwise construction starting from point D, between the equilibrium curve and operating line up to W, the number of stages for the desired separation is determined. 9.12.2 McCabe-Thiele Method When systems exhibit ideal behaviour, the time-consuming Ponchon-Savarit method of determining the number of ideal stages, can be replaced with the following technique. Let us begin our analysis by considering enriching section for total condensation of distillate as shown in Fig. 9.18. Fig. 9.18 Enriching section of a fractionator.262 Mass Transfer—Theory and Practice Assuming the application of equimolar counter diffusion, i.e. the molar flow rates are assumed to be constant for both the vapour and liquid steams irrespective of the stages, we get G, = Gy = Ga =G A total material balance gives G=L+D (9.82) Let the external reflux ratio R be given by ae) R=D"D then, G=DR+D=D(R+1) (9.83) A component balance for A in enriching section gives Gyne1 = Ley + Dyp (9.84) L D ie. Inst =| G [Fn +] G [XD (9.85) iS G (9.86) D_ OD 1 G"T+D Re ee R 1 Yat =| Rad [% +] Raq |*P (9.88) Equation (9.88) represents the operating line for enriching section, which has a R soe tg Eq. (9.88), we get | and an intercept of [ re i}: If x, = xp, then substituting in 1 Yaa = (qa) eo +Xp) = Yo (9.89) ite. when x, = Xp, Yast = Xp- Hence, this line passes through x = y = xp, i.e. it lies on the diagonal. This x point on the diagonal and the y-intercept [#23] permit us the construction of operating line for enriching section. Let us consider the stripping section as shown in Fig. 9.19.Distillation 263 Fig. 9.19 Stripping section. Material balance gives L=G+w (9.90) A component balance for A gives, xp = Gypsy + Wey (9.91) L Ww ED Ymei =| G J%m | AW (9.92) cL Ww Le. Ym+i = (5) Xm — (x) xw (9.93) Equation (9.93) describes the operating line for stripping section. The operating , L . w line has a slope of (47) and an intercept o-(75). Let us assume that x», = xw (Reboiler) Ymet Ww = I-w XW = Xw (9.94) ie. Xm = Ym + = XW Hence, the operating line passes through the point x = y = xw (ie. it lies on the diagonal). Having seen the analysis of enriching section and stripping section separately, let us analyze the feed plate, f, shown in Fig. 9.20.264 Mass Transfer—Theory and Practice Fig. 9.20 Feed plate section. A mass balance on feed plate gives F+L+G=G+T (L-L) =(G-G)-F ie (L-L)=(G-G)+F Enthalpy balance on feed plate gives F-Hp+L-H,,,+G-Hg,,, =G-He, +L-H,, As an approximation, Hg, ~ Hej, = Ho and Hy,, = Hy, = Hy (L-L)H, =(G-G)Hg + FH; - a G- CO ng + Hy Substituting for (E— L) from Eq, (9.97) we get [Se n= Ge Con, +Hp ie. eo A, +H, = G- =o Hg + Hp G- ae (H, - He) = (Hp - H,) (G-G@)]_ (Hy -H,) F |” i, —Ho) Substituting for (G - G) from Eq. (9.97), we get (Z-L)-F _ (Hp -H1) F (A, - He) (9.95) (9.96) (9.97) (9.98) 9.99) (9.100) (9.101) (9.102) (9.103) (9.104) (9.105) (9.106)Distillation 265 (9.107) _ (Hg - Hr) Gig H,) (9.108) H, ¢ Ae £ , as q, where q is the quantity of heat required to fe ~Ay convert one mole of feed at its thermal condition to a saturated vapour, to the molal latent heat of vaporization. Let us now define -L)_(Hg-H, q= 5 d= a (9.109) Similarly, G"@) =o) 1=@-)) (9.110) ie. (G-G) = Fq-}) (9.111) A solute balance above feed plate gives Gy = Lx + Dxp (9.112) A solute balance below feed plate gives Gy = [x- Way (9.113) Subtracting Eq. (9.112) from Eq. (9.113), we have (G-G)y = (LE - L)x ~ (Dxp + Wry) (9.114) Total component balance for the distillation column gives FZp = Dxp + Ww (9.115) Substituting Eqs. (9.109), (9.111) and (9.115) in Eq. (9.114), we get Fq-Dy = Fq:x- Fe, =-_4% __4F “G0 GD Equation (9.116) is the equation for feed line. It has a slope of g/q — 1 and passes through y = x = Zp. The various values of slope obtained under different thermal conditions of feed are given below and shown in Fig. 9.21. (9.116) 1. Cold feed I 2. Saturated liquid 3. Liquid + vapour VAY = 4, Saturated vapour 7 5. Superheated vapour x— Fig. 9.21 Feed line for different thermal conditions of feed.266 Mass Transfer—Theory and Practice Feed condition | Gr| Lr | Ho, | H,, | Enthalpy of feed, Hr Liquid below o|F|- | ar) He10 >1.0 boiling point Saturated liquid | 0 | F | - | He | He= Hi 1.0 eo Liquid + vapour | Gr | Le | Ho’ | Hi’ | Ho >Hr> Hi 1.0100 Ly Lp-F Saturated vapour | F | 0 | Hr | - Hp=He 0 0 Superheated F\o| a | - Hp> He <0 1.0t00 vapour * indicates Hg and H,, are enthalpies per mole of individual phases. Determination of q is as follows: (i) Cold feed From Eq. (9.109), we have (Hg = Hr) (He - Hi) Let T;, be the boiling point of mixture and T; be the feed temperature. Let Hg and H, be the enthalpies of saturated vapour and liquid respectively. If A is the latent heat of vaporization, Cp; is the specific heat of feed liquid and Tp is the reference temperature, then Hg = Cp(T,~To) +A q= Hy = Cp (Tp ~ Tp) and (Hg — H,) =A (9.117) g = (eu ~ Te) + A-Gra =To)] _ (Ce T - % -Tr -H) +4) (9.118) ie, quite (9.119) Gi) Saturated liquid (9.120) For saturated liquid Hp = Hi, ~. (iii) Mixture of liquid and vapour Let x be the mole fraction of liquid in feed in the case of liquid + vapour mixture. Then, Hp = xH, + (1 - )Hg (9.121)Distillation 267 [He ~ 2H, - He +H] Therefore, q ( He - H,) 1.0 _ x(Hof Hi) =a (9.122) (iv) Saturated vapour = (He Hr) “oH em) For saturated vapour H; = Hg, «. g= 0 (v) Superheated vapour Let Cpy be the specific heat of feed vapour Hg = Hg Hp = He + Cp,y (Tr - Ts) (9.124) — He -W “euler -T)) aoonae =) (9.125) Steps involved in the determination of number of trays The equilibrium curve along with the operating lines for both enriching and stripping sections to determine the number of stages is shown in Fig. 9.22. 1.0 os WZ 0 %w Fig. 9.22 Determination of number of stag stages by McCabe-Thiele method. Xp 1.0 1. Draw the equilibrium curve and diagonal. 2. Locate F, D and W corresponding to feed, distillate and residue compositions based on more volatile component. 3. Estimate xp/(R + 1) and locate it on y-axis as S. . Join SD, this is the operating line for enriching section. 5. From F draw q-line depending on feed condition. Let it cut the operating line for enriching section at T.268 Mass Transfer—Theory and Practice 6. Join TW-operating line for stripping section. 7. Construct stepwise from D to W and the steps so constructed will give the number of stages. 9.13 LOCATION OF FEED TRAY For an optimal design or when a column is designed first (wherein one goes for optimal design) the feed tray is located at the intersection of operating lines of enriching and exhausting sections of the tower. However, we may at times use a column which has been designed with some other ubjectives. Whenever the quality and condition of feed is fixed along with reflux ratio, xp and xy, the operating lines are fixed. It may so happen that in an existing column, the location of feed nozzle is fixed and it may not really lie at the optimal point as shown in Figs. 9.23(a), (b) and (c). 1.0 XW 5 %D1.0 Fig. 9.23(a) Optimal feed location. The point of intersection of the two operating lines is generally believed to be the point that demarcates enriching and exhausting sections. This normally occurs in the newly designed columns from a specific x,, xp, xp and condition of feed. However, in an existing column, designed for a different utility, the feed point location is fixed and may not be at the optimum location. Further, the feed entry point will not demarcate the enriching and exhausting sections. Generally when the reflux ratio and the xp values are fixed, the operating line for enriching section is fixed. Further, when the x, and the condition of the feed are fixed the operating line for exhausting section is fixed.270 Mass Transfer—Theory and Practice Once a feed enters a specific plate, below the point of intersection of operating lines and q-line (in an existing column), from the top plate to feed entry point, the operating line for enriching section is to be used and subsequently the operating line for exhausting section. Such an arrangement indicates a delayed feed entry. If the feed enters at a specific plate, above the point of inte:section of operating lines and q-line (in an existing column), from the top plate to feed entry point, the operating line for enriching section is to be used and subsequently the operating line for exhausting section. This arrangement indicates an early feed entry. In both the cases the number of stages estimated will always be more compared to the number of stages estimated with feed entering exactly at the point of intersection of operating lines and q-line. Consider the above three figures, Figure 23(a): Optimal design with 9 plates and the Sth plate is feed plate. Figure 23(b): An existing column with 10 plates and feed enters at 7th plate. Figure 23(c): An existing column with 10 plates and feed is introduced at 3rd plate. 