REPORT TO DEPARTMENT OF CHEMICAL ENGINEERING

EGE UNIVERSITY
FOR
COURSE: CHE386 CONCEPTUAL DESIGN II

DESIGN REPORT IV

DESIGN OF A CONTINUOUS DISTILLATION COLUMN

FOR A MULTICOMPONENT MIXTURE

SUBMITTED TO

Y.Doc.Dr. Serap CESUR

SUBMISSION DATE

25/05/2010

GROUP 3

05070008901 Ürün ARDA

05070008103 Berna KAYA
05070008849 Demet ACARGİL
05060008091 M. Serkan ACARSER
05060008017 Tayfun EVCİL

MAY 2010
Bornova-İZMİR
SUMMARY

Separation of multicomponent mixtures is very hard and expensive method in

industry. For high purity products and high percentage recovery, continuous distillation
columns are used.

In this study, a saturated vapor mixture which has 5 different components is tried to be
separated and with the help of assumptions, simplifications the plate type distillation column
design methods is tried to be explored.

In this report you can find the information about shortcut design in ideal and real
calculations, using the SRK model. The necessary assumptions were done for both real and
ideal calculations, and with the help of Fenske, Underwood and Kirkbridge equations, the
number of plates were found.

i
 TABLE OF CONTENTS

Summary ...................................................................................................................... i

1.0 Introduction .......................................................................................................... 1

2.0 Results..................................................................................................................... 3

2.1 Ideal System ..................................................................................................... 3

2.2 Real System (Non-Ideal) .................................................................................. 6

3.0 Discussion and Conclusion .................................................................................. 14

4.0 Nomenclature ...................................................................................................... 18

5.0 References ........................................................................................................... 19

6.0 Appendix ............................................................................................................. 20

6.1 Ideal System ................................................................................................... 20

6.2 Real System (Non-Ideal) ................................................................................ 27

 1.0 INTRODUCTION

Distillation is probably the most widely used separation process in the chemical and
allied industries; its applications ranging from the rectification of alcohol, which has been
practiced since antiquity, to the fractionation of crude oil. A good understanding of methods
used for correlating vapour-liquid equilibrium data is essential to the understanding of
distillation and other equilibrium-staged processes.

Distillation column design

The design of a distillation column can be divided into the following steps:

1. Specify the degree of separation required: set product specifications.

2. Select the operating conditions: batch or continuous; operating pressure.
3. Select the type of contacting device: plates or packing.
4. Determine the stage and reflux requirements: the number of equilibrium stages.
5. Size the column: diameter, number of real stages.
6. Design the column internals: plates, distributors, packing supports.
7. Mechanical design: vessel and internal fittings.

The principal step will be to determine the stage and reflux requirements. This is a
relatively simple procedure when the feed is a binary mixture, but a complex and difficult task
when the feed contains more than two components (multicomponent systems).

Process Description
The separation of liquid
mixtures by distillation depends on
differences in volatility between the
components. The greater the relative
volatilities, the easier the separation.
The basic equipment required for
continuous distillation is shown in
Figure1. Vapor flows up the column
and liquid counter-currently down the
column. The vapor and liquid are
brought into contact on plates, or
packing. Part of the condensate from
the condenser is returned to the top of
the column to provide liquid flow
above the feed point (reflux), and part
Figure 1. Distillation column (a) Basic column (b)
of the liquid from the base of the
Multiple feeds and side streams
column is vaporized in the reboiler and
returned to provide the vapor flow.

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 In the section below the feed, the more volatile components are stripped from the
liquid and this is known as the stripping section. Above the feed, the concentration of the
more volatile components is increased and this is called the enrichment, or more commonly,
the rectifying section. Figure1a shows a column producing two product streams, referred to as
tops and bottoms, from a single feed. Columns are occasionally used with more than one feed,
and with side streams withdrawn at points up the column, Figure1b. This does not alter the
basic operation, but complicates the analysis of the process, to some extent.

If the process requirement is to strip a volatile component from a relatively non-

volatile solvent, the rectifying section may be omitted, and the column would then be called a
stripping column. In some operations, where the top product is required as a vapor, only
sufficient liquid is condensed to provide the reflux flow to the column, and the condenser is
referred to as a partial condenser. When the liquid is totally condensed, the liquid returned to
the column will have the same composition as the top product. In a partial condenser the
reflux will be in equilibrium with the vapor leaving the condenser. Virtually pure top and
bottom products can be obtained in a single column from a binary feed, but where the feed
contains more than two components; only a single “pure” product can be produced, either
from the top or bottom of the column. Several columns will be needed to separate a
multicomponent feed into its constituent parts.

The problem of determining the stage and reflux requirements for multicomponent
distillations is much more complex than for binary mixtures. With a multicomponent mixture,
fixing one component composition does not uniquely determine the other component
compositions and the stage temperature.

Also when the feed contains more than two components it is not possible to specify
the complete composition of the top and bottom products independently. The separation
between the top and bottom products is specified by setting limits on two “key” components,
between which it is desired to make the separation.

SHORT-CUT METHODS FOR STAGE AND REFLUX REQUIREMENTS

Most of the short-cut methods were developed for the design of separation columns
for hydrocarbon systems in the petroleum and petrochemical systems industries, and caution
must be exercised when applying them to other systems. They usually depend on the
assumption of constant relative volatility, and should not be used for severely non-ideal
systems.
In this project, during the shortcut calculations, Fenske, Underwood, Gilliand and
Kirkbridge Equations were used. Trial and error procedures were all made in excel.

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2.0 RESULTS

2.1 Ideal System

Table 1. Properties of Components

M w,i ρi Antoine Constants Zi 1 λi
No Name
[kg/kmol] [kg/m3] A B C [%] [kJ/mol]
1 Methanol 32.04 791.8 7.87863 1473.11 230 15 35.14

2 Ethanol 46.07 789 8.1122 1592.864 226.184 25 38.58

Neopentanol
3 88.15 812 7.27679 1279.01 177.849 25 41.35
[Light Key]
n-Butanol
4 74.122 809.8 7.36366 1305.198 173.427 15 43.24
[Heavy Key]
5 1-Pentanol 88.15 814.4 7.18246 1287.625 161.33 20 44.83

Table 2. Calculated Values for the Feed Stream in Ideal System

F [kmol/h] 100 T dew [oC] 113.66
y1 0.15 n1 15 K1 5.14
y2 0.25 n2 25 K2 3.50
y3 0.25 n3 25 K3 1.02
y4 0.15 n4 15 K 4 [ref.] 0.86
y5 0.2 n5 20 K5 0.42

Table 3. Calculated Values for the Top Product in Ideal System

D [kmol/h] 63.6 T dew [oC] 96.84
P.R 1 0.98 n1 14.7 y1 0.231 K1 3.10
P.R 2 0.96 n2 24 y2 0.377 K2 2.00
P.R 3 0.95 n3 23.75 y3 0.373 K3 0.55
P.R 4 0.05 n4 0.75 y4 0.012 K 4 [ref.] 0.45
P.R 5 0.02 n5 0.4 y5 0.006 K5 0.21

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Table 4. Calculated Values for the Bottom Product in Ideal System
W [kmol/h] 36.4 T bubble [oC] 122.39 y i =K i x i
0.054
P.R 1 0.02 n1 0.3 x1 0.008 K1 6.57 y1
0.126
P.R 2 0.04 n2 1 x2 0.027 K2 4.59 y2
0.047
P.R 3 0.05 n3 1.25 x3 0.034 K3 1.37 y3
0.461
P.R 4 0.95 n4 14.25 x4 0.391 K 4 [ref.] 1.18 y4
0.312
P.R 5 0.98 n5 19.6 x5 0.538 K5 0.58 y5

Table 5. Calculated Values of Vapor Pressures of Components in Ideal System

Psat i [mmHg] Feed Top Bottom
Psat Methanol [mmHg] 3909.69 2352.49 4991.92
Psat Ethanol [mmHg] 2661.98 1517.50 3487.52
Psat Neopentanol [mmHg] 774.99 417.46 1039.42
Psat n-Butanol [mmHg] 656.70 342.30 894.23
Psat 1-Pentanol [mmHg] 316.28 156.67 440.62

Table 6. Calculated Values of Relative Volatilities of Components in Ideal System

Relative Volatility ,α ri
No Name
Feed Stream Top Product Bottom Product Average

1 Methanol 5.95 6.87 5.58 6.11

2 Ethanol 4.05 4.43 3.90 4.12

Neopentanol
3 1.18 1.22 1.16 1.19
[Light Key]
n-Butanol
4 1.00 1.00 1.00 1.00
[Heavy Key]
5 1-Pentanol 0.48 0.46 0.49 0.48

Table 7. Calculation of Minimum Number of Plates, θ, Minimum Reflux Ratio

and Feed Location in Ideal System
N min 34.33 θ 1.075 N R /N S 1.25
q 0 R D,min 3.577 λ ave, top [kJ/mol] 38.914
λ ave,bottom [kJ/mol] 43.836

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Table 8. Calculation of Actual Reflux Ratio, Actual Number of Plates, Feed Location, Height of
Column, Condenser Load (Q c ) and Reboiler Load (Q r ) in Ideal System

R D /R D,min 1.5 1.8 2.4

R D,act 5.366 6.439 8.585
X 0.281 0.385 0.522
Y 0.376 0.313 0.238
N act 56 51 46
NS 25 23 20
NR 31 28 26
L [kmol/h] 341.25 409.50 546.00
G [kmol/h] 404.85 473.10 609.60
Q c [kW] 4376.1 5113.9 6589.3
L [kmol/h] 341.25 409.50 546.00
G [kmol/h] 304.85 373.10 509.60
Q r [kW] 3712.1 4543.1 6205.2
H c [m] 28.5 26.0 23.5

Table 9. Required Calculations for the Fluid Velocity and Diameter of Column in Ideal System
MW avg [kg/kmol] 73.34
Wdot [kg/s] 0.742
ρ vap [kg/m3] 2.261
ρ liq [kg/m3] 811.63
It [m] 0.5
u v [m/s] 0.856
D c [m] 0.698

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 2.2 Real System (Non-Ideal)

Table 10. Properties of Components

No Name T c [K] P c [bar] ω ψ ε
1 Methanol 512.58 80.96 0.566 0.42748 0
2 Ethanol 516.25 63.84 0.637 Zc σ
3 Neopentanol [Light Key] 550.00 38.80 0.604 0.333333 1
R
4 n-Butanol [Heavy Key] 562.93 44.13 0.595 Ω
[cm3bar/molK]
5 1-Pentanol 586.15 38.80 0.594 0.08664 83.14

Table 11. Calculated Values of y i , n i and T r, i for the Feed Stream in Non-Ideal System
F [kmol/h] 100 T dew [oC] 106.6
y1 0.15 n1 15 T r,1 0.741
y2 0.25 n2 25 T r,2 0.736
y3 0.25 n3 25 T r,3 0.690
y4 0.15 n4 15 T r,4 0.675
y5 0.2 n5 20 T r,5 0.648

