UNIVERSITI TUNKU ABDUL RAHMAN

UGPA3071 PETROCHEMICAL LABORATORY

ACADEMIC YEAR 2017

TRIMESTER: MAY 2017

LAB INSTRCUTOR: DR. ONG YIT THAI

EXPERIMENT DATE: 12THJUNE 2017

SUBMISSION DATE: 6TH JULY 2017

EXPERIMENT 9: DISTILLATION USING PACKED COLUMN WITH REFLUX

GROUP: 2

NAME ID TRIMESTER

CHUA ZHENG FONG 1404065 Y3S1

CHUN GIM THIAM 1406023 Y3S1

DING SHI JIE 1405400 Y3S1

HENG SU CIN 1402799 Y3S1

LEOW GUO QUAN 1403851 Y3S1

DISTILLATION USING PACKED COLUMN WITH REFLUX

1. OBJECTIVES
a. To operate a distillation column with constant reflux ratio.
b. To carry out mass balance calculations on the distillation column.
c. To compare the performance for packed and tray columns for distillation process.
2. INTRODUCTION

Distillation is an equilibrium stage operation. In each stage, a vapour phase is contacted

with a liquid phase and mass is transfer from vapour to liquid and from liquid to vapour. The
more volatile components will concentrate in the vapour. Vapour leaving the top of the column
passes through a condenser, where it is partially or totally condensed. The liquid which results is
temporarily held in the refluxdrum. A liquid stream is withdrawn from the drum and returned to
the top tray of the column as reflux to promote separation. The vapour condensed in the
condenser will be withdrawn as distillate. Apart from that, the less volatile components will
concentrate in the liquid phase. The base of the column is typically used as a reservoir to hold
liquid leaving the bottom tray. A reboileracts as the heat source which supply heat energy to the
column by means ofboiling this liquid. The vapour which results, the boilup is returned to a few
trays above the reboiler into the column (Price, 2003). Separation of components from a liquid
mixture via distillation depends on the differences in boiling points of the individual components.
Also, depending on the concentrations of the components present, the liquid mixture will have
different boiling point characteristics. It is the process which depends on the difference between
the compositions of a boiling liquid mixture and the vapour mixture in equilibrium with the
liquid.

Stages installed in the column are able to enhance contact between the vapour and the
liquid in counter-clockwise direction. By definition, an ideal stage is the stage where the vapour
and liquid leave the stage in equilibrium. Consequently, the vapour composition functionally
depends on the liquid composition. Ideality is an approximation, but stage efficiencies can be
used to account for real cases. A key result of the ideal stage assumption is that liquid streams
leaving an ideal stage are assumed to be at their bubble point and vapour streams leave at their
dew point. When no azeotropes are present (relative volatility is above 1), both top and bottom
products may be obtained in any desired purity in case enough stages are provided and enough
reflux is available. The separability of two different components can be determined by the
relative volatility. Hypothetically, the greater the relative volatility, the greater the degree of
separability. In practice, there are limits to the number of stages and to the amount of reflux, so
not every separation can be accomplished. Theoretical limits on performance are imposed
by total reflux with minimum stages and minimum reflux with infinite number of ideal stages
(Price, 2003).

There are many types of distillation columns, each designed to perform specific types of
separations and each design differs in terms of configuration. In batch operation, the feed to the
column is introduced batch-wise – the column is charged with a ‘batch’ of a feed mixture after
which distillation is carried out. When the desired task is achieved, the next batch of feed is
introduced (Tham, 2016). Batch operation is normally applied in specialty chemical, biochemical,
and pharmaceutical industries.On the contrary, continuous columns on the other hand process a
continuous feed stream. They are capable of handling high throughputs and are the more
common of the two types (Tham, 2016).Continuous operation is primarily implemented in the
petrochemical and bulk chemical industries.

Columns can be further classified according to the nature of the feed that they are
processing: binary column in which the feed contains only two components and multi-
component column where the feed contains more than two components. Columns can also be
categorized according to the number of product streams they have. Distillation columns can also
be classified according to the type of intervals in the column:

1) Tray column – where trays of various designs are used to hold up the liquid to provide better
contact between vapour and liquid, hence better separation.
2) Packed column – where, instead of trays, packings are used to enhance contact between
vapour and liquid.

This experiment is designed to study the distillation of a binary mixture of ethanol and water in a
packed distillation column.

2.1. Theory

In this experiment, the feed is introduced batch-wise into the column. Figure 2.1.1
illustrates the most noticeable difference in the configurations. For batch operation, the feed is
initially charged into the reboiler at the beginning of batch operation. After a total reflux
operation, the distillate is continuously withdrawn while the bottom residue with a high-boiling-
temperature component is concentrated, making this a time-varying process. The batch column is
operated under constant reflux and variable ethanol composition. Under this condition, the
composition of distillate keeps varying from time to because the bottom still composition of the
more volatile component is continuously depleted (Kim, 2005).

Figure 2.1.1: Types of Distillation Processes: (a) Batch Distillation (b) Continuous Distillation.

The column used in this experiment was packed with raschig rings. These materials
provide a large surface area per unit volume for the distillation. Differing from a tray column
which operates stage-wise, the contact between both phases is continuous. The mass transfer can
be facilitated by means of continuous contact between both phases on the surface of the packed
bed. Hypothetically, packing materials are able to increase mass transfer between two phases.
One of the advantages of using packed column is that a packed column is cheaper for operation
using corrosive liquids. Besides, packed towers offer a lower pressure drop. Also, packed towers
are better at handling foaming systems (Costello, 2016).