9.14 REFLUX RATIO It is one of the important operating parameters in distillation, by which the quality of the products can be changed. Let us deal with the relationship between reflux ratio and the number of trays in the tower. 9.14.1 Determination of Minimum Reflux Ratio To determine the minimum reflux ratio, draw the q-line from F to cut the equilibrium curve at 7’. Join DT’ and extend it to intersect on y-axis and indicate it as S’. OS’ gives [a] from which Ryn is estimated as shown in Fig. 9.24. Normally at Rin Condition, the number of stages will be infinity as the equilibrium curve and operating line get pinched. Zz <— VA 0 Xw xX Xp 1.0 xe Fig. 9.24 Determination of minimum reflux ratio.Distillation 271 Steps involved in the determination of minimum reflux 1. Draw the equilibrium curve and diagonal. 2. Locate F, D and W corresponding to feed, distillate and residue compositions based on more volatile component. 3. Draw the q-line from F and allow it to intersect the equilibrium curve at 7’. 4. Join T’D and allow it to intersect the y-axis at S’. Yo 5. OS’ corresponds wf | from which Ryyjg» the minimum reflux ratio R, ‘min +1 is estimated. 9.14.2 Total Reflux At total reflux, all the distillate is returned to the column and no product is taken out as distillate. ie. D=0 L R===0 D Hence, the operating line (Eq. (9.88)] for enriching section is R 1 Yet =| Rat Pet Rad XP becomes, Ynat = In (9.126) i.e. it merges with the diagonal (x = y line) for both enriching and stripping sections. Under such circumstances, the minimum number of theoretical stages can be estimated by the same graphical procedure described in the Section of 9.12.2. For systems where the relative volatility is constant and under total reflux conditions the theoretical number of stages needed could be estimated analytically. YA Ya xa YB 1) Es] We know that for a binary system, a4 =272 Mass Transfer—Theory and Practice Let us apply this relationship to (m + 1)th plate Yor nt S Oya) =a) @.127) At total reflux D = 0 and =—%_ = 10 G R+1 Hence, from Eq. (9.126), we get On+0) (9.128) When n = 0, i.e. at the top of the column, x, = x9 Yi = Xo = Xp, when total condenser is used. Substituting for y, ,, in terms of x, in Eq. (9.128), we get x, A = Cay cy (9.129) = —*o_ = a1 When n = 0, dem =a) (9.130) x x, When n = 1, —1_=g,,—% 9.131 enn d-a 2 ax) ( ) Ant _ = a, 2 _ When n=n-1, C=) AB x,) (9.132) Substituting for x), x, ..., %,—1 from Eqs. (9.131) and (9.132), we get *o a) = (Ogp)" = ee zt) (9.133) Substituting n = Np + 1 (last stage, i.e. reboiler), we get Xo = (gy Nott N+ G=m) © Waxy) 9.134) As (Np+ Dith stage accounts for reboiler, xypo1 = YD p+) we . = (gy ie. Top Oa (9.135) Equation (9.135) is called Fenske equation. To apply this equation, a, the relative volatility must be fairly constant and the column has to be operated under total reflux conditions. This may not be possible in industries, but has theoretical importance. 9.14.3 Optimum Reflux Ratio At minimum reflux ratio the column requires infinite number of stages or trays. However, as reflux ratio increases from minimum, for a given feed and specifiedDistillation 273 quality of distillate and residue, the number of stages or trays decrease. At minimum reflux ratio when the stages or trays are infinite, the fixed cost and the maintenance cost are also infinite. However, the operating cost for operating condenser, reboiler etc. is the least. When the reflux increases, the trays or stages reduce but the column diameter has to be increased to handle larger capacities of liquid being recycled. The size of other accessories like condenser and reboiler increase which will result in a higher requirement of cooling water or heating. Ultimately this will result in a higher operating cost. Thus, the total cost which includes both operating cost and fixed cost, vary with reflux ratio and reach a minimum value for a certain reflux ratio which is called the optimum or economic reflux ratio. This value is normally in the range of 1.2 Rmin t0 1.5 Rmin- This is shown in Fig. 9.25. 4 Total cost i Operating cost 3 2 . & Fixed cost N4 NM] Root Reflux ratio Fig. 9.25 Effect of Reflux ratio on cost. 15 REBOILERS | Thermosyphon reboiler | HH Steam Condensate Fig. 9.26(a) Thermosyphon reboiler.274 ~~ Mass Transfer—Theory and Practice Internal reboiler Steam Condensate Bottom Fig. 9.26(b) Internal reboiler. Bottoms. ‘Steam ——+| Condensate Fig. 9.26(c) Jacketed kettle reboiler. They are heat exchangers of different configurations used to supply the heat to the liquid at the bottom of the column to vaporize them. In effect all the heat needed is basically supplied at the reboiler only. A simple Jacketed kettle is one such reboiler which has a low heat transfer area and hence vapour generation capacity will also be poor.Distillation 275 Condensate Bottoms Fig. 9.26(d) External reboiler Tubular heat exchangers (both of vertical and horizontal configurations) provide larger area of heat transfer. They can be placed inside the column or outside the column. When they are located inside, during cleaning of the exchanger, the distillation operation has to be stopped. However, when external reboilers are used, a standby exchanger is always kept which can be used during cleaning of the exchanger attached to the column. Thus, the distillation operation will proceed without any interruption. The liquid can flow either through the tube side or shell side. Reboilers can be heated by steam, oil or other hot fluids. Different types of reboilers are shown in Figs. 9.26(a)-(d). 9.16 CONDENSERS The condensers are generally heat exchangers of horizontal orientation with coolant flowing through the tube side. However, in rare instances vertical condensers are used with the coolant flowing on either side of the tubes. They are placed above the tower in the case of laboratory scale units for gravity flow of the condensed reflux to the topmost tray. Sometimes they are placed at ground level for easy maintenance, in which case the liquid is pumped from accumulator to the top tray. The coolant is normally water. The condensers may either be a total condenser or a partial condenser. Whenever a partial condenser is used, the condensate is returned as reflux and the vapour from condenser is the main distillate product. The partial condenser itself acts as one stage for separation. In an existing distillation column, if one desires to have a highly enriched distillate (richer than the designed value) then one can resort to partial condensation and obtain an enriched product. However, when a column is being designed fresh it is always preferable to go for additional trays compared to partial condensation technique for enrichment.276 Mass Transfer—Theory and Practice 9.17 USE OF OPEN STEAM Normally the heat needed for distillation is supplied through (by heat exchangers) reboilers. However, when an aqueous solution is fractionated to give non-aqueous solute as distillate and water as residue, the heat required may be supplied by open steam in which case the reboiler is not required. The schematic arrangement is shown in Fig. 9.27 and the overall material balance is given below. ~~ L=w 6 Xw y=0 Fig. 9.27 Open steam distillation. The equation for the operating line in enriching section is obtained as in the case of McCabe-Thiele method. 