Table 12. Calculated Values of α SRK,i , a i and b i for the Feed Stream in Non-Ideal System
α SRK,1 1.400 a1 1.34*107 b1 45.61
α SRK,2 1.442 a2 1.78*107 b2 58.25
α SRK,3 1.515 a3 3.49*107 b3 102.11
α SRK,4 1.542 a4 3.27*107 b4 91.89
α SRK,5 1.598 a5 4.18*107 b5 108.82

Table 13. Calculated Values of β i , q i and Zv i for the Feed Stream in Non-Ideal System
β1 0.00146 q1 9.321 Zv 1 0.9870
β2 0.00187 q2 9.672 Zv 2 0.9826
β3 0.00328 q3 10.829 Zv 3 0.9649
β4 0.00295 q4 11.281 Zv 4 0.9670
β5 0.00349 q5 12.166 Zv 5 0.9572

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Table 14. Calculated Values of I v i , Φv i and Zl i for the Feed Stream in Non-Ideal System
I v1 0.00148 Φv 1 0.988 Zl 1 0.00157
I v2 0.00190 Φv 2 0.984 Zl 2 0.00215
I v3 0.00339 Φv 3 0.968 Zl 3 0.00395
I v4 0.00304 Φv 4 0.970 Zl 4 0.00345
I v5 0.00364 Φv 5 0.961 Zl 5 0.00370

Table 15. Calculated Values of I l i , Φl i and K i for the Feed Stream in Non-Ideal System
Il 1 0.660 Φl 1 7.605 K1 7.70
Il 2 0.625 Φl 2 3.078 K2 3.13
Il 3 0.604 Φl 3 0.791 K3 0.82
l l
I4 0.618 Φ4 0.693 K4 0.71
Il 5 0.665 Φl 5 0.545 K5 0.57

Table 16. Calculated Values of α r,i , x i and f v i for the Feed Stream in Non-Ideal System
α r,1 10.78 x1 0.019 f v1 0.1501
α r,2 4.38 x2 0.080 f v2 0.2491
α r,3 1.14 x3 0.306 f v3 0.2451
α r,4 1.00 x4 0.210 f v4 0.1474
α r,5 0.79 x5 0.352 f v5 0.1947

Table 17. Calculated Values of f l i , Psat i , γ i and for the Feed Stream in Non-Ideal System
f l1 0.1501 Psat 1 [bar] 4.237 γ1 1.818
f l2 0.2491 Psat 2 [bar] 2.822 γ2 1.105
f l3 0.2451 Psat 3 [bar] 0.804 γ3 0.997
f l4 0.1474 Psat 4 [bar] 0.672 γ4 1.044
f l5 0.1947 Psat 5 [bar] 0.317 γ5 1.741

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Table 18. Calculated Values of y i , n i and T r, i for the Top Product in Non-Ideal System
D [kmol/h] 63.6 T dew [oC] 96.98
P.R 1 0.98 n1 14.7 y1 0.231 T r,1 0.722
P.R 2 0.96 n2 24 y2 0.377 T r,2 0.717
P.R 3 0.95 n3 23.75 y3 0.373 T r,3 0.673
P.R 4 0.05 n4 0.75 y4 0.012 T r,4 0.658
P.R 5 0.02 n5 0.4 y5 0.006 T r,5 0.631

Table 19. Calculated Values of α SRK,i , a i and b i for the Top Product in Non-Ideal System
α SRK,1 1.434 a1 1.38*107 b1 45.61
α SRK,2 1.479 a2 1.82*107 b2 58.25
α SRK,3 1.551 a3 3.57*107 b3 102.11
α SRK,4 1.578 a4 3.35*107 b4 91.89
α SRK,5 1.633 a5 4.27*107 b5 108.82

Table 20. Calculated Values of β i , q i and Zv i for the Top Product in Non-Ideal System
β1 0.00150 q1 9.798 Zv 1 0.9880
β2 0.00192 q2 10.181 Zv 2 0.9828
β3 0.00336 q3 11.373 Zv 3 0.9659
β4 0.00302 q4 11.840 Zv 4 0.9673
β5 0.00358 q5 12.758 Zv 5 0.9575

Table 21. Calculated Values of I v i , Φv i and Zl i for the Top Product in Non-Ideal System
I v1 0.00152 Φv 1 0.987 Zl 1 0.00187
I v2 0.00195 Φv 2 0.982 Zl 2 0.00255
I v3 0.00347 Φv 3 0.965 Zl 3 0.00426
I v4 0.00312 Φv 4 0.967 Zl 4 0.00385
I v5 0.00373 Φv 5 0.958 Zl 5 0.00430

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Table 22. Calculated Values of I l i , Φl i and K i for the Top Product in Non-Ideal System
I l1 0.590 Φl 1 3.108 K1 3.15
I l2 0.560 Φl 2 1.935 K2 1.97
I l3 0.582 Φl 3 0.551 K3 0.57
I l4 0.580 Φl 4 0.467 K4 0.48
I l5 0.606 Φl 5 0.226 K5 0.24

Table 23. Calculated Values of α r,i , x i and f v i for the Top Product in Non-Ideal System
α r,1 6.52 x1 0.073 f v1 0.2310
α r,2 4.08 x2 0.192 f v2 0.3755
α r,3 1.18 x3 0.655 f v3 0.3651
v
α r,4 1.00 x4 0.024 f 4 0.0116
α r,5 0.49 x5 0.027 f v5 0.0061

Table 24. Calculated Values of f l i , Psat i , γ i and for the Top Product in Non-Ideal System
f l1 0.2310 Psat 1 [bar] 3.149 γ1 1.000
f l2 0.3755 Psat 2 [bar] 2.032 γ2 0.964
f l3 0.3651 Psat 3 [bar] 0.559 γ3 0.997
f l4 0.0116 Psat 4 [bar] 0.459 γ4 1.031
f l5 0.0061 Psat 5 [bar] 0.210 γ5 1.089

Table 25. Calculated Values of x i , n i and T r, i for the Bottom Product in Non-Ideal System
W [kmol/h] 36.4 T bubble [oC] 128.5
P.R 1 0.02 n1 0.3 x1 0.008 T r,1 0.784
P.R 2 0.04 n2 1 x2 0.027 T r,2 0.778
P.R 3 0.05 n3 1.25 x3 0.034 T r,3 0.730
P.R 4 0.95 n4 14.25 x4 0.391 T r,4 0.713
P.R 5 0.98 n5 19.6 x5 0.538 T r,5 0.685

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Table 26. Calculated Values of α SRK,i , a i and b i for the Bottom Product in Non-Ideal System
α SRK,1 1.325 a1 1.27*107 b1 45.61
α SRK,2 1.361 a2 1.68*107 b2 58.25
α SRK,3 1.437 a3 3.31*107 b3 102.11
7
α SRK,4 1.465 a4 3.11*10 b4 91.89
α SRK,5 1.520 a5 3.98*107 b5 108.82

Table 27. Calculated Values of β i , q i and Zv i for the Bottom Product in Non-Ideal System
β1 0.00138 q1 8.341 Zv 1 0.9892
β2 0.00177 q2 8.629 Zv 2 0.9853
β3 0.00310 q3 9.709 Zv 3 0.9704
v
β4 0.00279 q4 10.130 Z 4 0.9721
β5 0.00330 q5 10.946 Zv 5 0.9638

Table 28. Calculated Values of I v i , Φv i and Zl i for the Bottom Product in Non-Ideal System
I v1 0.00140 Φv 1 0.990 Zl 1 0.00169
I v2 0.00179 Φv 2 0.987 Zl 2 0.00245
I v3 0.00319 Φv 3 0.973 Zl 3 0.00425
I v4 0.00286 Φv 4 0.975 Zl 4 0.00365
I v5 0.00342 Φv 5 0.967 Zl 5 0.00420

Table 29. Calculated Values of I l i , Φl i and K i for the Bottom Product in Non-Ideal System
I l1 0.599 Φl 1 8.223 K1 8.31
I l2 0.543 Φl 2 4.982 K2 5.05
I l3 0.548 Φl 3 1.576 K3 1.62
I l4 0.567 Φl 4 1.365 K4 1.40
I l5 0.580 Φl 5 0.719 K5 0.74

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Table 30. Calculated Values of α r,i , y i and f v i for the Bottom Product in Non-Ideal System
α r,1 5.93 y1 0.068 f v1 0.0687
α r,2 3.60 y2 0.139 f v2 0.1386
α r,3 1.16 y3 0.056 f v3 0.0548
α r,4 1.00 y4 0.548 f v4 0.5415
α r,5 0.53 y5 0.400 f v5 0.3921

Table 31. Calculated Values of f l i , Psat i , γ i and for the Bottom Product in Non-Ideal System
f l1 0.0687 Psat 1 [bar] 7.840 γ1 0.015
f l2 0.1386 Psat 2 [bar] 5.572 γ2 0.036
f l3 0.0548 Psat 3 [bar] 1.685 γ3 0.361
l sat
f 4 0.5415 P 4 [bar] 1.464 γ4 0.481
f l5 0.3921 Psat 5 [bar] 0.732 γ5 1.801

Table 32. Calculated Values of Relative Volatilities of Components in Non-Ideal System

Relative Volatility ,α ri
No Name
Feed Stream Top Product Bottom Product Average

1 Methanol 10.78 6.52 5.93 7.47

2 Ethanol 4.38 4.08 3.60 4.01

Neopentanol
3 1.14 1.18 1.16 1.16
[Light Key]
n-Butanol
4 1.00 1.00 1.00 1.00
[Heavy Key]
5 1-Pentanol 0.79 0.49 0.53 0.59

Table 33. Calculation of Minimum Number of Plates, θ, Minimum Reflux Ratio

and Feed Location in Non-Ideal System
N min 39.56 θ 1.051 N R /N S 1.25
q 0 R D,min 3.516 λ ave, top [kJ/mol] 38.914
λ ave, bottom [kJ/mol] 43.836

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Table 34. Calculation of Actual Reflux Ratio, Actual Number of Plates, Feed Location, Height of
Column, Condenser Load (Q c ) and Reboiler Load (Q r ) in Ideal System
R D /R D,min 1.5 1.8 2.4
R D,act 5.274 6.328 8.438
X 0.280 0.384 0.522
Y 0.376 0.313 0.238
N act 64 59 53
NS 28 26 24
NR 36 33 29
L [kmol/h] 335.40 402.48 536.64
G [kmol/h] 399.00 466.08 600.24
Q c [kW] 4312.9 5038.0 6488.2
L [kmol/h] 335.40 402.48 536.64
G [kmol/h] 299.00 366.08 500.24
Q r [kW] 3640.9 4457.7 6091.3
H c [m] 32.5 30.0 27.0

Table 35. Required Calculations for the Fluid Velocity and Diameter of Column
in Non-Ideal System
MW avg [kg/kmol] 89.42
Wdot [kg/s] 0.904
ρ vap [kg/m3] 2.715
ρ liq [kg/m3] 811.63
It [m] 0.5
u v [m/s] 0.781
D c [m] 0.737

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 Table 36. Calculated Values by Using ChemCAD 6.0.2 for Ideal and Non-Ideal System
Ideal System with Raoult’s Law Non-Ideal System with SRK Method
R D /R D,min 1.5 1.8 2.4 1.5 1.8 2.4
R D,act 5.2821 6.3386 8.4514 62.0107 6.7886 9.0515
NS 29.2254 26.1033 23.2336 31.2342 27.9023 24.8464
N act 57.9572 51.6570 45.8660 5.6572 55.2872 49.1205
Q c [kJ/h] -1.4678*107 -1.9449*107 -2.5049*107 -1.7721*107 -2.0733*107 -2.6756*107
Q r [kJ/h] 1.0981*107 1.5182*107 2.0782*107 1.3445*107 1.6457*107 2.2480*107
R D,min 3.5214 3.5214 3.5214 3.7715 3.7715 3.7715
N min 35.0220 35.0220 35.0220 37.6120 37.6120 37.6120

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3.0 DISCUSSION AND CONCLUSION

The object of this report is to design a multi-component distillation column for ideal
and non-ideal situations. Consider the case of the distillation of a multi-component mixture in
a multi-stage distillation column. As before, the number of degrees of freedom is determined
by the description rule (i.e., D.O.F. = number of variables set during construction or
controlled during operation by independent means). Generally, all the variables associated
with the feed, such as its composition, flow rate and enthalpy are set, as is the column
pressure, which leaves four degrees of freedom and two basic types of problems (design and
simulation), as was the case for a binary distillation.

