September 16, 2014

Prof. Pablo Traverso

Chemical Engineering Department
Polytechnic University of Puerto Rico

Dear Prof. Traverso,

Regards,

Francisco Rojas Roln # 73416

Ian Rodriguez Rivera #46633
Juan Rosario Mercedes #66752
Tatiana Rosario Falcn #75094

Polytechnic University of Puerto Rico

Hato Rey, Puerto Rico
Mass Transfer Unit Operations Laboratory
FA 2015
CHE 4131-22

Determination the efficiency of a distillation

column as a function of reflux ratio, using a
solution (Ethanol-Water).

Francisco Rojas Roln # 73416

Ian Rodriguez Rivera #46633
Juan Rosario Mercedes #66752
Tatiana Rosario Falcn #75094
Laboratory Date: September 23, 2015
Report Due Date: October 7, 2015

ABSTRACT

Table of Contents
ABSTRACT..................................................................................................................ii
OBJECTIVES..............................................................................................................1
THEORY......................................................................................................................2
Distillation......................................................................................................................2
Different types of distillation......................................................................................2
Raoults Law....................................................................................................................5
McCabe-Thiele Method for trayed towers...................................................................7
Rectifying Section...........................................................................................................8
Feed Section Operating Line (q-line).......................................................................11
Stripping Section..........................................................................................................16

EQUIPMENT.............................................................................................................20
EXPERIMENTAL DATA..........................................................................................22
NOMENCLATURE...................................................................................................25

List of Figures
Figure 1: FLASH VAPORIZATION

PROCESS DIAGRAM...............................................3

Figure 2: DIFFERENTIAL DISTILLATION

Figure 3: FRACTIONATOR

PROCESS DIAGRAM..................................4

WITH TOTAL CONDENSER AND PARTIAL REBOILER....5

Figure 4: RAOULT LAW EQUILIBRIUM

CURVE..........................................................7

Figure 5: CONTROL VOLUME FOR RECTIFYING

SECTION.......................................9

Figure 6: MCCABE-THIELE OPERATING LINE FOR THE RECTIFYING

SECTION. 10

Figure 7: MASS BALANCE AROUND FEED PLATE.

(WWW.SEPARATIONPROCESSES.COM )..............................................................12
Figure 8: COMPONENT BALANCE

FOR THE MORE VOLATILE COMPONENT .

(WWW.SEPARATIONPROCESSES.COM )..............................................................13
Figure 9: GRAPHICAL
CONDITIONS

INTERPRETATION FOR Q- LINE FOR TYPICAL FEED

(Benitez, 2009)..............................................................................16

Figure 10: STRIPPING SECTION DIAGRAM (Benitez, 2009)...................................17

Figure 11: DETERMINATION OF NUMBER OF EQUILIBRIUM
STAGE LOCATION.

STAGES AND FEED

(www.separationprocesses.com).......................................20

List of tables

TABLE 1: Q-VALUE FOR DIFFERENT CONDITIONS. (Benitez, 2009)....................11

OBJECTIVES

The following Objectives were:

1. Determine the variation with boil-up rate of pressure drop over the distillation
column.
2. Use a refractometer to determine mixture compositions.
3. Determine the overall column efficiency.
4. To carry out a distillation at constant reflux ratio, varying top and bottom
compositions with time.
5. Investigate the steady state distillation of a binary mixture under continuous
operation.
6. To investigate the effect of varying the feed position under continuous
operation.

THEORY

Distillation
Distillation is a process in which the components of a substance or liquid mixture are
separated by heating it to a certain temperature and condensing the resulting vapors.
Some substances have components that vaporize at different temperatures and thus can
be separated by condensing their vapors in turn. Distillation is also used as a
purification process in which non-volatile components are separated from volatile ones.
Distillation is most frequently carried out in multitray columns, although packed
columns have long been the preferred alternative when pressure drop is an important
consideration.

Different types of distillation

Flash vaporization is a single-stage operation where in a liquid mixture is partially
vaporized, the vapor is allowed to come to equilibrium with the residual liquid, and the
resulting vapor and liquid phases are separated and removed from the apparatus. It may
be batch or continuous. A typical flow sheet is shown schematically in Figure 1 for
continuous operation. The liquid feed is heated in a conventional tubular heat
exchanger. The pressure is then reduced, vapor forms at the expense of the liquid
adiabatically, and the mixture is introduced into a vapor-liquid separating vessel. The
liquid portion of the mixture leaves at the bottom of the separating vessel while the
vapor rises and leaves at the top.

