1.

INTRODUCTION

Distillation can be defined as a process in which a liquid or vapor mixture of two or

more substances is separated into its component fractions of desired purity, by the application
and removal of heat. Distillation process is based on differences in boiling points of the
components. While the lighter components move up the column, the heavier components fall
down. When the relative volatility between the separating components is high, distillation can
be cheaper than other separation methods [ 1].
In a distillation column a liquid feed containing the mixture of both liquids enters the
column at one or more points. The liquid flows over the plates, and vapor bubbles up through
the liquid via holes in the plates. As liquid travels down the column, vapor comes in contact
with it many times (due to the multiple plates). This is the critical process in distillation
columns. The liquid and vapor phases are brought into contact because as one molecule of
higher boiling material converts from vapor to liquid phase by energy release, another
molecule of the low boiling material utilizes the free energy to convert from liquid to vapor
phase. [1]
The base of the distillation column contains a large volume of liquid, which is mostly
the liquid with higher boiling point (in our example, this was water). Out of the base flows
some of this liquid, some of which is heated in the reboiler and returned to the column. This is
called the boil up. The remaining liquid is the bottom product. Some vapor escapes from the
top of the column and is returned to a liquid state in the condenser. Some of this liquid is
returned to the column as reflux, and the remainder is the top product or distillate.

Figure 1: The Distillation Process [1]

1
 Vapor and liquid phases on a given plate approach thermal, pressure and composition
equilibrium to an extent depending upon the efficiency of the plate.
Distillation process is commonly used in industry for separating and purifying materials
such as pre-purifying raw materials before they are fed to reactors and purifiying the reactor
pruducts.
Distillation can be classified into system composition (binary, multi component
distillation), the process configuration (distillation, absorption, stripping, azeotropic), the
equipment types (tray, packing), and process type (refining, petrochemical, chemical, gas
treating).
1.1. System Composition
There are two main distillation types which groups into chemical components in the system.
 Binary distillation is a separation process of two components. A good example is
seperating ethyl alcohol from water.
 Multi component distillation is the separation process of a mixture of chemicals.
Petroleum refining is a common example for multi component distillation.
1.2. Types of Distillation Columns
Distillation is classified into two types according to operating process which are
continuous distillation and batch distillation.
 Continuous distillation is feed is sent to the still all the time and product is drawn out
at the same time. The idea in continuous distillation is that the amount going into the still and
the amount leaving the still should always equal each other at any given point in time.
 Batch distillation is when the amount going into the still and the amount going out of
the still is not supposed to be the same all the time. The easiest example to use is like old
fashioned spirit making. The distiller fills a container at the start, then heats it, as time goes by
the vapors are condensed to make the alcoholic drink. When the proper quantity of overhead
(drink) is made, the distiller stops the still and empties it out ready for a new batch. This is
only a simple case, in industrial usage what goes on gets very complex. The disadvantages of
batch distillation are that only one pure product is removed and the process is not operated at
steady state. [2]
Both continuous and batch distillation are very important to industry. Continuous
distillation is most often used with big volume products like jet fuel, benzene, plastic
monomers. Batch distillation is most often used with smaller volume products and in plants
that make lots of different things and use the same still for many products (in different
batches).

2
 In this experiment we used binary batch distillation technique with a tray column. Also
the ethanol solution was the azeotropic system but no mass separating agent or entrainer was
used. Ethanol-water system can be purified approximately to 96%.
The performance of a distillation column is determined by many factors such as feed
conditions, internal liquid and fluid flow conditions, state of trays, weather conditions.
1.3. Total Reflux
Batch distillation can be operated at total reflux which is defined as returning all the
condensed vapors to the column. Steady state is reached as no product is removed. Operating
a column at total reflux is a convenient method of studying the performance of the column
because compositions are not change with time.
1.4. Constant Reflux Ratio
The reflux ratio is the liquid returning to the column to the distillate removed. When a
batch distillation is operated at a constant reflux ratio, an unsteady state process can be
observed. The composition in the still pot and the stages changes since product is removed.

1.5. Processing Sequence

Fractionation systems have different objectives. The major processing objectives set the
system type and the equipment configuration needed. The common objectives include
removing a light component from a heavy product, removing a heavy component from a light
product, making two products, or making more than two products. We will call these major
categories are called stripping, rectification, fractionation, and complex fractionation.