For a design problem, the goal is to determine the number of plates needed and the location of
the feed plate, and the following is generally specified

• Separation variable #1, the recovery of the light key component in the top (distillate)
product.
• Separation variable #2, the recovery of the heavy key component in the bottom
product.
• Condenser and reboiler loads
• Diameter and height of the column
• The fact that the optimal feed plate is used that minimizes the total number of plates.
• The reflux ratio.

Generally, in a multi-component distillation column, only two components will exist

in significant quantities in both the bottom and top products. These are the two key
components. The heavy non-key components will essentially all end up in the bottom product
while the light non-key components will essentially all end up in the top product. This is why
the separation variables described above are given in terms of the key components.

In our process, the components were methanol, ethanol, neopentanol, n-butanol and 1-
pentanol. Our feed rate was 100 kmol/h; the light-key component was neopentanol and the
heavy-key component was n-butanol. Our mole fractions in the feed were 15%, 25%,
25%,15% and 20% respectively (See Table 2). The separation targets for top and bottom
products were 95%. In order to find temperature and equilibrium constants for the feed, a
temperature was assumed. The Psat values were calculated at this temperature, by using
Antoine equation (See Table 5). The equilibrium constants were calculated with this assumed
temperature (See Table 2). By using Goal-seek, we equalized . The dew-point
temperature was calculated as 113.66°C. According to the calculated temperature, the
equilibrium constants were found as 5.14, 3.5, 1.02, 0.86, and 0.42. To calculate relative
volatilities of the components, the ratio of K value of each component to the K value of the
heavy-key product was taken. After this, the relative volatilities were found as, 5.95, 4.05,
1.18, 1 and 0.48 (See Table 6).

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 In the ideal calculation, since we only had specific target separation for the light-key
and heavy- key products were known (which was 95% for light-key at top and 95% for heavy
at the bottom), the other separations were assumed 98% for methanol, 96% for ethanol, 95%
for neopentanol, 5% for n-butanol and 2% 1-pentanol (See Table 3). The flow rate of top
product was found as 63.6 kmol/h. As a result, the mole fractions for the top product were
calculated as 0.231, 0.377, 0.373, 0.012, and 0.006 (See Table 3). In order to find temperature
and equilibrium constants, a temperature was assumed. The Psat values were calculated at this
temperature, by using Antoine equation (See Table 5).The equilibrium constants were
calculated with this assumed temperature. By using Goal-seek, we equalized . The
dew-point temperature was calculated as 96.84°C.According to the calculated temperature,
the equilibrium constants were found as 3.10, 2, 0.55, 0.45, and 0.21 (See Table 3). To
calculate relative volatilities of the components, the ratio of K value of each component to the
K value of the heavy-key product was taken. After this, the relative volatilities were found as,
6.87, 4.43, 1.22, 1 and 0.46 (See Table 6).

In the bottom product, the separations were assumed 2% for methanol, 4% for ethanol,
5% for neopentanol, 95% for n-butanol and 98% 1-pentanol (See Table 4). The flow rate of
bottom product was found as 36.4 kmol/h. As a result, the mole fractions for the top product
were calculated as 0.008, 0.027, 0.034, 0.391 and 0.538 (See Table 4). In order to find
temperature and equilibrium constants, a temperature was assumed. The Psat values were
calculated at this temperature, by using Antoine equation (See Table 5). The equilibrium
constants were calculated with this assumed temperature. By using Goal-seek, we
equalized . The dew-point temperature was calculated as 122.39°C. According
to the calculated temperature, the equilibrium constants were found as 6.57, 4.59, 1.37, 1.18
and 0.58 (See Table 4). To calculate relative volatilities of the components, the ratio of K
value of each component to the K value of the heavy-key product was taken. After this, the
relative volatilities were found as, 5.58, 3.90, 1.16, 1 and 0.49 (See Table 6).

The average relative volatilities of the components were determined by taking the
geometric mean of the components’ volatilities at the feed, top product and bottom product.
The values were 6.11, 4.12, 1.19, 1 and 0.48, respectively (See Table 6).

Fenske equation was used to calculate the minimum number of trays. As a result, the
minimum plate number was found as 34.33 (See Table 7).

To find the minimum reflux ratio, the θ parameter was calculated at saturated vapor
condition (q=0), and it must be between the relative volatilities of the light-key and heavy-key
component, and was calculated using Goal-seek. As a result, the θ value was found as 1.075.
Using Underwood equation, the minimum reflux ratio was determined as 3.57 (See Table 7).

The ratio of was assumed as 1.5, 1.8 and 2.4 respectively and the actual reflux
values were calculated and tabulated (See Table 8).

- 15 -
 The Gilliland correlation was used to calculate actual plate number. For this, X and Y
parameters were calculated and N actual was found as 56, 51 and 46, using the Y function and
N min value (See Table 8).

To determine the feed location, we used Kirkbridge equation. For N actual being 56, the
entry location was found as the 26th tray. The N R and N S values were tabulated (See Table 8).

To calculate reboiler and condenser duty, the average latent heat of vaporization was
calculated. Our reboiler and condenser were selected as total reboiler and condenser. As a
result, the reboiler duty was found as 3712.1kW for R min /R at 1.5. The condenser duty was
found as 4376.1kW for the same ratio. Other values were tabulated (See Table 8).

The height and diameter of the column were calculated lastly. The diameter was found
as 0.698m and the height was 28.5 m. Other values were tabulated (See Table 8 and 9).

In the case of the non-ideal system, the critical temperature, critical pressure, density,
molecular weight and acentric factor were looked up from Ref.4 (See Table 10). The
constants for the SRK Model were taken, a temperature was assumed and the reduced
temperatures were calculated accordingly. The parameters α SRK , a i, b i , β i and q i were
determined. Zv i was calculated using Goal-seek and Iv i and Φv i were determined by using the
related equations in Ref.2.Same procedure was followed for ZL i , IL i and ΦL i . The equilibrium
constants were determined using . The liquid mole fractions were calculated to be used in
Modified Raoult’s Law. The P i sat values were determined by Antoine equation. The vapor-
liquid equilibrium was proven by the equality of fugacity coefficients of vapor and liquid
phases. The activity coefficient was calculated from Modified Raoult’s Law. The assumed
dew-point temperature was checked using the γ i and Psat values, and from Goal-seek, the
actual dew-point temperatures was calculated as 106.6°C for feed, 96.98°C for top product.
Same procedure was applied to the bottom product to find bubble-point temperature, which
was found as 128.5°C. The average relative volatilities were calculated and found as 7.47,
4.01, 1.16, 1 and 0.59 respectively (See Table 32).

The Fenske, Underwood, Gilliland and Kirkbridge equations were used like in the
ideal system calculations. From these equations, N min was found as 39.56, θ was found as
1.051, R min was 3.516. For R min /R as 1.5, 1.8 and 2.4, our reflux ratios were found as 5.274,
6.328 and 8.438 respectively. For R min /R as 1.5, 1.8 and 2.4, N act were found as 64, 59, 53.
The feed locations were found and tabulated (See Table 34).

The condenser and reboiler duties were calculated like in the ideal system. Q c and Q r
were calculated and tabulated (See Table 34).

Finally, the diameter and height were calculated and were found as 0.737m and 32.5 m
respectively. Other values were tabulated (See Table 34 and 35).

- 16 -
 According to these results, it can be seen that the ideal system and non-ideal system
are slightly different from each other. For both systems, actual plate numbers decrease with
increasing R min /R. Also, height of the column decreases with increasing R min /R. Both Q c and
Q r increase with increasing R min /R, as expected.

In real systems, the relative volatilities of components are greater than the relative
volatilities of ideal system. Also, the number of plates used are greater than that of ideal
systems. The condenser and reboiler duties of real systems are less than the ideal system’s
duties. The diameter and height of the column in real systems are greater than the diameter
and height of the column in ideal systems. Finally, the most suitable reflux ratio for the real
system can be selected within the calculation of total and operation costs. However, the
optimum reflux ratio can be chosen without any calculations of costs and it can be seen in
Table 34 as 1.8 for this project.

In conclusion, the calculated values by using ChemCAD for the ideal and non ideal
systems were tabulated in table 36.

- 17 -
4.0 NOMENCLATURE

Symbol Name Unit

M w,i Molecular Weight of i Component [kg/kmol]
ρi Density of i Component [kg/m3]
ρ vap Vapor Density of i Component [kg/m3]
ρ liquid Liquid Density of i Component [kg/m3]
F Mol Number of Feed Stream [kmol/h]
D Mol Number of Top Product [kmol/h]
W Mol Number of Bottom Product [kmol/h]
ni Mole Number of i Component [kmol/h]
xi Mole Fraction of i Component
P.R. i Percentage Recovery of i Component
Ki Distribution Coefficient of i Component
sat
P Saturated Vapor Pressure [bar]
Pt Total Pressure [bar]
αi Relative Volatilities of i Component
N min Minimum Number of Plate
N act Actual Number of Plate
NS Number of Plate of Stripping Section
NR Number of Plate of Enriching Section
R D,min Minimum Reflux Ratio
R D,act Actual Reflux Ratio
λi Latent Heat of Vaporization
MW Molecular Weight of Mixing
uv Fluid Velocity [m/s]
Dc Diameter of Distillation Column [m]
Tr Reduce Temperature
f Fugacity
Φ Fugacity Coefficient
T Temperature [oC]
Tc Critical Temperature [K]
Pc Critical Pressure [bar]
Qr Reboiler Load [kJ/s]
Qc Condenser Load [kJ/s]

- 18 -
5.0 REFERENCES

1. Coulson, J.M., Richardson, J.F., Chemical Engineering Series - Chemical

Engineering Design, Vol. 6, 4th Ed., Great Britain Pergamon Press, 1977.