5 aL__R- FI _ XD ie. Slope = Gr Rt and intercept = Rel (9.136) However, let us analyze the exhausting section.Distillation 277 ‘A component balance gives Tx, + G0) = Gy,,4, + Lew (9.137) Tx, + GO) = Gyn, + Wy (9.138) (m+ = 0) (en ~¥y) (9.139) The operating line for exhausting section passes through (x = xy and y = 0) and (Xm, Ym+i)- Thus, the line passes through xy, the point in x-axis as shown in Fig. 9.28. After constructing the equilibrium curve and operating lines, by step-wise construction the number of stages are determined as in the case of McCabe-Thiele method. 1.0 0 Xp > 1.0 Fig. 9.28 Determination of number of stages in open steam distillation. If the steam entering the tower is superheated (Hg, vp.,), it will vaporize liquid on tray Np to the extent such that the steam will reach saturation (Hg, sq). An energy balance yields, sa) Nps iH (9.140) G=Gy,,,|1+ where AM is the molar latent heat of vaporization, and L=G-Gy,,, +Ly, (9.141) Using Eqs. (9.140) and (9.141), the L/G ratio is computed.278 Mass Transfer—Theory and Practice 9.17.1 Determination of Number of Trays 1. Draw the equilibrium curve and diagonal. 2. Locate F and D corresponding to the composition of feed and distillate respectively on diagonal. 3. Locate W corresponding to the composition of xy on x-axis. 4. Based on the reflux ratio and distillate composition, estimate wr and locate it on y-axis as S. 5. Join SD, this is the operating line for enriching section. From F draw q-line depending on feed condition and allow it to cut the operating line for enriching section SD, and locate the point of intersection as T. 7. Join TW. TW is the operating line for stripping section. 8. By stepwise construction starting from D up to W, the number of stages can be determined. 9. The minimum reflux ratio needed is estimated in the same manner as in the case of McCabe-Thiele method. 9.18 CONTINUOUS DIFFERENTIAL CONTACT- PACKED TOWER DISTILLATION Whenever we have heat sensitive materials to be distilled which require less contact time, packed towers are preferred. The pressure drop is also low and hence it is suitable for low pressure distillation operations. The height of column can be determined in the same way as for other mass transfer operations using packed towers by making a material balance across a differential section and integrating as indicated in Fig. 9.29. The material balance across the elemental section in enriching zone gives — aGy) d(Lx) Na = Gaz = Oi = gz = (9.142) zZ, (Gy; (Lx); z+ faz- f aGy)__ f° _d(Lx) aa * Katy; — ¥) Ka(x = x) (9.143) 0 Gra (Lx)a Assuming that G, L,k, andk{ are constants. (However, this has to be checked before using as k, and k, depending on the flow rates) = (Hyg)(Njg) (By definition) (9.144) G i dy Ka J (,-y) Ya (Suffix a indicates the point of intersection of operating lines)Distillation 279 Woxw Fig. 9.29 Analysis of packed distillation column. Based on liquid phase, Z, can be expressed as oe =) =(Hy)(N,) (By definition) (9.145) Similarly, the stripping section can also be analysed and it can be shown that, 2s = (Hig) (Nic) = (Hx) (Nu) (9.146) Total height Z = Z, + Zs (9.147) _ The determination of Hig or H,, can be done using the flow rates of vapour or liquid and vapour or liquid mass transfer coefficients. However, to determine Nig or Nj, one needs to find interfacial compositions. If the film coefficients are known, the interfacial concentrations can be determined from the operating line and equilibrium curve. These values are given by a line drawn with a slope of280 = Mass Transfer—Theory and Practice [- *| from the operating line to the equilibrium curve. The point at which this y line cuts operating line gives x and y values and the point of intersection with the equilibrium curve gives the interfacial compositions x; and y;, A number of such lines can be drawn which will give various sets of (x — x;) and (y; — y) values as shown in Fig. 9.30. Using these values, N,, or Nig can be determined. One should use Ni, or Nig (corresponding to H,, or Hjc) to determine the height depending on the resistance which is controlling the mass transfer. Yin Xw M2 Xp XH x Xp x——+ Fig. 9.30 Determination of interfacial conditions for packed distillation column. Further, if the equilibrium curve is essentially straight in the range of our application, then the expressions are simplified as dy H, eS =(Hyg)(Nig) “ (ra) M0 Mus (9.148) when gas phase is controlling and _a Ze = Hg f oy 7 Han Mou) (9.149) when liquid phase is controlling. In Eqs. (9.148) and (9.149) , (y* - y) and (x — x*) are the overall driving forces in terms of vapour and liquid phase composition respectively. Here, Hyg = and G = 00 Ka Ay = KaDistillation 281 1 lim We know that, K “ETE Vita Ki ki mk, Similarly, H,,g and H,,, can also be written as mG Ag = Hie +(%2) te (9.150) L Hyp = Hy +( 5) me (9.151) where m is the slope of the equilibrium curve. 9.18.1 Steps Involved in the Determination of the Height of Tower Draw the equilibrium curve and diagonal. Xp R+1 Locate F, D and W on diagonal corresponding to xp, xp and xy Join DS. This is the operating line for enriching section. From F draw q-line. Let the point of intersection on operating line DS for enriching section be T. Join TW. This is the operating line for stripping section. Locate S, corresponding to in y-axis. Pb) hy be s K A 7. From D to T and T to W draw lines of soe #5 or [-#] (as the y y case may be) to obtain (x; and y,) or (x* and y*) and (x and y) values. 8. x and y values are read from operating lines and (xj, y;) or (x*, y*) values are read from equilibrium curve. ax dy dx dy 5 9. Evaluate | Gy «lao of of oso graphically to determine Ny, or Nig OF Niot OF Niog: 10. Hy, Hig» Hog OF Hyp are determined with the help of liquid and vapour flow rates and mass transfer coefficients. 11. Height is then estimated based on the values from steps (9) and (10). 12. The tower diameter is normally set by the conditions at the top of stripping section because of large liquid flow rate at that point. 9.19 AZEOTROPIC DISTILLATION This is a technique which is used for the separation of binary mixtures which are either difficult or impossible to separate by ordinary fractionation. This happens when either the mixture to be separated has a very low relative volatility, in which case one may require high reflux ratio and more number of trays, or when the282 Mass Transfer—Theory and Practice mixture forms an azeotrope. Under such circumstances, a third component called an ‘entrainer’ is added to the binary mixture to form a new low boiling hetero- azeotrope with one of the components in the original mixture whose volatility is such that it can be separated from the other original constituent. A typical example for this operation is presented in the flow diagram of Fig. 9.31 where the separation of acetic acid (BP: 118.1°C) and water (BP: 100°C) mixture is demonstrated. This mixture has a low relative volatility and hence separation by conventional methods is not economical. Here Butyl acetate, which is slightly soluble in water, is added to the mixture from the top of the column as an entrainer. It forms a ‘hetero-azeotrope’ with all the water in the feed and readily distills out from the high boiling acetic acid and the acetic acid leaves as a residue product. The hetero-azeotrope on condensation forms two insoluble layers which can easily be separated. The water layer obtained is saturated with ester and vice versa. The ester layer saturated with water is returned back to the column as a source of entrainer for further separation. The aqueous layer is also sent to another column to separate water and ester. The separated ester is also sent back as entrainer. Sometimes the new azeotrope formed contains all the three constituents. In the dehydration of ethanol water mixture, benzene is added as an entrainer which gives a ternary azeotrope containing benzene (53.9 mole %), water (3.3 mole %) and ethanol (22.8 mole %) boiling at 64.9°C as