Reflux is a returned stream from distillate to the feed. The liquid that is refluxed is rich in
the desired top product. The down-flowing reflux liquid provides cooling and condensation of
the up-flowing vapours. As the top product will have a lower boiling point than the bottoms,
upon contacting the vapour stream, some of the reflux will vaporise. Meanwhile, some of the
bottoms product will condense, and fall back down the column. The purpose of reflux is to yield
purer distillate. Reflux ratio is calculated by Equation 2.1.1.

𝐿 𝑉−𝐷
𝑅= = ⋯ 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2.1.1
𝐷 𝐷

Where L = rate of liquid entering the top stage

D = distillate rate

Given a reflux ratio, the number of theoretical stages required for a given separation can
be determined graphically by using McCabe-Thiele method. The general equation of the
operating line can be expressed as Equation 2.1.2. Figure 2.1.2 shows the vapour-liquid
equilibrium curve (x-y diagram) and the operating line for the distillation process under general
reflux by using McCabe-Thiele method. As the reflux ratio is increased, the gradient of the
operating line for the rectification section moves towards a maximum value of 1. Physically,
what this means is that more and more liquid that is rich in the more volatile components are
being recycled back into the column.

𝑅 𝑥𝑑
𝑦= 𝑥+ ⋯ 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2.1.2
𝑅+1 𝑅+1

Where R is the reflux ratio and xd is the mole fraction of the liquid distillate collected at the top.

Figure 2.1.2: x-y Diagram for Distillation.

 If the distillation is carried out in a plate column, it is possible to calculate the number of
theoretical plates that are required for the distillation. This makes it possible to define a height of
the packed column which affects separation of a mixture equivalent to a theoretical plate. The
height so calculated is known as the Height Equivalent to a Theoretical Plate (HETP). If the
column is to be packed, then the height of packing can be estimated from Equation 2.1.3.

𝐻 = 𝑁 × 𝐻𝐸𝑇𝑃 ⋯ 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2.1.3

Where H = packing height

N = number of theoretical stages

The Fenske-Underwood-Gilliland method is widely used for making preliminary

designs.Fenske equation is used to calculate the minimum number of theoretical stage in
continuous fractional distillation. It is derived based on the assumptions that the stages are
equilibrium stages. This equation also assumes that constant molal overflow is valid and the
relative volatility, is constant. Equation 2.1.4 shows one of the many different but equivalent
versions of Fenske equation valid only for binary mixtures.In this equation, Nmin is the number of
equilibrium trays required at total reflux including the partial reboiler. The derivation steps are as
cited in Nptel (n.d.).

𝑥 𝑥
ln [(𝑥𝐷,𝑖 ) (𝑥𝐵,𝑗 )]
𝐵,𝑖 𝐷,𝑗
𝑁𝑚𝑖𝑛 = ⋯ 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2.1.4
ln 𝛼𝑎𝑣𝑒

Where xD,i = mole fraction of liquid ethanol in distillate

xB,i = mole fraction of liquid ethanol in bottom product

xD,j = mole fraction of liquid water in distillate

xB,j = mole fraction of liquid water in bottom product

𝛼𝑎𝑣𝑒 = √𝛼𝐷 × 𝛼𝐵

On the other hand, Underwood equation as shown in Equation 2.1.5 develops an

alternative way to calculate minimum reflux ratio in the case of separate pinch points in both the
stripping and rectifying sections. In this equation, one of the assumptions made is constant molal
overflow. Moreover, it is assumed that  for each component is the same in the upper and lower
invariant zones. The presence of non-distributing heavy non-keys results a pinch point of
constant composition at minimum reflux in the rectifying section whereas the presence of non-
distributing light non-keys, a pinch point will occur in the stripping section. Considering the
pinch point is in the rectifying section, the mass balance for component i around the top portion
of the rectifying section as illustrated inNptel (n.d.).

2
αi xDi
𝑅𝑚𝑖𝑛 + 1 = ∑ ⋯ 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2.1.5
αi − ∅
𝑖=1

Where i = relative volatility of component with respect to the heaviest component

xDi = mole fraction of component in distillate

𝜙 = root of equation

3. EQUIPMENT

The distillation column is made of borosilicate 3.3 glass with PTFE gaskets and stainless steel.
Please refer to the process flow diagram in Figure 3.1 and the description of labelling in Table
3.1.

1. Reboiler (B1) – a 10 L horizontal reboiler equipped with two 1,5 kW cartridge heaters (W1a
& W1b). The reboiler is supplied with liquid level switch LS-01, a temperature probe TIC-
201. The reboiler also comes with a charge port for feeding. A drain valve is fitted at the
bottom of the reboiler.
2. Sieve Tray Column (K1) – a DN 50 borosilicate column with 10 sieve trays and equipped 10
temperature probes, which are TI-101 and TI-110. A temperature probe TT-112 is available
for distillate temperature measurement. A differential pressure sensor is also provided to
measure the pressure drop across the sieve tray column. Column height: approximately 1 m.
3. Packed Column (K2) – a DN 50 column packed with 8 mm Raschig Ring. A temperature
probe TT-112 is available for distillate temperature measurement. A differential pressure
transmitter is also provided to measure the pressure drop across the packed column. Packing
height: approximately 1 m.
4. Top Condenser – a high efficiency condenser with 0.5 m2 exchange area and cooling water
connections.
5. Product Cooler – having 0.035 mm2 exchange area and cooling water connections.
6. Product Tank (B3&B4) – a 5 L graduated tank with venting connections and valves.
7. Feed Tank (B2) – a 30 L cylindrical tank with discharge and venting.

