Fractional Distillation

Fractional Distillation
MCCABE-THIELE METHOD
Less rigorous, enthalpy data not required.
Adequate for many applications, more commonly use because
of its simplicity
Uses graphical solution for binary mixture on equilibrium
diagram (x-y plot).
The method involves the plotting on the equilibrium
diagram 3 straight lines:
the rectifying section operating line (ROL),
the feed line (also known as the q-line) and
the stripping section operating line (SOL).
 The enriching
section or
rectifying section
of the column are
the stages (and
condenser) above
the feed stage.

 The stripping
section of the
column are the
stages (and
reboiler) below the
feed stage.

 The feed section of

the column is the
stage at which the
feed introduced
into the column
The McCabe-Thiele method is based on the assumption of
constant molar overflow which requires that:

•The molar heats of vaporization of the feed components are

equal

•For every mole of liquid vaporized, a mole of vapour is

condensed

•Heat effects such as heats of solution and heat transfer to and

from the distillation column are negligible.

•Uses constant molar overflow assumptions.

The Graphical Steps of the McCabe-Thiele Method
1. Draw the x-y diagram for the binary mixture of interest at
the operating pressure of the distillation column. Typically
y and x refer to the mole fraction of the light component.
2. Draw the 45-degree line.
3. Draw the feed line based on the quality (or energy content
of the feed).
4. Place the desired bottoms composition, xB, and the desired
distillate composition, xD, on the x-axis.
5. For a specified reflux ratio, R, draw the 'rectifying' line.
This rectifying line begins at the point xD on the 45-degree
line and has a slope of R / (R+1).
6. Draw the 'stripping' line by connecting the intersection of the
feed line and the rectifying line and the point xB on the 45-
degree line. This intersection and xB uniquely fix the stripping
line and thus its slope. We usually denote the slope of this line
by (S+1) / S where s is the vapor boil-up ratio.

7. Beginning at the point xD on the rectifying line, draw a

horizontal line to the equilibrium curve and then a vertical line
to the operating (rectifying or stripping) line.

8. Repeat step 7 forming a staircase until you reach or pass the

point xB on the 45-degree line.

9. Each point where the staircase intersects the equilibrium

curve denotes one stage in the column.
Rectifying Section Operating Line
Material balance around the envelope shown:
Overall Balance (Total): Vn+1 = Ln + D
Component Balance (MVC): Vn+1yn+1= Lnxn + D xD
Thus, we have
(Ln + D) yn+1 = Lnxn+ D xD
Under constant molal overflow assumption:
L1 = L2= .......... Ln-1 = Ln = Ln+1 = L = constant
V1 = V2= ......... Vn-1 = Vn = Vn+1 = V = constant
The subscripts can be dropped. Thus, the equation simplifies
to:
(L + D) yn+1 = L xn + D xD
Re-arranging in the form y = f(x), we have

𝐿 𝐷
𝑦𝑛+1 = 𝑥𝑛 + 𝑥𝐷
𝑉 𝑉
Reflux Ratio (R )
A reflux stream is a stream that essentially recycles a
portion of the vapor product stream back to the
"highest" drum (stage).

Introducing Reflux Ratio R = L / D,

𝐿 𝐷
𝑦𝑛+1 = 𝑥𝑛 + 𝑥𝐷
𝐿+𝐷 𝐿+𝐷
𝐷𝑖𝑣𝑖𝑑𝑖𝑛𝑔 𝑏𝑦 𝐷
𝐿 𝐷
𝑦𝑛+1 = 𝐷 𝑥𝑛 + 𝐷 𝑥𝐷
𝐿 +𝐷 𝐿 +𝐷
𝐷 𝐷 𝐷 𝐷
𝑅 1
𝑦𝑛+1 = 𝑥𝑛 + 𝑥𝐷
𝑅+1 𝑅+1
 This is the Operating Line Equation for the rectifying
section line in short.
 Characteristics:
 Straight Line Equation
 Slope R/(R+1), or L/V constant for given value of R
 Intercept (1/R+1) xD, constant for given R and purity
of distillate xD

In addition, if xn = xD, then yn+1 = xD.