distillate and ethanol (BP: 78.4°C) as residue. Benzene is separated and sent back to the top of the column as entrainer. Since water — ethanol are equally present in distillate, the mixture should be given a preliminary rectification to produce an alcohol rich binary azeotrope. Azeotropic distillation is shown in Fig. 9.31. Ester water azeotrope o4/ ti Acetic acid water Steam Glacial acetic acid separation column Glacial acetic acid Fig. 9.31 Azeotropic distillation.Distillation 283 9.19.1 Desired Properties of an Entrainer for @ Gi) ii) (iv) (vi) (vii) 9.20 Azeotropic Distillation Should be cheap and easily available. Chemically stable and inactive towards the solution to be separated. Non-corrosive. Non-toxic. Low latent heat of vaporization. Low freezing point to facilitate storage and easy handling. Low viscosity to provide high tray efficiency and minimum pumping cost. EXTRACTIVE DISTILLATION This method is also used under similar circumstances as in the case of azeotropic distillation. Here a third component called solvent is added, instead of entrainer, which alters the relative volatility of the original constituents, thus permitting the separation. The added solvent should have low volatility and not vaporized in the fractionator. One such example is the separation of toluene (BP: 110.8°C) from isooctane (BP: 99.3°C). Their separation is relatively difficult. In the presence of Phenol (BP: 181.4°C), the relative volatility of isooctane increases, so that with an increase in phenol content, the separation becomes more and more easy. A typical flow diagram of the process is shown in Fig. 9.32. Condensor Feed Isooctane removals column Toluene-Phenol separation Toluene Isooctane Reboiler Phenol + Toluene Fig. 9.32 Extractive distillation.284 Mass Transfer—Theory and Practice Here, the toluene-isooctane binary mixture is introduced in the middle of the column and phenol near the top of the column. Isooctane is readily distilled as an overhead product, while toluene and phenol are collected as residue. The residue from the tower is rectified in the auxiliary tower to separate toluene and phenol as distillate and residue respectively. Phenol is returned to the main column as solvent. Similarly a mixture of acetone (BP: 56.4°C) and methanol (BP: 64.7°C) can be separated by using Butanol (BP: 117.8°C) solvent. 9.20.1 Desired Properties of Solvent for Extractive Distillation High selectivity and capability to alter VLE for easy separation. Ability to dissolve the components in the mixture. Low volatility in order to prevent vaporization of solvent. Easy separability, for easier removal of solvent. Non-corrosive. Non-toxic. Cheap and easily available. Low freezing point. Low viscosity. Chemical stability and inertness towards the components to be separated. 9.21 COMPARISON OF AZEOTROPIC AND EXTRACTIVE DISTILLATION In both the processes an additional external agent is added, which is undesirable. Solvent to feed ratio in extractive distillation greater than 3 or 4 is found to be effective. Proper choice of material of construction and recovery technique are to be examined. However, of the two, extractive distillation is said to be more favoured than azeotropic distillation since (i) there is a greater choice of solvent, (ii) the smaller quantity of solvent to be volatilized. In spite of the above advantages, the azeotropic distillation is said to be more effective in the dehydration of ethanol from an 85.6 mole % Ethanol—water solution. In this case water is azeotroped with n-pentane and then separated rather than using extractive distillation with ethylene glycol as solvent. 9.22 LOW PRESSURE DISTILLATION ‘Whenever the heat sensitive materials are to be separated, as in the case of many organic mixtures, low pressure distillation will be effective. In this case the time of exposure of the substances to high temperature is kept minimum. Packed towers can be used for distillation under pressures of 50 to 250 mm Hg. Bubble cap and sieve trays can be used for pressure drops around 2.6 mm Hg and shower trays for pressure drops around 0.75 mm Hg. This is used in the separation of vitamins from animal and fish oils as well as the separation of plasticizers.Distillation 285 9.22.1 Molecular Distillation This is a very low pressure distillation where the absolute pressure is in the range of 0.003 mm Hg to 0.03 mm Hg. On reducing the absolute pressure, the mean free path of the molecules becomes large. If the condensing surface is placed at a distance from the vaporizing liquid, surface not exceeding few cms, only a few molecules will return to the liquid. The composition of the distillate will now be different from that given by normal vaporization and the ratio of the constituents is given by ( Pa Na _ molesof A _| \ Mao Ne moles of B~ (2s) Bs } (9.152) Ms°* In molecular distillation this ratio is maintained by allowing the liquid to flow in a thin film over a solid surface thus renewing the surface continually and at the same time maintaining low hold-up of liquid. A schematic arrangement of a device used for this type of distillation is shown in Fig. 9.33. The degassed liquid to be distilled is introduced at the bottom of the inner surface of the rotor, rotating at 400 to 500 rpm. A thin layer of liquid 0.05 to 0.1 mm spreads over the inner surface and travels rapidly to the upper periphery under centrifugal force. Heat is supplied to the liquid through the rotor from radiant electrical heaters. Vapors generated are condensed and collected in the collection troughs. The residue liquid is collected in the collection gutter and removed. The entire unit is maintained at low pressure, good enough for molecular distillation to occur. Normal residence time is of the order of 1 second and hence decomposition of mixture does not take place. Multiple units can be used to have multistage separation effects. Distillate out Cooling water To vacuum purge Rotor /<——— Thermal insulation Heater Feed Condenser Residue t rotor shaft Fig. 9.33 Molecular distillation.286 Mass Transfer—Theory and Practice 2. WORKED EXAMPLES 1. Compute the equilibrium data from the following data at 760 mm Hg pressure and calculate the relative volatility. VP of A, mm Hg | 760 | 830 | 920 | 1060| 1200] 1360 VP of B, mm Hg | 200 | 350} 420] 550) 690] 760 P; = 760 mm Hg Solution. P,,mmHg |760 | 830 | 920 | 1060 ] 1200] 1360 Ps,mmHg |200 | 350 | 420 |550 | 690 | 760 =| (Pr=Pa) —| Pata) We know that *4 -|& apy | anda =| —| r-Pa) x-[$E iy 10 0.854] 0.68 | 0.412 [0.137 }0 P, =| 222] 1.0 | 0.933 | 0.823 | 0.575 | 0.216 |o 7 @,, = VP of AVP of B| 3.80 2.37 [2.19 |1.93 | 1.74 |1.79 Average relative volatility: 2.303 The vapour pressure data for n-Hexane —n-Octane system is given below. Compute the equilibrium data and relative volatility for the system at a total pressure of 101.32 kPa. TC | piracy | PokPa) 68.7 101.32 16.1 79.4 136.7 23.1 93.3 197.3 37.1 107.2 284.0 57.9 125.7 456.0 101.32Distillation 287 Solution. TC mn | n—Octane ax Hexane | PakPa(B) 7° [+@-pa P, kPa (A) 687 101.32 161 629 | __1.000 1.00 1.000 94 136.7 Bl 592| 0.689 0930 093 933 1973 371 532]; 0401 0781 0.783 1072 2840 379 491 | __ 0.192 0538 0562 125.7 4560 | 101.32 450 0 0 0 3. Compute x-y data at 1 atm. Pressure from the following data: T 80.1 85 90 95) 100} 105} 110.6 VP, 760} 877| 1016} 1168) 1344] 1532] 1800 VPp -| 345) 405} 475] 577} 645] 760 Solution. T 80.1 | 85 | 90 | 95 | 100 | 105 | 110.6 VP, 760 | 877 | 1016 | 1168 | 1344 | 1532 | 1800 vP, | — | 345 | 40s | 475 | 577 | 645 | 760 a=} _ | 254] 2.51 | 2.46 | 233 | 238 | 2.37 VP, (AMS! Qgverage = 2.43) 1.0 | 0.78 | 0.58 | 0.411 | 0.239 | 0.13 | 0 1.0 | 0.9 | 0.777 | 0.632 | 0.423 | 0.26 | 0 4. A solution of methanol and ethanol are substantially ideal. Compute the VLE for this system at 1 atm pressure and relative volatility. 