EXAMPLE 1: McCabe-Thiele Method and Stage Efficiency in Binary Distillation In this example, we utilize our MATLAB code to visualize

the McCabe-Thiele graphical equilibrium-stage method and determine overall efficiency in a distillation process for a binary mixture of A and B. It consists of i) constructing the equilibrium curve, ii) drawing operating lines and feed line, iii) displaying the equilibrium stages, and iv) illustrating stage and overall efficiency. We use the commands plot and movie in MATLAB1 to visualize and animate the diagrams. i) Equilibrium Curve % Selection iflag = 0 : constant alpha % = 1 : use Antoine Eqn for x-y data % = 2 : read x-y data iflag=input('0 for constant alpha, 1 for Antoine Eq., 2 for actual data ') Three ways of determining the equilibrium relationship between liquid and vapor phases are introduced. First, if a constant relative volatility, AB =

KA y /x = A A where KA and KB are the KB yB / xB

volatility of A and B, respectively is assumed, the vapor composition yA can be determined at a given liquid composition, xA

yA =

AB xA 1 + xA ( AB 1)

(1.1)

Secondly, thermodynamic models can be used to determine the equilibrium relationship. If the component A and B form an ideal mixture, and the vapor pressure for the pure compounds,

Pi sat can be obtained from the Antoine equation2

log10 Pi sat = Ai

Bi t + Ci

(1.2)

where Ai, Bi and Ci are Antoine constants for component i. Using the function fzero in
B

sat MATLAB1 which finds a zero of a given function, a temperature that satisfies PA + PBsat = Ptotal

can be determined for a liquid composition xA and xB. The vapor composition then is calculated
B

from Daltons law and Raoults law: 2

sat PA yA = xA Ptotal

(1.3)

Finally, the liquid and vapor compositions, xA and yA can directly be read from the actual data. With the liquid and vapor compositions in equilibrium xA and yA, the equilibrium curve, i.e. the y x diagram is plotted. figure(1), clf for i = 1:itotal xnew=x+dx; if iflag==0 % Contant alpha ynew=a*xnew/(1+xnew*(a-1)); elseif iflag==1 % Using Antoine Eq. (2) t=fzero('antoine',tguess,optimset('disp','iter'),xnew,a1,b1,c1,a2,b2,c2,Ptotal); tguess=t; ynew=pvapor(a1,b1,c1,t)/Ptotal*xnew else % Actual Data xnew=xdata(i+1); ynew=ydata(i+1); end plot([x,xnew],[y,ynew],'b','LineWidth',2) % Plot y vs. x diagram (eq. curve) hold on title('McCabe-Thiele Method') xlabel('x') ylabel('y') axis([0 1 0 1]) axis('square') plot([x xnew], [x xnew], 'b--','LineWidth',2) hold on Frames(:,i)=getframe; x=xnew; y=ynew; end

ii) Operating Lines and Feed Line Under the assumption of constant molar overflow, i.e. constant molar liquid and vapor rates, L and V in the rectifying section (and L and V in the stripping section), the operating lines for the rectifying and stripping sections can be displayed using

 R 1 y = x+ xD R +1 R +1
V +1 1 y = B x xB VB VB

(1.4)

(1.5)

where R = L/D and VB = V / B are the reflux ratio and boil-up ratio, and D and B are the distillate and bottoms product rate, respectively. In Eqs. (1.4) and (1.5), xD and xB are the overhead product and bottom product composition, respectively. Meanwhile, the q-line which describes the feed condition can also be displayed using q zF y = x q 1 q 1 where q = (1.6)

LL is the ratio of the increase in molar flux rate across the feed stage to the molar F

feed rate, F, and zF is the feed composition. Once any two of these three parameters, the reflux ratio, R, boil-up ratio VB and feed condition q are specified, the operating lines from Eqs. (1.4) and (1.5), and the q-line from Eq. (1.6) are uniquely determined. iii) Theoretical Equilibrium Stages Once the equilibrium curve, operating lines and feed line are drawn, the equilibrium composition at each stage is determined by the McCabe-Thiele method. Starting from the distillate xD (or bottoms product xB), the procedure for plotting the graphical solution is as follows: a. Draw a horizontal line from (xD, xD) to the equilibrium curve b. Drop a vertical line to the operating line c. Repeat a and b until x reaches xB. When actual data is used for the equilibrium curve, the Matlab interpolation function called interp1 is used to find the intersection points in procedure a.1 The transfer in the operating line from the rectifying section to stripping section is made when the liquid composition, x passes that of the intersection of the two operating lines and feed line.

while x >= x_B % loop for stepping ynew=y % using constant alpha for eq. relation if iflag==0 xnew=ynew/(a-ynew*(a-1)); % using Antoine Eq. (2) for eq. relation elseif iflag==1 t=fzero('antoine2',tmid,optimset('disp','iter'),ynew,a1,b1,c1,a2,b2,c2,Ptotal); xnew=ynew*Ptotal/pvapor(a1,b1,c1,t); % using actual data for eq. relation else xnew=interp1(ydata,xdata,ynew); end plot([x,xnew],[y,ynew],'r','LineWidth',2) % a. Draw a horizontal line to the eq. curve hold on Frames(:,i)=getframe; pause i=i+1; x=xnew if x >= x_c %if x >= z % using the op. line for rectifying section y=LoverV_D*x+x_D/(R+1) else % using the op. line for stripping section y=LoverV_B*x-x_B/V_B end plot([xnew,x],[ynew,y],'r','LineWidth',2) % b. Draw a vertical line to the op. line hold on Frames(:,i)=getframe; pause % calculating # of stages if x >= x_B nstage=nstage+1 else nstage=nstage+x/x_B end end % c. Repeat a and b until x reaches x_B

iv) Stage and Overall Efficiency Using the Murphree vapor efficiency, EMV for each stage, the actual vapor composition can be obtained as2,3 yi = yi +1 + EMV ( yieq yn +1 ) (1.7)

where i+1 is the stage below and yieq is the composition in the vapor in equilibrium with the

liquid composition leaving stage i, xi. The overall efficiency, Eo is determined by the ratio of the number of the theoretical equilibrium stages to that of the actual stages, i.e. Eo = N t / N a .
REFERENCES

1. Pratap, R., Getting Started with MATLAB, A Quick Introduction for Scientists and Engineers (Oxford University Press, 2002). 2. McCabe, W. L., Smith, J. C. and Harriott, P., Unit Operations of Chemical Engineering (McGraw Hill, 6th ed., 2000) 3. Seader, J.D. and Henley, E.J., Separation Process Principles (John Wiley & Sons, 1998)

Obtain equilibrium data

Thermodynamic Input Constant relative volatility/ Antoine equation/ Actual data

Step 1: Display y vs. x diagram (eq. curve)

Design Input Reflux ratio & feed condition or Reflux ratio & boilup ratio or Boilup ratio & feed condition

Step 2: Display operating lines and feed line

Step 3: Determine theoretical equilibrium stages, Nt Horizontal line to equilibrium curve Vertical drop to operating line
Design Input

Murphree vapor efficiency, Emv

Step 4: Display new stepping based on Emv

Determine actual stages Na and overall efficiency Eo

Figure 1.1. Flow chart of Example 1: graphical method for binary distillation
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Figure 1.2. Snap shots of graphical output of Example 1: McCabe-Thiele method for binary distillation of acetone and toluene. a) Equilibrium curve from Antoine equations, b) operating lines and feed line for zA = 0.5, xD = 0.95, xB = 0.05, q = 0.5, R = 2, c) theoretical equilibrium stages, and d) actual stages (shown in dashed line) with Emv = 0.7.
B