NTU SCBE C2 - Distillation

C2: Distillation (Formal Report)
Table of Contents
Aim ..................................................................................................................................... 3
Abstract ............................................................................................................................... 3
Principles............................................................................................................................. 4
Equipment and Materials .................................................................................................. 18
Procedure .......................................................................................................................... 21
Results ............................................................................................................................... 23
Discussion ......................................................................................................................... 39
Conclusion ........................................................................................................................ 42
Appendix ........................................................................................................................... 43
Raw Data ........................................................................................................................... 45
References ......................................................................................................................... 46
Aim
The objective of this experiment was to investigate the dynamic behavior of a distillation
column. This was done by (i) determining the number of theoretical trays required for the
distillation of a binary mixture using the McCabe-Thiele and Fenske’s method (ii) calculating the
column efficiency (iii) studying the steady-state operation of the distillation of a binary mixture
(iv) determining the relationship between the reflux ratio and the column performance.
Abstract
The theoretical number of trays and column efficiency for a distillation column under
total and partial reflux was determined using the Fenske’s and McCabe-Thiel method. It was
found that both reflux conditions had the same theoretical number of trays and column efficiency
of 3 and 37.5% respectively. It was concluded that the reflux condition did not have a significant
impact on the theoretical number of trays or the column efficiency. This was mainly attributed to
the non-ideal feed location and the content of each tray not reaching vapor-liquid equilibrium due
to poor mass transfer. It was found that during steady state operation of the distillation column
that the column temperature generally increases down the column.

Principles
Distillation column
A distillation column is a unit operation that utilizes the difference in vapor pressure of
components in a mixture to separate the components. The main components of a distillation
column are the condenser, reboiler, and the column itself. During operation, the column has an
increasing temperature profile down the column which allows all the trays to be at a different
vapor-liquid equilibrium state. Mass transfer between the trays is then maintained by sending
back part of the outlet as liquid and vapor at the condenser and reboiler. This in effect results in
the separation of the feed mixture to give a top stream that is rich in the more volatile component
and a bottom stream that is rich in the less volatile component.
Figure 1 Schematic diagram of a typical distillation column

Constant molar overflow (CMO)
Constant molar overflow is an assumption that assumes uniform flowrate of liquid and
vapor in the rectifying and stripping section. This assumption simplifies the derivation of the
operating lines by eliminating the need for energy balance. The conditions for CMO to apply are
as follow:
• Constant heat of vaporization that is not a function of composition (Ideal liquid)
• Sensible heat and heat of mixing is negligible relative to latent heat
• No heat lost to surrounding
• Uniform pressure profile in column
The mathematical form of the CMO assumption is:
Rectifying Section
𝐿1 = 𝐿2 = 𝐿3 = ⋯ = 𝐿𝑛 = 𝐿
𝑉1 = 𝑉2 = 𝑉3 = ⋯ = 𝑉𝑛 = 𝑉
Stripping Section
𝐿̅1 = 𝐿̅2 = 𝐿̅3 = ⋯ = 𝐿̅𝑛 = 𝐿̅
𝑉̅1 = 𝑉̅2 = 𝑉̅3 = ⋯ = 𝑉̅𝑛 = 𝑉̅
The equations imply that both the liquid and vapor molar flow rate in the rectifying section
and stripping section are uniform.

Mass Balance and Operating Lines
In the experiment, the distillation of a binary ethanol-water mixture was investigated. The
CMO (constant molar flowrate) assumption was assumed to be true to facilitate the derivation of
the operating lines. All concentrations used are that of the more volatile component, ethanol.
Tray numbering convention
For the following derivation for the operating lines, the following tray numbering system
sown in Figure 1 is adopted for the rectification and stripping sections:
Figure 2 Depicts tray numbering system adopted for derivation of operating lines
The tray that is closest to the condenser is labeled as tray 1 while the last tray is labeled
tray N. The tray that is directly above the feed tray is labeled as tray n and the one directly below
is labeled as tray m.
Rectifying section operating line
Overall and component mass balances could be done around the section called the ‘rectifying
section’ outlined in the red boundary shown below in Figure 2.
Overall Balance:
𝑉𝑛+1 = 𝐿𝑛 + 𝐷
Component Balance:
𝑦𝑛+1 𝑉𝑛+1 = 𝑥𝑛 𝐿𝑛 + 𝑥𝐷 𝐷
Rearranging the component balance,
𝐿𝑛 𝐷
𝑦𝑛+1 = 𝑥𝑛 + 𝑥𝐷
𝑉𝑛+1 𝑉𝑛+1
Substituting in the overall mass balance,
𝐿𝑛 𝑉𝑛+1 − 𝐿𝑛
𝑦𝑛+1 = 𝑥𝑛 + 𝑥𝐷
𝐿𝑛 𝐿𝑛
𝑦𝑛+1 = 𝑥𝑛 + 𝑥𝐷 (1 − )
Applying CMO assumption,
𝐿 𝐿
𝑦𝑛+1 = 𝑥𝑛 + 𝑥𝐷 (1 − )
𝑉 𝑉
By doing a mass balance on the condenser, it can be found that:
𝑉 =𝐿+𝐷
Substituting the expression into the main equation,
𝐿 𝐿+𝐷 𝐿
𝑦𝑛+1 = 𝑥𝑛 + 𝑥𝐷 ( − )
𝑉 𝑉 𝑉
𝑳 𝑫
𝒚𝒏+𝟏 = 𝒙𝒏 + 𝒙𝑫 ( )
𝑽 𝑽
Figure 3 Rectifying section of distillation column