1473.11 Jog [P, mm] setianot = 7.84863 - G39 7 eG 1554.3 log [P, mm] ganot = 8.04494 — 359 Ee oy, Solution. In this problem one has to compute the vapour pressure values at different temperatures. The temperature range is fixed by keeping the pressure as288 Mass Transfer—Theory and Practice 760 mm Hg for each component. Thus, in the following equation for Methanol, 1473.11 (230 + °C) Setting the vapour pressure as 760 mm Hg (at BP, vapour pressure equals the prevailing pressure), we get the temperature as 66.53°C, which is the boiling point of Methanol. Similarly, by setting P as 760 mm Hg in the equation for ethanol, log [P, mm] Methanot = 7.84863 - 1554.3 log [P, mm] prnanoi = 8.04494 — 26+ we get the boiling point of Ethanol as 78.33°C. This fixes the range of temperature. rc 66.53 | 70 2 14 16 8 78.33] V.P. of Methanol, P.mm 760 | 867.5 | 934.94 |1006.6 1082.79 1163.6 |1177.4 V.P. of Ethanol, P,mm 467.8 | 541.77 | 588.66 | 638.9 | 692.66 | 750.14 | 760 Relative volatility, P, a= p 1.625] 1.601] 1.588] 1.576] 1.563, 1.551 | 1.549 -7i=?s *4= (P= Pp) 1.0 0.67 | 0.495] 0.329] 0.173 0.024 | 0.0 = Paka yap 1.0 0.765] 0.609] 0.436] 0.244 0.0365] 0.0 Average relative volatility = 1.579 5. Methanol and Ethanol form an ideal solution. Compute the VLE data at 760 mm Hg pressure, Vapour pressure Data: Vapour pressure, mm Hg | 200 | 400 | 760 | 1520 Temperature,°C, Ethanol | 48.4 | 62.5 | 78.4| 97.5 Temperature,°C, Methanol | 34.8 | 49.9 | 64.7| 84.0 Plot vapour pressure vs temperature for both the components and compute T vs. VP for Methanol and T vs. VP for Ethanol as shown in Fig. 9.34.Distillation 289 Solution. 100 oo Ethanol 80+ 2 ”| Methanol oo ana 50 40 30 200 400 600 800 1000 1200 1400 1600 Vapour pressure, mm Hg Fig. 9.34 Example 5 Vapour Pressure-temperature plot. vP.of | VP. of a a Tempera. | Ethanol, | Methanol, | x4 = 7p— Bs | Ya == 2 mm Hg (B) | mm Hg (A) 4 Pe * 647 430 760 10 10 670 470 830 0.806 0.880 70.0 540 950 0.537 oon 30 620 1080 0.304 0.432 16.0 700 1200 0.120 0.189 784 760 1300 00 0.0 6. It is desired to separate a feed mixture containing 40% heptane and 60% ethyl benzene, such that 60% of the feed is distilled out. Estimate the composition of the residue and distillate when the distillation process is (i) equilibrium distillation, and (ii) differential distillation. Equilibrium Data: x} 0} 0.08 | 0.185 | 0.251 | 0.335 | 0.489 | 0.651 | 0.79 | 0.914 | 1.0 y] 0} 0.233 | 0.428 | 0.514 | 0.608 | 0.729 | 0.814 | 0.910 | 0.963 | 1.0 x, y: Mole fraction of heptane in liquid and vapour phase respectively.290 Mass Transfer—Theory and Practice Solution. (i) Plot the equilibrium data and draw the diagonal. Draw a line with a slope of -W/D = — 0.4/0.6 = —0.667 from a point on the diagonal corresponding to xp = 0.4 and its intersection on the equilibrium curve and read them as x, and yp as shown in Fig. 9.35. Xp = 0.24 and yp = 0.5 0 0.2 04 06 08 1.0 x— Fig. 9.35 Example 6 Solution for flash distillation. (ii) Compute and plot it against x as shown in Fig. 9.36 yrx O {0.08 [0.185 [0.251 | 0.335 |0.489 [0.651 |0.79 | 0.914 1.0 0 |0.233 |0.428 |0514 |0.608 |0.729 |0814 |091 |0.963 | 1.0 © |0.153 |0.243 |0.263 |0.273 |0.240 |0.163 |0.12 {0.049 | 0 a |654 |4.12 |380 |366 |417 |613 |833 |2041 |a We know that de fF] gf 1 .o-n "w= loa] = 0916 By trial and error, find the x-co-ordinate which will give the area under the curve as 0.916 from zp = 0.4. x, = 0.2. By making component balance, Yp = 0.533.Distillation 291 01 0.2 04 06 08 x— Fig. 9.36 Example 6 Solution for differential distillation. 7. A feed mixture containing 50 mole % Hexane and 50 mole % Octane is fed into a pipe still through a pressure reducing valve and flashed into a chamber. The fraction of feed converted to vapour is 0.6. Find the composition of the distillate and residue x 0 45 19.2 | 40 | 69 100 y 0 17.8 53.8 | 78 | 93.2 100 x, y mole percent of Hexane in liquid and vapour phase respectively Solution. Draw the equilibrium curve and diagonal. From the feed point draw a line with a slope of w)__04 [-% =~ 9g = 0.667 From graph shown in Fig. 9.37, we get .275, yp = 0.65 xy =292 Mass Transfer—Theory and Practice 1.0 02275 94 05 06 08 1.0 x— Fig. 9.37 Example 7 Flash distillation. 8. A equimolar feed mixture containing A and B is differentially distilled such that 70% of the feed is distilled out. Estimate the composition of the distillate and residue. Equilibrium data x {0 |1 |8 | 14] 21} 29 | 37 | 46 | 56 | 66 | 97) 100 y |0 |3 | 16] 28] 39] 50| 59 | 65 | 76 | 83 | 99] 100 x, y: mole fraction of benzene in liquid and vapour phase respectively. Solution. x © | 0.01 | 0.08 | 0.14 | 0.21 | 0.29 | 0.37 | 0.46 | 0.56 | 0.66 | 0.97} 1.0 y 0 | 0.03 | 0.16 | 0.28 | 0.39 | 0.50 | 0.59 | 0.65 | 0.76 | 0.83 | 0.99 | 1.0 yr O | 0.02 | 0.08 | 0.14 | 0.18 | 0.21 | 0.22 | 0.19 | 0.20 | 0.17} 0.02] 0Distillation 293 1 Plots against x as shown in Fig. 9.38 We know that, ae yy) in (y-x) LW Let the feed be 100 moles Therefore, D = 70 moles and W = 30 moles tof] er 2° Ey In| ay | =!] Jo | = 1.204 soe By trial and error, locate x, such that J Q—x) = 1.204 We get, Xy = 0.23 Making material balance, we get F=W+D Fre = W xy + Dyp Substituting for various quantities, we get 100 x 0.5 = 30 x 0.23 + 70 x yp Solving, we get, yp = 0.616 ow. Xp 00 02 040506 08 10 Xe— Fig. 9.38 Example 8 Solution for differential distillation.294 Mass Transfer—Theory and Practice 9. A liquid mixture of components A and B containing 30 mole percent A is 10. subjected to differential distillation. What percentage of the original mixture must be distilled off in order to increase the concentration of A in the residue to 65 mole percent? The relative volatility of B in respect of A is 2.15. Solution. Fx0.4615 7 Ww nv come =|> a i . F Solving, t |= a7 ‘olving, we ge [| 115 Therefore, if F = 100 kmol, W = 12.91 kmol. Hence, 87.09% of feed has to be distilled. Nitrobenzene (NB) has to be steam distilled. If the vaporization efficiency is 85%, estimate the amount of nitrobenzene in the distillate if 100 kg of steam is present in distillate. The distillation takes place at a total pressure of 760 mm Hg. Vapour pressure data for nitrobenzene: TC 44.4 | 71.6 | 84.9 | 99.3 ]115.4|125.8 |139.9| 185.8 |210.6 VP of NB mm Hg 1 5 |10 | 20 | 40 | 60 |100 |400 |760 Vapour pressure of water: T’C 20 40 60 80 100 VP of water, mm Hg 17.5 | 55.3 | 149.4 | 355.1 | 760 TC) |71 B 80 82 90 96 100 Ps 5 15S 9 10 14 175 21 Pa 242.5 | 340 355 4125 | 515 605 760 Solution. From total vapour pressure curve: Boiling point of mixture = 99.0°C At 99°C, vapour pressure of nitrobenzene = 20 mm Hg vapour pressure of water = 740 mm Hg *Distillation 295 Vaporization 7 = [(Actual NB/Actual water)] Actual NB Actual water . ] (all in moles) Theoretical NB Theoretical water 0.85 = Actual NB Theoretical NB | Actual water Be ee water = 0.85 x 20123 1 of NB/kg of steam 740 x 18 = 0.85 x0.1847 = 0.157 kg of NB/kg of steam Mass of NB per 100 kg of steam = 15.7 kg 800 760 700 ‘Sum of vapour pressures 650 550 eeeaee 8 8 8 8 Vapour pressure, mm Hg —= » 8 a a 20 40 60 80 100 120 140 160 180 200 220 To Fig. 9.39 Example 10 Determination of boiling point for steam distillation.296 1. Mass Transfer—Theory and Practice A methanol-water solution containing 36 mole % methanol at 26.7°C is continuously distilled to yield a distillate containing 91.5 mole % methanol and a residue containing 99 mole % water. The feed enters at its bubble point. Distillate is totally condensed and refluxed at its bubble point. (i) Find the minimum reflux ratio. (ii) For a reflux ratio of 3, estimate the number of plates by Ponchon-Savarit method. Enthalpy data: xory mole Enthalpies of Enthalpies of fraction of saturated liquid Saturated vapour methanol kJ/mol kJ/mol 0 8000 48000 1 7500 39000 Equilibrium data: x, % 4 10 20 30 50 70 90 95 y % | 23 42 58 66 8 87 96 | 98.15 x, y are mole fractions of methanol in liquid and vapour phase respectively. Solution. (i) xp = 0.36, x, = (1 - 0.99) = 0.01, Xp = 0.915 Both feed and Reflux are at bubble point. Plot H-x-y diagram and xy diagram as shown in Fig. 9.40. By intrapolation, Hg, = 39765 kJ/kmol Locate F corresponding to xr = 0.36 on the bubble point curve. Through F draw a tie line and extend it to intersect the vertical line drawn at xp = 0.915 nin (from graph) = 62500 ki/kmol _ @rin = He) _ (62500 - 39765) Rain = (He, —H;,) ~ (39765— 7542.5) ~ 705° Minimum reflux ratio = 0.7056 Gi) For R=3 (Q'-He) __(Q’-39765) R= (He, = H,,) 39765 -7542.5) QO = 136432.5 kJ/kmolDistillation 297 140000. 