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 lis equipments, iid equilibrium data is the basis for design of distillation operation 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238 = Mass Transfer—Theory and Practice BPofB 7—— BP ofA 0 1.0 xy¥—> 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, af, also changes in such cases.Distillation 239 / A ° 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 cuve Liquid VP ofA M N a cA Di yvs P VP ofB ja R ° xy 70 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, dag is defined as the ratio of vapour pressure of A to that of B. PB ie. Gay = y 9.1) Raoult’s law states that when a gas and a liquid are in equilibrium, the partial pressure of A, p, 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, Pe = Pate 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 (9.4) O45 = = Ya ~\le% Pan = xa (9.5) I-x, Rearranging, we get pra ¥¥q(Gqp -D 06) and more simply as ax 1+x@-1) ae 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 Eqs. (9.2) and (9.3), pa = xa Pa Po = %p Pp = (1-44) Pp 98) For a binary system, Pat Pp = Pr=%q Pa + (1~%4) Pp= Ppt xa (Pa-Ps) (9.9) _ Pr=Ps) *4* PP) (9.10) From the vapour pressure data at each temperature, x4 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 cies 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. Fig. 9.4 Minimum boiling azeotrope at constant temperature.242 Mass Transfer—Theory and Practice oP, P: Constant vapour yvs T : 8 Bp, 5 "4 5 ® xvsT Liquid ° xy 1.0 Fig. 9.5 Minimum boiling azeotrope at constant pressure. 10 y: 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 243 Fig. 9.7 Maximum boiling azeotrope at constant temperature. Vapour P: Constant Temperature ——> 8 Liquid 0 %Y— 10 Fig. 9.8 Maximum boiling azeotrope at constant pressure. 1.0 0 x 1.0 Fig. 9.9 VLE of maximum boiling azeotrope.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 ¢ Azcotropic 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 <——_—__ Batch Continuous ‘Simple/ Flash/ | | Differential Equilibrium ‘Stagewise contact ms > Differential distillation distillation (Tray tower) oontaaa (Packed tower) fy 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 of separating such mixtures.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 (9.11) 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 BPofA BP ofB ‘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, ¢ 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 Distilate Residue Heat Fig. 9.12 Differential distillation. Making a component balance, we get Lx = y* dL + (L~ dl) (x - dx) (9.12) Les yt dL + Le ~ Lie xb + dy. (9.13) (C2 Product of two very small quantities) Then, dL(y* - x) = Ldx (9.14) dl dx Gta 0.15) Integrating between limits x = xp =F xeay L=W F x, Jt-loe LS x) (9.16) wk, Ft a noef =a @.17) x 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 »* f+@-balDistillation 247 Hence, replacing y in terms of Eq. (9.7), we get F dx » Z-J|/—_—_ (9.18) “\Tie(a-1x] RHS of Eq. (9.18) = J} -—f-— . (9.19) [r+(@-1)x] On simplification, [1+ (a -1)x]dx lf (+ (@-Dxldx - fa —1—ax+x] Pax] fax-x-ax 1+ (@ -I)xdx [1+ (@ -Dxddx “J a@ == =D) I d= @= 0) dx dx 1 A B =learsecn aS “@- wS](4)-(e))a-ma-» __ 1 fAd-x)+ BQ) “(@=Ds x@=x) L_[pax pdx 2 wall + [a ]-me-9 Substituting the limits for x as xp and xy, we get dx—In(1 =x) 1 = G@aplins = Ind = 9)]-In(1-x) poner xp) _), @-ae)]_ jp O-ae) asl") mga aw) , F) 1 [ (ap) _yp(=xe))]_ 