Stripping section operating line
Overall and component mass balances could be similarly done around the section called
the ‘stripping section’ outlined in the red boundary shown below in Figure 3.
Overall Balance:
𝐿̅𝑚 = 𝑉̅𝑚+1 + 𝐵
Component Balance:
𝑥𝑚 𝐿̅𝑚 = 𝑦𝑚+1 𝑉̅𝑚+1 + 𝑥𝐵 𝐵
Rearranging the component balance,
𝐿̅𝑚 𝐵
𝑦𝑚+1 = 𝑥𝑚 − 𝑥𝐵
𝑉̅𝑚+1 𝑉̅𝑚+1
Substituting in the overall mass balance,
𝐿̅𝑚 𝐿̅𝑚 − 𝑉̅𝑚+1

𝑦𝑚+1 = 𝑥𝑚 − 𝑥𝐵
𝑉̅𝑚+1 𝑉̅𝑚+1
𝐿̅𝑚 𝐿̅𝑚
𝑦𝑚+1 = 𝑥𝑚 − 𝑥𝐵 ( − 1)
𝑉̅𝑚+1 𝑉̅𝑚+1
Applying CMO assumption,
𝐿̅ 𝐿̅
𝑦𝑚+1 = 𝑥𝑚 − 𝑥𝐵 ( − 1)
𝑉̅ 𝑉̅
By doing a mass balance on the reboiler, it can be found that:
𝐿̅ = 𝑉̅ + 𝐵
Substituting the above expression into the main equation,

𝐿̅ 𝑉̅ + 𝐵
𝑦𝑚+1 = 𝑥𝑚 − 𝑥𝐵 ( − 1)
𝑉̅ 𝑉̅
𝑳̅ 𝑩
𝒚𝒎+𝟏 = 𝒙𝒎 − 𝒙𝑩 ( )
̅
𝑽 ̅
𝑽
Figure 4 Stripping section of distillation column

Feed section operating line
At the feed tray section depicted in Figure 4 and 5, both rectifying section and stripping
section will meet, and the operating lines of the sections will intersect. The two operating line
equations from before can be written as:
𝐿 𝐷
𝑦= 𝑥 + 𝑥𝐷 ( )
𝑉 𝑉
𝐿̅ 𝐵
𝑦= 𝑥 − 𝑥𝐵 ( )
𝑉̅ 𝑉̅
Rearranging the equations,
𝑦𝑉 = 𝑥𝐿 + 𝑥𝐷 𝐷
𝑦𝑉̅ = 𝑥𝐿̅ − 𝑥𝐵 𝐵
Subtract the 2nd equation from the 1st,
𝑦(𝑉 − 𝑉̅ ) = 𝑥𝐿 − 𝑥𝐿̅ + 𝑥𝐷 𝐷 + 𝑥𝐵 𝐵
From the overall mass balance of the whole column, we know:
𝐹𝑧𝐹 = 𝑥𝐷 𝐷 + 𝑥𝐵 𝐵
Hence,
𝑦(𝑉 − 𝑉̅ ) = 𝑥𝐿 − 𝑥𝐿̅ + 𝐹𝑧𝐹
Dividing all terms by F,
(𝑉 − 𝑉̅ ) (𝐿 − 𝐿̅)
𝑦 =𝑥 + 𝑧𝐹
𝐹 𝐹
Let the term 𝑞 , the feed liquid fraction, be defined as:
(𝐿 − 𝐿̅)
𝑞=
𝐹
From the feed tray balance depicted in Figure 5, it can be derived that:
(𝑉 − 𝑉̅ )
𝑞 = 1+
𝐹
Substituting the definition of q into the main equation,
𝑦(𝑞 − 1) = 𝑥𝑞 + 𝑧𝐹
Rearranging yields the feed operating line,
𝒒 𝒛𝑭
𝒚= 𝒙+
(𝒒 − 𝟏) (𝒒 − 𝟏)
Figure 5 Feed tray section of distillation column

Figure 6 Feed Tray enlarged with labeled streams
Reflux Ratio
The reflux ratio of a column is the ratio of the moles of liquid coming out of the condenser
that is sent back to the column versus the moles that is exiting the column as distillate. From the
mass balance around the condenser shown in Figure 7, the reflux ratio, R, is numerically equal to
Lo /D.
Figure 7 Mass Balance boundary around condenser

Boil-up ratio
The boil-up ratio of a column is the ratio of moles of vapor coming out of the condenser
that is sent back to the column versus the moles of liquid that is exiting the column as the bottom
product. From the mass balance around the condenser shown in Figure 8, the boil-up ratio, Vb, is
numerically equal to 𝑉̅ /B.
Figure 8 Mass Balance boundary around reboiler
McCabe-Thiel Method
This method is a graphical method that utilizes the CMO assumption to find the outlet
product concentrations given a certain reflux ratio. After applying the CMO assumption, the
operating lines for the rectifying and stripping sections will be:
Rectifying Section
𝑳 𝑫
𝒚𝒏+𝟏 = 𝒙𝒏 + 𝒙𝑫 ( )
𝑽 𝑽
Stripping Section
𝑳̅ 𝑩
𝒚𝒎+𝟏 = 𝒙𝒎 − 𝒙𝑩 ( )
̅
𝑽 ̅
𝑽
By substituting the definition of the reflux and boil-up ratios, R= Lo/D and Vb = 𝑉̅ /B, the
operating lines can be expressed as:
Rectifying Section
𝑹 𝟏
𝒚𝒏+𝟏 = 𝒙𝒏 + 𝒙𝑫 ( )
𝑹+𝟏 𝑹+𝟏
Stripping Section
𝟏 + 𝑽𝒃 𝟏
𝒚𝒎+𝟏 = 𝒙𝒎 − 𝒙𝑩 ( )
𝑽𝒃 𝑽𝒃
The number of trays will always be a discrete number. However, in the McCabe-Thiel
method, the operating lines are represented as continuous lines as shown in Figure 9. Using the
VLE curve and the operating lines, we can graphically determine the composition of each tray.
In the experiment, it can be inferred that y1, the vapor composition of the 1st tray is equal
to x d due to total condensation in the condenser. Using y1, we can determine the liquid
composition of the 1st tray by using the VLE curve. This is followed by determining y2, the vapor
composition of the 2nd tray, using the rectifying operating line. This ‘cascading’ process can be
repeated until we reach tray n, the tray directly above the feed tray, at which point the cascading
is carried out using the stripping operating line. The cascading process is repeated until the
composition of the last VLE is above xb, the target bottom product purity.
The number of vapor liquid equilibrium will be equal to the number of trays plus one re-
boiler. Hence, the theoretical number of trays can be calculated by subtracting 1 from the number
of equilibriums on the VLE curve.
Figure 9 McCabe-Thiele diagram for binary mixture distillation

