Chapter 7

Distillation of Binary Mixtures

Chapter 7: Distillation of Binary Mixtures

Graphical Methods for Analyzing Binary Distillation

In Chapter 5: We described a graphical method for analyzing multistage separation systems which involved drawing operating lines and equilibrium curves and stepping off stages. This approach is equivalent to the algebraic method and group methods. This approach was demonstrated using absorption and stripping.

Todays lecture will focus on:

Extending these types of analysis to multisection cascades. We begin by describing a typical binary distillation column. We then describe the process generally and make important definitions. We perform mass balances to get operating lines. We plot equilibrium data to get an equilibrium curve. We step of stages noting the cross-over between sections.

Chapter 7: Distillation of Binary Mixtures

McCabe-Thiele Method for Trayed Towers

Absorption and stripping cascades are common methods for separating vapor and liquid mixtures. A more complete separation can be achieved by combining these processes into a binary distillation column.
L0 (absorbent) 1 2 Absorption N1 N LN VN+1 (vapor to be separated) L1
Total condenser Reflux drum Reflux Distillate

V1

LN+1 (liquid to be separated) N N1

VN

Stripping 2 1 V0 (stripper)

Distillation
Overhead vapor Rectifying section stages Feed Stripping section stages

1 2 f N

Feed Stage Boilup Partial reboiler Bottoms

Chapter 7: Distillation of Binary Mixtures

Distillation Column

Total condenser

Reflux drum Rectifying section stages Reflux Feed Feed Stage Distillate

Stripping section stages

Boilup

Bottoms Partial reboiler

Chapter 7: Distillation of Binary Mixtures

McCabe-Thiele Method for Trayed Towers

The general countercurrent-flow, multistage, binary distillation column shown below consists of A column of N theoretical stages A total condenser to produce a reflux liquid to act as an absorbent and a liquid distillate A partial reboiler to produce boilup vapor to act as a stripping agent and a bottoms product An intermediate feed stage. This configuration allows one to achieve a sharp separation, except in cases where an azeotrope exists where one of the products will approach the azeotropic concentration. Distillation
Overhead vapor Total condenser Reflux drum Reflux Distillate

The goal of distillation is to achieve a distillate rich in the light key and a bottoms rich in the heavy key.

Rectifying section stages Feed Stripping section stages

1 2 f N

Feed Stage Boilup Partial reboiler Bottoms

Chapter 7: Distillation of Binary Mixtures

McCabe-Thiele Method for Trayed Towers

The feed contains a more volatile component (the light key, LK) and a less volatile component (the heavy key, HK). At the feed temperature and pressure it may consist of a liquid, vapor or mixture of vapor and liquid. The feed composition is given by the light key mole fraction ZF. The bottoms composition is given by the LK mole fraction XB, whereas the distillate composition is given by the LK mole fraction XD. The difficulty in achieving the separation is determined by the relative volatility, between the LK=1, and the HK=2.
Total condenser

Distillation
Overhead vapor Rectifying section stages Feed (L/V) LK mole fraction zF Stripping section stages

Reflux drum Reflux Feed Stage Boilup Partial reboiler Bottoms LK mole fraction xB Distillate LK mole fraction xD

1,2 = K1 / K2
If the two components form an ideal solution then Raoults Law applies and:

1 2 f N

Ki = Pi s / P
The relative volatility is then just the ratio of the vapor pressures:
s s 1,2 = P 1 /P 2
Chapter 7: Distillation of Binary Mixtures

Only a function of T

As T increases (pressure incresaes), decreases until at some point it becomes equal to one and no separation is possible.
6

McCabe-Thiele Method: Equilibrium Curve

We can rewrite the relative volatility in terms of the mole fractions of the light key in a binary mixture as follows:
y (1 x1 ) y1 / x1 y1 / x1 = = 1 y2 / x2 (1 y1 ) / (1 x1 ) x1(1 y1 )

1,2 = K1 / K2 =

For close boiling point components the temperature, and thus will be nearly constant in the column. Solving for the mole fraction of the LK in the vapor gives: 1,2 x1 y1 = 1 + x1 ( 1,2 1) For components which do not have close boiling points will vary depending on composition. The equilibrium curve will appear similar to that of fixed , but wont fit the equation above for constant .
Equilibrium curve y1 45 line Increasing relative volatility y1 45 line

Chapter 7: Distillation of Binary Mixtures

x1

x1
7

Thermodynamic Considerations and Phase Equilibria: Binary Fluids

Tb(B)

Lets consider a binary mixture AB, where B is a heavy component (high boiling point) and A is a light component (low boiling point). A T-x phase diagram of AB mixture, where x is a mole fraction of component a might look like this at some constant pressure P. This phase diagram can be also transformed in y-x diagram where composition of vapour phase in terms of mole fraction of component A is plotted as function of the liquid phase composition.
Chapter 7: Distillation of Binary Mixtures