4, O- a0) io »()=veen (25) w(4=22)] nay) ap F (lise) eee Xw (Ge) (2) = att dp (= xy)248 Mass Transfer—Theory and Practice ole} “pin Faxes) _ ap lf ae daw) (Dna y) (all y ] AF F(- xp) _ ay F(l- xp nF xy) a-=) oul tee) F(l= xp) _ Waa ay) > (= xw) F(l-xp) ]_ wn[ft=2) Distitate vapour 2. Yo Ho Pressure reduction valve a WX Hy Fig. 9.13 Flash distillation.Distillation 249 A total material balance, gives, F=W+D (9.21) A component balance gives, Fig = Ww + Dyp (9.22) An enthalpy balance gives, FHp+ Q = WHy + DHp ie. (He +2) = WHy +DHp (9.23) From Eqs. (9.21) and (9.22), we get (W + D)Zp= Wry + Dyp (9.24) W [2p ~ xy] = -DIZp— yo) (9.25) _W _ Zr -yp) D © Gr - xy) 0.26) Similarly from Eqs. (9.21) and (9.23), we get p [Bl ~ 9.27 [[#B)-m| ” Ww D Fr — Aw) =~ Ze — Yo) (9.28) Dividing Eq. (9.25) by F, we get 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. (1-9) @r-2w =f 00-2) (929) Zp ~ aw for +f 30> So ~ Ser Zp -3w=F Op ~ 39) Zr+ aw F- = fio Z =) Yor + + xy ge (9.30) So Eg. (9.30) can be called an operating line drawn with a slope of [(f— 1)/f] and simplified as, (9.31) The feed point is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 = Zs) 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, Hp + Q/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 I respectively. Ll Slope =- WID Xw Ze x Fig. 9.14 Estimation of composition of products in flash distillation.Distillation 251 on Hgvsy Hyvsx > Slope = -WID x——> 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 o: remains fairly constant. Modified Rayleigh’s equation can be applied for material balance, Frpp I" L (ee ] (9.32) an Free I" 7 al (9.33) 7 Fxrp |_, | Frrc I" Similarly, In [ Wine | =In [ Ware | (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, Xp 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 wa. Xwe and Xyc 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 of varies significantly, the Rayleigh’s equation of the x oe Jro5 has to be used taking two components at a time. Here also Wo 20-4) 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 = mix; (9.36) where m; = vapour pressure of component/total pressure. The suffix i denotes the component. ie. Yip = mi Cw) 9.37) _W _Qp~Zr) We know that —7y= Goze) from Eq, (9.26)] W _ Qin ~Zir) D~ Grok) (9.38) -Z, - [yo ut | 39 Zp 22 iF or (9.40) ie (9.41)Distillation 258 (9.42) and (9.43) yj, pis evaluated using Eq, (9.42) and x,w is evaluated using Eq. (9.43) by assuming (WID) value and finally checked for its validity by using Ex,w=10; Ly,p= 1.0 9.11.1 Steps Involved © From vapour pressure, determine m for each component. © Assume W/D value and determine x,y and yz) © Check whether Ex, y and Zy,,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; Lyip = 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 Il: Full distillation unit Envelope Ill: Enriching/Rectifying section Envelope 1V: 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 Heat loss |—te] 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 L/D, Qc the load on condenser, Qg the heat supplied in reboiler and Q, the total heat loss.Distillation Considering envelope I and making a mass balance, G=D+h G,=D+RD=D(R+1) ‘A component balance gives Gy = DZp + Lor Making an energy balance, we get GiHo, = Lo, + Dp + Oc Qc = GiHg, - Lolli, - DHp Substituting for G, from Eq. (9.45), we get Qc = [D(R + 1) Hg,] - RDH,, - DHp [(R + 1H, ~ Rig - Ho) Considering envelope Il and making an energy