Fenske Method
Fenske method is a numerical way to solve for the theoretical number of trays. This
method assumes constant relative volatility, large reflux, and CMO. This method consists of
using the equation below to solve for n, the theoretical number of trays.
𝑥 𝑥
log [(𝑥𝐴 ) ( 𝑥𝐵 ) ]
𝐵 𝐷 𝐴 𝐵
𝑛+1=
log [(𝛼𝐴𝐵 )𝑎𝑣𝑔 ]
Where,
n is the theoretical number of trays,
xA is the mole fraction of the MVC (most volatile component),
xB is the mole fraction of the LVC (least volatile component),
(𝛼𝐴𝐵 )𝑎𝑣𝑔 is the average volatility.
The average volatility can be found using the equation below:
(𝛼𝐴𝐵 )𝑎𝑣𝑔 = √(𝛼𝐴𝐵 )𝐷 (𝛼𝐴𝐵 )𝐵
Overall Column Efficiency
The column efficiency is defined by the below equation:
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑇𝑟𝑎𝑦𝑠

𝐸= × 100%
𝑁𝑢𝑚𝑏𝑒𝑟 𝐴𝑐𝑡𝑢𝑎𝑙 𝑇𝑟𝑎𝑦𝑠
Gas Chromatography
Gas Chromatography is a method that is commonly used to determine the composition of
a sample mixture. It works based on the principle that different molecules have different retention
time in a separation tube called a ‘column’. The sample mixture to be tested is injected into the
‘column’ of the Gas Chromatograph and travels down the column in the carrier gas. The more the
molecules of a species interacts with the column, the longer the retention time. This effect
separates the different molecules. The area under a peak is proportional to the amount of analyte
present in the sample. Hence, using the correlation below and further calculations, the
concentration can be calculated from the area of each peak.
𝐴𝑟𝑒𝑎 𝑜𝑓 𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝑃𝑒𝑎𝑘 = (1,372,660,756 × 𝑚𝑜𝑙 𝑜𝑓 𝐸𝑡𝑂𝐻) + 37.073268
𝐴𝑟𝑒𝑎 𝑜𝑓 𝑊𝑎𝑡𝑒𝑟 𝑃𝑒𝑎𝑘 = (530,329,224 × 𝑚𝑜𝑙 𝑜𝑓 𝐻2𝑂) − 12.410895
Equipment and Materials
Materials
• 30 mol% ethanol-water mixture (denatured with trace of methanol)
Equipment
• UOP3CC Distillation Column Unit
• Gas Chromatograph (GC)

Distillation Column Unit
A UOP3CC distillation column unit was used in this experiment to study binary distillation. A
diagram and schematic diagram of the unit is shown in Figure 10 and 11 respectively.
Figure 10 Diagram of UOP3CC distillation column unit

(Source: Che.utah.edu, 2020. [Online]. Available: https://www.che.utah.edu/site-specific-resources/chemical-
engineering/department_equipment/Projects_Lab/S_Distillation_Column/MANUAL_Armfield_Distillation_Column.pdf.
[Accessed: 30- Sep- 2020])
Figure 11 Schematic Diagram of UOP3CC distillation column unit

(Source: Che.utah.edu, 2020. [Online]. Available: https://www.che.utah.edu/site-specific resources/chemical-
engineering/department_equipment/Projects_Lab/S_Distillation_Column/MANUAL_Armfield_Distillation_Column.pdf.
[Accessed: 30- Sep- 2020])
Procedure
The experiment consisted of 2 parts: (a) Distillation under total reflux (b) Continuous distillation
at reflux ratio of 3:1.
Part A (Total Reflux)
1) 8 and 5 liters of the binary ethanol-water mixture was loaded into the boiler and feed tank
respectively.
2) All of the switches were changed to the ‘I/O port’ setting on the console unit. Both valve
V6 and V7 were opened to allow the manometer to balance out and this was followed by
closing the valves in the order of V6 to V7.
3) All valves were closed except for V10, which should be open.
4) The Reflux Valve, Reboiler, and Feed pump were turned on by pressing the red button on
the console unit.
5) Using the software interface on the lab computer, the feed pump speed was set to
approximately 30-40. After this was done, the setup was allowed to run until the feed
reaches just before the feed tray.
6) The feed was stopped by switching off the feed pump on the software interface.
7) Valve V5 was opened and the flowrate of the cooling water was adjusted to 3 L/min to
allow cooling water to flow into the condenser.
8) The mode of operation of the setup was changed to ‘PID1’ on the software interface. This
was followed by increasing the heater output to approximately 40.

9) The setup was allowed to run for approximately 40 minutes to reach steady state, at
which point T1 to T8 remained approximately constant.
10) Valve V6 and then V7 were both opened and closed in the same order. The pressure drop
reading on the manometer was then taken down.
11) In order to collect the top product, the line was flushed opening valve V3 and collecting
the initial 5ml in a waste container. After this was done, a sample of the top product was
collected in a small container.
12) The small container was labeled with ‘T’.
13) The bottom product was collected in a similar fashion by repeating step 11-12 on valve
V2.
14) 2 more sets of samples were collected with 10 minutes between each collection by
repeating step 11-13.
15) The temperatures T1 to T4 on the software interface were taken down.
Part B (3:1 Reflux)
1) The mode of operation of the setup was changed to ‘PID2’ on the software interface. This
was followed by changing the reflux ratio to 3:1 on the software interface under ‘mode of
operation’
2) Valve V1 was opened
3) The feed was fed into the column by setting the feed pump speed such that the liquid
level in the reboiler remains approximately constant with time.