T1

T2 T3 T4 Tb(A)

x1 y4 y3

x2

x3 y1

x4 y2

y3 y4

xA

T4 T3

yA
y1

T2

T1

xA

Specifications for the McCabe-Thiele Method

Specifications F zF P Total Feed Rate Mole fraction composition of the feed Column operating pressure (assume uniform in column) Phase condition of the feed @P Vapor-liquid equilibrium curve for the binary @P Type of overhead condenser (total or partial) Mole fraction composition of the distillate Mole fraction composition of the bottoms Ratio of reflux to minimum reflux

xD xB R/Rmin Results D B Nmin Rmin R VB N

Distillate flow rate Bottoms flow rate Minimum number of equilibrium stages Minimum reflux ratio, Lmin/D Reflux ratio, L/D Boilup ratio, V/B Number of equilibrium stages Optimal feed- stage location Stage vapor and liquid compositions

Chapter 7: Distillation of Binary Mixtures

McCabe-Thiele Method: Column Mass Balance

A mass balance in the LK component around the column gives:
FzF = x D D + x B B

A total mass balance around the column gives:

F = D+ B

1 2
Feed (L/V)
F, zF

Reflux

Distillate D, xD

f N
Boilup Bottoms
B, xB

So we know that the mole fraction of the light key of the feed is between that of the distillate and bottoms:
z x F B D = F x x D B

If D, F, are zF, specified, then either xD or xB can be specified.

Chapter 7: Distillation of Binary Mixtures

10

McCabe-Thiele Method: Rectifying Section

The rectifying section extends from stage 1 to the stage just above the feed stage.

If we perform a material balance in the light key around the n stages of the rectifying section including the condenser:
Vn +1y n+1 = Ln x n + DxD
Feed (L/V)
ZF

1 n f N

Reflux Distillate L, xD= x0 xD

Boilup Bottoms

Which we can rearrange to find:

L D yn+1 = n x n + x Vn+1 Vn +1 D

xB

If L and V are constant in the column from stage to stage, then this is a straight line. L xn

1 n

Reflux Distillate L0, xD= x0 xD

Chapter 7: Distillation of Binary Mixtures

V yn+1

11

McCabe-Thiele Method: Constant Molar Overflow

If L and V are constant, then this is a straight line. This requires that: 9 The two components have equal and constant enthalpies of vaporization 9 The heat capacity changes are negligible compared to the heat of vaporization 9 The column is well insulated so heat loss is negligible 9 The pressure in the column is uniform 1 These conditions lead to the condition of constant molar overflow.
Feed (L/V)
ZF

yn+1 =

Ln D xn + xD Vn+1 Vn +1

Reflux

Distillate

n f N

L, xD= x0 xD

For this condition the amount of vapor transferred to the liquid stream in each stage is equal to the amount of liquid transferred to the vapor stream. Thus the liquid and vapor stream flow rates are constant in the entire section.
Chapter 7: Distillation of Binary Mixtures

Boilup Bottoms

xB

12

McCabe-Thiele Method: Rectifying Section Operating Line

yn+1 = Ln D xn + x Vn+1 Vn +1 D

In the case of constant molar overflow we can then drop the stage subscripts:

1
Feed (L/V)
ZF

Reflux

Distillate

y =

L D x + xD V V

We define this equation as the operating line of the rectifying section.

n f N

L, xD= x0 xD

Boilup Bottoms
xB

The liquid entering stage one is the reflux L and its ratio to the distillate L/D is the reflux ratio R. If we have constant molar overflow, then R is a constant and

L R L L/ D = = = V L + D L / D + D / D R +1
and

D D 1 = = V L + D R +1
Chapter 7: Distillation of Binary Mixtures

13

McCabe-Thiele Method: Operating Line

We can then rewrite:

y=

L D x + xD V V
1 n L, xn f
Reflux Distillate

as

y=

R 1 x+ xD R +1 R +1

If R and XD are specified then we can graph the line shown in the following plot.

xD= x0
V, yn+1

xD

y1 y2 y Equilibrium curve Rectifying Section Operating line Slope=L/V=R/(R+1)<1

y=

1 xD R +1
45 line

x
Chapter 7: Distillation of Binary Mixtures

x1

x0=xD
14

McCabe-Thiele Method: Stripping Section

The stripping section extends from the stage just below the feed stage to the bottom stage N. If we perform a material balance in the light key around the bottom stages of the rectifying section including the condenser we have:

Lx m = Vym +1 + Bx B
Which we can rearrange and use the constant molar overflow assumption to find:

L B y = x xB V V
Feed (L/V)

1 n f N

Reflux Distillate L, xD= x0 xD

We define this equation as the operating line of the stripping section. Since:

zF

Boilup Bottoms
xB

L=V + B
VB is called the boilup ratio.