Figure 1: FLASH VAPORIZATION PROCESS DIAGRAM

Another type of distillation is the differential distillation. In here, a batch of liquid is

charged to a kettle or still fitted with some sort of heating device as in Figure 2. The
charge is boiled slowly and as rapidly as they form the vapors are withdrawn to a
condenser, where they are liquefied.

The condensate (distillate) is collected in a

receiver. The first portion of the distillate would be the richest in the more volatile
substance. As the distillation proceeds, the vaporized product becomes leaner. The
distillate can, therefore, be collected in several separate batches, called cuts, to give a
series of distilled products of various purities.

Figure 2: DIFFERENTIAL

DISTILLATION PROCESS DIAGRAM

Continuous Rectification: Binary system is other type of distillation. It is a multistage,

countercurrent distillation operation. For a binary solution, with certain exceptions, it is
ordinarily possible by this method to separate the solution into its components,
recovering each in any state of purity desired. The operation consists of a column
containing the equivalent of N theoretical stages arranged in a two-section cascade; a
total condenser in which the overhead vapor leaving the top stage is totally condensed
to give a liquid distillate product and liquid reflux that is returned to the top stage; a
partial reboiler in which liquid from the bottom stage is partially vaporized to give a
liquid bottoms product and vapor boil-up that is returned to the bottom stage; and an
intermediate feed stage. The feed, which contains a more volatile component-the light
key, LK and a less volatile component-the heavy key, HK enters the column at a feed
stage, f. At the feed stage pressure, the feed may be liquid, vapor, or a mixture of liquid
and vapor, with its overall mole fraction composition with respect to the light
component denoted zF. Vapor rising in the section above the feed (called the enriching
or rectifying section) is washed with liquid to remove or absorb the heavy key. In the

section below the feed (stripping or exhausting section), the liquid is stripped of the
light key by the rising vapor. The mole fraction of the light key in the distillate is x D,
while the mole fraction of the light component in the bottoms product is x w. Inside the
tower, the liquids and vapors are always at their bubble points and dew points,
respectively, so that the highest temperatures are at the bottom, the lowest at the top.
The entire device is called fractionator. Figure 3 shows this process.

Figure 3: FRACTIONATOR WITH TOTAL

CONDENSER AND PARTIAL REBOILER

Raoults Law
Raoult's law is a law of thermodynamics established by French chemist Franois-Marie
Raoult in 1882. Raoult's law states that the vapor pressure of a solvent above a solution

is equal to the vapor pressure of the pure solvent at the same temperature scaled by the
mole fraction of the solvent present. Raoult's law for a single component in an ideal
solution is stated as:
y a P=X A P A

(1)

Where:

PA is the vapor pressure of pure A at the equilibrium temperature

P is the equilibrium pressure
YA is the concentration of A in vapor
XA is the concentration of A in liquid

If the liquid phase does not behave ideally, a modified form of raoults law is:
y a P=X A A P A

(2)

Where;

A is the activity coefficient of species A in solution.

Using the Wilson equation to calculate the activity coefficients the equation obtained is:

ln A =ln ( x A + x B 12 ) + x B

12
21

x A + x B 12 x B + x A 21

(3)

Where,
ij =

[ ]

aij
Vi
exp
Vj
RT

Where,

Vi and Vj are the molar volumes at temperature of pure liquids

T is the temperature

(4)

aij

is a constant independent of composition and temperature

To obtain the constant independent of the temperature for a binary system the equation
is the following:

aij =

PA A
PB B

(5)

To draw the equilibrium curve for a binary solution in the equation 6 assumes values
for xA to obtain the value of yA to draw the equilibrium line.
y a=

a AB X A
1+(a AB1) X A

(6)

Figure 4: RAOULT LAW EQUILIBRIUM

CURVE

McCabe-Thiele Method for trayed towers

McCabe and Thiele (1925) developed an approximate graphical method for combining
the equilibrium-distribution curve for a binary system with operating-line curves for the
rectifying and stripping sections of a fractionator to estimate, for a given feed mixture
and column operating pressure, the number of equilibrium stages and the amount of
reflux required for a desired degree of separation of the feed. The graphical nature of
the McCabe-Thiele method greatly facilitates the visualization of many of the important
aspects of multistage distillation.
The McCabe-Thiele method hinges upon the fact that, as an approximation, the
operating lines on the xy diagram can be considered straight for each section of a

fractionator between points of addition or withdrawal of streams. This is true only if

the total molar flow rates of liquid and vapor do not vary from stage to stage in each
section of the column. This is the case if:
The two components have equal and constant molar latent heats of vaporization.
Sensible enthalpy changes and heat of mixing are negligible compared to latent heats of
vaporization.
Heat losses are negligible.
The pressure is uniform throughout the column (negligible pressure drop)

Rectifying Section
The rectifying section extends from the top stage, to just above the feed stage, , as
shown in figure 3. Consider a top portion of the rectifying stages, including the total
condenser.