2. J.M. Smith, H.C. Van Ness, M.M. Abbott, Introduction to Chemical Engineering
Thermodynamics, 2005, 7th Ed., Mc Graw Hill Company, Singapore.

3. Felder, R.M., Rousseau, R.W., Elementary Principles of Chemical Process, 2nd Ed.,
John Willey and Sons Inc, USA, 1986.

4. Yaws C.L., Yaws' Handbook of Thermodynamic and Physical Properties of Chemical

Compounds, Lamar University, Beaumont, Texas, Norwich, New York, 2004

- 19 -
6.0 APPENDIX

6.1 Ideal System D=63.6 kmol/h

G n1=14.7 kmol/h
(See Table 4). n2=24 kmol/h
L
D n3=23.75 kmol/h
F=100 kmol/h
n4=0.75 kmol/h
n1=15 kmol/h
n5=0.4 kmol/h
n2=25 kmol/h
n3=25 kmol/h
n4=15 kmol/h
n5=20 kmol/h
G W=36.4 kmol/h
n1=0.3 kmol/h
n2=1 kmol/h
L n3=1.25 kmol/h
W n4=14.25 kmol/h
n5=19.6 kmol/h

The mixture of methanol, ethanol, neopentanol, n-butanol and 1-pentanol was fed to the
column as 100 kmol/h. The given data for the feed, top and bottom product was tabulated in
Table 2, 3, 4.

 Calculation of Mole Numbers of Components in Feed Stream

F = 100 kmol h
x1 = 0.15 n1 = 0.15 ×100 = 15 kmol h
x2 = 0.25 n2 = 0.25 ×100 = 25 kmol h
x3 = 0.25 n3 = 0.25 ×100 = 25 kmol h
x4 = 0.15 n4 = 0.15 ×100 = 15 kmol h
x5 = 0.20 n5 = 0.20 ×100 = 20 kmol h

 Assumption of Percentage Recoveries for Top Product

n=
i nFi × P.Ri
P.R.1 = 0.98
n1 = 14.7 kmol / h
15 × 0.98 =
P.R.2 = 0.96
n2 =25 × 0.96 =24kmol / h
P.R.3 = 0.95
n3 = 23.75kmol / h
25 × 0.95 =
P.R.4 = 0.05
n4 =
15 × 0.05 =0.75kmol / h
P.R.5 = 0.02
n5 =20 × 0.02 =0.4kmol / h

- 20 -
 =x1 14.7
= / 63.6 0.231
xdi = n i / D =x2 24
= / 63.6 0.377
D = 14.7 + 24 + 23.75 + 0.75 + 0.4 =x3 23.75
= / 63.6 0.373
D = 63.6kmol / h =x4 0.75
= / 63.6 0.012
=x5 0.4
= / 63.6 0.006

 Assumption of Percentage Recoveries for the Bottom Product

n=
i nFi × P.Ri
P.R.1 =
1 − 0.98 =
0.02
n1 = 0.3kmol / h
15 × 0.02 =
P.R.2 =
1 − 0.96 =
0.04
n2 =25 × 0.04 =1kmol / h
P.R.3 =
1 − 0.95 =
0.05
n3 = 1.25kmol / h
25 × 0.05 =
P.R.4 =
1 − 0.05 =
0.95
n4 = 14.25kmol / h
15 × 0.95 =
P.R.5 =
1 − 0.02 =
0.98
n5 =20 × 0.98 =19.6kmol / h

=x1 0.3
= / 36.4 0.008
xdi = n i /W =x2 1/=
36.4 0.027
W= 0.3 + 1 + 1.25 + 14.25 + 19.6 =x3 1.25
= / 36.4 0.034
W = 36.4kmol / h =x4 14.25
= / 36.4 0.391
=x5 19.6
= / 36.4 0.538

 Calculation of Temperature, K-values & Relative Volatilities for the Feed Stream

Dew point temperature for feed

Dew point temperature for the feed was assumed as 100 oC. All calculations was done
c c
yi
∑ xi
by using this temperature in excel. However = ∑=
=i 1 =i 1 K i
1.00 value could not be

obtained. So the dew point temperature was calculated as 113.66 oC by using “Goal Seek”
method in Excel and shown below.

K i = yi / xi
yi
∑ xi
=
i
∑=
K
i
1.00
i

B
log P sat= A − T in oC ; P in mmHg ( A, B and C constants were shown inTable 2)
T +C
o
Tdew = 113.66 C ( feed stream)
Pt = 760mmHg
sat 1473.11 sat
log Pmethanol =
7.87863 − ; Pmethanol 3909.69 mmHg
=
113.66 + 230
For other components see in Table 5.

- 21 -
 Pi sat sat
Pmethanol 3909.69
Ki
= , K=
methanol = = 5.14
Pt Pt 760
sat
sat
Pethanol 2661.98 Pneopentanol 774.99
K=
ethanol = = 3.5 , K neopentanol
= = = 1.02
Pt 760 Pt 760
sat
Pn-butanol 656.70 P1−satpentanol 316.28
K=
n-butanol = = 0.86 , K1-=
pentanol = = 0.42
Pt 760 Pt 760
Ki K methanol 5.14
αi
= , α methanol,n-butanol
= = = 5.95
K HK K n-butanol 0.86
K ethanol 3.5 K neopentanol 1.02
α ethanol ,n-butanol
= = = 4.05 , α neopentanol,n-butanol
= = = 1.18
K n-butanol 0.86 K n-butanol 0.86
K n-butanol 0.86 K1- pentanol 0.42
α n-butanol , n-butanol = = = 1 , α 1- pentanol,n-butanol
= = = 0.48
K n-butanol 0.86 K n-butanol 0.86

With excel calculation (goal seek) we found T dew =113.66 oC

 Calculation of Temperature, K-values & Relative Volatilities for the Top Product

Dew point temperature for top

Dew point temperature for the top was assumed as 90 oC. All calculations was done by
c
yi
c

∑ xi
using this temperature in excel. However = ∑=
=i 1 =i 1 K i
1.00 value could not be obtained.

So the dew point temperature was calculated as 96.84 oC by using “Goal Seek” method in
Excel and shown below.

K i = yi / xi
yi
∑ xi
=
i
∑=
Ki
1.00
i

B
log P sat= A − T in oC ; P in mmHg ( A, B and C constants were shown inTable 2)
T +C
Tdew = 96.84 oC (top stream)
Pt = 760mmHg
sat 1473.11 sat
log Pmethanol =
7.87863 − ; Pmethanol 2352.49 mmHg
=
96.84 + 230
For other components see in Table 5.

- 22 -
 Pi sat sat
Pmethanol 2352.49
Ki
= , K=
methanol = = 3.1
Pt Pt 760
sat
sat
Pethanol 1517.50 Pneopentanol 417.46
K=
ethanol = = 2 , K neopentanol
= = = 0.55
Pt 760 Pt 760
sat
Pn-butanol 342.30 P1−satpentanol 156.67
K=
n-butanol = = 0.45 , K1-=
pentanol = = 0.21
Pt 760 Pt 760

Ki K methanol 3.10
αi
= , α methanol,n-butanol
= = = 6.87
K HK K n-butanol 0.45
K ethanol 2 K neopentanol 0.55
α ethanol ,n-butanol
= = = 4.43 , α neopentanol,n-butanol
= = = 1.22
K n-butanol 0.45 K n-butanol 0.45
K n-butanol 0.45 K1- pentanol 0.21
α n-butanol , n-butanol = = = 1 , α 1- pentanol,n-butanol
= = = 0.46
K n-butanol 0.45 K n-butanol 0.45

With excel calculation (goal seek) we found T dew =96.84 0C

 Calculation of Temperature, K-values & Relative Volatilities for the Bottom Product

Bubble point temperature for bottom

Bubble point temperature for the top was assumed as 120 oC. All calculations was
c c

∑ yi
done by using this temperature in excel. However=
=i 1 =i 1
∑=
xK i i 1.00 value could not be

obtained. So the bubble point temperature was calculated as 122.39 oC by using “Goal Seek”
method in Excel and shown below.

K i = yi / xi
∑ yi
=
i
∑=
xK
i
i i 1.00

B
log P sat= A − T in oC ; P in mmHg ( A, B and C constants were shown inTable 2)
T +C
Tbubble =122.39 oC (bottom stream)
Pt = 760mmHg
sat 1473.11 sat
log Pmethanol 7.87863 −
= ; Pmethanol 4991.92 mmHg
=
122.39 + 230
For other components see in Table 5.

- 23 -
 Pi sat sat
Pmethanol 4991.92
Ki
= , K=
methanol = = 6.57
Pt Pt 760
sat
sat
Pethanol 3487.52 Pneopentanol 1039.42
K=
ethanol = = 4.59 , K neopentanol
= = = 1.37
Pt 760 Pt 760
sat
Pn-butanol 894.23 P1−satpentanol 440.62
K=
n-butanol = = 1.18 , K1-=
pentanol = = 0.58
Pt 760 Pt 760

Ki K methanol 6.57
αi
= , α methanol,n-butanol
= = = 5.58
K HK K n-butanol 1.18
K ethanol 4.59 K neopentanol 1.37
α ethanol ,n-butanol
= = = 3.90 , α neopentanol,n-butanol
= = = 1.16
K n-butanol 1.18 K n-butanol 1.18
K n-butanol 1.18 K1- pentanol 0.58
α n-butanol , n-butanol = = = 1 , α 1- pentanol,n-butanol
= = = 0.49
K n-butanol 1.18 K n-butanol 1.18

With excel calculation (goal seek) we found T bubble =122.39 0C

 Calculation of Average Relative Volatilities

α average,i = 3 α top ,i × α bottom ,i × α feed ,i , α methanol = 3

5.95 × 6.87 × 5.58 = 6.11

α ethanol= 3
4.05 × 4.43 × 3.9= 4.12 , α neopentanol= 3
1.18 ×1.22 ×1.16= 1.19
α n-butanol = 3
1 × 1 × 1= 1 , α 1- pentanol = 3
0.48 × 0.46 × 0.49 = 0.48

 Calculation of Minimum Number of Plates by Using Fenske Equation

x x   0.373 0.391 
log  LK , D × HK ,W  log  ×
 x HK , D x LK ,W   0.012 0.034 
=N min = ; N min = 34.33
log α LK ,avg log1.19

 Calculation of q-Parameter

We used saturated vapor for the feed stream; so q-parameter must be taken as zero (q=0).