Then

L V + B VB + 1 = = V VB V

VB =

V B

L xm

V ym+1

m+1 and

Boilup

y=

VB + 1 1 x x VB VB B

V, yB

This is also the operating line of the stripping section .

N
L, xN

Bottoms
B, xB
15

Chapter 7: Distillation of Binary Mixtures

McCabe-Thiele Method: Stripping Section

V +1 1 y= B x x VB VB B
If VB and XB are specified then we can graph this as the line shown in the following plot. L xm V ym+1
Boilup

m+1 N L, xN

V, yB
Bottoms

B, xB

Ym+1 y yN Stripping Section Operating Line Slope=L/V=(VB+1)/VB 45 line Equilibrium curve

yB

y=

VB + 1 1 x x VB VB B

x
Chapter 7: Distillation of Binary Mixtures
B

xN x

xm
16

Feed Stage Considerations

In determining the operating lines for the rectifying and stripping sections we needed the bottoms and distillate compositions and reflux and reboil ratios. The compositions can be independently specified, but R and VB are related to the vapor to liquid ratio in the feed.

Subcooled Liquid L

Bubble Point Liquid

Partially Vaporized L

V<V
L

V =V

V = VF + V

L> F+L V
Dew Point Vapor

L= F+L

L = L + LF

V = F +V

Superheated Vapor

V > F +V

Chapter 7: Distillation of Binary Mixtures

L=L

L<L

V
17

Feed Conditions
Consider the cases where the feed is not a supercooled liquid or a superheated vapor:
Mass balance around the reboiler: Mass balance around the condenser: Mass balance around the column: Vapor entering the rectifying section: Liquid entering the stripping section:

L = B +V V = D+ L VF + LF = D + B V = V + VF L = L + LF VF + L L = D + L V V = L + D VF
In other words, the vapor entering the rectifying section is the vapor entering the condenser minus the feed vapor flow rate.

Substitute this into the column balance: VF + L L = D + B Substitute in the reboiler balance:

So except in the cases where the feed is a supercooled liquid or superheated vapor the boilup is related to the reflux by the material balance:

V = L + D VF
Dividing by B gives the boilup ratio:

VB

V L + D VF = B B

Distillation operations can be specified by the reflux ratio or boilup ratio although the reflux ratio (or R/Rmin) is most often specified.
Chapter 7: Distillation of Binary Mixtures 18

The q-line
First, we define the parameter q by:

q=

LL F

Subtracting the two operating lines:

yV = Lx + Dx D
Gives:

minus

yV = Lx Bx B

y(V V ) = (L L)x + Dx D + BxB

Dx D + Bx B = Fz F

Using a material balance in the LK:

y(V V ) = (L L)x + Fz F
Using a material balance around the feed stage to elminate vapor flow rates:

F +V + L = V + L V V = F + L L
q z x F y= q 1 q 1
Chapter 7: Distillation of Binary Mixtures

y(F + L L) = (L L)x + Fz F

Simplifying and using the definition of q results in the q-line:

x = zF y = z F

The q-line has slope q/(q-1) and intercepts the 45 degree line at y=zF
19

Construction Lines for McCabe-Thiele Method

y
Equilibrium curve Rectifying Section: Operating line Slope=L/V=R/(R+1)<1

yN

q z x F y= q 1 q 1

q-line

y=

L D x + xD V V

45 line

Stripping Section: Operating line Slope=L/V=(VB+1) /VB

yB xB x=zF xD

y=

L B x xB V V

Chapter 7: Distillation of Binary Mixtures

20

Feed Stage Location Using McCabe-Thiele

Equilibrium curve 1 y 2 3 y 3 yN 4 yN 5 yB 4 2 Equilibrium curve 1

yB

xB

x=zF

xD

xB

x=zF

xD

Feed stage located one tray too low.

Feed stage located one tray too high.

Chapter 7: Distillation of Binary Mixtures

21

Construction Lines for McCabe-Thiele Method

Equilibrium curve 1 y 2

yN

4 yB xB x=zF xD

Chapter 7: Distillation of Binary Mixtures

22

Summary
This lecture: We extended the analysis used for absorption and stripping to binary distillation. We described a typical binary distillation configuration. We made definitions such as reflux ratio, constant molar overflow, etc. We described operating lines. We plotted the equilibrium curve. We stepped through stages to show the change in composition as you go through the column.

Next lecture well continue our discussion of binary distillation and the McCabe Thiele method.

Chapter 7: Distillation of Binary Mixtures

23