Figure 3.1: Process Flow Diagram for Distillation Column Unit.

 Table 3.1: Description of Tags in Figure 3.1.

Tag Description Units Range

TT 101 to TT 110 Column temperature °C 0.0 – 100.0
TT 111 Feed temperature °C 0.0 – 100.0
TT 112 Top column temperature °C 0.0 – 100.0
TIC 201 Reboiler temperature °C 0.0 – 100.0
FI 102 Entrainer flowrate ml/min 0.0 – 150.0
KS 01 Timer based reflux controller s 0 - 9999
Position 1: Total reflux
Position 2: Total distillate
Position 3: Timer controlled reflux
DPT 301 Differential pressure mmH2O 0 - 400
W1a & 1b Heater power W 0 - 3000
LS 01 Reboiler level switch - -

4. APPARATUS
1. Refractometer
2. Droppers
3. Measuring cylinders 25 ml
4. Beakers 100 ml
5. MATERIALS
1. Ethanol
2. Distilled Water
6. PROCEDURES
6.1. Calibration Procedures
1. Two 100 mL of beakers, two 25 mL of measuring cylinders and three droppers were
prepared.
2. Approximately 100 mL of ethanol liquid was poured into a beaker from the ethanol
sample bottle to avoid any wastage.
 3. Approximately 1 mL of ethanol was dropped into a cylinder using a dropper and
approximately 9 mL of water was dropped into another measuring cylinder using
another dropper.
4. Both of the liquids were poured into a beaker.
5. The mixture of ethanol and water was stirred well.
6. The mixture was extracted by a dropper and put into the measuring prism of the
refractometer
7. The refractive index of the solution was measured and the results was recorded.
8. The measuring prism of refractometer was cleaned with distilled water and dried.
9. The solution left in the beaker was poured into the waste bottle.
10. Steps 3-9 were repeated eight more times by changing the volume of ethanol and water.
For an example, if 2 mL of ethanol was measured, then 8 mL of water was measured.
The total volume of solution was always fixed 10 mL.
11. Then, step 3-9 were also repeated by replacing the mixture solution to pure ethanol and
pure water solutions.
12. All the results were tabulated in Table 8.1.
13. Graph 8.1 was plotted.
6.2. General Startup Procedures
1. The reboiler B1, feed tank B2, product tank B3 and B4 were washed.
2. The type of packed column required was selected and installed on the demonstrator.
3. The reservoir tank and make-up tank were filled up with distilled water until ¾ full. It
was ensured that the flow back inlet was not exceeded by the water level of reservoir.
4. The main power supply was switched on and the control panel was switched on.
5. The container of wet bulb was filled up.
6. The water heater was switched on and the desired operating temperature was set to
90 °C.
7. The by-pass valve was opened once the desired temperature was reached.
8. The water pump on the control panel was switched on and the by-pass valve was
regulated to obtain the desired flow rate.
9. The air blower on the control panel was switched on and the controller was regulated to
obtain the desired speed.
 10. The system was allowed to reach steady state for 5 minutes.
6.3. Operating Procedures
1. The mixture containing 40 % by volume of ethanol and 60 % by volume of distilled
water was prepared.
2. Then, the mixture was filled in to the reboiler B1 and feed tank B2.
3. The reflux timer was set to 30 seconds for set 1 and 60 seconds for set 2.
Set 1: Product liquid return to column (reflux)
Set 2: Product liquid to tank B3 (distillate)
4. The feed pump P1 was switched on when the distillate was condensed into the product
tank B3. The pump stroke was adjusted to obtain a flow rate of approximately 60 mLPM,
then the reflux control (KS-01) was set to position 3 (Timer controlled reflux).
5. The top and bottom temperatures were recorded in Table 8.2 once the stable condition
was reached.
6. Samples from the distillate and bottom product are collected at each 10-minute interval.
The remaining bottom product in product tank B4 was discarded every time after the
sample was collected.
7. The refractive indices for all samples are measured and recorded in Table 8.2. Their
compositions were determined by extrapolating the RI to its respective mole fraction in
Graph 8.1.
8. The mole fraction of each sample was recorded in Table 8.4.
9. The final distillate was collected from product tank B3 to measure its volume and
density.
7. PRELAB QUESTIONS

Plot the VLE graph for ethanol-water system by using CHEMSOF binary-VLE spreadsheet.

Figure 7.1: Binary-VLE Spreadsheet for Ethanol-Water System (Zafar, 2016).

8. DATA SHEET AND RESULTS

Table 8.1: Calibration Data for Refractive Indices of Ethanol-Water Mixtures.