4) After 1.5L of feed was fed into the column, Valve V6 and then V7 were both opened and
closed in the same order. The pressure drop reading on the manometer was then taken
down.
5) 3 sets of samples were then taken by repeating the exact procedure in step 11-14 of Part
(a).
6) The temperatures T1 to T4 on the software interface were taken down.
Results
A. Overall efficiency under total reflux conditions
1) Determination of column efficiency via Fenske’s method
The column efficiency was calculated by first determining the theoretical number of trays
required via the Fenske’s Method (applicable under total reflux) and then dividing it by the
actual number of trays. The Fenske equation is shown below and to use it, the (1) the molar
fraction of A and B in the distillate and bottom product and (2) the average volatility were
determined. Variables (1) were determined using the Gas Chromatography results while variable
(2) was determined using the Antoine equations of ethanol and water.
Equation 1 The Fenske equation
𝑥 𝑥
log [(𝑥𝐴 ) ( 𝑥𝐵 ) ]
𝐵 𝐷 𝐴 𝐵
𝑛+1=
Where,

To solve for xA and xB , the amount of ethanol and water in each sample was first calculated from
the area of the peaks using the following correlation equations.
The values of xA and xB was then determined using the following equations:
𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝐴𝑚𝑜𝑢𝑛𝑡
𝑥𝐴 =
𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝐴𝑚𝑜𝑢𝑛𝑡 + 𝑊𝑎𝑡𝑒𝑟 𝑎𝑚𝑜𝑢𝑛𝑡
𝑥𝐵 = 1 − 𝑥𝐴
(Sample calculation in Appendix A)
Table 1 Results of gas chromatography for distillate under total reflux
Ethanol Area Ethanol Amt Water Area Water Amt 𝑥𝐴

Reflux XA XB ( )
(μV*s) (μg) (μV*s) (μg) 𝑥𝐵
Total 1960.7 1.40E-06 168.0 3.40E-07 0.8047 0.1953 4.120
Total 2262.4 1.62E-06 194.7 3.90E-07 0.8059 0.1941 4.152
Total 2222.5 1.59E-06 187.7 3.77E-07 0.8084 0.1916 4.219
(Sample calculation in Appendix B)
Table 2 Results of gas chromatography for bottom product under total reflux
Ethanol Area Ethanol Amt Water Area Water Amt 𝑥𝐵

Reflux XA XB ( )
(μV*s) (μg) (μV*s) (μg) 𝑥𝐴
Total 1179.4 8.32E-07 1258.6 2.40E-06 0.2577 0.7423 2.880
Total 1323.0 9.37E-07 1397.9 2.66E-06 0.2605 0.7395 2.839
Total 1076.5 7.57E-07 1135.8 2.17E-06 0.2591 0.7409 2.859
𝑥 𝑥
Using the above results, the values of (𝑥𝐴 ) and (𝑥𝐵 ) were calculated,
𝐵 𝐷 𝐴 𝐵
𝑥𝐴 4.120 + 4.152 + 4.219

( ) =
𝑥𝐵 𝐷 3
𝑥𝐴
( ) = 4.164 (4 𝑠. 𝑓. )
𝑥𝐵 𝐷
𝑥𝐵 2.880 + 2.839 + 2.859

( ) =
𝑥𝐴 𝐵 3
𝑥𝐵
( ) = 2.859 (4 𝑠. 𝑓. )
𝑥𝐴 𝐵
Method 1 (Raoult’s Law)
In order to calculate the average relative volatility, the relative volatility at the top and
bottom plate must be found.
The relative volatility of two species A and B is defined as:

𝑦
(𝑥𝐴 )
𝛼𝐴𝐵 = 𝑦𝐴
(𝑥𝐵 )
𝐵
By assuming ideal liquid and vapor phase, Raoult’s Law will be valid. Hence, the
relativity was rewritten in terms of partial pressure:
Raoult’s Law can be expressed as,
𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
Rearranging,
𝑦𝑖 𝑃𝑖𝑠𝑎𝑡
=
𝑥𝑖 𝑃
Hence, the expression of relative volatility was written as,
𝑃 𝑠𝑎𝑡
( 𝐴𝑃 )
𝛼𝐴𝐵 =
𝑃 𝑠𝑎𝑡
( 𝐵𝑃 )
𝑃𝐴𝑠𝑎𝑡
𝛼𝐴𝐵 =
𝑃𝐵𝑠𝑎𝑡
The partial pressure of ethanol and water was then expressed using the Antoine equations
of ethanol and water [1],[2].

1598.673
105.24677−𝑇−46.424
𝛼𝐴𝐵 = 1435.264
104.6543−𝑇−64.848
The equilibrium temperature of the top tray and the bottom most tray are T1 and T8
respectively, hence, T1 and T8 were substituted into the above equation to yield (𝛼𝐴𝐵 )𝐷 and
(𝛼𝐴𝐵 )𝐵 .
For total reflux, T1 and T8 are 78.9oC and 82.5oC respectively, hence,
1598.673
10^(5.24677 − )
(78.9 + 273.15) − 46.424
(𝛼𝐴𝐵 )𝐷 =
1435.264
10^(4.6543 − )
(78.9 + 273.15) − 64.848
100.01596
(𝛼𝐴𝐵 )𝐷 = −0.34310
10
(𝛼𝐴𝐵 )𝐷 = 2.286 (4 𝑠. 𝑓. )
1598.673
10^(5.24677 − )
(82.5 + 273.15) − 46.424
(𝛼𝐴𝐵 )𝐵 =
1435.264
10^(4.6543 − )
(82.5 + 273.15) − 64.848
100.07685
(𝛼𝐴𝐵 )𝐷 =
10−0.28124
(𝛼𝐴𝐵 )𝐷 = 2.281 (4 𝑠. 𝑓. )
Therefore, the average volatility was calculated to be:
(𝛼𝐴𝐵 )𝑎𝑣𝑔 = √2.286 ∗ 2.281
(𝛼𝐴𝐵 )𝑎𝑣𝑔 = 2.284 (4 𝑠. 𝑓. )
𝑥 𝑥
log [(𝑥𝐴 ) ( 𝑥𝐵 ) ]
𝐵 𝐷 𝐴 𝐵
𝑛+1=
log [4.164 ∗ 2.859]