balance, we have Heat in = Heat out Qs + FH = DHp + WHy + Oc + Op Heat added in reboiler Qg = DHp + WHw + Qc + Q, - Fr 255, (9.44) (9.45) (9.46) (9.47) (9.48) (9.49) (9.50) (9.51) Now, let us consider envelope Ill, the enriching section and make mass and energy balance. A total mass balance yields, Gra = Ly + D A component balance gives, GrsrYner = Ltn + DZp An energy balance gives, GrsiHe,,, WH, + DHp + Oc Let 0 = (Net heat ou/Net moles out) = [Senger Then, Eq. (9.54) becomes Get Heya = Ln Hi, + DQ" Eliminating D from Eq. (9.53) using Eq. (9.52), we get (Gnas nes) = Ln = (Gres - LndZo (GreMZp ~ Ynsil = LalZo ~ ¥n) tn _ Zo = Yn) Gur (Zp — Xn) where (Ly/G, 4 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 Ly _ (Q' - Ho) Ga @-H,,) 059) Equating Eq. (9.58) with Eq. (9.59), we get Ly _ Zp ~ Yass) _ (O'~Ho,) Git @Zp-%) Q-H,,) Cy Equation (9.60) represents a straight line passing through (Heyes Ynei) At Grots (Ary Xp) at L, 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). (Q" - He...) Gri (Q"— Hy, ) Substituting for G,,, in the above expression from Eq. (9.52), we have by OMe) Gav) @-H,) (9.61) . (yep) _ O'- Ha) te L, (Q-He,,.) ; D)_ (O-4,) i " [2] *OrHe,) D _ He, ~ He) Tt, @-He,,) (9.62) L, _ (Q'-Ha,,,) D ~ (g,, = H1,) (0.63) When n = 0, it indicates the condenser and for n = 0, we get ly _O'- Ha) D fig = Hi, (9.64) ie. R, the external reflux ratio = 40 — Length of line ApGi (9 65) D ~ Length of line G,Ly 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, @’). Ly _ Zp ~Ynsi) oa D ~ Ona =%) {from Eq. (9.58)] Let us consider envelope IV in the stripping section. A mass balance yields B Ga +W (9.66) A component balance yields Darn = GuitYmer + Wey, (9.67) Lm Xm ~ Gar Ym +1 = Wes (9.68) ‘An energy balance yields Ln Hig + On = Got Hones + WHw (9.69) Let Q’= C= On) (9.70) Tn “Hi, ~ Gnsr Ho,,, = WO” (9.71) Eliminating W from Eqs. (9.66) and (9.68), we get Lm msi = Xw) 9.72) Smet mW) on”) Similarly eliminating W from Eqs. (9.66) and (9.71), we have (Hons, ~ 2") L Gus Hy, — 2") (9.73) Hence from Eqs. (9.72) and (9.73), we get (9.74) 1+/ Gms Gt Hence, rearrangement of Eq. (9.74) using Eq. (9.66) gives W _ Osi = 4w) pie neta w)) (975) inst m — XW)258 Mass Transfer—Theory and Practice Geass (9.76) Equation (9.76) represents a line passing through (xy, Q”), (tm H,) and Ome H,,,,,) where Q” represents net heat out /Net moles out and xy dendtes moles of ‘A oul/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 9.71) A component balance gives FZp = Dyp + Wry (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 _ (2p ~Xw) _ (Hr ~Q") WG-2) Q'-Hp) Ce Equation (9.80) represents a line passing through (Zp, @’), (Z;, Hp) and (xw, 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 xy in both the diagrams and draw vertical lines from zp in positive y-axis direction and from x in the negative y-axis direction. 3. Locate F(xp, Hy) in the H-x, y diagram. _ @- Ha) © (He, -H,) where H,. Hz, 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 Hvsx 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 Risin: 4, Obtain Q’ using the given reflux ratio, RDistillation 259 a 04 06 os = 1.0 x Fig. 9.17%(a) Determination of number of stages by Ponchon-Savarit method.260 = Mass Transfer—Theory and Practice Fig. 9.17(b) Determination of minimum reflux in Ponchon-Savarit method.10. i Distillation 261 Locate Ap (yp, Q’) using the H,, Hy, and reflux ratio. Join Ap with F and project it to cut the vertical line at xy and that point is Aw. 