420000: 100000 80000 07 05. 04 0.2 0.1 Xy= 0.01 0.915 6% 0.2 04 06 08 xp 1.0 x— Fig. 9.40 Example 11 Ponchon-Savarit method.298 Mass Transfer—Theory and Practice 12. We know that Ap, Aw and F(Zp, Hp) lie on a straight line (Zp -Z) _ (Hp -0") (xp - tr) (Q’- Hr) Q” = -73004.5 kJ/kmol Locate Ap(Q’, xp) and A,(Q”, x,) on H,y diagram. Randomly draw construction lines starting from Ap and A, and obtain the operating curves for both sections on xy-diagram. Stepwise construction between equilibrium curve and operating curve will give the number of stages. Number of stages (including reboiler) = 6 Number of plates in tower = 6 - 1 = 5 A continuous distillation column is used to separate a feed mixture at its boiling point, containing 24 mole % acetone and 76 mole % methanol into a distillate product containing 77 mole % acetone and a residue product containing 5 mole % acetone. A reflux ratio of twice the minimum is to be used. The overall plate efficiency is 60%. Determine the number of plates required for the separation. Equilibrium data: x | 0.0] 0.05] 0.1 | 0.2 | 0.3 | 04 | 05 | 06 | 0.7 108 109 [1.0 y | 0.0 [0.102 |0.186 | 0.322 | 0.428 |0.513 | 0.586 | 0.656] 0.725 |0.82 | 0.9 [1.0 Solution. x, y Mole fraction of acetone in liquid and vapour phase respectively. xp= 0.24, xp =0.77, x, = 0.05 Rectuat = 2Rmin Noverar = 60% Plot xy diagram and draw the feed line with its corresponding slope of infinity to equilibrium curve and let it be F. Let the point D on the diagonal corresponds to Xp. Join DF and extend it to y-axis. The point of intersection is = 0.19 (from Fig. 9.41) . Rin = 3.053 Rectuat = 6-106 xp 0.77 Resa #1 = 7.106 ~ 108 Locate 0.108 on y-axis and let it be A. Join AD. The point of intersection of AD with feed line is Q. DQ is the operating line for enriching section. Locate W on diagonal corresponding to xw = 0.05. Join W and Q. WO is the operating line for stripping section. By stepwise construction the number of stages = 14 (including reboiler) o Number of plates is 13 (Theoretical) Actual number of plates = 2 = 21.7, ie. 22 platesDistillation 299 02 04 06 08 10 — Fig. 9.41 Example 12 McCabe-Thiele method. 13. A fractionating column separates a liquid mixture entering at 5000 kmol/h containing 50 mole % A and 50 mole % B into an overhead product of 95 mole % A and a bottom product of 96 mole % B. A reflux ratio of twice the minimum will be used and the feed enters at its boiling point. Determine the number of theoretical stages required and the location of feed point. Equilibrium data: x | 0.03 | 0.06 | 0.11 | 0.14 | 0.26 | 0.39 | 0.53 | 0.66 | 0.76 | 0.86} 1.0 y | 0.08 | 0.16 | 0.27 | 0.33 | 0.50 | 0.63 | 0.71 | 0.83 | 0.88 | 0.93 | 1.0 +, y mole fraction of A in liquid and vapour phase respectively. Solution. xp=05, xp = 0.95, xy = 0.04 Feed-saturated liquid F = 5000 kmol/h Total condenser (@ Total material balance F=D+W Component balance Fp = Dxp + Wxy 5000=D+W a)300 Mass Transfer—Theory and Practice (5000 x 0.5) = (D x 0.95) + (W x 0.04) (2) 5000=D+W Distillate D = 2527.5 kmol/h Residue W = 2472.5 kmol/h Gi) Rmin = (& - YO" - ¥’)] (0.95 — 0.720) Rain = [ (0.720 - | ee Also, by graphical xp/(Rmin + 1) = 0.46 and Ryin = 1.065 Gil) Recua = 2 % Rnin Racal = 2 X Rmin = 2X 1.045 = 2.09 (Taking Rin Value as 1.045) Xp _ 095 R+) ~ Gooey ~ 07 With the above intercept, draw both enriching and stripping operating curves. By McCabe-Thiele method, Number of plates (including reboiler) = 11 Number of plates in tower = 11 - 1 = 10 The location of feed tray is 6th tray. 02 04 06 08 10 Fig. 9.42 Example 13 McCabe-Thiele method. 14. A mixture of benzene and toluene containing 38 mole % of benzene is to be separated to give a product of 90 mole % benzene at the top, and the bottom product with 4 mole % benzene. The feed enters the column at itsDistillation 301 boiling point and vapour leaving the column is simply condensed and provide product and reflux. It is proposed to operate the unit with a reflux ratio of 3.0. Locate the feed plate and number of plates. The vapour pressures of pure benzene and toluene are 1460 and 584 mm Hg respectively. Total pressure is 750 mm Hg. Solution. vapour pressure of pure benzene _ 1460 _ vapour pressure of pure toluene 584 ce ax +(@-Da) Compute equilibrium data. y x 0 0.1 | 0.2 | 03 | 04 | 05 | 06 | 0.7 | 08 | 0.9 | 1.0 y O | 0.22 | 0.38 | 0.52 | 0.63 | 0.71 | 0.79 | 0.85 | 0.91 | 0.96 | 1.0 Draw the equilibrium curve, diagonal and locate feed, distillate and residue points as shown in Fig. 9.43. xp _ 09 [R+l] 341 we can get the number of stages. No. of stages = 8 (including reboiler) and feed plate is 4 Locate the intercept = 2.25 and by stepwise construction 0 01 02 03 04 O05 06 OF 08 O09 10 x— Fig. 9.43 Example 14 McCabe-Thiele method.302 15. Mass Transfer—Theory and Practice It is desired to separate a mixture of 50% vapour and 50% saturated liquid in a plate type distillation column. The feed contains 45 mole % A and the top product is to contain 96 mole % A. The bottom product is to contain 5 mole % A. Determine the minimum reflux ratio and the number of theoretical plates needed if a reflux ratio of twice the minimum is used. Eq. data: x 0 O.1 | 0.16] 0.3 | 04 | 05 | 06 | 0.7 | 08 | 09] 1.0 y. O {0.215 | 0.30 | 0.52 | 0.625 | 0.725 | 0.78 | 0.89 | 0.89 | 0.95 | 1.0 x,y: mole fraction of A in liquid and vapour phase respectively. x JL [e255 0.33 Solution. 0.96 Rain +1= 033 Reig = 1.909 q = 0.5 (Fraction of liquid) . q |_ 05 _ Slope of q-line [4] =o5-17 1° Ractusl = 2.0 X Rmin = 2.0 X 1.909 = 3.818 Yo _]__0.96 [a + i] = zg1ee1 01% Number of stages = 10 1.0 08 06 | qrine slope = -1.0 04 02 Fig. 9.44 Example 15 McCabe-Thiele method.16. 17. Distillation 303 A fractionating column separates a liquid mixture containing 50 weight % chloroform and 50 weight % carbon disulphide into an overhead product of 94 weight % CS, and a bottom product of 95 weight % chloroform. A reflux ratio of twice the minimum will be used and the feed enters at its boiling point. Determine the number of theoretical stages required. Equilibrium data: x | 0.03 | 0.06 | 0.11 | 0.14 | 0.26 | 0.39 | 0.53 | 0.66 | 0.76 | 0.86 | 1.0 y | 0.08 | 0.16 | 0.27 | 0.33 | 0.50 | 0.63 | 0.71 | 0.83 | 0.88 | 0.93 | 1.0 x, y mole fraction of carbon disulphide in liquid and vapour phase respectively. Solution. Molecular weight of carbon disulphide = 76 Molecular weight of chloroform = 119.5 50 weight % of carbon disulphide, xp= —+~4— = 0.611 (in mole fraction) 50, 50 76 119.5 Similarly, the distillate and residue compositions in terms of mole fraction of carbon disulphide are yp = 0.961 and x, = 0.076 respectively. yi From graph (Fig. 9.45), ( R a i } = 0.49 ‘min Rrrin = 0.96 Rycy = 2 X Rin = 1.92 YD =P _ | = 0.329 = 0.33 es (= + i) Number of theoretical stages (from Fig. 9.45) including reboiler = 9 A laboratory rectification column is operated at atmospheric pressure and at total reflux, for benzene-chlorobenzene mixture. Samples of liquid from the condenser and reboiler analyze 95 mole percent benzene and 98 mole percent chlorobenzene respectively. Assuming a perfect reboiler, a total condenser, constant molal overflow and no heat loss from the tower, calculate the actual number of plates in the column. The average plate efficiency is 70%. The relative volatility of benzene to chlorobenzene is 4.13.304 Mass Transfer—Theory and Practice 1.0 08 06 y 04 0.33 02 Xp= 0.61 x, =0.961 00 & 02 04 06 08 1.0 xo Fig. 9.45 Example 16 McCabe-Thiele method. Solution. ax >" ¥@-Dal Compute equilibrium data. x}]o0 O.1 | 0.2 [ 03 04 | 05 | 06 | 0.7 | 08 | 09 | 10 y | 0 | 031 | 0.51 [0.64 0.73 | 0.81 | 0.86 | 0.91 | 0.94 | 0.97 | 1.0 Draw the equilibrium curve, diagonal and locate feed, distillate and residue points. By stepwise construction, the number of stages determined is 5. Hence, the theoretical