BEE 499/599 Biofuel Feedstocks and Production

Distillation Fundamentals
Biological and Ecological Engineering Department, Oregon State University

Raoults Law
For a binary mixture: pA = PA xA and pB = PB xB and pA xA + pB xB = P
where pA ,pB and P are partial pressure of A, B and total system pressure respectively.
Also, xA + xB = 1, where xA and xB are mole fractions of A and B in the liquid
respectively.
Mole fraction of A and B in the vapor can be determined by:

yA =

pA
; yB =
P

pB
;
P

yA + yB =

pA + pB
=1
P

Relative volatility

AB =

yA /xA
yB /xB

yA /xA
(1yA )/(1xA )

For ideal mixtures which obey Raoults law perfectly,

AB =

yA /xA
yB /xB

(PA xA )/P
(PB xB )/P

PA
PB

Although theoretically separation is possible if > 1, mixtures are separated by simple

distillation only if > 1.05.

Distillation with Reflux: McCabe-Thiele Method

Assumptions:
1. Equimolar overflow through the tower between the feed inlet, top tray and feed inlet,
bottom tray.
2. Latent heats of the two components are equal.
3. Sensible heat differences are negligible.
4. Distillation column design can be divided into three stages:

V1,y1

V2,y2

L1,x1

L0,x0

Figure 1: Flash Distillation.

Before a complete distillation column can be analyzed, a counter current single stage of
a distillation column/ flash distillation equations will be instructive.
Overall mass balance around the nth tray:
Vn+1 + Ln1 = Vn + Ln

(1)

Vn+1 yn+1 + Ln1 xn1 = Vn yn + Ln xn

(2)

Component balance:
Distillation column can be divided into three sections namely, enriching section,
stripping section and feeding tray. Feeding tray is the tray/stage of distillation column
where the feed is introduced. Enriching section consists of the trays above the feed tray
and is so named because in this section, rising vapors are enriched in more volatile
component. Since liquid is stripped off of the more volatile component in the section below
feeding tray, it is called stripping section.

V1, y1

Condenser
y1= xD

L, xD

D, xD

Enriching
Section

F, xF

Stripping
Section

W, xW
R
Reboiler

Figure 2: Distillation Column.

In the analysis for the distillation column, each of these sections is considered
separately along with the distillation column as a whole. Overall mass balance and
component balance for the volatile component is performed for each section with the
assumptions made above. These equations are used to derive relationship between vapor
and liquid in each section and then correlated to the feed using energy balance. Quality of
the feed is determined by a q-line. This results in a set of equations describing the
operating lines for enriching and stripping sections. Intersection of these three lines on the
VLE diagram indicated the location of the feeding tray in the distillation columns.
1. Distillation column:
Overall mass balance around the distillation column:
F =D+W

(3)

F xF = DxD + W xW

(4)

Component balance:

V1, y1

y1= xD
L, xD

D, xD

2
n

Vn+1, yn+1 Ln, xn

n+1

Enriching Section

F, xF

Figure 3: Enriching Section.

2. Enriching section:
Overall mass balance around the control volume:
Vn+1 = D + Ln

(5)

Component balance:
Vn+1 yn+1 = DxD + Ln xn
D
Ln
xn +
xD
yn+1 =
Vn+1
Vn+1
Ln
Defining Reflux ratio,R =
D
Ln
R

=
Vn+1
R+1
1
D
=

Vn+1
R+1
R
1
yn+1 =
xn +
xD
R+1
R+1

(6)

(7)

Above equation (Eqn. 7) is the equation for the Rectification/enriching line.

F, xF
Stripping Section

Lm, xm

Vm+1, ym+1
m+1

W, xW
Rebo
boiler

Figure 4: Stripping Section.

3. Stripping section:
Overall mass balance around the control volume:
Vm+1 = Lm W

(8)

Vm+1 ym+1 = Lm xm W xW

(9)

Component balance:
ym+1 =

Lm
W
xm +
xW
Vm+1
Vm+1

The above equation defines the stripping line.