Figure 5: CONTROL VOLUME FOR RECTIFYING

SECTION

A material balance for the light key over the envelope shown in figure 4 for the total
condenser and stages l to n is as follows.
V n+1 y n+1=D x D + Ln x n

y n+1=

Ln
D
x+
x
V n +1 n V n+ 1 D

(7)

(8)

For constant molar overflow, Vn+1, = V = constant; Ln = L = constant and equation two
can be written as:
y n+1=

L
D
xn+ xD
V
V

(9)

Equation 3 is the operation line for the rectification section using the flows.

The liquid entering the top stage is the external reflux rate, Lo, and its ratio to the
distillate rate, Lo/D, is the reflux ratio, R. For the case of a total condenser, with reflux
returned to the column at its bubble point, L o = L and R = L/D, a constant in the
rectifying section. Since V= L + D:
L
L
L
D
R
=
=
=
V L+ D
L
R+1
D+1

(10)

D
D
1
1
=
=
=
V L+ D
L
R+1
D+1

(11)

Combining equations 3, 4 and 5.

y=

R
1
x+
x
R+1
R+ 1 D
(12)

10

Equation 6 is the operation line for the rectification (ROL) section using the reflux
ratio.
If values of R and xD are specified, equation 6 plots as a straight line on the xy diagram
with intersection at y= xD on the 45 line, slope= R/(R + l), and intersection at y= x D /
(R + 1) for x = 0.

Figure 6: MCCABE-THIELE OPERATING

LINE FOR THE RECTIFYING SECTION

As shown in figure 5 the operating line connects the concentrations of the more volatile
component in the vapor 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.
The method starts off by identifying the point x D on the diagonal. Starting from (x D, y1)
on the diagonal, where y1 = xD, draw a horizontal line to the left until it touches the

11

equilibrium curve: this gives the point (x 1, y1). From this point (x1, y1) draw a vertical
line down to the rectifying operation line (ROL). This gives the point (x 1, y2). In this
manner we had obtained one triangle where the horizontal distance is (x D - x1) and the
vertical distance is (y1 - y2). One triangle is equivalent to one theoretical tray.
The difference (xD - x1) represents the decrease in the concentration of the more volatile
component in the liquid phase as its moves down one tray, from tray 1 to tray 2. The
difference (y1 - y2) represents the increase in the concentration of the more volatile
component in the vapour phase as its moves up one tray, from tray 2 to tray 1.

Feed Section Operating Line (q-line)

Determination the feed condition (q):
The feed enters the distillation column may consists of liquid, vapor or a mixture of
both. Some portions of the feed go as the liquid and vapor stream to the rectifying and
stripping sections. The moles of liquid flow in the stripping section that result from the
introduction of each mole of feed, denoted as q. The limitations of the q-value as per
feed conditions are shown in Table 1. [4]

TABLE 1: Q-VALUE FOR DIFFERENT CONDITIONS. (Benitez, 2009)

Feed condition
Subcooled liquid
Bubble-point liquid

q-value
>1
1

12

LF
V
=1 F
F
F

Partially vaporized
Dew-point vapor
Superheated vapor

0
<0

For Obtain the q value a mass balance for the more volatile component is
necessary. See the Figure below for a feed tray and consider F moles/hr of feed,
with fraction q of liquid.

Figure 7: MASS BALANCE AROUND FEED PLATE.

(WWW.SEPARATIONPROCESSES .COM)
Liquid flow = q F moles/hr
Vapor flow = (1-q) F moles/hr

Overall material balance:

L' = L + q F

(13)

V = V' + (1-q) F

(14)

13

Figure 8: COMPONENT BALANCE FOR THE MORE VOLATILE COMPONENT .