𝑛= −1
log [2.284]
𝑛 = 2.999 (4 𝑠. 𝑓. )
However, n is the number of trays and must be an integer, hence,
𝑛= 3
To calculate column efficiency,

𝐸= × 100%
3
𝐸, 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑟𝑒𝑓𝑙𝑢𝑥 = × 100%
8
𝐸, 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑟𝑒𝑓𝑙𝑢𝑥 = 37.5 %

However, method 1 is not very appropriate for the binary distillation of an ethanol-water
mixture. This is because there are strong interactions between molecules of ethanol and water
that results in a positive deviation of the activity coefficient. Therefore, a method to determine
the average volatility of the mixture that does not assume ideal liquid and vapor would be more
appropriate. An alternative method to carry out the Fenske method is outlined below:
Method 2 (Graphical Method)
From the results of the gas chromatography, the average x A and xB for both distillate and
bottom product were calculated. The yA and yB were then be obtained using the x-y graph of
ethanol-water mixture as shown in Figure 12.
Figure 12 x-y diagram of ethanol-water mixture with xA and XB labeled

Using the formula below, the relative volatility of distillate and bottom product was
found:
𝑦
(𝑥𝐴 )
𝛼𝐴𝐵 = 𝑦𝐴
(𝑥𝐵 )
𝐵
The results are summarized in below:
Table 3 Results from graphical determination of vapor mole fraction
Distillate Bottom Product

Reflux xA xB yA yB xA xB yA yB (𝛼𝐴𝐵 )𝐷 (𝛼𝐴𝐵 )𝐵
Total 0.8063 0.1937 0.8100 0.1900 0.2591 0.7409 0.5600 0.4400 1.024 3.639
Partial 0.7354 0.2646 0.7300 0.2700 0.2051 0.7949 0.5300 0.4700 0.973 4.369
The average volatility was then calculated,
(𝛼𝐴𝐵 )𝑎𝑣𝑔 = √1.024 ∗ 3.639
(𝛼𝐴𝐵 )𝑎𝑣𝑔 = 1.930 (4 𝑠. 𝑓. )
𝑥 𝑥
log [(𝑥𝐴 ) ( 𝑥𝐵 ) ]
𝐵 𝐷 𝐴 𝐵
𝑛+1=
log [4.164 ∗ 2.859]

𝑛= −1
log [1.930]
𝑛 = 2.767 (4 𝑠. 𝑓. )
However, n is the number of trays and must be an integer, hence,
𝑛= 3

𝐸= × 100%
3
𝐸, 𝑡𝑜𝑡𝑎𝑙 𝑟𝑒𝑓𝑙𝑢𝑥 = × 100%
8
𝐸, 𝑡𝑜𝑡𝑎𝑙 𝑟𝑒𝑓𝑙𝑢𝑥 = 37.5%
2) Column Temperature Profile (Total Reflux)
Figure 13 Temperature Profile of the column under total reflux

B. Effect of reflux ratios on the separation
1) Column Temperature Profile (Partial Reflux, R=3)
Figure 14 Temperature Profile of the column under partial reflux (R=3)
2) McCabe-Thiel Method
The McCabe-Thiel method outlined in the principle section of the report was used to
construct a McCabe-Thiel diagram that could be used to determine the theoretical number of
trays.
Distillate and Bottom Product Composition
The raw data from the Gas Chromatography was used to find the composition of the
distillate and the bottom product (Sample Calculation in Appendix A). The results are
summarized in the table below:

Table 4 Results of gas chromatography for distillate under partial reflux
Ethanol Area Ethanol Amt Water Area Water Amt

Reflux XA XB
(μV*s) (μg) (μV*s) (μg)
Partial 2156.4 1.54E-06 255.3 5.05E-07 0.7536 0.2464
Partial 2024.7 1.45E-06 268.6 5.30E-07 0.7321 0.2679
Partial 2112.6 1.51E-06 298.4 5.86E-07 0.7206 0.2794
Table 5 Results of gas chromatography for bottom product under partial reflux
Ethanol Area Ethanol Amt Water Area Water Amt

Reflux XA XB
(μV*s) (μg) (μV*s) (μg)
Partial 1223.5 8.64E-07 1672.3 3.18E-06 0.2139 0.7861
Partial 1102.1 7.76E-07 1538.7 2.92E-06 0.2097 0.7903
Partial 740.4 5.12E-07 1132.0 2.16E-06 0.1919 0.8081
The average values of xA and xB for both distillate and bottom product were calculated:
Distillate
0.7536 + 0.7321 + 0.7206

𝑥𝐴 =
3
𝑥𝐴 = 0.7354 (4 𝑠. 𝑓. )
𝑥𝐵 = 1 − 𝑥𝐴
𝑥𝐵 = 1 − 0.7354
𝑥𝐵 = 0.2646 (4 𝑠. 𝑓. )
Bottom Product
0.2139 + 0.2097 + 0.1919