- 24 -
  Calculation of θ-Parameter

c α i ,ave × x f ,i
∑
i =1 α i , ave − θ
=1 − q , α HK < θ < α LK

α met ,ave × x f ,met α eth ,ave × x f ,eth α neo ,ave × x f ,neo α n −but ,ave × x f ,n −but α1− pent ,ave × x f ,1− pent
+ + + + − 1 + q =0
α met ,ave − θ α eth ,ave − θ α neo ,ave − θ α n −but ,ave − θ α1− pent ,ave − θ

6.11× 0.15 4.12 × 0.25 1.19 × 0.25 1× 0.15 0.48 × 0.20

+ + + + − 1 + 0 =0
6.11 − θ 4.12 − θ 1.19 − θ 1−θ 0.48 − θ

θ = 1.075

 Calculation of Minimum Reflux Ratio, R Dmin by Using Underwood Equation

c α ir × xD ,i
∑ = RD min + 1
i =1 α ir − θ

6.11× 0.231 4.12 × 0.377 1.19 × 0.373 1× 0.012 0.48 × 0.006

RD min
= + + + + = −1 0
6.11 − 1.075 4.12 − 1.075 1.19 − 1.075 1 − 1.075 0.48 − 1.075
RD min = 3.577

= D min * β1
RDactual R= 3.577
= *1.5 5.366
= D min * β 2
RDactual R= 3.577 *1.8 = 6.439
= D min * β 3
RDactual R= 3.577
= * 2.4 8.585

 Calculation of Actual Plate Number by Using Gilliand Correlation

R - RDmin 5.366 − 3.577

=X = = 0.281
R +1 5.366 + 1

 1.805   1.805 
Y=
1 − exp 1.490 + 0.315 X − 0.1  =1 − exp 1.490 + 0.315 × 0.281 − 0.376
=
 X   (0.281)0.1 

N − N min Y + N min
=Y ⇒N
=
N +1 1− Y
0.376 + 34.33
=N N=
actual = 56 plates
1 − 0.376

For other reflux ratios, the calculated values were tabulated in Table 8.

- 25 -
  Calculation of N R and N S for the Feed Location by Using Kirk Bridge Method

 NR   W x   xb , LK  
2
 36.4  0.15  0.034 2 
log =
= 0.206 log    f . HK =  0.206 log  =   0.09691

 D   x f , LK     
 NS     xd , HK    63.6  0.25  0.012  
NR
= 1.25 , = N R N act − N S
NS
N act 56
N= = = 25 , N= 56 − 25 = 31
S
NR 1.25 + 1
R
+1
NS

 Calculation of Condenser and Reboiler Loads, Q c and Q r

L
F=
W +D , L=
G +W , RD =
D
L
RD 5.366
= = ,=L 341.25kmol / h
63.6

c c
=λave,top ∑=
λi yi and λave,bottom ∑λ i xi ( for results see in Table 7 )
=i 1 =i 1

G =+
L D , G= 404.85kmol / h
341.25 + 63.6 =
 kmol kJ  1h 1000 mol
Qc G * λave ,top
= Qc  404.85
,= × 38.914 × × = 4376.1 kJ s ( kW )
 h mol  3600 s 1 kmol
L−L L − 341.25
q= , q= 0=
F 100
L= L= 341.25 , G =L − W =341.25 − 36.4 , G =304.85kmol / h
 kmol kJ  1h 1000 mol
=Qr G * λave ,bottom
= , Qr  304.85 * 43.836 × = × 3712.1 kJ s ( kW )
 h mol  3600 s 1 kmol

 Calculation of Column Diameter and Height

N
=MW ∑
= MW * y
i =1
, y
i Wi Wi xi K i

yWmethanol = xmethanol K methanol = 0.008 × 6.57 = 0.054 ( for other components see Table 9 )
MW = (32.04*0.054) + (46.07 *0.126) + (88.15*0.047) + (74.122*0.461) + (88.15*0.312) = 73.34kg / kmol
 *W = 73.34 kg × 36.4 kmol × 1 h =
W = MV 0.742 kg s
kmol h 3600 s
P × MW = ρ × R × T

- 26 -
 P × MW 1× 73.34
ρvap
= = = 2.261 kg m3
R ×T 0.082 × (122.39 + 273.15)
c
ρliq = ∑ρ x =
i =1
i i 791.8 × 0.008 + 789 × 0.027 + 812 × 0.034 + 809.8 × 0.391 + 814.4 × 0.538

= 811.63 kg m3
1/2
 ρ − ρv 
uv = ( 2
−0.171* l + 0.27 * lt − 0.047 *  l
t )
 ρv 
1/2
 811.63 − 2.261 
uv = (
−0.171*0.52 + 0.27 *0.5 − 0.047 * 

)
2.261  = 0.856 m s

4W 4 × 0.742
Dc = = =0.698 m , H c =lt × ( N + 1) =0.5 × (56 + 1) = 28.3 m
πρv uv π × 2.261× 0.856
For other reflux ratios the results were in Table 9.

6.2 Real System (Non-Ideal)

 For Feed Stream

Dew point temperature for the feed was assumed as 100 oC. All calculations was done by
c
y
using this temperature in excel. However Pt × ∑ i * = 1.00 value could not be obtained. So
i =1 γ i Pi

the dew point temperature was calculated as 106.6 oC (379.75 K) by using “Goal Seek”
method in Excel and shown below.
T
Tr ,i = , T [ K ] , Tc [ K ]
Tc ,i
379.75 379.75 379.75
Tr ,1
= , Tr ,2 = 0.736 =
= 0.741 = , Tr ,3 = 0.690
512.58 516.25 550.00
379.75 379.75
Tr ,4 = 0.675 =
= , Tr ,5 = 0.648
562.93 586.15

1 + ( 0.480 + 1.574ωi − 0.176ωi2 )(1 − Tr1,i2 ) 

2
α SRK ,i =
 
Tc ,i , ωi were taken in Reference 2 and tabulated in Table 10
1 ( 0.480 + 1.574 × 0.566 − 0.176 × 0.5662 )(1 − 0.7411 2 )  =
2
α SRK ,1 =+
  1.400
1 ( 0.480 + 1.574 × 0.637 − 0.176 × 0.637 2 )(1 − 0.7361 2 )  = 1.442
2
α SRK ,2 =+
 

1 ( 0.480 + 1.574 × 0.604 − 0.176 × 0.604 )(1 − 0.690 )  =

2

α SRK ,3 =+ 2 12
 1.515

1 ( 0.480 + 1.574 × 0.595 − 0.176 × 0.5952 )(1 − 0.6751 2 )  =

2
α SRK ,4 =+
  1.542
1 ( 0.480 + 1.574 × 0.594 − 0.176 × 0.5942 )(1 − 0.6481 2 )  =
2
α SRK ,5 =+
  1.598

- 27 -
 α i R 2Tc ,i
ai ψ= , Tc ,i [ K ] , Pc ,i [bar ] , R 83.14 cm3bar molK
Pc ,i
ψ was taken in Reference 2 and tabulated in Table 10
1.400 × 83.142 × 512.58
a1 =
0.42748 × 1.34 ×107
=
80.96
1.442 × 83.142 × 516.25
a2 =
0.42748 × 1.78 ×107
=
63.84
1.515 × 83.142 × 550.00
=a3 0.42748 × = 3.49 ×107
38.80
1.542 × 83.142 × 562.93
a4 =
0.42748 × 3.27 ×107
=
44.13
1.598 × 83.142 × 586.93
a5 =
0.42748 × 4.18 ×107
=
38.80
RT
Ω c ,i ,
bi = Tc ,i [ K ] , Pc ,i [bar ] , R =
83.14 cm3bar molK
Pc ,i
Ω was taken in Reference 2 and tabulated in Table 10
83.14 × 512.58
b1 =
0.08664 × 45.61
=
80.96
83.14 × 516.25
b2 = 0.08664 × 58.25
=
63.84
83.14 × 550.00
b3 = 0.08664 × 102.11
=
38.80
83.14 × 562.93
b4 = 0.08664 × 91.89
=
44.13
83.14 × 586.15
b5 = 0.08664 × 108.82
=
38.80
bi P
βi ≡ , T [ K ] , P [bar ] , R =
83.14 cm3bar molK
RT
45.61×1.013 58.25 ×1.013
=β1 = 0.00146 = , β2 = 0.00187
83.14 × 379.75 83.14 × 379.75
102.11×1.013 91.89 ×1.013
=β3 = 0.00328 = , β4 = 0.00295
83.14 × 379.75 83.14 × 379.75
108.82 ×1.013
β5 = = 0.00349
83.14 × 379.75

- 28 -
 ai
qi ≡ , T [ K ] , R = 83.14 cm3bar molK
bi RT
1.34 × 107 1.78 × 107
q1 ≡ = 9.321 , q2 ≡ 9.672
=
45.61× 83.14 × 379.75 58.25 × 83.14 × 379.75
3.49 × 107 3.27 × 107
q3 ≡ = 10.829 , q4 ≡ 11.281
=
102.11× 83.14 × 379.75 91.89 × 83.14 × 379.75
4.18 × 107
q5 ≡ = 12.166
108.82 × 83.14 × 379.75
Z iv − βi
1 βi − qi βi
Z iv =+
( Ziv + εβi )( Ziv + σβi )
Z iv − 0.00146
0=
1 + 0.00146 − 9.321× 0.00146 − Z iv
( Zi + 0 × 0.00146 )( Zi + 1× 0.00146 )
v v

Z iv value for methanol was calculated as 0.987 by above equation from Goal Seek in Excel
And for the other components, Z iv values were tabulated in Table 14, 21, 28.
1 Z v + σβi
I iv = ln iv
σ − ε Z i + εβi
1 0.9870 + 1× 0.00146 1 0.9826 + 1× 0.00187
=I1v ln = 0.00148 = , I 2v ln = 0.00190
1− 0 0.9870 + 0 1− 0 0.9826 + 0
1 0.9649 + 1× 0.00328 1 0.9670 + 1× 0.00295
I 3v = ln = 0.00339 , I 4v = ln 0.00304
1− 0 0.9649 + 0 1− 0 0.9670 + 0
1 0.9572 + 1× 0.00349
I 5v = ln = 0.00364
1− 0 0.9572 + 0
ln Φ iv = Z iv − 1 − ln ( Z iv − βi ) − qi I iv ; Φ iv = exp  Z iv − 1 − ln ( Z iv − βi ) − qi I iv 
=Φ1v exp 0.9870 − 1 − ln ( 0.9870 − 0.00146 ) − 9.321× =0.00148 0.988
=Φ v2 exp 0.9826 − 1 − ln ( 0.9826 − 0.00186 ) − 9.672 × =
0.00190  0.984
=Φ 3v exp 0.9649 − 1 − ln ( 0.9649 − 0.00328 ) − 10.829 × 0.00339  =
0.968
=Φ v4 exp 0.9670 − 1 − ln ( 0.9670 − 0.00295 ) − 11.281× =0.00304  0.970
=Φ 5v exp 0.9572 − 1 − ln ( 0.9572 − 0.00349 ) − 12.166 × =
0.00364  0.961
 1 + βi − Z il 
Z i =βi + ( Z i + εβi )( Z i + σβi ) 
l l l

 qi βi 
 1 + 0.00146 − Z il 
=0 0.00146 + ( Z il + 0 × 0.00146 )( Z il + 1× 0.00146 )   − Zi
l

 9.321× 0.00146 
l
Z i value for methanol was calculated as 0.00157 by above equation from Goal Seek in Excel
And for the other components, Z il values were tabulated in Table 14, 21, 28.