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,= G.= Gy =G A total material balance gives G=L+D (9.82) Let the external reflux ratio R be given by oa R=D"D then, G=DR+D=D(R+1) (9.83) ‘A component balance for A in enriching section gives yng) = Lin + Dyp (9.84) ie. (9.85) (9.86) (9.87) _[_2& 1 Yn =) RG [*n tT] Req PO (9.88) Equation (9.88) represents the operating line for enriching section, which has a Xp Rel slope of [ F 4 i] and an intercept of [ |: If x, = xp, then substituting in Eq, (9.88), we get 1 Ral | (Rt + 2D) = Yo (9.89) Ynet ive, when x, = Xp, Ynet = Ape Hence, this line passes through x = y = xp, ice. it lies on the diagonal. This x point on the diagonal and the y-intercept [#1] permit us the construction of operating line for enriching section. Let us consider the stripping section as shown in Fig. 9.19.Distillation 263 Yon Fig. 9.19 Stripping section. Material balance gives L=G+w (9.90) ‘A component balance for A gives, Vines + Way 9.91) -(£),,-(% Ymet =| fem oS Equation (9.93) describes the operating line for stripping section. The operating (9.92) (9.93) line has a slope of ( ) and an intercept of L-w Let us assume that x = xy (Reboiler) (9.94) ie, 3m = Ym +1 = tw Hence, the operating line passes through the point x = y = xw (Le. 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+lL+G=G+E (L-L)=(G-G)-F ie. (L-L) =(G-G)+F Enthalpy balance on feed plate gives F-Hp+L-Hy,,+G-Hg,,, =G-Hg, +L Hy, As an approximation, Hg, ~ Hey. = ic and Hy, = Hy, = Hy (E-L)H, = (G-G@)H, + FH e E-Dy, GD, on, Substituting for (L - L) from Eq. (9.97) we get [¢ °F = G- CO, Hp G- oe CO nn Hy = =O y+ H, ~ Hg) = (Hp ~ A) (G-@)]_ (Hy -H,) F (A, ~ Hg) Substituting for (G—G) from Eq. (9.97), we get (L-L)-F _ (Hp -H,) Fo (H, ~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 (E=L) _ (Hy ~ Hy) +1 (9.107) ie. _ (Hg - Hp) an H,) (9.108) (Hg - Hr) . . . Let us now define “2 “"F) as g, where q is the quantity of heat required to (Hg ~ 11) convert one mole of feed at its thermal condition to a saturated vapour, to the molal latent heat of vaporization. =) _ (He — Hr) 4° Fig -H,) (9.109) Similarly, @-) (9.110) ie. (G-G) = Fq-1) (9.111) A solute balance above feed plate gives Gy = Lx + Dxp (9.112) A solute balance below feed plate gives Gy = Lx - Way (9.113) Subtracting Eq. (9.112) from Eq. (9.113), we have (G-G)y =(E- L)x -(Dxp + Way) (9.114) Total component balance for the distillation column gives Fp = Dxp + Wr (9.115) Substituting Eqs. (9.109), (9.111) and (9.115) in Eq. (9.114), we get Fq- Wy = Fq-x~ Fe, y pares (9.116) Equation (9.116) is the equation for feed line. It has a slope of g/q — 1 and passes through y Zp. ‘The various values of slope obtained under different thermal conditions of feed are given below and shown in Fig. 9.21. 1. Cold feed | 2. Saturated liquid 3, Liquid + VAS or 4, Saturated vapour ‘7 & Sipe vat x— Fig. 9.21 Feed line for different thermal conditions of feed.266 Mass Transfer—Theory and Practice Feed condition | Gr| Le | Ho, | Hi, | Enthalpy of feed, Hr Liquid below | 0 | F | - | He | He< He >10 >1.0 boiling point Saturated liquid | 0 | F | - | He | He= 1.0 ° Liquid + vapour | Gr | Ly | He’ | Hi’ | Ho >He> Hi 1.000 Saturated vapour | F | 0 | He | - | Hr=Ho 0 0 ‘Superheated Flo|a| - Hp> He <0 10100 vapour * indicates Hg and H, are enthalpies pet mole of individual phases. Determination of q is as