𝑥𝐴 =
3
𝑥𝐴 = 0.2052 (4 𝑠. 𝑓. )
𝑥𝐵 = 1 − 𝑥𝐴
𝑥𝐵 = 1 − 0.2052
𝑥𝐵 = 0.7948 (4 𝑠. 𝑓. )
Feed Conditions
Two unknowns, the feed composition and feed liquid fraction, were needed to construct
the feed operating line for the McCabe-Thiel diagram. The composition of the feed was given to
be zF = 0.3. The value of q, the moles of liquid flow in the stripping section that resulted from the
introduction of each mole of feed, was not given. Hence, it was calculated using energy balance
on the feed tray.
In the experiment, the ethanol-water mixture feed was originally in liquid phase and was
not in a vapor liquid equilibrium (VLE). Therefore, it was inferred that it was a sub-cooled feed
with q, the liquid fraction>1. Another way to infer this is by comparing the boiling point of the
most volatile compound (MVP) and the feed inlet temperature, T14. The feed temperature
obtained from the software interface was 41.6 oC and is lower than the boiling temperature of
ethanol (78.4oC). Hence, it must be the case that q>1.

From the energy of the feed tray, the following expression of q can be found:
(𝑇𝑏 − 𝑇𝑓 )
𝑞 = 1 + 𝐶𝑝𝐿
𝜆
Where,
𝐶𝑝𝐿 is the specific heat capacity of liquid,
𝑇𝑓 is the feed temperature,
𝑇𝑏 is the bubble point temperature,
𝜆 is the heat of vaporization.
Heat Capacity Calculation
The heat capacity of pure ethanol at 40 oC and 45oC are 0.6360 and 0.6484 cal*g -1*OC-1
[3]. Using linear interpolation, the heat capacity of pure ethanol at 41.6oC (feed temperature) was
calculated.
(41.6 − 40)
𝐶𝑃,𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = 0.6360 + (0.6484 − 0.6360) ∗
(45 − 40)
cal
𝐶𝑃,𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = 0.6400
g°C
J
𝐶𝑃,𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = 2.678 (4 𝑠. 𝑓. )
g°C
The heat capacity of pure water at 41.6oC was calculated with the following equation [2]:
𝑇 𝑇 2 𝑇 3 𝑇 2
𝐶𝑃,𝑤𝑎𝑡𝑒𝑟 = −203.606 + 1523.290 − 3196.413 + 2474.455 + 3.855326
1000 1000 1000 1000
(41.6 + 273.15) 41.6 + 273.15 2 41.6 + 273.15 3

𝐶𝑃,𝑤𝑎𝑡𝑒𝑟 = −203.606 + 1523.290 ∗ − 3196.413 ∗ ( ) + 2474.455 ∗ ( )
1000 1000 1000
41.6 + 273.15 2
+ 3.855326 ÷ ( )
1000
𝐶𝑃,𝑤𝑎𝑡𝑒𝑟 = −203.606 + 479.455 − 316.661 + 77.157 + 38.916
𝐽
𝐶𝑃,𝑤𝑎𝑡𝑒𝑟 = 75.261
𝑚𝑜𝑙 𝐾
𝐽 𝑚𝑜𝑙
𝐶𝑃,𝑤𝑎𝑡𝑒𝑟 = 75.261 ∗
𝑚𝑜𝑙 𝐾 18.015𝑔
𝐽
𝐶𝑃,𝑤𝑎𝑡𝑒𝑟 = 4.178
𝑔𝑜 𝐶
By assuming ideal mixture and assuming an ethanol mole fraction of 0.3, the heat capacity of the
mixture was obtained:
𝐶𝑃,𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 0.3 ∗ 2.678 + 0.7 ∗ 4.178
𝐽
𝐶𝑃,𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 3.731 (4 𝑠. 𝑓. )
𝑚𝑜𝑙 𝐾
The pressure in the column was assumed to be at 1atm. The bubble point of the mixture,Tb, was
taken to be the atmospheric boiling temperature of pure ethanol of 78.4oC.
Graphical Determination of Heat of Vaporization
The heat of vaporization at feed temperature (106.8oF) was found from the H-x,y diagram
shown below. The heat of vaporization of feed was found to be 850 Btu/lb which is 1977.1 J/g in
SI units.
Figure 15 H-x,y diagram of ethanol-water binary mixture (Source:

https://www.et.byu.edu/~rowley/ChEn273/Topics/Energy_Balances/Nonreacting_Systems/Enthalpy_Conc
_Diag/Balances_Enth_CD.htm)
By substituting all values found above into the equation below, the value of q was determined.
(𝑇𝑏 − 𝑇𝑓 )
𝑞 = 1 + 𝐶𝑝𝐿
𝜆
(78.4 − 41.6) 𝐽 𝑔°𝐶

𝑞 = 1 + 3.731 ∗
1977.1 𝑔°𝐶 𝐽
𝑞 = 1.069 (4 𝑠. 𝑓. )
Feed Operating Line
With the value of q and zF known, the equation of the feed operating line was written as:
𝑞 𝑧𝐹
𝑦= 𝑥+
(𝑞 − 1) (𝑞 − 1)
1.069 0.3
𝑦= 𝑥+
(1.069 − 1) (1.069 − 1)
𝒚 = 𝟏𝟓. 𝟒𝟗𝒙 + 𝟒. 𝟑𝟓
Rectifying Operating Line
R 1
y = xn + xD ( )
R+1 R+1
It was given that R = 3 and distillate ethanol mole fraction xD = 0.7354, therefore,
3 1
y = xn + 0.7354( )
3+1 3+1
𝐲 = 𝟎. 𝟕𝟓𝐱 𝐧 + 𝟎. 𝟏𝟖
McCabe-Thiel Diagram
The rectifying and feed operating lines were plotted on to the x-y diagram for ethanol-
water mixture. The stripping line was then plotted by connecting the intersection of the rectifying
and feed lines with the point (x B, xB). It was determined from the diagram that the number of
theoretical steps is 4.
Figure 16 McCabe-Thiel diagram of distillation of ethanol-water mixture
The number of trays plus reboiler equals 4, hence the number of theoretical trays is 3.