➢ Stripping systems remove light material from a heavy product.

➢ Rectification systems remove heavy material from a light product.

➢ Fractionation systems remove a light material from a heavy product and a heavy material
from a light product at the same time.

➢ Complex fractionation makes multiple products from either a single tower or a complex
of towers combined with recycle streams between them. A good example of a multiple
product tower is a refinery crude distillation tower making rough cuts of naphtha
(gasoline), kerosene (jet fuel), and diesel from the same tower. A good example of a
complex tower with internal recycle streams is a Petlyck (baffle) tower making three on-
specifications products from the same tower. [2]

1.6. McCabe-Thiele Method

For a binary system, the classic McCabe-Thiele graphical technique can be used to
design the distillation column and to explore the effect of process variables. The technique

3
uses a number of assumptions concerning the operation of the distillation column. In order to
use the McCabe-Thiele analysis, one needs the vapor-liquid equilibrium for the system plotted
as a y versus x diagram. The second part is the operating line for the column which is a
formulation of the mass balance from stage to stage; this requires the overall gas and liquid
flows and the selected reflux ratio. When the distillation is continuous and feed enters the
middle of the column, there are separate operating lines (mass balances) for the column above
and below the point of feed introduction. For batch distillation, there is only one operating
line since the molar flows of gas and liquid are constant throughout the column. The number
of stages is determined by moving from equilibrium to operating curve such as occurs in the
column. This generates a step structure which gives the number of stages. While the method is
simple to do in practice, it takes some analysis to understand the concepts. [3]

Figure 2: Theoretical Trays by McCabe-Thiele Method [3]

1.7. Equipment Type

Distillation equipment includes two major categories, trays and packing.

➢ Trays force a rising vapor to bubble through a pool of descending liquid. The higher the
number of stages, the better the separation, which can be obtained.

➢ Packing creates a surface for liquid to spread on. The thin liquid film has a high surface
area for mass-transfer between the liquid and vapor. [3]

4
 By the experiment, we investigated the separation of ethanol from water by observing
the effect of reflux ratio on distillate composition in a binary distillation column. The
experiment would continue until the mass fraction of ethanol of distillate 87%. Also, there
was a chance to determine the efficiency of binary distillation column.

2. EXPERIMENTAL
2.1 Equipment
The equipment that is used is The Armfield Batch Distillation Column has the same
configuration as a modern full size binary batch distillation column. The main parts of the
binary distillation column are reboiler, packed column, plate distillation column, condensate
collecting vessel and thermocouples.
2.2 Procedure
(For set 1-2-3-4-5):

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 A mixture sample from the reboiler tank was taken in order to determine the initial
concentration of the mixture. Three different concentrations were determined by using
pycnometers. Weight of the pycnometer was measured and density was calculated for them. A
relationship between density and volumetric fraction was read from table, so the initial
concentration and the other concentrations can be calculated like this way. Temperature
values in each tray were measured in five minutes time intervals until they stayed
approximately constant. Then, in order to observe the effect of the reflux ratio on the distillate
composition five different set were applied. These sets were the total reflux, 10 reflux ratio, 5
reflux ratio, 2 reflux ratio and 1 reflux ratio respectively. A McCabe-Thiele method was used
in the calculation parts to determine the experimental tray numbers.

6
 Figure 3: Schematic diagram of distillation column [4]

3. RESULT & DISCUSSION

The aim of this experiment is to investigate the separation of ethanol from water by
observing the effect of reflux ratio on distillate composition in a binary batch distillation
column. The experiment was carried out until the mass fraction of ethanol of distillate is
87 %.

Table 1. Equilibrium Data in mass fraction for Water-Ethanol Mixture

EQUILIBRIUM LINE
xA yA
0 0
0,02 0,192
0,05 0,377

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 0,1 0,527
0,2 0,656
0,3 0,713
0,4 0,746
0,5 0,771
0,6 0,794
0,7 0,822
0,8 0,858
0,9 0,912
0,94 0,942
0,96 0,959
0,98 0,978
1 1

Before starting the experiment the volume of pycnometer is calculated by using water.