(10)

n+1
V, y

Ln+1, xn+1

F, xF
Vm, ym

L, x
m

Figure 5: Feed Tray.

4. Feed tray and Equation for q-line:
Heat needed to vaporize 1 mol of feed at entering conditions
Molar latent heat of vaporization of feed


HV HF
q =
HV HL

q =

(11)

Where,
HV is the molar enthalpy of the feed at dew point.
HL is the molar enthalpy of the feed at bubble (boiling) point.
HF is the molar enthalpy of the feed at the entering conditions.
q = 1 for feed (F) at boiling point. q > 1 for cold feed
Overall mass balance around the feed tray.
F + Ln+1 + Vm = V + L
Ln+1 L = V Vm F

(12)

Conducting energy balance around the feed tray.

V HV + LHL = Ln+1 HL + Vm HV + F HF
V HV Vm HV = (Ln+1 L)HL + F HF
Substituting Eqn. 12 and Eqn. 11 in the above Eqn.,

(13)

V (HV HL ) Vm (HV HL ) = F (HF HL )



HF HL
V Vm = F
HV HL
V Vm = (1 q)F
Vm V = (q 1)F

(14)

Substituting Eqn. 14 in Eqn. 12

L Ln+1 = qF

(15)

Based on the equimolar flow assumption, we can write

V1 = ...Vn = Vn+1 = V 6= Vm
Vm = Vm+1 ... = VN

L1 = L2 = ...Ln 6= L
L = Lm+1 = ...Lm = LN

Using the above Eqns. we can modify Eqn. 6 and 9 as

Vn+1 yn+1 = DxD + Ln xn V y = DxD + Ln+1 xn+1
Vm+1 ym+1 = Lm xm W xW Vm ym = Lx W xW
While equimolar assumption is valid for enriching and stripping section
separately, it is not valid for the feed tray section (i.e.V 6= Vm and L 6= Ln+1 ). In this
tray, feed is being added under different conditions as indicated by quality factor q.
Therefore, depending on the condition of the feed, varying amounts of vapor and
liquid will be added to the vapor and liquid flows from feed tray. Since the change in
composition of vapor and liquid will be continuous, we require y = ym and x = xn+1
ONLY for the feed tray.
With this additional requirement of continuous variation in composition, and we can
further simply the above equation as,
V y = Ln+1 x + DxD
Vm y = Lx W xW
(Vm V )y = (L Ln+1 )x (DxD + W xW )

(16)

Substituting Eqn. 4 in the above equation we obtain,.

(Vm V )y = (L Ln+1 )x F xF

(17)

Substituting Eqns. 14 and 15 in the above equation we obtain the q-line equation.
y=

q
1
x
xF
q1
q1

(18)

The three design equations needed for the design of distillation column can be summarized
as:
1
R
xn +
xD
R+1
R+1
W
Lm
xm +
xW
Stripping line: ym+1 =
Vm+1
Vm+1
q
1
q line: y =
x
xF
q1
q1
Enriching line: yn+1 =

(19)

Fenske Equation: Minimum Number of theoretical trays

Minimum number of steps/trays for distillation can be estimated from the following
expression.


xD 1xW
log 1x
D xW
Nmin =
(20)
logav

However, av is dependent on composition. For small variations in , av = 1 W , where

1 is the relative volatility of the overhead vapor and W is the relative volatility of the
bottoms liquid.
Minimum Reflux ratio
Minimum reflux ratio (Rmin ) occurs when the intersecting point between the enriching line
and q-line falls on VLE curve. Such a separation will require infinite steps/trays for
distillation of the feed.
Rmin
xD y
=
(21)
Rmin + 1
xD x
Where,
xD is the concentration of distillate.
x, y are the composition of the liquid and vapor at the point of intersection on the
VLE-curve.
Overall Tray Efficiency
The overall tray efficiency is defined as the ratio of number of ideal trays by number of
actual trays required for the separation.
EO =