plates required is 4. — 5.71 = 6. Actual plates required will be 7>=18. Distillation 305 0 0.2 04 06 08 *0 14.0 x— Fig. 9.46 Example 17 McCabe-Thiele method. Alternatively, we can use the Fenske equation and determine the number of stages. YD = (qyNevs _*Ww Oy)" Taw 0.95 Np, 0.02 (1- 0.95) = G13) (1- 0.02) 19 =(4.13)%P+! x 0.02041 Hence, Np + 1 = 4.82 stages =5 stages Therefore, the theoretical number of plates = 4 Actual plates required will be a = 5.71=6 (Same as obtained from the graphical procedure) A continuous rectification column is used to separate a binary mixture of A and B. Distillate is produced at a rate of 100 kmol/hr and contains 98 mole % A. The mole fractions of A in the liquid (x) and in the vapour (y) respectively from the two adjacent ideal plates in the enriching section are as follows:306 = Mass Transfer—Theory and Practice x y 0.65 0.82 0.56 0.76 The latent heat of vaporization is the same for all compositions. Feed is a saturated liquid. Calculate the reflux ratio and the vapour rate in the stripping section. Solution. Yq = 0.82 Xq= 0.65 net Yn41 = 0.76 Solving, we get 0.76R + 0.76 = 0.65R + 0.98 Reflux ratio, R = 2 In the stripping section, For a saturated feed q = 1.0 (G-G) q=1.0= F19. 20. Distillation 307 ie. G=G=L+D = D(R + 1) = 100(2 + 1) = 300 kmolh A continuous rectifying column treats a mixture containing 40% benzene and 60% toluene and separates into a distillate product containing 98% benzene and a bottom product containing 98% toluene. The feed enters as a liquid at its boiling point. If a reflux ratio of 3.5 is used, estimate height of the tower. The average height of a transfer unit is 0.7 m. The overall resistance to mass transfers lies in vapour phase. Equilibrium data: x 0.1 0.2 0.3 04 0.5 0.6 0.7 0.8 0.9 y 0.22 | 0.38 | 0.51 | 0.63 | 0.70 | 0.78 | 0.85 | 0.91 | 0.96 x, y: mole fraction of benzene in liquid and vapour phase respectively. Solution. y 0.98 | 0.92 | 0.81 | 0.74 |0.655} 0.57 | 0.44 |0.318} 0.2 | 0.1 | 0.02 7 0.995 | 0.96 | 0.89 | 0.83 | 0.75 |0.655}0.543] 0.43 | 0.30 |0.183} 0.05 66.67} 25 | 12.5 |11.11}10.53}11.76} 9.71 | 8.93 | 10 |12.05)33.33 O’-y) y is from operating line and y’ is obtained from equilibrium curve for a specific x value. xp=04, xy =(1-0.98)=0.02, R=35, HTU=07 [xp(R + 1)] = (0.98/ (3.5 +1)] = 0.218 Overall mass transfer lies in vapour phase. So the slope ~ [(I/kx)/ (1/ky)] becomes vertical, y and y” values are obtained at the intersection of operating and equilibrium curves. dy 7 = 13.175 J [5 - si Z = HTU x NTU = 0.7 x 13.175 = 9.22 m Feed rate to a distillation column is 400 kmol/hr. The overhead product rate is 160 kmoW/h. The mole fraction of more volatile component in distillate is 94%. The residue contains 5% of more volatile component. The reflux ratio is 4. The mole fraction of vapour leaving a plate is 0.4, whereas the mole fraction of liquid coming to the same plate is 0.3. Assuming constant molal overflow, determine the condition of feed. Solution. Feed rate: 400 kmol/h Distillate, D: 160 kmol/h Therefore, flow rate of residue, W: 240 kmol/h The composition of distillate xp = 0.94308 Mass Transfer—Theory and Practice 01 02 03 04 05 06 07 08 09 10 + 70 65 60 50 45 30 25 15 10 0 02 04 06 08 10 Fig. 9.47 Example 19 packed distillation.21, Distillation 309 The composition of residue x,, = 0.05 Reflux ratio: 4 Ynet = 0.94 Xm = 0.05 We know that Tn = Guy, + W (Eq. 9.67] Since, the molal overflow rate is constant, L,, _(_L Ww Ym =| Pow = | Dow Jw (Eq. 9.94] Substituting, we get, 240 0.4 0.05 240 ) Solving, we get T= 880 kmol/h From Eq. (9.67) we get . Gust = Lm —W = 880 - 240 = 640 kmol/h = G,, = G (Due to constant molal flow rate). Feed rate = 400 kmol/h p L Reflux ratio = D* 4 Hence, L = 4D = 640 kmol/h. L = 880 kmol/h We also know that L-L) _ (He -Hr) 92 = Ga (Eq. 9.110) ” L=L+qF Substituting, we get 880 - 640 . a 9 = Jpg — = 0.6 (Fraction of liquid) Hence, the feed is a mixture of 60% liquid and 40% vapour. The feed rate to a binary distillation column is 200 kmol/hr and 75% of it is vaporized. Distillate flow rate is 120 kmol/h with 95% composition of more volatile component. Reboiler steam demand is 4000 kg/h. Latent heat of steam used in reboiler is 2304 kJ/kg. Latent heat of liquid to be distilled is 32000 kJ/kmol. Determine the reflux ratio.310 - Mass Transfer—Theory and Practice Solution. We know that L =L+qF (from Eq. 9.110) G=(R+D (from Eq. 9.84) From Eq. (9.111), we get 9 _ E-v., =@- (G-G =Fq@-) G=G+Fq-1) ie. G=(R+1)D+ Fq-1) Fraction of vapour = (1 - q) = 0.75 Fraction of liquid = q = 0.25 G = (R + 1)120 + 2000.25 - 1) = (R + 1)120 - 150 = 120R - 30 G Steam needed for the reboiler m, = wes eam m, Aseam = GAjeed = (120R ~ 30)Afeea ‘ms Asteam = 4000 x 2304 = 9.216 x 10° kI/nr = (120R ~ 30)Afeea ie. 9.216 x 10° = (120R — 30)32000 Solving, we get R= 2.65. EXERCISES Compute the VLE data from the following vapour pressure data at 760 mm. Hg. Pressure assuming ideal solution. Temperature,°C 984 | 105 | 110 | 120 |1256 Vapour pressure of A, mm Hg | 760 | 940 | 1050 | 1350 | 1540 Vapour pressure of B, mm Hg | 333 | 417 | 484 | 650 | 760 Ans: Xa | 1.0 | 0.655 | 0.487 | 0.157 | 0.0 ya | 1.0 | 0.810 | 0.674 | 0.279 | 0.0Distillation 311 2. A mixture containing benzene and toluene with 50 mole % benzene is flash distilled such that 70% of the feed is distilled out. Estimate the composition of the distillate and residue. If the same quantity of distillate is obtained by simple distillation, estimate the composition of the residue and distillate. Equilibrium data: x 0.1 0.2 [03 [04 |05 |06 |0.7 |08 ] 0.9 y 0.22 | 0.38 | 0.51 | 0.63 | 0.70 | 0.78 | 0.85 | 0.91 | 0.96 x, y: mole fraction of benzene in liquid and vapour phase respectively. (Ans: (i) -W/D = -0.3/0.7 = - 0.429 Yp = 0.56 and x, = 0.35 (From graph) (ii) xy = 0.245 and yp = 0.61) 3. A simple batch still is used to distill 1000 kg of a mixture containing 60 mass % ethyl alcohol and 40 mass % water after distillation, the bottom product contains 5 mass % alcohol. Determine the composition of the overhead product, its mass and mass of the bottom product. The equilibrium data: x 15 10 20 30 40 50 60 y |36 51.6 65.5 ml 74 76.7 78.9 where x and y are weight percent of ethyl alcohol in liquid phase and vapour phase respectively. (Ans: Residue = 192.28 kg; Distillate 807.72 kg; Yp = 0.731 mass % alcohol) 4. A liquid mixture containing 50 mole % acetone and rest water is differentially distilled at 1 atm. pressure to vaporize 25% of the feed. Compute the composition of the composited distillate and residue. VLE data at 1 atm. pressure is given below. x, mole fraction of acetone in liquid 0.1 0.2 | 03 04 | 06 | 07 0.9 y, mole fraction of acetone in vapour 0.76 | 0.82 | 0.83 | 0.84 | 0.86 | 0.87 | 0.94 5. A solution of 40 mole % of acetic acid in water is flash distilled at atmospheric pressure, until 60 mole % of the feed was distilled. Compute the compositions of the distillate and residue.312 8. Mass Transfer—Theory and Practice Equilibrium data: Mole fraction of acetic acid in Liquid, x | 0.07 | 0.15 | 0.27 | 0.37 | 0.50 | 0.62 | 0.72 | 0.82 | 0.90 | 1.0 Vapour, y | 0.05 | 0.11 | 0.20 | 0.28 | 0.38 | 0.49 | 0.60 | 0.73 | 0.80 | 1.0 (Ans: x, = 0.53 and yp = 0.65 in terms of water) Feed mixture containing equimolar quantities of ‘A’ and ‘B’ is differentially distilled such that 60 mole % of feed is distilled out. Estimate the composition of distillate and residue. x 0 0.157 0.312 0.487 | 0.655 1.0 y 0 0.279 0.492 0.674 | 0.810 1.0 x, y are mole fractions of A in liquid and vapour phase respectively. (Ans: x,, = 0.335 and yp = 0.61) A equimolar feed mixture containing Benzene and Toluene is distilled such that 60% of feed is distilled out. Estimate the composition of distillate and residue by taking the relative volatility as 2.5 for (i) Simple distillation, (ii) Equilibrium distillation. (Ans: (i) xy = 0.29, yp = 0.64 and (ii) xy = 0.365, yp = 0.59) It is desired to separate a feed mixture of ‘A’ and ‘B’ containing 50 mole % A to a product such that 60% feed is distilled out. Estimate the composition of residue and distillate if (i) simple distillation is carried out and (ii) equilibrium distillation is carried out. VLE data: x | 0 | 5 | 10) 15 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 | 100 10 y | O | 11 | 21 | 30 | 38 | S51 | 63 | 72 | 78 | 85 | 91 | 96 | 100 x, y are mole % of A in liquid and vapour phase respectively. (Ans: (i) xy = 0.3, yp = 0.63, (ii) xw = 0.36, yp = 0.59) It is desired to separate a feed mixture of 100 kmol containing 60% heptane and 40% ethyl benzene such that 60 kmol of the feed is distilled out. Determine the composition of residue and distillate if the distillation is (i) Flash distillation and (ii) Differential distillation. x | 0 | 0.08 | 0.185 | 0.251 | 0.335 | 0.489 | 0.651 | 0.79 | 0.914 | 1.0 y | 0 | 0.233} 0.428 | 0.514 | 0.608 | 0.729 | 0.814 | 0.91 0.963 | 1.0 x, y is the mole fraction of heptane in liquid and vapour phase respectively. (Ans: (i) xy = 45%, yx = 20%; (ii) xy = 37.5, yp = 75%) A liquid mixture containing 50 mole % n-heptane and 50 mole % n-octane is differentially distilled until the residue contains 33% n-heptane. Calculatei. 