Table 2. Volume Determination of Pycnometer

Water density(g/cm3) at 23 C 0,99754
tare of pycnometer(g) 19,495
total mass (g) 29,639
V=m/ρ
volume of pycnometer(cm3) 10,16901578
29.639-19.495/ 0.99754=
10.17 cm3 ( The volume of pycnometer)

Table 3. Determination of Fractions in re-boiler (initial condition) at 22 C

measurement measurement measurement average standard error %
1 2 3 deviation
volume (ml) 10,17 10,17 10,17 10,17 0 0
tare (g) 19,495 19,495 19,495 19,495 0 0
total mass (g) 29,4564 29,4781 29,4579 29,4641 0,00989489 0,00033229
2 9
mass of 9,9614 9,9831 9,9629 9,9691 0,00989489 0,00098212
sample (g) 2
density (g/ml) 0,9795 0,9816 0,9796 0,9802 0,00097294 9,65703E-05
9

As can be known above, the volume of pycnometer was calculated and after that the density
was calculated by using this volume. 3 trials were done to establish the standard deviation of
it. Later, density was used to obtain the initial mass fraction of ethanol in ethanol-water
mixture.

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Table 4. Density Measurement of mixture at initial tank condition
First Trial at 22 C 0,979585013
Second Trial at 22 C 0,98171895
Third Trial at 22 C 0,97973252

Table 5. Initial mass fraction of ethanol in ethanol mixture

First Trial at 22 C 10.8
Second Trial at 22 C 10.8
Third Trial at 22 C 10.8
Average mass fraction 10.8

Initially, the system was operated at total reflux. The temperature of each tray and tank was
measured to observe each tray whether they reached to pseudo steady state or not. Heater with
initial value of 0.8 KW was manipulated to obstacle the boiling of the mixture at tank;
whereas roughly 15 min is counted to observe the effect of changed heater’s severity. The
temperature change for each tray is given below as table 6.

Table 6. Temperature changing with respect to time for each tray and tank
time(min Temperatur
) e of Trays
( C)
T1(at tray 8) T2(at T3(at T4(at T5(at T6(at T7(at T8(at T9(tank
tray 7) tray 6) tray5) tray 4) tray 3) tray 2) tray 1) )
3 22,9 22,5 22,3 22,5 22,8 22,3 22,3 22,4 40,6
8 23 22,4 22,3 22,5 22,9 22,4 22,3 22,6 48,5
13 22,9 22,4 22,4 22,5 22,9 22,4 22,5 23,6 56,2
18 22,8 22,2 22,3 22,4 22,8 22,5 23,1 26,1 64,7
23 22,7 22,3 22,5 22,8 22,9 24 26,5 37,2 76,5
28 22,7 22,6 22,9 23,3 23,7 29,2 36,8 46,3 84,6
33 22,8 23,1 23,7 24 70 78,1 79,8 81,3 89,7
38 78,1 78,6 78,6 78,9 79,7 80,3 82,1 84 90,4
43 78,2 78,6 78,5 78,4 78,9 79,1 80 81 90,7
48 78,3 78,4 78,4 78,4 79 79 79,8 80,9 90,8
53 78,3 78,4 78,4 78,4 78,9 78,9 79,7 80,9 90,8
58 78,3 78,4 78,4 78,4 78,9 78,8 79,7 80,9 90,8
63 78,3 78,4 78,4 78,3 78,9 78,8 79,7 80,7 90,7
68 78,4 78,4 78,4 78,3 78,9 78,8 79,7 80,7 90,7
Average 78,2714 78,4571 78,443 78,443 79,0286 79,100 80,100 81,300 90,7000
values
Standard 0,0881 0,0904 0,0728 0,1917 0,2763 0,5014 0,8229 1,1071 0,1309

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deviation
Error % 0,0099 0,0104 0,0068 0,0468 0,0966 0,3179 0,8454 1,5076 0,0189

Standard deviation is calculated when the tray is at steady state and the values are so small.
This means that our data are accurate.

After each tray reached to steady state, the example was taken from distillation still.

The mass fraction was calculated by tracing same procedure.