Number of ideal trays

Number of actual trays

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Using McCabe-Thiele Method

Generally, McCabe-Thiele method is used as a graphical method for determining the
number of stages. However, many computer programs have been developed for automating
the same. One method for using McCabe-Thiele method on computer is explained below.
The three design equations needed for the design of distillation column are:
1
R
xn +
xD
R+1
R+1
Lm
W
Stripping line: ym+1 =
xm +
xW
Vm+1
Vm+1
q
1
q line: y =
x
xF
q1
q1
Enriching line: yn+1 =

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(24)

Before developing the algorithm for a computer code, various intersection points
between VLE curve and operating lines must be identified.
1. Intersection point of Enriching line and 450 line: xE = xD and yE = xD .
2. Intersection point of Stripping line and 450 line: xS = xW and yS = xW .
3. Intersection point of q line and 450 line: xq = xF and yq = xF .
4. Intersection point of Enriching line and q line: This can be determined by noting
that the coordinates (x, y) at intersection point will satisfy both enriching line and q
line equations.
yn+1 (Enriching line)
R
1

xn +
xD
R+1
R+1
xn (Enriching line)
1
R
xi +
xD

R+1
R+1
xi
yi

= y(q line) = yi(intersection point)

q
1
=
x
xF
q1
q1
= x(q line) = xi (intersection point)
q
1
=
xi
xF
q1
q1
xD
xF
+ R+1
q1
=
q/(q 1) R/(R + 1)
R
xD
=
xi +
R+1
R+1

(25)
(26)

Using the intersection points xi , yi and xS , yS , stripping line equation can be redefined as
follows.


yi yS
(x xS )
(27)
y yS =
xi xS

Substituting the values for xS , yS and simplifying, the stripping line equation in terms of
the intersection point between enriching line and q-line is:


yi xW
(xi xW )
(28)
y=
xi xW

Finally the design equations to be used for computer algorithm are:

1
R
x+
xD = E(x)
R+1
R+1
q
1
q line: y =
x
xF = Q(x)
q1
q1
xD
xF
+ R+1
q1
Intersection point: xi =
q/(q 1) R/(R + 1)
R
xD
Intersection point: yi =
xi +
R+1
R + 1

yi xW
(x xW ) = S(x)
Stripping line: y =
xi xW
Enriching line: y =

(29)
(30)
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Algorithm
1. Start.
2. Define VLE curve equation (yV LE = V LExy (x) and xV LE = V LEyx (y))for the
given binary system.
3. Define xF , xD , R and q
4. Define y = E(x), y = Q(x) and y = S(x) as the enriching, q and stripping line
equations respectively.
5. Determine the intersection point between q-line and enriching line (xi , yi).
6. Set y1 = xD and determine x1 = V LEyx (y1 ) as the liquid and vapor compositions of
the first stage.(first stage in enriching section stage)
7. Set y2 = E(x1 ) and determine x2 = V LEyx (y2 ) as the liquid and vapor
compositions of the second stage.
8. Set y3 = E(x2 ) and determine x3 = V LEyx (y3 ) as the liquid and vapor
compositions of the third stage.
9. Repeat the steps until xn xi . n is the location of the feed tray.
10. Set yn+1 = S(xn ) and determine xn+1 = V LEyx (yn+1 ) as the liquid and vapor
compositions of the n+1 stage (first stage in stripping section stage).
11. Set yn+2 = S(xn+1 ) and determine xn+2 = V LEyx (yn+2 ) as the liquid and vapor
compositions of the n+2 stage.
12. Repeat the steps until xN xW . Total number of stages is N.
13. Stop.
Example VLE equation for Ethanol-water binary system.
x = 185.08y 6 529.11y 5 + 565.45y 4 276.62y 3 + 61.605y 2 4.7299y
y = 95.619x6 + 277.54x5 315.154 + 178.27x3 52.662x2 + 8.0868x + 0.0148

Where, x and y are mole fraction of ethanol in liquid and vapor respectively.

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