Water,H2O Ethanol,C2H5OH Refractive
Volume Volume Volume Volume Index, RI
Percent,% Measured,Vm(±0.1𝑚𝐿) Percent,% Measured,Vm(±0.1𝑚𝐿) (±0.0001 𝑛𝐷)
100.0 10.0 0.0 0.0 1.3335
90.0 9.0 10.0 1.0 1.3356
80.0 8.0 20.0 2.0 1.3375
70.0 7.0 30.0 3.0 1.3404
60.0 6.0 40.0 4.0 1.3429
50.0 5.0 50.0 5.0 1.3446
40.0 4.0 60.0 6.0 1.3451
30.0 3.0 70.0 7.0 1.3451
20.0 2.0 80.0 8.0 1.3433
10.0 1.0 90.0 9.0 1.3413
0.0 0.0 100.0 10.0 1.3359

Table 8.2: Refractive Indices of Top and Bottom Products at 10-Minute Intervals.
Time Distillate Bottom Product
(±0.1𝑚𝑖𝑛) Temperature Refractive Index, RI Temperature Refractive Index, RI
(±0.1 °C) (±0.0001 𝑛𝐷) (±0.1 °C) (±0.0001 𝑛𝐷)
1st 2nd Ave 1st 2nd Ave
0.0 64.6 1.3451 1.3452 1.3452 82.9 1.3410 1.3412 1.3411
10.0 65.7 1.3451 1.3451 1.3451 83.4 1.3405 1.3404 1.3405
20.0 66.5 1.3449 1.3450 1.3450 83.9 1.3397 1.3397 1.3397
30.0 67.0 1.3449 1.3447 1.3448 84.5 1.3389 1.3393 1.3391
40.0 67.2 1.3443 1.3445 1.3444 85.2 1.3387 1.3386 1.3387
50.0 67.5 1.3438 1.3439 1.3439 85.9 1.3364 1.3367 1.3366
60.0 67.4 1.3431 1.3433 1.3432 86.8 1.3359 1.3359 1.3359
To find the respective mole of each mixture with different volume and the mole percent of
ethanol and water, the parameters listed in Table 8.1 are substituted in the following formulae:

When 1.0 mL of ethanol and 9.0 mL of water are mixed,

Weight of ethanol:

𝑚 = 𝜌𝑉

𝑘𝑔 1000𝑔 1 𝑚3
= 789 3 ( ) × 1.0 𝑚𝐿 ( )
𝑚 1𝑘𝑔 1 × 106 𝑚𝐿
= 0.789 𝑔

Number of mole of ethanol:

𝑚
𝑛 =
𝑀𝑊

0.789 𝑔
= 𝑔
46.069 𝑚𝑜𝑙

= 0.01713 𝑚𝑜𝑙

Where n = number of mole

ρ = density

V = volume

m = weight

MW = molecular weight
Weight of water:

𝑚 = 𝜌𝑉

𝑘𝑔 1000𝑔 1 𝑚3
= 1000 ( ) × 9.0 𝑚𝐿 ( )
𝑚3 1𝑘𝑔 1 × 106 𝑚𝐿
= 9.00 𝑔

Number of mole of water:

𝑚
𝑛 =
𝑀𝑊

9.00 𝑔
= 𝑔
18.015 𝑚𝑜𝑙

= 0.49958 𝑚𝑜𝑙

0.789 𝑔
𝑊𝑒𝑖𝑔ℎ𝑡 𝑝𝑒𝑟𝑐𝑒𝑛𝑡 𝑜𝑓 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = × 100 % = 8.06007 %
0.789 𝑔 + 9.00 𝑔

0.01713 𝑚𝑜𝑙
Mole fraction of ethanol = = 0.03315
0.01713 𝑚𝑜𝑙 + 0.49958𝑚𝑜𝑙

The calculation steps are repeated for other mixtures with different amounts of ethanol and water.
The results are tabulated in Table 8.3. Then, Graph 8.1 is plotted from the data in Table 8.3.
 Table 8.3: Composition Table Based on Refractive Index.
Purity of ethanol: > 96 %
Density of ethanol: 789 kg/m3
Density of water: 1000 kg/m3
Volume of Volume of Mole Fraction Weight Percent of Refractive Index
Ethanol (±0.1 Water (±0.1 ml) of Ethanol Ethanol (%) (±0.0001 nD)
ml)
0.0 10.0 0.00000 0.00000 1.3335
1.0 9.0 0.03315 8.06007 1.3356
2.0 8.0 0.07161 16.47526 1.3375
3.0 7.0 0.11679 25.26956 1.3404
4.0 6.0 0.17060 34.46920 1.3429
5.0 5.0 0.23579 44.10285 1.3446
6.0 4.0 0.31638 54.20197 1.3451
7.0 3.0 0.41857 64.80113 1.3451
8.0 2.0 0.55240 75.93840 1.3433
9.0 1.0 0.73523 87.65584 1.3413
10.0 0.0 1.00000 100.00000 1.3359
 Graph of RI vs Mole Fraction of Ethanol
1.346

1.344

1.342

1.34
RI (nD)

1.338

1.336

y = -0.0477x4 + 0.1471x3 - 0.1759x2 + 0.079x + 1.3335

1.334
R² = 0.9916

1.332
0.00000 0.10000 0.20000 0.30000 0.40000 0.50000 0.60000 0.70000 0.80000 0.90000 1.00000
Mole Fraction of Ethanol

Graph 8.1: Calibration Graph for Refractive Indices of Ethanol-Water Mixtures.

The composition of each sample collected are determined by extrapolating the respective
refractive indices from Graph 8.1. The results are the tabulated in Table 8.4.

Table 8.4: Data Collection and Measurement.