Table 7. Determination of density of distillate at total reflux

measureme measureme measureme
standard error
nt nt nt average
deviation %
1 2 3
volume (ml) 10.17 10.17 10.17 10.17
tare (g) 19.495 19.495 19.495 19.495
0,0145459
total mass (g) 27.6784 27.6909 27.7074 27,692
04
mass of sample 0,0145459
8.1834 8.1959 8.2124
(g) 8,1972 04
0.80473989 0.80596912 0,8061002 0,0014304
density (g/ml) 0.8075917
6 2 39 16

From Perry’s handbook the mass fraction of ethanol is determined when the system was
operated at total reflux.

Table 8. Density Measurement of mixture at total reflux

First trial at 27C 0,80473
Second trial at 25 C 0,80596
Third trial at 23 C 0,80759

Table 9. Mass fraction of ethanol in ethanol mixture at total reflux

First trial at 27C 93,5
Second trial at 25 C 92,7
Third trial at 23 C 92

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At total reflux, mass fraction of ethanol in distillate still is % 92.7 which is average value of
the trials. This mass fraction is high because our aim is to obtain % 87 ethanol mixture.
In order to determine efficiency, the number of theoretical trays should be determined. The
number of theoretical tray can be obtained by using McCabe-Thile method. The system has
only enriching section because of binary batch distillation column. McCabe method can be
used for binary systems too.

Operating line can be found using below formula.

yn+1 = (R/R+1)*xn + (xD/R+1)

For total reflux; reflux ratio goes to infinity. For that reason slope of operating line is 1.

Figure 4: Theoretical Tray Determination for Total Reflux

11
To determine theoretical stages, the distillate and initial compositions were marked at Figure
4. The distillate composition value is 0.927 while the initial composition is 0.11. We start
from the distillate composition and go down until we reach the bottom composition. The
number of theoretical stages is five trays. However, number of theoretical trays includes
reboiler. To calculate number of ideal trays, we should exclude the reboiler from obtained the
number of trays.

The efficiency of column can be calculated by number of ideal trays/ number of actual trays.
From this equation, number of theoretical tray = 5-1 (reboiler) =4

Overall Tray Efficiency = (4/8) *100= 50 %.

Minimum number of theoretical tray occurs in total reflux but distillate composition is higher
at total reflux. At total reflux system is closed, and the distillate returns to reboiler so the
ethanol concentration is high at total reflux. This prevents water vapor goes to distillate.

The same procedure was used to find out mass fraction of ethanol in distillate at relux 10.

Table 10.Determination of density of distillate at reflux ratio 10

measuremen measuremen measuremen
standard
t t t average
deviation
1 2 3
volume (ml) 10.17 10.17 10.17 10.17
tare (g) 19.495 19.495 19.495 19.495
0,01354590
total mass (g) 27.772 27.815 27.7074 27.793
4
mass of sample 0,01354590
8.277 8.32 8.2996
(g) 8,2988 4
0,81606 0,00123041
density (g/ml) 0.813944341 0.818172878 0.816166781
4 6

Table 11.Mass fraction of ethanol in ethanol mixture at reflux ratio 10

First trial at 24 C 90,8
Second trial at 21 C 90
Third trial at 21 C 90,5

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At reflux ratio 10, the distillate composition is 90 %. It is higher than the desired composition
of 87 %.
Operating line can be found using below formula.

yn+1 = (R/R+1)*xn + (xD/R+1)

yn+1 =(10/11)* xn+( xD/11)

According to this operating line equation, the operating line was drawn.

Figure 5: Theoretical Tray Determination for Reflux Ratio 10:1

The distillate composition and initial composition were show at Figure 5 0.9, 0.1,
respectively. The number of theoretical trays was concluded by drawing triangles from
operating line to equilibrium line. As it can be seen from Figure 5, the number of theoretical
trays is 5.2. However, it contains reboiler tray. Hence, number of trays is 4.2 (5.2-1).

Overall Tray Efficiency = (4.2/8) *100= 52.5 %.

The number of theoretical tray increased compare with total reflux, it is expected. Since
minimum number of trays is needed for total reflux. If reflux ratio decreases slope of
operating line will decrease. Therefore, number of tray increases.
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Table 12. Determination of density of distillate at reflux ratio 5
measuremen measuremen measuremen
standard
t t t average
deviation
1 2 3
volume (ml) 10.17 10.17 10.17 10.17
tare (g) 19.495 19.495 19.495 19.495
total mass (g) 27.7765 27.7836 27.7772 27.7791 0,0531904
mass of sample 8,145644
8.1439 8.15508 8.144557 0,0039128
(g) 1
0,00038477
density (g/ml) 0.813944341 0.818172878 0.816166781 0,816064
7

Table 13. Mass fraction of ethanol in ethanol mixture at reflux ratio 5

First trial at 24 C 87
87,
Second trial at 23 C 5
Third trial at 22 C 88

At reflux ratio 5, the distillate composition is 87.5 %. The aim of this experiment is to achive
87 % distillate so it can be good choice to operate at reflux ratio 5.
Operating line can be found using below formula.

yn+1 = (R/R+1)*xn + (xD/R+1)

yn+1 =(5/11)* xn+( 5/11)

According to this operating line equation, the operating line was drawn.

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 Figure 6: Theoretical Tray Determination for Reflux Ratio 5:1

To determine theoretical stages, the distillate and initial compositions were marked at Figure
6. The distillate composition value is 0.875 while the initial composition is 0.9. The number
of theoretical tray is 5.4. Since the re-boiler is considered as a theoretical step, the number of
theoretical trays in a tower is equal to the number of theoretical steps minus 1. Therefore,
there are 4.4 theoretical trays.

Overall Tray Efficiency = (4.4/8) *100= 55.5 %.

The mass fraction was calculated by tracing same procedure at reflux ratio 2.

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Table 14. Determination of density of distillate at reflux ratio 2
measuremen measuremen measuremen
standard
t t t average
deviation
1 2 3
volume (ml) 10.17 10.17 10.17 10.17
tare (g) 19.495 19.495 19.495 19.495
0.010197
total mass (g) 27.7989 27.8166 27.8165 27.8106
8
mass of sample
8.3039 8.3216 8.3215 0.004989
(g) 8.3156
0.81774
density (g/ml) 0.816589 0.818333022 0.8183203 0.001021
6

Table 15. Mass fraction of ethanol in ethanol mixture at reflux ratio 2

First trial at 22 C 87.9
Second trial at 22 C 87
Third trial at 22 C 84

At reflux ratio 2, the distillate composition is 86.6 %. It is less than desired distillate
composition.
Operating line can be found using below formula.

yn+1 = (R/R+1)*xn + (xD/R+1)

yn+1 =(2/11)* xn+( 2/11)

According to this operating line equation, the operating line was drawn.

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 Figure 7: Theoretical Tray Determination for Reflux Ratio 2:1

As it can be seen from Figure 7, the number of theoretical trays is 5.7. We should exclude the
re-boiler from obtained the number of trays. Therefore, number of theoretical trays is 4.7.
(5.7-1)
Overall Tray Efficiency = (4.7/8) *100= 59 %.

The same procedure was used to find out mass fraction of ethanol in distillate at reflux 1.

Table 16. Determination of density of distillate at reflux ratio 1

measuremen measuremen measuremen
standard
t t t average
deviation
1 2 3
volume (ml) 10.17 10.17 10.17 10.17
tare (g) 19.495 19.495 19.495 19.495
27.8658 0.010197
total mass (g) 27.8693 27.8575 27.8707
7 8
mass of sample
8.3743 8.3625 8.3757 0.004989
(g) 8.3171
0.82474
density (g/ml) 0.82351 0.82235 0.82365 0.001021
6

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Table 17. Mass fraction of ethanol in ethanol mixture at reflux ratio 1
86,
First trial at 24 C 4
86,
Second trial at 24 C 4
Third trial at 24 C 86

At reflux ratio 1, the distillate composition is 86.3%. It is less than desired distillate
composition.
Operating line can be found using below formula.
yn+1 = (R/R+1)*xn + (xD/R+1)
yn+1 =(1/11)* xn+( 1/11)

According to this operating line equation, the operating line was drawn.

Figure 8: Theoretical Tray Determination for Reflux Ratio 1:1

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Figure 8. illustrates that the system has 7 theoretical trays. Since the re-boiler is considered as
a theoretical step, the number of theoretical trays in a tower is equal to the number of
theoretical steps minus 1. Therefore, there are 6 theoretical trays.

Overall Tray Efficiency = (6/8) *100= 75 %.

Figure 9: Change in Temperature with Reflux Ratio

During the experiment, temperatures of all the trays are measured for each reflux ratio
value. The change in temperature with reflux ratio is represented in figure 1. According to the
figure, the temperature is highest in the first tray (feed tray) and decreasing toward the top
trays. More distilled is returned to the system when the recycle ratio is increased and because
of this, the temperature of the plates increase due to low boiling point of ethanol.

Table 18. Illustration of Density and Mass Fraction of Distillate for Each Condition
Condition Density Mass Fraction of Distillate
Total reflux 0,806100239 92,7
Reflux Ratio 10:1 0,816064 90
Reflux Ratio 5:1 0,816064 87,50
Reflux Ratio 2:1 0.817746 86,6
Reflux Ratio 1:1 0.824746 86,3

The mass fraction of distillate is at maximum value for total reflux when compared to
other reflux ratio. As the reflux ratio gets higher so does the mass fraction of distillate. For
instance, at total reflux, all distillate returns the column so distillate concentration in re-boiler
is high. By doing this, it is prevented that more water does not mix with distillate. Due to
cycling existence, distillate composition will be high. On the other hand, if there is not total
reflux ratio, distillated ethanol moves through column. Hence, ethanol concentration in re-
boiler decreases and the more ethanol composition in re-boiler mean that distillation is
difficult. This causes lower mass fraction.

Table 19. Tray Efficiency for each Condition

Condition Efficiency %
Total reflux 50

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 Reflux Ratio 10:1 52.5
Reflux Ratio 5:1 55.5
Reflux Ratio 2:1 59
Reflux Ratio 1:1 75

Overall tray efficiency is defined with a formula as given below;

E0=number of theoretical traysnumber of actual trays
As can be seen from Table 19 the mass fraction of ethanol in distillate was obtained 92,7%
when the process was being worked at total reflux ratio and according to Table 19., the
efficiency of tray at total reflux is 50%. This means that even having 50 % tray efficiency was
concluded as 92.7 % mass fraction of ethanol in distillate. For instance, when reflux ratio is
1:1, the tray efficiency is 75%. When compared these examples, overall column efficiency for
total reflux is higher than the others.

4. CONCLUSION

The goal of this experiment is to obtain 87%w.t distillate by altering the reflux ratio in batch
distillation column. The reflux ratios are set as total reflux, 10:1, 5:1, 2:1 and 1:1.Distillate
compositions are obtained as 92.7, 90, 87.50, 86.6, 86 with respect to altered reflux ratio.
Highest composition occurred when the total reflux ratio was applied. McCabe-Thile method
was applied to determine the number of theoretical trays and efficiency was calculated by
using the number of theoretical and actual trays for each reflux ratios. Minimum number of
theoretical trays was obtained at total reflux while maximum efficiency of column existed at
total reflux. It is impossible to get distillate above 95.6 % w.t due to existence of azeotrope
point; whereas azeotrope point can be broken by changing the reflux ratios and composition at
re-boiler. The higher composition of ethanol is at re-boiler, the more chance to break
azeotrope point. However, this procedure is valid for this system. Also, there are two ways to
break azeotrope point at literature as pressure swing distillation n and adding another
component called as entrainer. At total reflux, the system is closed system so it will reach to

20
equilibrium. When the temperature stays constant for each trays, the system is operated under
pseudo-steady state. Our aim is achieved at reflux ratio 5:1, because the mass fraction is
87.5%. Therefore, it is suitable to use this reflux ratio. Heater was manipulated to avoid
boiling of water-ethanol mixture preventing to reach to pseudo-steady state. After altering the
heater severity for each step, it was waited roughly 15 min owing to observe the effect of
manipulated heater.

5. REFERENCES

[1] Online search, http://lorien.ncl.ac.uk/ming/distil/distiltyp.html

[2] Christie J. Geankoplis, “Transport Processes and Separation Process Principles” 4. edition
[3] Online search, www.see.ed.ac.uk/procalcs/mixtures/NISOL04
[4] www.engr.pitt.edu/chemical/lab-manuals

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