𝐸= × 100%
3
𝐸, 𝑡𝑜𝑡𝑎𝑙 𝑟𝑒𝑓𝑙𝑢𝑥 = × 100%
8
𝐸, 𝑡𝑜𝑡𝑎𝑙 𝑟𝑒𝑓𝑙𝑢𝑥 = 37.5%
Discussion
Column Efficiency
The table below summarizes the theoretical and actual number of trays, and the
corresponding column efficiency for total and partial reflux conditions.
Table 6 Summary of theoretical number of trays and column efficiency
Reflux Theoretical no. of Trays Actual no. of Trays Column Efficiency

Condition (%)
Total 3 8 37.5
Partial 3 8 37.5
Both total and partial reflux (R=3) gave the same column efficiency of 37.5%. This
phenomenon of low column efficiency for both conditions might be explained by VLE not being
reach in the trays due to poor liquid vapor contact. Figure 17 shows the normal operation with
good liquid vapor contact. This poor mass transfer between the liquid phase and the vapor phase
might be due to weeping or entrainment, where the liquid passes through the perforations on the
trays or the vapor flowrate is too high, respectively. Figure 18 shows how poor mass transfer
(which causes VLE to be not achieved) increases the actual number of steps.
The other reason that might have caused the discrepancy is the assumption that the
ethanol-water mixture is ideal. Ethanol-water binary mixtures are non-ideal with ethanol and
water molecules interacting strongly. The utilization of a thermodynamical model like NRTL to
take into account the non-ideal interaction would yield more accurate results compared to using
Raoult’s Law.
Figure 17 Depiction of vapor bubbling through sieve tray (Source:

http://chemknowhow.blogspot.com/2014/10/functions-of-tray-in-distillation-column.html)
Figure 18 McCabe-Thiel diagram for complete VLE (green) and incomplete VLE (yellow)
Optimum feed location
From Figure 16, the ideal feed location for partial distillation (R=3) would be at the
reboiler (tray 4). This is because it is the 1st point after the intersection of the rectifying and
stripping lines and therefore results in the feed having the most similar composition to the
internal column composition. Apart from the fact that the ideal feed location is the reboiler, it is
theoretically impossible to position the feed entry at tray 1,2, or 3. This is due to the very small
boil up ratio, Vb, that caused the stripping line to be very steep. This can be seen on Figure 16,
where the cascading could not have been done using the stripping line at tray 1,2, or 3 as the
stripping line is not under the VLE curve.
From Figure 11, it can be seen that the feed location used in the experiment was the 5th
tray. It would not be a fair comparison if the theoretical and actual feed location were compared
as in both case the number of trays is different. However, it should be noted that the theoretical
optimum feed location is at the reboiler while the actual feed location is in the center of the
column. This poor positioning of the feed location is most likely the cause for the low column
efficiency for both total and partial reflux cases.
Conclusion
The theoretical number of trays and column efficiency determined by Fenske’s method
for total reflux condition was 3 and 37.5% respectively. On the other hand, the theoretical number
of trays and column efficiency obtained for the partial reflux condition determined via the
McCabe-Thiel method was the same and was 3 and 37.5% respectively. Therefore, the reflu x
condition of the column did not have a significant effect on the column efficiency and more
studies will need to be done to understand its effects. The low efficiency of the column obtained
was attributed to the non-ideal feed stream location and the poor mass transfer between the liquid
and vapor phase in the trays. The temperature profile of the column was found to be increasing
from the top to the bottom of the column.

Appendix
Appendix A (Sample calculation for xA and xB of distillate, sample 1)
1960.7 = (1,372,660,756 × 𝑚𝑜𝑙 𝑜𝑓 𝐸𝑡𝑂𝐻) + 37.073268
1960.7 − 37.073268
𝑚𝑜𝑙 𝑜𝑓 𝐸𝑡𝑂𝐻 =
1,372,660,756
𝑚𝑜𝑙 𝑜𝑓 𝐸𝑡𝑂𝐻 = 1.401 × 10−6 (4 𝑠. 𝑓. )
168.0 = (530,329,224 × 𝑚𝑜𝑙 𝑜𝑓 𝐻2𝑂) − 12.410895
168.0 + 12.410895
𝑚𝑜𝑙 𝑜𝑓 𝐻2𝑂 =
530,329,224
𝑚𝑜𝑙 𝑜𝑓 𝐻2𝑂 = 3.402 × 10−7 (4 𝑠. 𝑓. )
𝑥𝐴 =
1.401 × 10−6
𝑥𝐴 =
1.401 × 10−6 + 3.402 × 10−7
𝑥𝐴 = 0.8046 (4 𝑠. 𝑓. )
𝑥𝐵 = 1 − 𝑥𝐴
𝑥𝐵 = 1 − 0.8046
𝑥𝐵 = 0.1954 (4 𝑠. 𝑓. )
𝑥𝐴
= 4.1178 (4 𝑠. 𝑓. )
𝑥𝐵
Appendix B (Sample calculation for xA and xB of bottom product, sample 1)
1179.4 = (1,372,660,756 × 𝑚𝑜𝑙 𝑜𝑓 𝐸𝑡𝑂𝐻) + 37.073268
1179.4 − 37.073268
𝑚𝑜𝑙 𝑜𝑓 𝐸𝑡𝑂𝐻 =
1,372,660,756
𝑚𝑜𝑙 𝑜𝑓 𝐸𝑡𝑂𝐻 = 8.322 × 10−7 (4 𝑠. 𝑓. )
1258.6 = (530,329,224 × 𝑚𝑜𝑙 𝑜𝑓 𝐻2𝑂) − 12.410895
1258.6 + 12.410895
𝑚𝑜𝑙 𝑜𝑓 𝐻2𝑂 =
530,329,224
𝑚𝑜𝑙 𝑜𝑓 𝐻2𝑂 = 2.397 × 10−6 (4 𝑠. 𝑓. )
𝑥𝐴 =
8.322 × 10−7
𝑥𝐴 =
8.322 × 10−7 + 2.397 × 10−6
𝑥𝐴 = 0.2577 (4 𝑠. 𝑓. )
𝑥𝐵 = 1 − 𝑥𝐴
𝑥𝐵 = 1 − 0.2577
𝑥𝐵 = 0.7423 (4 𝑠. 𝑓. )
𝑥𝐵
= 2.880 (4 𝑠. 𝑓. )
𝑥𝐴
Appendix C
Raw Data
Table 7 Results of Gas Chromatography
Top Bottom
Pressure Ethanol Water Ethanol Water
Reflux Sample # drop Area Area Area Area
(mmH2O) (μV*s) (μV*s) (μV*s) (μV*s)
1 83 1960.7 168.0 1179.4 1258.6
Total 2 83 2262.4 194.7 1323.0 1397.9
3 83 2222.5 187.7 1076.5 1135.8
1 78 2156.4 255.3 1223.5 1672.3
3:1
2 76 2024.7 268.6 1102.1 1538.7
Reflux
3 76 2112.6 298.4 740.4 1132.0
Table 8 Temperature readings of T1 to T4
Temperature/Mode Total 3:1