Heater power: 2000 W
Reflux ratio: 0.5
% of ethanol in the feed stream: 40 % by volume
Time Distillate Bottom Product
(±0.1𝑚𝑖𝑛) Temp RI Mole Temp RI Mole
(±0.1 °C) (±0.0001 𝑛𝐷) Fraction (±0.1 °C) (±0.0001 𝑛𝐷) Fraction
0.0 64.6 1.3452 0.37937 82.9 1.3411 0.12912
10.0 65.7 1.3451 0.41345 83.4 1.3405 0.11457
20.0 66.5 1.3450 0.43251 83.9 1.3397 0.09763
30.0 67.0 1.3448 0.46088 84.5 1.3391 0.08627
40.0 67.2 1.3444 0.50357 85.2 1.3387 0.07920
50.0 67.5 1.3439 0.54655 85.9 1.3366 0.04289
60.0 67.4 1.3432 0.59829 86.8 1.3359 0.03248
9. DATA ANALYSIS
9.1. Comparing Experimental Data with Theoretical Answer

Finding Theoretical Answer

To calculate the density of the feed, ρF :

𝑀𝑎𝑠𝑠, 𝑚𝐹
𝜌𝐹 =
𝑉𝑜𝑙𝑢𝑚𝑒, 𝑉𝐹

1 𝑘𝑔
9.5743 𝑔 × 1000 𝑔
= 1𝐿 1 𝑚3
10 𝑚𝐿 × 1000 𝑚𝐿 × 1000 𝐿

𝑘𝑔
= 957.43
𝑚3

To calculate the mass of the feed, F:

𝐹 = 𝜌𝐹 𝑉𝐹

𝑘𝑔 1 𝑚3
= 957.43 3 ( ) × 5.0 𝐿
𝑚 1000 𝐿

= 4.78715 𝑘𝑔

To calculate the density of the distillate, ρD at 60th minute:

𝑀𝑎𝑠𝑠, 𝑚𝐷
𝜌𝐷 =
𝑉𝑜𝑙𝑢𝑚𝑒, 𝑉𝐷

1 𝑘𝑔
9.0179 𝑔 × 1000 𝑔
= 1𝐿 1𝑚3
10 𝑚𝐿 × 1000 𝑚𝐿 × 1000 𝐿

𝑘𝑔
= 901.79
𝑚3

To calculate the mass of the distillate, D at 60th minute:

𝐷 = 𝜌𝐷 𝑉𝐷
 𝑘𝑔 1 𝑚3
= 901.79 3 × 1200 𝑚𝐿 ( )
𝑚 1 × 106 𝑚𝐿

= 1.08215 𝑘𝑔

xB = 0.06794 molEtOH/molB
𝑔
0.06794 𝑚𝑜𝑙 𝐸𝑡𝑂𝐻 × 46.069 𝑚𝑜𝑙
𝑥𝐵 = 𝑔 𝑔
0.06794 𝑚𝑜𝑙 𝐸𝑡𝑂𝐻 × 46.069 𝑚𝑜𝑙 + (1 − 0.06794)𝑚𝑜𝑙 𝐻2 𝑂 × 18.015 𝑚𝑜𝑙

𝑥𝐵 = 0.15712 𝑔𝐸𝑡𝑂𝐻 /𝑔𝐵

The theoretical composition of the distillate, xD is found through material balance:

𝐹𝑥𝐹 = 𝐷𝑥𝐷 + 𝐵𝑥𝐵

𝐹𝑥𝐹 − 𝐵𝑥𝐵
𝑥𝐷 =
𝐷

𝐹𝑥𝐹 − (𝐹 − 𝐷)𝑥𝐵
=
𝐷

(4.78715 𝑘𝑔 × 0.34469) − (3.70500 𝑘𝑔 × 0.15712)

=
1.08215 𝑘𝑔

= 0.98688 𝑔𝐸𝑡𝑂𝐻 /𝑔𝐷

Comparing Experimental Data with Theoretical Answer at 60th minute

Experimental data:

𝑥𝐷 = 0.61150 𝑚𝑜𝑙 𝐸𝑡𝑂𝐻 /𝑚𝑜𝑙𝐷

𝑔
0.61150 𝑚𝑜𝑙 𝐸𝑡𝑂𝐻 × 46.069
𝑚𝑜𝑙
= 𝑔 𝑔
0.61150 𝑚𝑜𝑙 𝐸𝑡𝑂𝐻 × 46.069 𝑚𝑜𝑙 + (1 − 0.61150)𝑚𝑜𝑙 𝐻2 𝑂 × 18.015 𝑚𝑜𝑙

= 0.80100 𝑔𝐸𝑡𝑂𝐻 /𝑔𝐷

Theoretical answer:

𝑥𝐷 = 0.98688 𝑔𝐸𝑡𝑂𝐻 /𝑔𝐷

𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑏𝑜𝑡ℎ 𝑥 𝑣𝑎𝑙𝑢𝑒𝑠
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑑𝑎𝑡𝑎 − 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑛𝑠𝑤𝑒𝑟
=| × 100 %|
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑑𝑎𝑡𝑎

0.80100 − 0.98688
=| × 100 %|
0.80100

= 23.20629 %

9.2. Performing McCabe-Thiele Method

Since the feed entered the column at its boiling temperature, the feed is a saturated liquid.

For a saturated liquid, the feed quality is 1.0.