Thus, the operating line passed through the point (xD, xD)
on the 45o diagonal line.
The operating line connects the concentrations of the more
volatile component in the vapour and liquid between 2
adjacent phases. By plotting the operating line on the
equilibrium curve, we can graphically construct using the
"staircase" construction to determine the number of theoretical
stages required for the separation in the rectifying section.
Explained in the figure.
 FEED SECTION OPERATING LINE (Q-LINE)
Figure below is explained for a feed tray and consider F
moles/hr of feed, with fraction q of liquid; thus
Consider the section of the distillation column (see the Figure
below) at the tray where the feed is introduced (known as the
feed tray location), say tray f :

Source: http://www.separationprocesses.com/Distillation/DT_Chp04j.htm

The feed may consists of liquid, vapour or a mixture of

both. The quantities of the liquid stream and vapour stream
in the rectifying and stripping sections may change abruptly
because of the addition of the feed strReC a13m
53,
Definition:
q = The moles of liquid flow in the stripping section that results from the
introduction of each mole of feed.

𝑕𝑒𝑎𝑡𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑𝑡𝑜𝑐𝑜𝑛𝑣𝑒𝑟𝑡 1 𝑚𝑜𝑙𝑒𝑓𝑒𝑒𝑑𝑡𝑜𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑𝑣𝑎𝑝𝑜𝑢𝑟
𝑞=
𝑚𝑜𝑙𝑎𝑟𝑕𝑒𝑎𝑡𝑜𝑓𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛𝑜𝑓𝑡𝑕𝑒𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑𝑙𝑖𝑞𝑢𝑖𝑑

𝑛𝑜𝑜𝑓𝑚𝑜𝑙𝑒𝑠𝑜𝑓𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑𝑙𝑖𝑞𝑢𝑖𝑑𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑𝑜𝑛𝑡𝑕𝑒𝑓𝑒𝑒𝑑𝑝𝑙𝑎𝑡𝑒
𝑞=
𝑚𝑜𝑙𝑒𝑠𝑜𝑓𝑓𝑒𝑒𝑑𝑎𝑑𝑑𝑒𝑑𝑡𝑜𝑡𝑕𝑒𝑑𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑖𝑜𝑛𝑡𝑜𝑤𝑒𝑟
 The value of q can be controlled by adjusting the amount of preheat the
feed stream is subjected to before entering the column.
 For different feed conditions, q has the following numerical limits:
 Cold feed (below bubble point) q > 1
 Feed at bubble point (saturated liquid) q = 1
 Feed partially vapour 0 < q < 1
 Feed at dew point (saturated vapour) q = 0
 Feed superheated vapour q < 0
 If the feed is a mixture of liquid and vapour, then q is the fraction of the
feed that is liquid. For example, if a feed is 25% liquid and 75% vapour,
then q = 0.25.
RC 1353, Dr. Venkata Subrahmanyam
Chunduri, Dr. D N V Satyanarayana
liquid flow = q F moles/hr
vapour flow = (1-q) F moles/hr
Overall material balance:
L' = L + q F; L - L' = - q F
V = V' + (1-q) F ; V - V' = (1 - q ) F
Rectifying section operating line: V y = L x + D xD--------1
Stripping section operating line: V' y = L' x - B xB-----------2
Subtracting 2-1;(V - V') y = (L - L' ) x + D xD + B xB
At the feed point where the two lines operating lines intersect:
Substituting
V - V' = (1 - q ) F and L - L' = - q F
In addition, from component balance around the entire column:
F xF = D xD + B xB
Thus, (1 - q ) Fy = - q F x + F xF;
(1 - q ) y = - q x + xF
Re-arranging in the form y = f(x), we have:
𝑞 1
𝑦= − 𝑥+ 𝑥F
1−𝑞 1−𝑞
 For a given feed condition, xF and q are fixed, therefore the
q-line is a straight line with slope -q / (1-q) and intercept xF /
(1-q).
 The diagonal line is y=x, both line will meet at one point , to
find the point of intersection, put first x=y; y = xF
 Then put y = x , then x = xF
 i.e. the q-line passes through the point (xF, xF) on the 45o
diagonal.
 Different values of q will result in different slope of the q-
line.
 Note that the q-line passes through the point (xF, xF) on the
45o diagonal for all values of q.
Calculating q
 q can be interpreted as the heat required to convert 1 mole of
feed from its entering condition to a saturated vapour; divided
by the molal latent heat of vaporization.