- 29 -
 1 Z l + σβi
I il = ln il
σ − ε Z i + εβi
1 0.00157 + 1× 0.00146 1 0.00215 + 1× 0.00187
=I1l ln = 0.660 = , I 2l ln = 0.625
1− 0 0.00157 + 0 1− 0 0.00215 + 0
1 0.00395 + 1× 0.00328 1 0.00345 + 1× 0.00295
I 3v = ln = 0.604 , I 4v = ln 0.618
1− 0 0.00395 + 0 1− 0 0.00345 + 0
1 0.00370 + 1× 0.00349
I 5v = ln = 0.665
1− 0 0.00370 + 0
ln Φ li = Z il − 1 − ln ( Z il − βi ) − qi I il ; Φ li = exp  Z il − 1 − ln ( Z il − βi ) − qi I il 
=Φ1l exp 0.00157 − 1 − ln ( 0.00157 − 0.00146 ) − 9.321
= × 0.660  7.605
=Φ l2 exp 0.00215 − 1 − ln ( 0.00215 − 0.00186 ) − 9.672
= × 0.625 3.078
=Φ 3l exp 0.00395 − 1 − ln ( 0.00395 − 0.00328 ) − 10.829 × 0.604  =
0.791
=Φ l4 exp 0.00345 − 1 − ln ( 0.00345 − 0.00295 ) − 11.281
= × 0.618 0.693
=Φ 5l exp 0.00370 − 1 − ln ( 0.00370 − 0.00349 ) − 12.166
= × 0.665 0.545

Φ li 7.605 3.078
Ki
= K1
, = K 2 = 3.13
= 7.70 , =
Φ iv 0.988 0.984
0.791 0.693 0.545
K3
= K 4 = 0.71 , =
= 0.82 , = K 5 = 0.57
0.968 0.970 0.961

Ki K methanol 7.70
αi
= , α methanol,n-butanol
= = = 10.78
K HK K n-butanol 0.71
K ethanol 3.13 K neopentanol 0.82
α ethanol ,n-butanol
= = = 4.38 , α neopentanol,n-butanol
= = = 1.14
K n-butanol 0.71 K n-butanol 0.71
K n-butanol 0.71 K1- pentanol 0.57
α n-butanol , n-butanol = = = 1 , α 1- pentanol,n-butanol
= = = 0.79
K n-butanol 0.71 K n-butanol 0.71
yi 0.15 0.25
xi
= , x1
= x2 = 0.08
= 0.019 , =
Ki 7.70 3.13
0.25 0.15 0.20
=x3
= 0.306
= , x4
= 0.210
= x5
,= 0.352
0.82 0.71 0.57
fi v =
yi Φ iv P , f1v =
0.15 × 0.988 ×1.013 =
0.1501
f 2v =0.25 × 0.984 ×1.013 =0.2491 , f3v =0.25 × 0.968 ×1.013 =0.2451
f 4v =0.15 × 0.970 ×1.013 =0.1474 , f5v =0.20 × 0.961×1.013 =0.1947

fi l =
xi Φ li Pt , f1l =
0.019 × 7.605 × 1.013 =
0.1501
f 2l =0.08 × 3.078 ×1.013 =0.2491 , f3l =0.306 × 0.791×1.013 =0.2451
f 4l =0.21× 0.693 ×1.013 =0.1474 , f5l =0.352 × 0.545 ×1.013 =0.1947

- 30 -
 In Vapor-Liquid Equilibrium, fugacity of liquid and vapor must be equal to each other. So,
our results support this condition. ( fi l = fi v )
B
log P sat= A − T in oC ; P in mmHg ( A, B and C constants were shown inTable 1)
T +C
Tdew =106.6 oC ( feed stream)
Pt = 760mmHg
sat 1473.11 sat 1 atm 1.013 bar
log Pmethanol =7.87863 − ; Pmethanol =3178.72 mmHg × × =4.237 bar
106.6 + 230 760 mmHg 1 atm
For other components see in Table 17, 24, 31.
yi Φ iv Pt
yi Φ iv Pt xi γ i P=
= i
*
, γi
xi Pi *
0.15 × 0.988 ×1.013 0.15 × 0.984 ×1.013
=γ1 = 1.818 = , γ2 = 1.105
0.019 × 4.237 0.080 × 2.822
0.25 × 0.968 ×1.013 0.25 × 0.970 ×1.013
=γ3 = 0.997 = , γ4 = 1.044
0.306 × 0.804 0.210 × 0.672
0.20 × 0.961×1.013
γ5 = = 1.741
0.352 × 0.317
yi
With excel calculation (goal seek), Pt × ∑ 1.00 we found T dew =106.6 oC
=
i γ i Pi
sat

 For Top Product

Dew point temperature for the feed was assumed as 90 oC. All calculations was done by
c
yi
using this temperature in excel. However Pt × ∑ 1.00 value could not be obtained.
=
i =1 γ i Pi
sat

So the dew point temperature was calculated as 96.98 oC (370.13 K) by using “Goal Seek”
method in Excel and shown below.
T
Tr ,i = , T [ K ] , Tc [ K ]
Tc ,i
370.13 370.13 370.13
Tr ,1
= , Tr ,2 = 0.717 =
= 0.722 = , Tr ,3 = 0.673
512.58 516.25 550.00
370.13 370.13
Tr ,4 = 0.658 =
= , Tr ,5 = 0.631
562.93 586.15

- 31 -
 1 + ( 0.480 + 1.574ωi − 0.176ωi2 )(1 − Tr1,i2 ) 
2
α SRK ,i =
 
Tc ,i , ωi were taken in Reference 2 and tabulated in Table 10
1 ( 0.480 + 1.574 × 0.566 − 0.176 × 0.5662 )(1 − 0.7221 2 )  =
2
α SRK ,1 =+
  1.434
1 ( 0.480 + 1.574 × 0.637 − 0.176 × 0.637 2 )(1 − 0.7171 2 )  = 1.479
2
α SRK ,2 =+
 

1 ( 0.480 + 1.574 × 0.604 − 0.176 × 0.604 )(1 − 0.673 )  =

2

α SRK ,3 =+ 2 12
 1.551

1 ( 0.480 + 1.574 × 0.595 − 0.176 × 0.5952 )(1 − 0.6581 2 )  =

2
α SRK ,4 =+
  1.578
1 ( 0.480 + 1.574 × 0.594 − 0.176 × 0.5942 )(1 − 0.6311 2 )  =
2
α SRK ,5 =+
  1.633
α i R 2Tc ,i
ai ψ=
, Tc ,i [ K ] , Pc ,i [bar ] , R 83.14 cm3bar molK
Pc ,i
ψ was taken in Reference 2 and tabulated in Table 10
1.434 × 83.142 × 512.58
a1 =
0.42748 × 1.38 ×107
=
80.96
1.479 × 83.142 × 516.25
a2 =
0.42748 × 1.82 ×107
=
63.84
1.551× 83.142 × 550.00
=a3 0.42748 × = 3.57 ×107
38.80
1.578 × 83.142 × 562.93
a4 =
0.42748 × 3.35 ×107
=
44.13
1.633 × 83.142 × 586.93
a5 =
0.42748 × 4.27 ×107
=
38.80
RT
Ω c ,i ,
bi = Tc ,i [ K ] , Pc ,i [bar ] , R =
83.14 cm3bar molK
Pc ,i
Ω was taken in Reference 2 and tabulated in Table 10
83.14 × 512.58
b1 =
0.08664 × 45.61
=
80.96
83.14 × 516.25
b2 = 0.08664 × 58.25
=
63.84
83.14 × 550.00
b3 = 0.08664 × 102.11
=
38.80
83.14 × 562.93
b4 = 0.08664 × 91.89
=
44.13
83.14 × 586.15
b5 = 0.08664 × 108.82
=
38.80

- 32 -
 bi P
, T [ K ] , P [bar ] , R =
βi ≡ 83.14 cm3bar molK
RT
45.61×1.013 58.25 ×1.013
=β1 = 0.00150 = , β2 = 0.00192
83.14 × 370.13 83.14 × 370.13
102.11×1.013 91.89 ×1.013
=β3 = 0.00336 = , β4 = 0.00302
83.14 × 370.13 83.14 × 370.13
108.82 ×1.013
β5 = = 0.00358
83.14 × 370.13
ai
qi ≡ , T [ K ] , R = 83.14 cm3bar molK
bi RT
1.38 × 107 1.82 × 107
q1 ≡ = 9.798 , q2 ≡ 10.181
=
45.61× 83.14 × 370.13 58.25 × 83.14 × 370.13
3.57 × 107 3.35 × 107
q3 ≡ = 11.373 , q4 ≡ 11.840
=
102.11× 83.14 × 370.13 91.89 × 83.14 × 370.13
4.27 × 107
q5 ≡ = 12.758
108.82 × 83.14 × 370.13
Z iv − βi
1 βi − qi βi
Z iv =+
( Ziv + εβi )( Ziv + σβi )
Z iv − 0.00150
0=
1 + 0.00150 − 9.798 × 0.00150 − Z iv
( i
Z v
+ 0 × 0.00150 )( i
Z v
+ 1 × 0.00150 )
Z iv value for methanol was calculated as 0.988 by above equation from Goal Seek in Excel
And for the other components, Z iv values were tabulated in Table 13, 20, 27.
1 Z v + σβi
I iv = ln iv
σ − ε Z i + εβi
1 0.9880 + 1× 0.00150 1 0.9828 + 1× 0.00192
=I1v ln = 0.00152 = , I 2v ln = 0.00195
1− 0 0.9880 + 0 1− 0 0.9828 + 0
1 0.9659 + 1× 0.00336 1 0.9673 + 1× 0.00302
=I 3v ln = 0.00347 = , I 4v ln = 0.00312
1− 0 0.9659 + 0 1− 0 0.9673 + 0
1 0.9575 + 1 × 0.00358
I 5v = ln = 0.00373
1− 0 0.9575 + 0
ln Φ iv = Z iv − 1 − ln ( Z iv − βi ) − qi I iv ; Φ iv = exp  Z iv − 1 − ln ( Z iv − βi ) − qi I iv 
=Φ1v exp 0.9880 − 1 − ln ( 0.9880 − 0.00150 ) − 9.798 × =
0.00152  0.987
=Φ v2 exp 0.9828 − 1 − ln ( 0.9828 − 0.00192 ) − 10.181× =
0.00195 0.982
=Φ 3v exp 0.9659 − 1 − ln ( 0.9659 − 0.00336 ) − 11.373 × 0.00347  =
0.965
=Φ v4 exp 0.9673 − 1 − ln ( 0.9673 − 0.00302 ) − 11.840 × 0.00312
=  0.967
=Φ 5v exp 0.9575 − 1 − ln ( 0.9575 − 0.00358 ) − 12.758 × =
0.00373 0.958

- 33 -
  1 + βi − Z il 
Z =βi + ( Z + εβi )( Z + σβi ) 
i
l
i
l
i
l

 qi βi 
 1 + 0.00150 − Z il 
=0 0.00150 + ( Z il + 0 × 0.00150 )( Z il + 1× 0.00150 )   − Zi
l

 9.798 × 0.00150 
l
Z i value for methanol was calculated as 0.00187 by above equation from Goal Seek in Excel
And for the other components, Z il values were tabulated in Table 14, 21, 28.
1 Z l + σβi
I il = ln il
σ − ε Z i + εβi
1 0.00187 + 1× 0.00150 1 0.00255 + 1× 0.00192
=I1l ln = 0.590 = , I 2l ln = 0.560
1− 0 0.00187 + 0 1− 0 0.00255 + 0
1 0.00426 + 1× 0.00336 1 0.00385 + 1× 0.00302
=I 3v ln = 0.582 = , I 4v ln = 0.580
1− 0 0.00426 + 0 1− 0 0.00385 + 0
1 0.00430 + 1× 0.00358
I 5v = ln = 0.606
1− 0 0.00430 + 0
ln Φ li = Z il − 1 − ln ( Z il − βi ) − qi I il ; Φ li = exp  Z il − 1 − ln ( Z il − βi ) − qi I il 
=Φ1l exp 0.00187 − 1 − ln ( 0.00187 − 0.00150 ) − 9.798
= × 0.590  3.108
=Φ l2 exp 0.00255 − 1 − ln ( 0.00255 − 0.00192 ) − 10.181
= × 0.560  1.935
=Φ 3l exp 0.00426 − 1 − ln ( 0.00426 − 0.00336 ) − 11.373 × 0.582  =
0.551
=Φ l4 exp 0.00385 − 1 − ln ( 0.00385 − 0.00302 ) − 11.840
= × 0.580  0.467
=Φ 5l exp 0.00430 − 1 − ln ( 0.00430 − 0.00358 ) − 12.758
= × 0.606  0.226

Φ li 3.108 1.935
Ki
= K1
, = K 2 = 1.97
= 3.15 , =
Φ iv 0.987 0.982
0.551 0.467 0.226
K3
= K4
= 0.57 , = K5
= 0.48 , = = 0.24
0.965 0.967 0.958

Ki K methanol 3.15
αi
= , α methanol,n-butanol
= = = 6.52
K HK K n-butanol 0.48
K ethanol 1.97 K neopentanol 0.57
α ethanol ,n-butanol
= = = 4.08 , α neopentanol,n-butanol
= = = 1.18
K n-butanol 0.48 K n-butanol 0.48
K n-butanol 0.48 K1- pentanol 0.24
α n-butanol , n-butanol = = = 1 , α 1- pentanol,n-butanol
= = = 0.49
K n-butanol 0.48 K n-butanol 0.48

- 34 -
 yi 0.231 0.377
=xi , =x1 = 0.073 ,=x2 = 0.192
Ki 3.15 1.97
0.373 0.012 0.006
=x3 = 0.655 ,=x4 = 0.024 ,=x5 = 0.027
0.57 0.48 0.24
fi v =
yi Φ iv P , f1v =
0.231× 0.987 ×1.013 =
0.2310
f 2v = 0.377 × 0.982 ×1.013 = 0.3755 , f3v = 0.373 × 0.965 ×1.013 = 0.3651
f 4v = 0.012 × 0.967 ×1.013 = 0.0116 , f5v = 0.006 × 0.958 ×1.013 = 0.0061

fi l =
xi Φ il Pt , f1l =
0.073 × 3.108 × 1.013 =
0.2310
f 2l = 0.192 ×1.935 ×1.013 = 0.3755 , f3l = 0.655 × 0.551×1.013 = 0.3651
f 4l = 0.024 × 0.467 ×1.013 = 0.0116 , f5l = 0.027 × 0.226 ×1.013 = 0.0061

In Vapor-Liquid Equilibrium, fugacity of liquid and vapor must be equal to each other. So,
our results support this condition. ( fi l = fi v )

B
log P sat= A − T in oC ; P in mmHg ( A, B and C constants were shown inTable 1)
T +C
Tdew = 96.98 oC (top stream)
Pt = 760mmHg
sat 1473.11 sat 1 atm 1.013 bar
log Pmethanol =7.87863 − ; Pmethanol =2362.789 mmHg × × =3.149 bar
96.98 + 230 760 mmHg 1 atm
For other components see in Table 17, 24, 31.
yi Φ iv Pt
yi Φ iv Pt xi γ i P=
= i
sat
, γi
xi Pi sat
0.231× 0.987 ×1.013 0.377 × 0.982 ×1.013
=γ1 = 1= , γ2 = 0.964
0.073 × 3.149 0.192 × 2.032
0.373 × 0.965 ×1.013 0.012 × 0.967 ×1.013
=γ3 = 0.997 = , γ4 = 1.031
0.655 × 0.559 0.024 × 0.459
0.006 × 0.958 ×1.013
γ5 = = 1.089
0.027 × 0.210
yi
With excel calculation (goal seek), Pt × ∑ =1.00 we found T dew =96.98 oC
i γ i Pi
sat

- 35 -
  For Bottom Product
Bubble point temperature for the feed was assumed as 120 oC. All calculations was done
c

∑x γ i i Pi sat
by using this temperature in excel. However i =1
= 1.00 value could not be obtained.
Pt
So the bubble point temperature was calculated as 128.5 oC (401.65 K) by using “Goal Seek”
method in Excel and shown below.
T
Tr ,i = , T [ K ] , Tc [ K ]
Tc ,i
401.65 401.65 401.65
Tr ,1
= , Tr ,2 = 0.778 =
= 0.784 = , Tr ,3 = 0.730
512.58 516.25 550.00
401.65 401.65
Tr ,4 = 0.713 =
= , Tr ,5 = 0.685
562.93 586.15

1 + ( 0.480 + 1.574ωi − 0.176ωi2 )(1 − Tr1,i2 ) 

2
α SRK ,i =
 
Tc ,i , ωi were taken in Reference 2 and tabulated in Table 10
1 ( 0.480 + 1.574 × 0.566 − 0.176 × 0.5662 )(1 − 0.7841 2 )  =
2
α SRK ,1 =+
  1.325
1 ( 0.480 + 1.574 × 0.637 − 0.176 × 0.637 2 )(1 − 0.7781 2 )  = 1.361
2
α SRK ,2 =+
 
1 ( 0.480 + 1.574 × 0.604 − 0.176 × 0.6042 )(1 − 0.7301 2 )  =
2
α SRK ,3 =+
  1.437
1 ( 0.480 + 1.574 × 0.595 − 0.176 × 0.5952 )(1 − 0.7131 2 )  =
2
α SRK ,4 =+
  1.465
1 ( 0.480 + 1.574 × 0.594 − 0.176 × 0.5942 )(1 − 0.6851 2 )  =
2
α SRK ,5 =+
  1.520
α i R 2Tc ,i
ai ψ= , Tc ,i [ K ] , Pc ,i [bar ] , R 83.14 cm3bar molK
Pc ,i
ψ was taken in Reference 2 and tabulated in Table 10
1.325 × 83.142 × 512.58
a1 =
0.42748 × 1.27 ×107
=
80.96
1.361× 83.142 × 516.25
a2 =
0.42748 × 1.68 ×107
=
63.84
1.437 × 83.142 × 550.00
=a3 0.42748 × = 3.31×107
38.80
1.465 × 83.142 × 562.93
a4 =
0.42748 × 3.11×107
=
44.13
1.520 × 83.142 × 586.93
a5 =
0.42748 × 3.98 ×107
=
38.80

- 36 -
 RT
Ω c ,i ,
bi = Tc ,i [ K ] , Pc ,i [bar ] , R =
83.14 cm3bar molK
Pc ,i
Ω was taken in Reference 2 and tabulated in Table 10
83.14 × 512.58
b1 =
0.08664 × 45.61
=
80.96
83.14 × 516.25
b2 = 0.08664 × 58.25
=
63.84
83.14 × 550.00
b3 = 0.08664 × 102.11
=
38.80
83.14 × 562.93
b4 = 0.08664 × 91.89
=
44.13
83.14 × 586.15
b5 = 0.08664 × 108.82
=
38.80
bi P
βi ≡ , T [ K ] , P [bar ] , R =
83.14 cm3bar molK
RT
45.61×1.013 58.25 ×1.013
=β1 = 0.00138 = , β2 = 0.00177
83.14 × 401.65 83.14 × 401.65
102.11×1.013 91.89 ×1.013
=β3 = 0.00310 = , β4 = 0.00279
83.14 × 401.65 83.14 × 401.65
108.82 ×1.013
β5 = = 0.00330
83.14 × 401.65
ai
qi ≡ , T [ K ] , R = 83.14 cm3bar molK
bi RT
1.27 ×107 1.68 ×107
q1 ≡ = 8.341 , q2 ≡ =8.629
45.61× 83.14 × 401.65 58.25 × 83.14 × 401.65
3.31× 107 3.11× 107
q3 ≡ = 9.709 , q4 ≡ =10.130
102.11× 83.14 × 401.65 91.89 × 83.14 × 401.65
3.98 ×107
q5 ≡ = 10.946
108.82 × 83.14 × 401.65
Z iv − βi
1 βi − qi βi
Z iv =+
( Ziv + εβi )( Ziv + σβi )
Z iv − 0.00138
0=
1 + 0.00138 − 8.341× 0.00138 − Z iv
( Zi + 0 × 0.00138)( Zi + 1× 0.00138)
v v

Z iv value for methanol was calculated as 0.9892 by above equation from Goal Seek in Excel
And for the other components, Z iv values were tabulated in Table 13 20, 27.

- 37 -
 1 Z v + σβi
I iv = ln iv
σ − ε Z i + εβi
1 0.9892 + 1× 0.00138 1 0.9853 + 1× 0.00177
= I1v
ln = 0.00140 , I 2v = ln 0.00179
1− 0 0.9892 + 0 1− 0 0.9853 + 0
1 0.9704 + 1× 0.00310 1 0.9721 + 1× 0.00279
=I 3v ln = 0.00319 = , I 4v ln = 0.00286
1− 0 0.9704 + 0 1− 0 0.9721 + 0
1 0.9638 + 1× 0.00330
I 5v = ln = 0.00342
1− 0 0.9638 + 0
ln Φ iv = Z iv − 1 − ln ( Z iv − βi ) − qi I iv ; Φ iv = exp  Z iv − 1 − ln ( Z iv − βi ) − qi I iv 
=Φ1v exp 0.9892 − 1 − ln ( 0.9892 − 0.00138 ) − 8.341× =0.00140  0.990
=Φ v2 exp 0.9853 − 1 − ln ( 0.9853 − 0.00177 ) − 8.629 × 0.00179
=  0.987
=Φ 3v exp 0.9704 − 1 − ln ( 0.9704 − 0.00310 ) − 9.709 × 0.00319  = 0.973
=Φ v4 exp 0.9721 − 1 − ln ( 0.9721 − 0.00279 ) − 10.130 × 0.00286
=  0.975
=Φ 5v exp 0.9638 − 1 − ln ( 0.9638 − 0.00330 ) − 10.946 × 0.00342
=  0.967

 1 + βi − Z il 
Z il =βi + ( Z il + εβi )( Z i
l
+ σβi )  
 qi βi 
 1 + 0.00138 − Z il 
=0 0.00138 + ( Z + 0 × 0.00138 )( Z + 1× 0.00138 ) 
i
l
i
l
 − Zi
l

 8.341× 0.00138 
Z il value for methanol was calculated as 0.00169 by above equation from Goal Seek in Excel
And for the other components, Z il values were tabulated in Table 14, 21, 28.
1 Z l + σβi
I il = ln il
σ − ε Z i + εβi
1 0.00169 + 1× 0.00138 1 0.00245 + 1× 0.00177
=I1l ln = 0.599 = , I 2l ln = 0.543
1− 0 0.00169 + 0 1− 0 0.00245 + 0
1 0.00425 + 1× 0.00310 1 0.00365 + 1× 0.00279
I 3v = ln = 0.548 , I 4v = ln 0.567
1− 0 0.00425 + 0 1− 0 0.00365 + 0
1 0.00420 + 1× 0.00330
I 5v = ln = 0.580
1− 0 0.00420 + 0
ln Φ li = Z il − 1 − ln ( Z il − βi ) − qi I il ; Φ li = exp  Z il − 1 − ln ( Z il − βi ) − qi I il 
=Φ1l exp 0.00169 − 1 − ln ( 0.00169 − 0.00138 ) − 8.341
= × 0.599  8.223
=Φ l2 exp 0.00245 − 1 − ln ( 0.00245 − 0.00177 ) − 8.629
= × 0.543 4.982
=Φ 3l exp 0.00425 − 1 − ln ( 0.00425 − 0.00310 ) − 9.709 × 0.548 =1.576
=Φ l4 exp 0.00365 − 1 − ln ( 0.00365 − 0.00279 ) − 10.130
= × 0.567  1.365
=Φ 5l exp 0.00420 − 1 − ln ( 0.00420 − 0.00330 ) − 10.946
= × 0.580  0.719

- 38 -
 Φ li 8.223 4.982
Ki
= K1
, = K 2 = 5.05
= 8.31 , =
Φ iv 0.990 0.987
1.576 1.365 0.719
=K3
= 1.62
= K4
, = 1.40
= K5
, = 0.74
0.973 0.975 0.967

Ki K methanol 8.31
αi
= , α methanol,n-butanol
= = = 5.93
K HK K n-butanol 1.40
K ethanol 5.05 K neopentanol 1.62
α ethanol ,n-butanol
= = = 3.60 , α neopentanol,n-butanol
= = = 1.16
K n-butanol 1.40 K n-butanol 1.40
K n-butanol 1.40 K1- pentanol 0.74
α n-butanol , n-butanol = = = 1 , α 1- pentanol,n-butanol
= = = 0.53
K n-butanol 1.40 K n-butanol 1.40
yi =K i xi , y1 =8.31× 0.008 =0.068 , y2 =5.05 × 0.027 =0.139
y3 =1.62 × 0.034 =0.056 , y4 =1.40 × 0.391 =0.548 , y5 =0.74 × 0.538 =0.400
fi v =yi Φ iv P , f1v =0.068 × 0.99 ×1.013 =0.0687
f 2v = 0.139 × 0.987 ×1.013 = 0.1386 , f3v = 0.056 × 0.973 × 1.013 = 0.0548
f 4v = 0.548 × 0.975 ×1.013 = 0.5415 , f5v = 0.400 × 0.967 ×1.013 = 0.3921

fi l =
xi Φ li Pt , f1l =
0.008 × 8.223 × 1.013 =
0.0687
f 2l = 0.027 × 4.982 ×1.013 = 0.1386 , f3l = 0.034 ×1.576 ×1.013 = 0.0548
f 4l = 0.391×1.365 ×1.013 = 0.5415 , f5l = 0.538 × 0.719 ×1.013 = 0.3921

In Vapor-Liquid Equilibrium, fugacity of liquid and vapor must be equal to each other. So,
our results support this condition. ( fi l = fi v )
B
log P sat= A − T in oC ; P in mmHg ( A, B and C constants were shown inTable 1)
T +C
Tbubble = 128.5 oC (bottom stream)
Pt = 760mmHg
sat 1473.11 sat 1 atm 1.013 bar
log Pmethanol =7.87863 − ; Pmethanol =5881.758 mmHg × × =7.840 bar
128.5 + 230 760 mmHg 1 atm
For other components see in Table 17, 24, 31.

- 39 -
 yi Φ iv Pt
yi Φ iv Pt xi γ i P=
= i
sat
, γi
xi Pi sat
0.068 × 0.99 ×1.013 0.139 × 0.987 ×1.013
=γ1 = 0.015 = , γ2 = 0.036
0.008 × 7.840 0.027 × 5.572
0.056 × 0.973 × 1.013 0.548 × 0.975 ×1.013
γ3 = = 0.361 , γ 4 = 0.481
0.034 ×1.685 0.391×1.464
0.400 × 0.967 ×1.013
γ5 = = 1.801
0.538 × 0.732
c

∑x γ i i Pi sat
With excel calculation (goal seek), i =1
= 1.00 we found T bubble =128.5 oC
Pt

 Calculation of Average Relative Volatilities

α average,i= 3 α top ,i × α bottom ,i × α feed ,i , α methanol = 3

10.78 × 6.52 × 5.93= 7.47

α ethanol = 3
4.38 × 4.08 × 3.60 = 4.01 , α neopentanol = 3
1.14 ×1.18 ×1.16 = 1.16
α n-butanol = 3
1 × 1 × 1= 1 , α 1- pentanol = 3
0.79 × 0.49 × 0.53 = 0.59

 Calculation of Minimum Number of Plates by Using Fenske Equation

x x   0.373 0.391 
log  LK , D × HK ,W  log  ×
 xHK , D xLK ,W   0.012 0.034 
=N min = ; N min = 39.56
log α LK ,avg log1.16

 Calculation of q-Parameter

We used saturated vapor for the feed stream; so q-parameter must be taken as zero (q=0).

 Calculation of θ-Parameter

c α i ,ave × x f ,i
∑
i =1 α i , ave − θ
=1 − q , α HK < θ < α LK

α met ,ave × x f ,met α eth ,ave × x f ,eth α neo ,ave × x f ,neo α n −but ,ave × x f ,n −but α1− pent ,ave × x f ,1− pent
+ + + + − 1 + q =0
α met ,ave − θ α eth ,ave − θ α neo ,ave − θ α n −but ,ave − θ α1− pent ,ave − θ

7.47 × 0.15 4.01× 0.25 1.16 × 0.25 1× 0.15 0.59 × 0.20

+ + + + − 1 + 0 =0
7.47 − θ 4.01 − θ 1.16 − θ 1−θ 0.59 − θ

θ = 1.051

- 40 -
  Calculation of Minimum Reflux, R Dmin by Using Underwood Equation
c α ir × xD ,i
∑ = RD min + 1
i =1 α ir − θ

7.47 × 0.231 4.01× 0.377 1.16 × 0.373 1× 0.012 0.59 × 0.006

RD min
= + + + + = −1 0
7.47 − 1.051 4.01 − 1.051 1.16 − 1.051 1 − 1.051 0.59 − 1.051
RD min = 3.516

= D min * β1
RDactual R= 3.516*1.5
= 5.274
= D min * β 2
RDactual R= 3.516*1.8 = 6.328
= D min * β 3
RDactual R= 3.516*
= 2.4 8.438

 Calculation of Actual Plate Number by Using Gilliand Correlation

R - RDmin 5.274 − 3.516

=X = = 0.280
R +1 5.274 + 1

 1.805   1.805 
Y=
1 − exp 1.490 + 0.315 X − 0.1  =1 − exp 1.490 + 0.315 × 0.280 − 0.376
=
 X   (0.280)0.1 

N − N min Y + N min
=Y ⇒N
=
N +1 1− Y
0.376 + 39.56
=N N=
actual = 64 plates
1 − 0.376

For other reflux ratios, the calculated values were tabulated in Table 34.

 Calculation of N R and N S for the Feed Location by Using Kirk Bridge Method

 NR   W x   xb , LK  
2
 36.4  0.15  0.034 2 
  f . HK
log =
=  0.206 log     
=

 0.206 log    =   0.09691
 NS   D   x f , LK
   xd , HK    63.6  0.25  0.012  
NR
= 1.25 , = N R N act − N S
NS
N act 64
N= = = 28 , N= 64 − 28 = 36
S
NR 1.25 + 1
R
+1
NS

- 41 -
  Calculation of Condenser and Reboiler Loads, Q c and Q r

L
F=
W +D , L=
G +W , RD =
D
L
RD 5.274
= = ,=L 335.4 kmol / h
63.6

c c
=λave,top
i i ave ,bottom ∑=
λ y and λ ∑λ i xi ( for results see in Table 33)
=i 1 =i 1

G =+
L D , G= 399.00kmol / h
335.4 + 63.6 =
 kmol kJ  1h 1000 mol
Qc G * λave ,top
= Qc  399.00
,= × 38.914 × × = 4312.9 kJ s ( kW )
 h mol  3600 s 1 kmol
L−L L − 335.4
q= , q= 0=
F 100
L= L= 335.4 , G =L − W =335.4 − 36.4 , G =299.00 kmol / h
 kmol kJ  1h 1000 mol
=Qr G * λave ,bottom
= , Qr  299.00 * 43.836 × = × 3640.9 kJ s ( kW )
 h mol  3600 s 1 kmol

 Calculation of Column Diameter and Height

N
=MW ∑
= MW * y
i =1
, y i Wi Wi xi K i

yWmethanol = xmethanol K methanol = 0.008 × 8.31 = 0.068 ( for other components see Table 35)
MW = (32.04*0.068) + (46.07 *0.139) + (88.15*0.056) + (74.122*0.548) + (88.15*0.400) = 89.42 kg / kmol
 × W = 89.42 kg × 36.4 kmol × 1 h = 0.904 kg s
W = MV
kmol h 3600 s
P × MW = ρ × R × T
P × MW 1× 89.42
ρvap =
= = 2.715 kg m3
R ×T 0.082 × (128.5 + 273.15)
c
ρliq = ∑ρ x =
i =1
i i 791.8 × 0.008 + 789 × 0.027 + 812 × 0.034 + 809.8 × 0.391 + 814.4 × 0.538= 811.63 kg m3
1/2
 ρ − ρv 
uv = ( 2
−0.171* l + 0.27 * lt − 0.047 *  l
t  )
 ρv 
1/2
 811.63 − 2.715 
uv = (
−0.171*0.52 + 0.27 *0.5 − 0.047 * 
 2.715
)
 = 0.781 m s

4W 4 × 0.904
Dc = = =0.737 m , H c =lt × ( N + 1) =0.5 × (64 + 1) =32.5 m
πρvuv π × 2.715 × 0.781
For other reflux ratios the results were in Table 35.

- 42 -