At t = 0 min

To construct top operating line:

𝑅 1
𝑦𝑛+1 = 𝑥𝑛 + 𝑥
1+𝑅 1+𝑅 𝐷

0.5 1
𝑦𝑛+1 = 𝑥𝑛 + (0.37937)
1 + 0.5 1 + 0.5

1
𝑦𝑛+1 = 𝑥𝑛 + 0.25291
3

Graph 9.2.1: x-y Plot of EtOH-H2O Mixture at 0th Minute.

Number of theoretical stage(s): 5

Optimum feed stage: 3

𝐻
𝐻𝐸𝑇𝑃 =
𝑁

1𝑚
=
5

= 0.20 𝑚
At t = 60 min

To construct top operating line:

𝑅 1
𝑦𝑛+1 = 𝑥𝑛 + 𝑥
1+𝑅 1+𝑅 𝐷

0.5 1
𝑦𝑛+1 = 𝑥𝑛 + (0.61150)
1 + 0.5 1 + 0.5

1
𝑦𝑛+1 = 𝑥𝑛 + 0.40767
3

Graph 9.2.2: x-y Plot of EtOH-H2O Mixture at 60th Minute.

Number of theoretical stage(s): ∞

Optimum feed stage: Undefined

𝐻
𝐻𝐸𝑇𝑃 =
𝑁

1𝑚
=
∞

= 0.0 𝑚
9.3. Performing Fenske Equation
For distillate when t = 0 min,

Antoine equation is applied to find vapour pressure:

′
𝐵
ln 𝑃𝐸𝑡𝑂𝐻 (𝑘𝑃𝑎) = 𝐴 −
𝑇(°𝐶) + 𝐶

Where P’EtOH = vapour pressure of ethanol

A, B and C = Antoine constants

T = Temperature

′
3795.17
𝑙𝑛 𝑃𝐸𝑡𝑂𝐻 (𝑘𝑃𝑎) = 16.8958 −
64.6 + 230.918
′
𝑃𝐸𝑡𝑂𝐻 = 57.59106 𝑘𝑃𝑎

3885.7
𝑙𝑛 𝑃𝐻′ 2 𝑂 (𝑘𝑃𝑎) = 16.3872 −
64.6 + 230.17

𝑃𝐻′ 2 𝑂 = 24.65693 𝑘𝑃𝑎

Applying Raoult’s Law:

𝑃 = ∑ 𝑥𝑖 𝑃𝑖′
𝑖=1

′
𝑃 = 𝑥𝐸𝑡𝑂𝐻 𝑃𝐸𝑡𝑂𝐻 + 𝑥𝐻2 𝑂 𝑃𝐻′ 2 𝑂

= 0.37937 × 57.59106 𝑘𝑃𝑎 + (1 − 0.37937) × 24.65693 𝑘𝑃𝑎

= 37.15115 𝑘𝑃𝑎
′
𝑥𝐸𝑡𝑂𝐻 𝑃𝐸𝑡𝑂𝐻
𝑦𝐸𝑡𝑂𝐻 =
𝑃

0.37973 × 57.59106 𝑘𝑃𝑎

=
37.15115 𝑘𝑃𝑎

= 0.58809
To find relative volatility between ethanol and water, αij:

𝑦𝑖 𝑥𝑗
𝛼𝐷 =
𝑥𝑖 𝑦𝑗

0.58809 × (1 − 0.37937)
𝛼𝐷 =
0.37937 × (1 − 0.58809)

= 2.33569

The calculation steps above are repeated for distillateat each sampling time. The results are
tabulated in Table 9.2.1.

Table 9.2.1: Calculated Parameters for Distillates.

Time Distillate
(±0.1 𝑚𝑖𝑛) Temp xEtOH P’EtOH P’H2O P (kPa) yEtOH 𝛼𝐷
(±0.1 °C) (kPa) (kPa)
0.0 64.6 0.37937 57.59106 24.65693 37.15115 0.58809 2.33569
10.0 65.7 0.48301 60.40025 25.89545 42.56161 0.68545 2.33247
20.0 66.5 0.53791 62.51515 26.82896 46.02492 0.73064 2.33014
30.0 67.0 0.56901 63.86841 27.42677 48.16243 0.75457 2.32869
40.0 67.2 0.58629 64.41658 27.66903 49.21375 0.76740 2.32811
50.0 67.5 0.59774 65.24628 28.03581 50.27800 0.77569 2.32725
60.0 67.4 0.61150 64.96872 27.91310 50.57261 0.78557 2.32754
Similarly, the calculation steps above are repeated for bottom product at each sampling time to
tabulate Table 9.2.2.

Table 9.2.2: Calculated Parameters for Bottom Products.

Time Bottom Product
(±0.1𝑚𝑖𝑛) Temp xEtOH P’EtOH P’H2O P (kPa) yEtOH 𝛼𝐵
(±0.1 °C) (kPa) (kPa)
0.0 82.9 0.12912 121.78555 53.28201 62.12719 0.25311 2.28568
10.0 83.4 0.11109 124.15111 54.34701 62.10155 0.22209 2.28441
20.0 83.9 0.09763 126.55488 55.42980 62.37374 0.19809 2.28316
30.0 84.5 0.08627 129.49054 56.75297 63.02804 0.17724 2.28165
40.0 85.2 0.07920 132.98701 58.33002 64.24285 0.16395 2.27991
50.0 85.9 0.07328 136.56181 59.94361 65.55819 0.15265 2.27817
60.0 86.8 0.06794 141.27528 62.07300 67.45400 0.14229 2.27595