 Based on this definition, we can derive the formula for the

case whereby q > 1 (cold liquid feed) and q < 0 (superheated
vapour feed).
 Thus, we have for cold liquid feed,
𝐶𝑝,𝑙 𝑇𝑏𝑝 − 𝑇𝐹 + 𝜆
q=
𝜆
 and for superheated vapour feed,
𝐶𝑝,𝑣 𝑇𝐹 − 𝑇𝑏𝑝
q= −
𝜆
Where Tbp is the bubble point, and Tdp is the dew point of the
feed respectively.
q-line slopes
 The parameter q is the mole fraction of liquid in the feed
and
 the slope of the q-line is:-q / (1-q).
 For example, if the feed is a saturated liquid it has no vapor,
thus q = 1 and the slope of the q-line is infinite which
means the line is vertical. As another example, if the feed is
all saturated vapor, q = 0 and the slope of the q-line is 0
which means that the line is horizontal.
 Some example q-line slopes are presented in Figure.
q-line slopes
  Stripping Section Operating Line
 Analysis of the stripping section is not really required, as
SOL can be automatically fixed once ROL and q-line are
drawn.
 The SOL is the last line to draw, by connecting xB on the
diagonal to the point of intersection between the ROL and
q-line. With ROL fixed, when the q-line changes the SOL
changes as well.

RC 1353, Dr. Venkata Subrahmanyam

 Assuming constant molal overflow
 L'm = L'm+1= .... = L' = constant
 V'm = V'm+1= ..... = V' = constant
 Material balance:
Overall : L' = V' + B'
 MVC : L' xm = V' ym+1 + B xB
 Substituting, and re-arrange in the form y = f(x), we obtain
𝐿′ 𝐵
 𝑦𝑚+1 = 𝑥𝑚 − 𝑥𝐵
𝑉′ 𝑉′

 Again, dropping the subscripts "m+1" and "m" we have:

𝐿′ 𝐵
 𝑦= 𝑥− 𝑥𝐵
𝑉′ 𝑉′
  Substituting V' = L' - B: we have the stripping operating line
𝐿′ 𝐵
𝑦= ′
𝑥− ′ 𝑥𝐵
𝐿 −𝐵 𝐿 −𝐵
 This is straight line with slope ( L' / (L' - B)) and intercept
( B xB / L' - B )
 In addition, when x = xB , y = xB, i.e. the operating line
passed through ( xB, xB ) on the 45o diagonal line.
 Using the equilibrium diagram, the stripping section
operating line can be drawn and the number of theoretical
stages in the stripping section can be done in the same
manner.
 Reminder: The last "stage" on the graphical construction
represents the reboiler.
 The first step is to draw equal sized vertical and
horizontal axes of a graph.
 Draw the 45 degree line.
 Then draw the equilibrium line using the VLE data points
 draw vertical lines from the horizontal axis up to the x = y
line for the feed and for the desired compositions of the top
distillate product and the corresponding bottoms product.

 draw the operating line for the rectifying section (the

section above the feed inlet) of the distillation column.
 Draw the operating line for feed line.
• Draw the 'stripping' line by connecting the intersection of
the feed line and the rectifying line and the point xB on the
45-degree line.
• Beginning at the point xD on the rectifying line, draw a
horizontal line to the equilibrium curve and then a vertical
line to the operating (rectifying or stripping) line.
• Repeat the above step forming a staircase until you reach or
pass the point xB on the 45-degree line.
• Each point where the staircase intersects the equilibrium
curve denotes one stage in the column.
• The number of stages can be counted from the graph.