(WWW.SEPARATIONPROCESSES .COM )
Rectifying section:

V y = L x + D xD

(15)

Stripping section:

V' y = L' x - B xB

(16)

At the feed point where the two lines operating lines intersect:

(V - V) y = (L - L) x + D xD + B xB

(17)

We have:
V - V' = (1 - q) F

(18)

L - L' = - q F

(19)

14

In addition, from component balance around the entire column:

F xF = D xD + B xB
Thus, (1 - q) F y = - q F x + F xF

(20)
(21)

Re-arranging in the form y = f(x), we have:

y=

q
1
x+
x
( 1q ) ( 1q ) F

(22)

The feed tray can be made up of liquid, vapor, or a mixture of both, in which the
behavior of the streams depends abruptly on this entrance. An overall material and
energy balance around the feed plate must be made,

F+ L+V st =V + Lst

F H F + L H L, f 1 +V st H G ,f +1=V H G , f + Lst H L , f

(23)

(24)

The molar enthalpies of the liquids and vapors can be assumed as the same value,
because inside the tower all of them are saturated and the temperature and compositions
changes are small.

( Lst L ) H L, f =( V st V ) H G , f + F H F

Combining the energy balance with the mass balance,

15

(25)

L st L H v , f H f
=
=q
F
H v ,f H L, f

(26)

For convenience, the condition of the feed is represent by the q value, which is defined
as, the heat needed to vaporize 1 mol of feed at entering conditions, divided by the
molar latent heat of vaporization of feed.

q=

( H v H L ) +C pL ( T v T f )
H v H L

(27)

The energy balance considerations around any stage that has an external feed must take
into account the thermal quality of the feed stream. By this the feed can be introduced
under five different conditions.[3]

Different values of q will result in different slope of the q-line. See the Figure
8 below.

16

Figure 9: GRAPHICAL INTERPRETATION FOR Q-LINE FOR TYPICAL

CONDITIONS (Benitez, 2009)
Stripping Section

FEED

The section which extends from the feed to the bottom is what is known as the stripping
section represented in Figure 6. The purpose of this area is to remove light components
from a heavy stream. To obtain an operating line for this section of the distillation
column a similar analysis to the rectifying section it must be consider a material balance
for the light key in which the partial reboiler is included.
y=

Lst
W
x
x
V st
V st W
(28)

17

Figure 10: STRIPPING SECTION DIAGRAM (Benitez, 2009)

Where, Lst and Vst are the total molar flows in the stripping section. Vst represents the
boil-up, which is the vapor rate leaving the stripping section, and its ratio to the bottom
product rate is the boil-up ratio,
V B=

V st
W

(29)

To simplify the mass balance of this section, the overall balance of the reboiler is used
to rewrite each term
Lst =V st +W

L st V st +W V B +1
=
=
V st
V st
VB

18

(30)

(31)

Combining Eq. 16, 17 and 19, the operation line for the stripping section is obtained,

y=

V B +1
1
x
x
VB
VB W

(32)

This is one of the many different but equivalent versions of the Fenske equation valid
only for binary mixtures: [3]

log
N=

[(

Xd
1X d

)(

1X b
Xb

)]

(33)

log avg

Where:

N is the minimum number of theoretical plates required at total reflux (of which
the reboiler is one),

Xd is the mole fraction of more volatile component in the overhead distillate,

Xb is the mole fraction of more volatile component in the bottoms,

avg is the average relative volatility of the more volatile component to the
less volatile component.

For a multi-component mixture the following formula holds. For ease of expression, the
more volatile and the less volatile components are commonly referred to as the light
key (LK) and the heavy key (HK), respectively. Using that terminology, the above
equation may be expressed as:
\

19

log
N=

[( )( )]
LK d
HK d

HK b
LK b

log avg
(34)

If the relative volatility of the light key to the heavy key is constant from the column
top to the column bottom, then

avg

is simply

. If the relative volatility is not

constant from top to bottom of the column, then the following approximation may be
used:
= ( t ) ( b )

(35)

Where:

is the relative volatility of light key to heavy key at top of column,

is the relative volatility of light key to heavy key at bottom of column.

The above forms of the Fenske equation can be modified for use in the total reflux
distillation of multi-component feeds. It is also helpful in solving liquidliquid
extraction problems, because an extraction system can also be represented as a series of
equilibrium stages and relative solubility can be substituted for relative volatility. [4]

The number of actual plates required for a given separation is the number of triangles
that can be drawn between the operating lines and the equilibrium curve. The last
triangle on the diagram represents the reboiler as shown in Figure 8.

20

Figure 11: DETERMINATION

OF NUMBER OF EQUILIBRIUM STAGES AND FEED

STAGE LOCATION . (www.separationprocesses.com)

To translate ideal plates into actual plates the plate efficiency must be known. The
overall efficiency is simple to use but is the least fundamental. It is defined as the ratio
of the number of ideal plates needed in an entire column to the number of actual plates.
[4]

E=

Number of theoretical plates

100
Number of actual plates
(36)

21

EQUIPMENT

22

PROCEDURE

23

EXPERIMENTAL DATA

24

CALCULATIONS

REFERENCE

1.