of operation Reflux Reflux
T1 78.9 79.2
T2 79.1 79.5
T3 78.7 79.3
T4 79.3 80.1
T5 79.2 81.2
T6 81 83
T7 79.8 81.7
T8 80.6 83
T9 82.5 83.1
T10 79.5 79.8
T11 28.2 28.1
T12 31.1 30.3
T13 38.1 41.2
T14 23.8 41.6
References
[1] "Ethanol", Webbook.nist.gov, 2020. [Online]. Available:
https://webbook.nist.gov/cgi/cbook.cgi?ID=C64175&Mask=4&Type=ANTOINE&Plot=on
. [Accessed: 02- Oct- 2020].
[2] "Water", Webbook.nist.gov, 2020. [Online]. Available:
https://webbook.nist.gov/cgi/cbook.cgi?ID=C7732185&Mask=4&Type=ANTOINE&Plot=
on. [Accessed: 02- Oct- 2020].
[3] M. Stephens and J. Olson, "Measurement of excess molar heat capacities by differential
scanning calorimetry", Thermochimica Acta, vol. 76, no. 1-2, pp. 79-85, 1984. Available:
10.1016/0040-6031(84)87005-7 [Accessed 2 October 2020].
-End of Report-

NTU SCBE C2 - Distillation

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C2: Distillation (Formal Report)

C2: Distillation (Formal Report)

Equipment and Materials .................................................................................................. 18

Raw Data ........................................................................................................................... 45

that the column temperature generally increases down the column.

components in a mixture to separate the components. The main components of a distillation

and a bottom stream that is rich in the less volatile component.

Figure 1 Schematic diagram of a typical distillation column

Constant molar overflow (CMO)

• Constant heat of vaporization that is not a function of composition (Ideal liquid)

• Sensible heat and heat of mixing is negligible relative to latent heat

• No heat lost to surrounding

• Uniform pressure profile in column

The mathematical form of the CMO assumption is:

𝐿̅1 = 𝐿̅2 = 𝐿̅3 = ⋯ = 𝐿̅𝑛 = 𝐿̅

𝑉̅1 = 𝑉̅2 = 𝑉̅3 = ⋯ = 𝑉̅𝑛 = 𝑉̅

and stripping section are uniform.

Mass Balance and Operating Lines

Tray numbering convention

sown in Figure 1 is adopted for the rectification and stripping sections:

Rectifying section operating line

section’ outlined in the red boundary shown below in Figure 2.

Rearranging the component balance,

Substituting in the overall mass balance,

Applying CMO assumption,

By doing a mass balance on the condenser, it can be found that:

Substituting the expression into the main equation,

Figure 3 Rectifying section of distillation column

Stripping section operating line

𝑥𝑚 𝐿̅𝑚 = 𝑦𝑚+1 𝑉̅𝑚+1 + 𝑥𝐵 𝐵

Rearranging the component balance,

Substituting in the overall mass balance,

𝐿̅𝑚 𝐿̅𝑚 − 𝑉̅𝑚+1

Applying CMO assumption,

By doing a mass balance on the reboiler, it can be found that:

Substituting the above expression into the main equation,

Figure 4 Stripping section of distillation column

Feed section operating line

equations from before can be written as:

Rearranging the equations,

Subtract the 2nd equation from the 1st,

From the overall mass balance of the whole column, we know:

𝑦(𝑉 − 𝑉̅ ) = 𝑥𝐿 − 𝑥𝐿̅ + 𝐹𝑧𝐹

Dividing all terms by F,

Let the term 𝑞 , the feed liquid fraction, be defined as:

Substituting the definition of q into the main equation,

Rearranging yields the feed operating line,

Figure 5 Feed tray section of distillation column

Figure 6 Feed Tray enlarged with labeled streams

Figure 7 Mass Balance boundary around condenser

numerically equal to 𝑉̅ /B.

Figure 8 Mass Balance boundary around reboiler

operating lines can be expressed as:

of equilibriums on the VLE curve.

Figure 9 McCabe-Thiele diagram for binary mixture distillation

n is the theoretical number of trays,

xA is the mole fraction of the MVC (most volatile component),

xB is the mole fraction of the LVC (least volatile component),

(𝛼𝐴𝐵 )𝑎𝑣𝑔 is the average volatility.

The average volatility can be found using the equation below:

(𝛼𝐴𝐵 )𝑎𝑣𝑔 = √(𝛼𝐴𝐵 )𝐷 (𝛼𝐴𝐵 )𝐵

Overall Column Efficiency

The column efficiency is defined by the below equation: