MT 405: Multicomponent Distillation

1. Objectives:
• To perform multi-component distillation of methanol-ethanol-butanol in a laboratory-
scale packed column.
• To determine the number of theoretical stages offered by the existing column using
batch distillation under total reflux.
• To simulate the performance of the laboratory column using ASPEN.
• To compare the experimental results with that obtained by simulation.
• To use the experimentally validated simulator and obtain the best possible design and
operating conditions for the desired performance.

2. Theory
2.1.Distillation
Distillation is a method of separation of components from a liquid mixture that depends
on the differences in boiling points of the individual components and the distributions of the
components between a liquid and gas phase in the mixture. The liquid mixture may have
different boiling point characteristics depending on the concentrations of the components
present in it. Therefore, distillation processes depend on the vapor pressure characteristics of
liquid mixtures. The vapor pressure is created by supplying heat as a separating agent. In the
distillation, the new phases differ from the original by their heat content. During most of the
century, distillation was by far the most widely used method for separating liquid mixtures of
chemical components. This is a very energy-intensive technique, especially when the relative
volatility of the components is low. It is mostly carried out in multi-tray columns. A packed
column with efficient structured packing has also led to increased use in distillation.

Fig 1: Multi-purpose Set-up for Batch/Continuous Distillation

2.1.1 Vapor Pressure:
Vapor Pressure: The vaporization process changes liquid to a gaseous state. The
opposite process of this vaporization is called condensation. At equilibrium, the rates of these
two processes are the same. The pressure exerted by the vapor at this equilibrium state is termed
the vapor pressure of the liquid. It depends on the temperature and the quantity of the liquid
and vapor. From the following Clausius-Clapeyron Equation or by using Antoine Equation, the
vapor pressure can be calculated.
Clausius-Clapeyron Equation:
𝑷𝒗 𝝀 𝟏 𝟏
𝒍𝒏 ( 𝒗 ) = ( ) ( − )
𝑷𝟏 𝑹 𝑻𝟏 𝑻

where, 𝑷𝒗 and 𝑷𝒗𝟏 are the vapor pressures in Pascal at absolute temperature 𝑻 and 𝑻𝟏 in K. 𝝀
is the molar latent heat of vaporization which is independent of temperature.
Antoine Equation:
𝑩
𝒍𝒏(𝑷𝒗 )(𝑷𝒂𝒔𝒄𝒂𝒍) = 𝑨 −
𝑻+𝑪
2.1.2 Relative Volatility:
Relative volatility is a measure of the differences in volatility between two components,
and hence their boiling points. It indicates how easy or difficult a particular separation will be.
The relative volatility of component ‘A’ with respect to component ‘B’ in a binary mixture is
defined as,
𝑷𝒗𝑨
𝜶𝑨𝑩 =
𝑷𝒗𝑩
𝒚𝑨
⁄𝒙𝑨
𝜶𝑨𝑩 =𝒚
𝑩⁄
𝒙𝑩
where, 𝒚𝑨 = mole fraction of component ‘A’ in the vapor, 𝒙𝑨 = mole fraction of component
‘A’ in the liquid. In general, relative volatility of a mixture changes with the mixture
composition.
For binary mixture, 𝒙𝑩 = 𝟏 − 𝒙𝑨. Hence, the above Equation can be rearranged, for more
volatile component as:
𝜶𝑨𝑩 𝒙𝑨
𝒚𝑨 =
𝟏 + (𝜶𝑨𝑩 − 𝟏)𝒙𝑨
2.1.3 Vapor-Liquid Equilibrium (VLE):
It is useful for graphical design in determining the number of theoretical stages required
for a distillation column. The VLE plot expresses the bubble-point and the dew-point of a
binary mixture at constant pressure. The curved line in Figure 2 is called the equilibrium line
and it describes the compositions of the liquid and vapor in equilibrium at some fixed pressure.
 Fig 2: Vapor-Liquid Equilibrium plot
2.1.4 Reflux Ratio:
Reflux ratio is defined as,
𝐹𝑙𝑜𝑤 𝑟𝑒𝑡𝑢𝑛𝑒𝑑 𝑎𝑠 𝑟𝑒𝑓𝑙𝑢𝑥
𝑅=
𝐹𝑙𝑜𝑤 𝑜𝑓 𝑡𝑜𝑝 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑡𝑎𝑘𝑒𝑛 𝑜𝑓𝑓
As the reflux ratio is reduced, the number of stages required to achieve desired distillate
purity increases till the pinch point occurs where the separation can be achieved with infinite
stages. This minimum reflux ratio can be calculated by Underwood equation:
𝛼𝑖 𝑧𝑖,𝑓
∑( )=1−𝑞
𝛼𝑖 − θ
𝛼𝑖 𝑧𝑖,𝐷
∑( ) = 1 + 𝑅𝑚𝑖𝑛
𝛼𝑖 − θ
where,
𝑧𝑖,𝑓 = Feed composition

𝑧𝑖,𝐷 = Distillate composition

𝐿
θ= = Absorption factor for the heavy key component
𝑉𝑘𝑟

𝑞 = mole fraction of liquid in the feed

𝑅𝑚𝑖𝑛 = Minimum reflux ratio
For total reflux we can calculate the minimum number of stages using Fenske equation
which is given by,
 𝑥 1−𝑥
log [(1 −𝑑𝑥 ) ( 𝑥 𝑏 )]
𝑑 𝑏
𝑁=
log (𝛼𝑎𝑣𝑔 )

where,
𝑥𝑑 = mole fraction of the light key component in distillate
𝑥𝑏 = mole fraction of the light key component at bottom
𝛼𝑎𝑣𝑔 = mean of relative volatilities at top and bottom of the column

2.2.Gas Chromatography:
Gas chromatograph is an analytical instrument used to analyse the different components
in a sample. An analytical method using a gas chromatograph is called gas chromatography
(GC).

Fig 3: Typical GC Configuration

As shown in Figure 3, the GC consists of a flow control section, a sample injection port,
a column, a column oven, and a detector in which is connected to a data processor. Carrier
gases such as helium (He), nitrogen (N2) or hydrogen (H2) are preferred to be supplied at a
constant flow rate to the sample to the injection port. A separation tube called a column is
connected between the sample injection port and the detector, all three parts are maintained at
an appropriate temperature. The sample injected into the sample injection port instantaneously
vaporizes and flows into the column with the carrier gas. In the column, a liquid stationary
phase (for example, silicone polymers) is chemically bonded or coated, the vaporized sample
is repeatedly dissolved and vaporized in the liquid stationary phase and travels downstream
with the carrier gas.
Since the process of dissolving and vaporizing the sample in the stationary phase
depends on the physicochemical properties such as the boiling point and the nature of the
column, the time of dissolving in the liquid phase and the time of vaporizing will be different
for each compound. Therefore, even when mixed components are injected, the time for the
components to arrive at the column exit is different, and separation can be detected. The column
exit connects to a detector and when substances other than the carrier gas are eluted from the
column, the detector converts them into electrical signals which are amplified and sent to a data
processor. By analyzing the electric signal of the detector on the data processor, the GC will
be able to identify the sample and determine its quantity. Under certain conditions, the time to
reach the detector (retention time) is the same after injection of the compound. By injecting the
standard sample and the unknown sample, and comparing the retention times, quantitation can
be done by comparing the sizes of their peaks.
2.2.1. Thermal Conductivity Detector (TCD):
The thermal conductivity detector (TCD), also known as a Katharometer, is a bulk
property detector and a chemical specific detector commonly used in gas chromatography. This
detector senses changes in the thermal conductivity of the column effluent and compares it to
a reference flow of carrier gas. Since most compounds have a thermal conductivity much less
than that of the common carrier gases of helium or hydrogen, when an analyte elutes from the
column the effluent thermal conductivity is reduced, and a detectable signal is produced. The
TCD consists of an electrically heated filament in a temperature-controlled cell. Under normal
conditions there is a stable heat flow from the filament to the detector body. When an analyte
elutes and the thermal conductivity of the column effluent is reduced, the filament heats up and
changes resistance. This resistance change is often sensed by a Wheatstone bridge circuit which
produces a measurable voltage change. The column effluent flows over one of the resistors
while the reference flow is over a second resistor in the four-resistor circuit.

2.2.2. Flame Ionization Detector (FID):

The flame ionization detector is a scientific instrument that measures analytes in a gas
stream. It is frequently used as a detector in gas chromatography. The measurement of ion per
unit time makes this a mass sensitive instrument. The operation of the FID is based on the
detection of ions formed during combustion of organic compounds in a hydrogen flame. The
generation of these ions is proportional to the concentration of organic species in the sample
gas stream. To detect these ions, two electrodes are used to provide a potential difference. The
positive electrode acts as the nozzle head where the flame is produced. The other, negative
electrode is positioned above the flame. The ions thus are attracted to the collector plate and
upon hitting the plate, induce a current. This current is measured with a high-
impedance picoammeter and fed into an integrator. The manner in which the final data is
displayed is based on the computer and software. In general, a graph is displayed that has time
on the x-axis and total ion on the y-axis.
3. Procedure:
3.1. Experimental Procedure:
1) Fill the kettle with the component mixture and start the reboiler and cooling water
pump.
2) The weight of methanol, ethanol and butanol is taken as 1.5 kg, 0.75 kg and 0.75 kg
respectively.
3) When the reflux drum has sufficient level, start reflux flow, with no distillate flow to
achieve total reflux.
4) Take temperature readings of the three zones and reboiler at every 10 minutes till the
steady state is reached.
5) Collect samples from the three zones, distillate and reboiler and analyse using G.C.
6) Start distillate flow rate to achieve 1.5 reflux ratio.
7) Repeat 3 and 4.
3.2. GC Analysis:
1) Add approximately 1 gm of cyclohexanone to every sample to act as a reference. Note
down the weights of samples.
2) Inject 2 ml of each sample into gas chromatograph and record the plot.
3) Note the area fraction of each component in the plot.
4) Calculate the actual compositions by multiplying the respective response factors.
4. Observation Table:
4.1.Total Reflux:
1) For Temperature:
Time T1 T2 T3 T4 T5 T6
t = 0 min
t = 10 min
t = 20 min
t = 30 min
t = 40 min
2) For Gas Chromatography:
Weight Weight of Area of Area of Area of Area of
of cyclohexanone methanol ethanol Butanol cyclohexanone
Sample
Sample
1
Sample
2
Sample
3
Sample
4
Sample
5

4.2.Reflux Ratio = 1.5:

1) For Temperature:
Time T1 T2 T3 T4 T5 T6
t = 0 min
t = 10 min
t = 20 min
t = 30 min
t = 40 min
 2) For Gas Chromatography:
Weight Weight of Area of Area of Area of Area of
of cyclohexanone methanol ethanol Butanol cyclohexanone
Sample
Sample
1
Sample
2
Sample
3
Sample
4
Sample
5

5. Calculation Procedure:
1) Calculate area ratio for all species from GC data.
2) Multiply by respective response factors to obtain mass ratios with respect to
cyclohexanone (reference material).
3) Calculate mole fractions from mass ratios and weights of the samples.
4) Calculate saturation pressure from Antoine equation at the bottom and top
temperatures.
5) Calculate minimum number of trays from Fenske equation and minimum reflux ratio
from Underwood equation.
6. Calibration Curve:
6.1.Methanol Calibration Data:
Weight Weight of Area of Area of Weight Area Ratio
of Cyclohexanone Methanol Cyclohexanone Ratio (M/CH)
Methanol (CH) (M) (CH) (M/CH)
(M)
1.001 5 5.95 94.05 0.2002 0.063264221

2.001 5 13.74 86.26 0.4002 0.15928588

3.01 5 22.18 77.82 0.602 0.285016705

4.003 5 30.22 69.78 0.8006 0.43307538

5 5 40.28 59.72 1 0.674480911

WR v/s AR y = 1.293x + 0.1829

R² = 0.967
1.2
Weight Ratio (M/CH)

1
0.8
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8
Area Ratio (M/CH)
6.2. Ethanol Calibration Data:
Weight Weight of Area of Area of Weight Area Ratio
of Cyclohexanone Ethanol Cyclohexanone Ratio (E/CH)
Ethanol (CH) (M) (CH) (E/CH)
(E)
1 5 8.71 91.29 0.2 0.095410231

2 5 19.42 80.58 0.4 0.24100273

3 5 28.72 71.28 0.6 0.40291807

4 5 31.34 68.66 0.8 0.456452083

5 5 39.81 60.19 1 0.661405549

WR v/s AR y = 1.4527x + 0.0604

R² = 0.9787
1.2
Weight Ratio (E/CH)

1
0.8
0.6
0.4
0.2
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Area Ratio (E/CH)
6.3. Butanol Calibration Data:
Weight Weight of Area of Area of Weight Area Ratio
of Cyclohexanone Butanol Cyclohexanone Ratio (B/CH)
Butanol (CH) (B) (CH) (B/CH)
(B)
1 5 16.56 83.44 0.2 0.198465964

2 5 26.14 73.86 0.4 0.353912808

3 5 36.76 63.24 0.6 0.581277672

4 5 43.93 56.07 0.8 0.78348493

5 5 49.23 50.77 1 0.969667126

WR v/s AR y = 1.0115x + 0.016

R² = 0.9974
1.2
Weight Ratio (B/CH)

0.8

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2
Area Ratio (B/CH)