Applying Fenske Equation to find minimum theoretical stages, Nmin:

When t = 0 min,

𝑥 𝑥
ln [(𝑥𝐷,𝑖 ) (𝑥𝐵,𝑗 )]
𝐵,𝑖 𝐷,𝑗
𝑁𝑚𝑖𝑛 =
ln 𝛼𝑎𝑣𝑒

0.37937 1−0.12912
ln [(0.12912) (1−0.37937)]
=
ln [√(2.33569)(2.28568)]

= 1.69142

The calculation steps above are repeated for other sampling times. The results are tabulated in
Table 9.2.3.
 Table 9.2.3: Minimum Stages Required.
Time (±0.1 𝑚𝑖𝑛) 𝛼𝐷 𝛼𝐵 𝛼𝑎𝑣𝑒 𝑁𝑚𝑖𝑛
0.0 2.33569 2.28568 2.31055 1.69142
10.0 2.33247 2.28441 2.30832 2.40481
20.0 2.33014 2.28316 2.30653 2.84271
30.0 2.32869 2.28165 2.30505 3.15873
40.0 2.32811 2.27991 2.30388 3.35721
50.0 2.32725 2.27817 2.30258 3.51717
60.0 2.32754 2.27595 2.30160 3.68567

9.4. Performing Underwood Equation

To find root of equation, ∅:

2
αi xFi
∑ =1−q
αi − ∅
i=1

Where αi = volatility of component relative to the heaviest component

xFi = mole fraction of component in feed

q = feed quality

For distillate when t = 0 min,αi = 2.33569

2.33569 × 0.17060 1 × (1 − 0.17060)

+ =0
2.33569 − ∅ 1−∅

1st guess: ∅ = 1.85

2.33569 × 0.17060 1 × (1 − 0.17060)

+ = −0.15535
2.33569 − 1.85 1 − 1.85

2nd guess: ∅ = 1.95

2.33569 × 0.17078 1 × (1 − 0.17078)

+ = 0.16007
2.33569 − 1.95 1 − 1.95
By further trials or interpolation, ∅ = 1.90223

The root of equation is substituted into Underwood equation to find minimum reflux, Rmin:

2
αi xDi
𝑅𝑚𝑖𝑛 + 1 = ∑
αi − ∅
𝑖=1

2.33569 × 0.37937 1 × (1 − 0.37937)

𝑅𝑚𝑖𝑛 = + −1
2.33569 − 1.90223 1 − 1.90223

𝑅𝑚𝑖𝑛 = 0.35634

The calculation steps above are repeated to find the root of equation and minimum reflux at each
sampling time. Then, the results are tabulated in Table 9.3.1.

Table 9.3.1: Root of Equation and Minimum Reflux at Each Sampling Time.
Sampling Time αEtOH xD,EtOH ∅ Rmin
0.0 2.33569 0.37937 1.90223 0.35634
10.0 2.33247 0.41345 1.90046 1.03368
20.0 2.33014 0.43251 1.89917 1.39447
30.0 2.32869 0.46088 1.89838 1.59952
40.0 2.32811 0.50357 1.89806 1.71323
50.0 2.32725 0.54655 1.89758 1.78944
60.0 2.32754 0.59829 1.89774 1.87879
10. DISCUSSION

For distillate, the composition of ethanol obtained experimentally is 23.20629 % lesser

than the composition of ethanol obtained theoretically. The percentage error for distillate is quite
a large number which is more than 10.0 %. This number shows that the experiment work was not
accurate enough. One of the possible reasons is that the distillate was not drained off from
product tank B3 at every 10-minute interval after collecting the sample as what had been
practiced when collecting bottom products. As a result, the actual composition of ethanol in
distillate was disrupted by the composition of ethanol at previous sampling time. Therefore, the
composition of ethanol obtained at the last sampling time would be significantly lesser than the
theoretical answer. It is recommended to drain off the distillate from product tank B3 after each
collection of sample to ensure the purity of the distillate obtained. Besides, it is deduced that the
steady state had not been reached by the system when the last set of data was recorded since the
results obtained did not tail off considerably at the last sampling time. Therefore, a different
composition is obtained using material balance. Apart from that, the uncertainties of the data
extrapolated from Graph 8.1 are very large. Large uncertainties will result in the inaccurate
results of the compositions at each sampling time. Moreover, it is speculated that the refractive
index meter was not properly cleaned when it was tested with another solution. The refractive
index meter used in this experiment was highly sensitive. Even the slightest amount of impurities
could influence its reading. One must be very attentive to ensure the refractive index meter was
clean. Therefore, the readings obtained from this experiment would not be affected by the
impurities. Furthermore, ethanol used in this experiment was the component with high volatility
under room temperature. The ambient temperature when the experiment was conducted was even
higher. They could be vaporised easily when transferring to sample bottles and refractive index
meter. As such, the compositions of ethanol in distillates and bottom products were lost
significantly. To improve, the samples in sample bottles must be enclosed tightly with caps as
soon as they were collected from the product tanks. Transferring of the samples must also be
done quickly to minimise the vaporisation of ethanol. In addition, the results could be further
diminished by the readings from refractive index meter when the medium becomes less dense
upon the high ambient temperature because the refractive index of a component was
temperature-dependent (Ohara, 2017).
 Usually, reflux ratio is calculated by Equation 2.1.1. However, reflux ratio is operated in
terms of time in manual operation. Before operating the distillation column, reflux timer set 1
was set to 30 seconds while set 2 was set to 60 seconds. In other words, the condensate from
condenser would return back to column for 30 seconds and get routed out as distillate for 60
seconds. Therefore, the reflux ratio is 30:60 or 0.5. According to Graph 9.2.2, the number of
theoretical stages is infinite when reflux ratio of 0.5 is applied. After performing Underwood
Equation it is found that the minimum reflux ratio at 60th minute is 1.79254. The minimum
reflux ratio is the limiting reflux where the operating line either touches the equilibrium curve or
intersects the equilibrium curve at the q-line. The minimum reflux ratio will require an infinite
number of trays to attain the specified separation of xD and xB. A separation could not be
achieved when reflux ratio applied is below the minimum reflux ratio (Porter, 2011). The reasons
of getting inaccurate compositions are as discussed above. It is also observed that as the reflux
ratio increases from 0.5 to 1.79254, the number of theoretical plates required decreases from
infinite to 4.54947. Figure 10.1 as cited in Cheah (2017) shows the relationship between number
of theoretical stages and reflux ratio.