Wikipedia contributors. (2014, September 2). McCabeThiele method.

Retrieved from Wikipedia: http://en.wikipedia.org/wiki/McCabe
%E2%80%93Thiele_method

2.

Armfield. (2009, Fecruary). Continuous Distillation Column. Continuous

Distillation Column Instruction Manual(21).

25

3.

Benitez, J. (2009). Mass Transfer Operations. Wiley.

4.

Copyright SM Cheah 2000 (e-HOME, n.d. 2012). Continuous distillation

column.
http://www.separationprocesses.com/Distillation/MainSet1.htm

5.

26

NOMENCLATURE

Name

Symbol

Units

Temperature at top of column

Temperature at second tray
Temperature at third tray
Temperature at fourth tray
Temperature at fifth tray
Temperature at sixth tray
Temperature at seventh tray
Temperature at bottom of column
Temperature at reboiler
Temperature of column exit vapor
Cooling water entry temperature
Cooling water exit temperature
Condensate/top product temperature
Cooling water flow rate
Total pressure drop across column
Vacuum pump pressure relief valve
Continuous feed valve
Reboiler sample extraction valve
Condenser sample extraction valve
Top product receiver sample valve
Cooling water flow control valve
Bottom manometer connection
Top manometer connection
Dosing vessel flow control valve
Condensate decanter bypass valve
Drain valve
Product recycling valve
Vacuum pump water supply control
Vacuum pump flow control valve
Feed molar flow rate
Distillate molar flow rate
Bottom molar flow rate
Mole fraction of more volatile

T1
T2
T3
T4
T5
T6
T7
T8
T9
T10
T11
T12
T13
F11
P
PRV1
V1
V2
V3
V4
V5
V6
V7
V8
V10
V11
V12
V14
V15
F
D
W

C
C

C
L/hr
mmH2O
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
dimensionless
mole/s
mole/s
mole/s

zF

dimensionless

yD

dimensionless

xw

dimensionless

component in the feed

Mole fraction of more volatile
component in the distillate
Mole fraction of more volatile
component in the bottom

27

Feed stage
Rate net of heating
Molar enthalpy in the feed
Molar enthalpy in the feed
Molar enthalpy in the feed
Relative volatility in bottom
Relative volatility in distillate

f
Q
HF
HD
Hw
B, ABB
D, ABD
av

dimensionless
KW
J/mole
J/mole
J/mole
dimensionless
dimensionless

ntheoretical
nactual
E
xAf
xAD
xBD
xAB
xBB

dimensionless
dimensionless
dimensionless
dijmensionless
dimensionless
dimensionless
dimensionless
dimensionless

y*

dimensionless

y*AD

dimensionless

y*AB

dimensionless

R
m
n

dimensionless
dimensionless
dimensionless

xA

dimensionless

xB

dimensionless

n Ad

mole

n Bd

mole

Specific heat of ethanol

C PA

J /gK

Specific heat of water

C PB

J /gK

Specific heat of the mixture

Heat of vaporization of the mixture

CPL
mix

J/g K
J/g

Ethanol heat of vaporization

J/g

Average relative volatility

Number of theoretical plates
Number of actual plates
Efficiency
Mole fraction of ethanol in the feed
Mole fraction of ethanol in the distillate
Mole fraction of water in the distillate
Mole fraction of ethanol in the bottom
Mole fraction of water in the bottom
Equilibrium mole fraction of more

dimensionless

volatile component in gas

Ethanol equilibrium mole fraction in
gas phase in the distillate
Ethanol equilibrium mole fraction in
gas phase in the bottom
Reflux Ratio
Graph slope
Number of theoretical plates
Mole fraction of more volatile
component
Mole fraction of least volatile
component
Number of moles of ethanol (A)
contained in distillate.
Number of moles water (B) contained
in distillate.

28

Water heat of vaporization

J/g

Liquid entering in the top stage

Molar flow of the liquid in the stripping

L0

mole/s

Lst

mole/s

mole/s

Vst

mole/s

mole/s

VB

dimensionless

Section
Molar flow of the liquid across the
column
Molar flow of the vapor in the stripping
section
Molar flow of the liquid across the
column
Boil- up ratio
Energy required to convert 1 mole of
feed from its condition HF to a
q
saturated vapor, divided by the molal
latent heat of evaporation
Reboiler power
Molar fraction of the more volatile

dimensionless
q- reboiler, qreboiler

KW

dimensionless

dimensionless

component in liquid phase

Molar fraction of the more volatile
component in vapor phase

29