12. 13. 14. 15. Distillation 313 the % vaporization and the composition of the composited distillate. If the residue with the same composition is achieved in an equilibrium still, estimate the composition of the distillate and total moles distilled assuming a@=217. (Ans: yp n-heptane = 0.617, total moles distilled = 60 ml/h; vaporization: 60%; (ii) yp = 0.52% vaporization: 89.47%) A mixture of 30 mole % Naphthalene and 70 mole % Dipropylene glycol is differentially distilled at 100 mm Hg until a final distillate containing 55 mole % Naphthalene is obtained. Determine the amount of residue and the composition of residue. VLE data: x |5.4 | 11.1 | 28.0 | 50.6 | 68.7 | 80.6 | 84.8 | 88 y | 22.3) 41.1 | 62.9 | 74.8 | 80.2 | 84.4 | 86.4 | 88 A mixture containing 30 mole % Hexane, 45 mole % Heptane and 25 mole % Octane is subjected to flash distillation. If 60 mole % of the feed is vaporized and condensed, calculate the composition of vapour leaving the separator. (m values for Hexane, Heptane and Octane: 2.18, 0.99 and 0.46 tespectively) A binary mixture containing 55 mole % n-heptane and 45 mole % n-octane at 27°C is subjected to differential distillation at atmospheric pressure with 60 mole % of the feed liquid is distilled. Assuming a relative volatility of n-heptane with respect to n-octane is 2.17, determine the composition of the charge in still and that of distillate. (Ans: composition of n-heptane xy = 0.38, yp = 0.665) Continuous fractionating column operating at 1 atm is designed to separate 13600 kg/hr of a solution of benzene and toluene. Feed is 0.4-mole fraction benzene. Distillate contains 0.97 mole fraction benzene and residue contains 0.98 mole fraction toluene. A reflux ratio of twice the minimum is used. Feed is liquid at its saturation temperature and reflux is returned at saturation. Determine: (i) Quantities of products in kg/hr (i) Minimum reflux ratio (iii) Number of theoretical plates The average relative volatility for the given system is 2.56. (Ans: (i) D = 5524.2 kg/h w = 8075.8 kg/h; (ii) Rm = 1.487; (iii) 13) A solution of carbon tetra chloride and carbon disulfide containing 50 mole % of each is to be fractionated to get a top and a bottom product of 95% and 6% carbon disulfide respectively. The feed is a saturated liquid at its boiling point and is fed at the rate of 5000 kg/hr. A total condenser is314 16. 17. 18. 19. Mass Transfer—Theory and Practice used and reflux returned to the top plate as a saturated liquid. The equilibrium data at 1 atm pressure is given below: x 0 | 0.06 | 0.11 | 0.26 | 0.39 | 0.53 | 0.66 | 0.76 | 0.86 | 1.0 y 0 | 0.16 | 0.27 | 0.50 | 0.63 | 0.75 | 0.83 | 0.88 | 0.93 | 1.0 where x, y are mole fractions of carbon disulfide in liquid and vapour phase respectively. (i) Determine the product rate in kg/hr. (ii) What is the minimum reflux ratio? (iii) Determine the theoretical number of plates required and the feed plate location if the tower is operated at twice the minimum reflux ratio. A mixture of 35 mole % A and 65 mole % B is to be separated in the fractionating column. The concentration of A in the distillate is 93 mole % and 96% A in the feed is recovered in the distillate. The feed is half vapour and reflux ratio is to be 4.0. The relative volatility of A to B is 2.0. Calculate the number of theoretical plates in the column and locate the feed plate. A continuous fractionating column, operating at atmospheric pressure, is to be designed to separate a mixture containing 30% CS, and 70% CCl, into an overhead product of 96% CS, and a bottom product of 96% CCl, (all mole percent). A reflux ratio of twice the minimum will be used and the overall efficiency of the column is estimated to be 65%. Feed enters at its boiling point. Determine the number of plates to be provided and the correct location of the feed plate. Equilibrium data: x | 0.0296 | 0.0615 | 0.258 | 0.390 | 0.532 | 0.663 | 0.758 | 0.860 y | 0.0823 | 0.1555 | 0.495 | 0.634 | 0.747 | 0.830 | 0.880 | 0.932 A continuous fractionating column, operating at atmospheric pressure, is to separate a mixture containing 30 mole % CS, and 70 mole % CCl, into an overhead product of 95 mole % CS, and a bottom product of 95 mole % CCl,. The feed enters the column as liquid at its boiling point. Assuming an overall plate efficiency of 70% and a reflux ratio of 3.16, determine the number of plates to be provided. Mole fractions of CS, in liquid (x) in equilibrium with mole fraction CS in vapour (y) are given below. Equilibrium data: x |2.96 | 11.06] 25.8 |53.18|66.3 | 75.75 | 86.04 y |8.23 | 26.6 | 49.5 | 74.7 | 83.0 | 88.0 | 93.2 A feed containing 50 mole % heptane and 50 mole % octane is fed into a pipe still through a pressure reducing value and then into a flash discharging chamber. The vapour and liquid leaving the chamber are assumed to be in20. 21. 22. Distillation 315 equilibrium. If the fraction of feed converted to vapour is 0.5, find the composition of the top and bottom plates. The following table gives VLE data: x, mole fraction of {1.0 |0.69 |0.4 |0.192 | 0.045 | 0.0 heptane in vapour phase y, mole fraction of|/1.0 | 0.932 | 0.78 | 0.538 | 0.178 | 0.0 heptane in vapour phase (Ans: x, = 0.31 yp = 0.69) A continuous distillation column is used to separate a feed mixture containing 24 mole % acetone and 76 mole % methanol into a distillate product containing 77 mole % acetone and a residue product containing 5 mole % acetone. The feed is A saturated liquid. A reflux ratio of twice the minimum is used. The overall stage efficiency is 60%. Determine the number of plates required for the separation. Equilibrium data: x{0.0] 0.05] 0.1 | 0.2 | 03 | 04 | OS | 06 | 0.7 | 08 | 10 y | 0.0 | 0.102 | 0.186 | 0.322 | 0.428 | 0.513 | 0.586] 0.656 | 0.725 | 0.80 | 1.0 (x, y mole fraction of acetone in liquid and vapour phase respectively) (Ans: 24 stages) The enthalpy-concentration data for a binary system is given below: x, mole fraction of A 0.0 | 0.25 | 0.407 | 0.62 | 0.839} 1.0 y, mole fraction of A 0.0 | 0.396 | 0.566 | 0.756 | 0.906 | 1.0 A, kcal/kmol 280 | 180 | 145 | 195 | 260 | 380 Hg, kcal/kmol 1000 | 1030 | 955 | 895 | 885 | 880 Rest of the data could be obtained by extrapolation. A feed mixture with an initial composition of 30 mole % A is to separate into an overhead product of 95 mole % A and a 4 mole % bottom product. Determine the ideal number of stages needed if the reflux ratio is twice the minimum reflux ratio. Feed enters as a saturated liquid. Xp =0.3, xp =0.95, x, =004, R=24 A mixture containing 50 mole % A and 50 mole % B is distilled in a packed column to yield a top product containing 94 mole % A and a bottom product containing 95 mole % B. The feed enters a saturated vapour. Estimate the height of the packing needed if the height of a transfer unit is 0.5 m. A reflux ratio of 1.5 times the minimum is to be used. The relative volatility of A with respect to B is 2.5. (Ans: NTU = 11.25, Ht = 5.625 m)