Figure 10.1: Relationship between R and N.

In this experiment, it is noted that the distillation column unit is operated in counter-
current mixing model. It is designed with the feed heated up in the reboiler at the bottom of the
column while distillate condensed in the condenser on the top of the column and refluxed back to
the column. The condensed liquid will sink continuously to the bottom of the column as it is
denser. This flow pattern appreciably prevents channelling of feed, which will decrease the mass
transfer between two phases, from occurring (Hatem, 2015). On the other hand, the vaporised
feed will float to the top of the column as it is less dense. As such, the contact area between two
different phases is maximised. Larger contact area enhances the mass transfer in the distillation
process. Subsequently, two different components are separated due to the difference in densities.
The gas phase is condensed and collected from the top of the column as the distillate and the
liquid phase is collected from the bottom of the column as the bottom product.

Raschig rings are stacked in the packed column to aid ethanol vapours travelling towards
the condensing unit while stopping vapours of other harmful substances from proceeding
upwards. As such, purer and stronger ethanol can be obtained when these rings are used in the
distillation column (Ibrew, 2016). In the case of facilitating mass transfer of ethanol, raschig
rings provide high surface area per unit volume for mass transfer while maintaining the
maximum free space in the column. As the liquid phase runs down the column, the surface of
raschig rings is completely covered, while the gas phase goes up. Thereby, the flow rate of the
gas bubbles from the bottom to the top can be reduced. Due to the longer residence time in the
column, the mass transfer of ethanol to the gas bubbles is enhanced (Hatem, 2015). Furthermore,
the vapour and the liquid are in continuous contact on the surfaces of the packed bed, so the
particles can interact more efficiently. Hence, the tendency towards equilibrium is increased as
the liquid phase and the gas phase pass each other in a small space (Ibrew, 2016). As a result,
higher separation efficiency can be achieved.

When conducting the experiment, the size change in gas bubbles is observable. The gas
bubbles invariably become smaller all the way from the bottom to the top of the column. This
can be explained by Marangoni effect which creates interfacial tension gradients for mass
transfer of ethanol among two phases. According to Zuiderweg & Harmens (1958), liquid films
are stabilised when the surface tension of the reflux increases down the column. As the gas
bubbles rise to the top, the surface tension decreases. In this way, a surface tension gradient is
created. This phenomenon will cause the rapid movement in the surface and lead to a spreading
of surface. In other words, the films are broken into small bubbles. Once the bubbles are formed,
the heavier component (water) will preferentially saturate at the spot between adjacent bubbles
as shown in Figure 10.2. Mass transfer is aided with the lower surface tension around the bubbles
because the large concentration difference in the liquid surface promotes the mass transfer of
ethanol into gas bubbles. Consequently, the distillate with higher composition of ethanol can be
obtained from the top of the column.

Figure 10.2: Schematic Illustration of the Stabilisation of Vapour Bubbles. Shaded Areas Denote
Liquid of Lower Surface Tension (Zuiderweg & Harmens, 1958).

11. CONCLUSION

Material balance calculation is carried out to find the composition of ethanol in distillate. The
theoretical answer is 0.98688 gEtOH/gD while the experimental data is 0.80100 gEtOH/gD. The
experimental data is 23.20629 % lesser than the composition of ethanol obtained theoretically
due to the errors discussed above. For the sample collected at the last sampling time, the number
of theoretical stages determined by means of McCabe-Thiele method is infinity when a reflux
ratio of 0.5 is applied. The number of theoretical stages determined by means of Fenske equation
is 3.68567. The minimum reflux ratio determined by means of Underwood equation is 1.87879.
Since the reflux ratio actually applied in the operation is below the minimum reflux ratio, the
separation is unrealizable. Consequently, McCabe-Thiele method exhibits an infinite number of
theoretical stages. As the reflux ratio is increased to 1.87879, the number of theoretical stages is
decreased to 3.68567. Hence, it is concluded that the greater the reflux ratio, the smaller the
number of theoretical stages required to achieve a separation. Thereby, it is easier to separate two
different components. Packing materials in a packed column enhances mass transfer between
two phases by means of maximising the surface area per unit volume of contact between two
phases. Therefore, packed column can achieve better mass transfer. The hypotheses stated are
accepted.
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