follows: () Cold feed From Eq, (9.109), we have _ (He -Hr) (Hg — Hy) 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.z is the specific heat of feed liquid and Tp is the reference temperature, then Hg =Cp(Ty-To) +4 Hy = Cp, (Tp — Tp) and (Hg — H,) =A (9.117) gx Cee=T)+ A= (Coats = TN _ (Coals ~ Yo ~Tr ~ Ho) +0 (9.118) ie. q=l +See“) (9.119) i) Saturated liquid For saturated liquid Hp = Hy, :- q= 10 ii) Mixture of liquid and vapour Let x be the mole fraction of liquid in feed in the case of liquid + vapour ‘mixture. Then, Hr = xH, + (1 - Hg (9.121)Distillation 267 [oe = *H), ~ Hg + xe] Therefore, a= (ig) 1. a AS ae (9.122) (iv) Saturated vapour (He - Hr) q= Ge-H) (9.123) For saturated vapour Hy = Ho, - (v) Superheated vapour Let Cpy be the specific heat of feed vapour Hg = He =0 Hr = He + Cpy (Tr - Ty) (9.124) ga Hee * Cour) ons) 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 Xo. Ret Al Ww XP XD x o% Fig. 9.22 Determination of number of stages by McCabe-Thiele method. 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. 4, 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 pe 01.0 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, xe 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.x— Fig. 9.23(c) Early feed entry.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 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. 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. 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 Rain +1 Normally at Ryn Condition, the number of stages will be infinity as the equilibrium curve and operating line get pinched. az it as S*. OS’ gives [ as | from which Rnin is estimated as shown in Fig. 9.24. VA 0 Xw Xp %> 1.0 x 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 qline from F and allow it to intersect the equilibrium curve at T’. 4, Join T’D and allow it to intersect the y-axis at S’. Yo. 5. OS’ corresponds of 225 from which Ry» the minimum reflux ratio 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. Hence, the operating line [Eq. (9.88)] for enriching section is J), Jo Yt =| Rat | * | ReT] becomes, Ya = he (9.126) .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 Ja xaJ|_| Lye We know that for a binary system, @4p = 2B 2a Xp Xp272 Mass Transfer—Theory and Practice Let us apply this relationship to (n + 1)th plate Yast Sash ee T= Yad T= Sead @.127 At total reflux D = 0 and £ =—_ = 1.0 a “Re” Hence, from Eq. (9.126), we get On+1) = Xn (9.128) When n = 0, ie. at the top of the column, x, = x9 1 = Xo = Xp, When total condenser is used. Substituting for y, ,, in terms of x, in Eq. (9.128), we get Seg Sas Ox) Ta Coen = —_=q,,—1 When n = 0, Tp a (9.130) When n = 1, Gq 9.131) Set ng When n=n-1, ds.) d-x,) (9.132) Substituting for x), 22, ..., X,-1 from Eqs. (9.131) and (9.132), we get a rs) =(@, 4B)" =a dex (9.133) Substituting n = Np + 1 (last stage, i.e. reboiler), we get =(q)Nett__2Nett d-~) Gaya (9.134) As (Np+ Lith stage accounts for reboiler, xype1 = Xy ; Yo = (qy¥ett _>w. ie, dy)” Tay) (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. ' Total cost . Operating cost g : Fat N4 _— Rpt Reflux ratio Fig. 9.25 Effect of Reflux ratio on cost. 9.15 REBOILERS ‘Thermosyphon reboiler 4 4-— Steam ‘Condensate Fig. 9.26(a) Thermosyphon reboiler.274° Mass Transfer—Theory and Practice Intemal reboiler | Bottom Fig. 9.26(b) Internal reboiler. aa 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.