Chapter 3: Fractionation

Rules of Thumb for Chemical Engineers, 5th Edition

by Stephen Hall

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 Antoine Constants
Problem Statement:
A B C
Construct a table of vapor-liquid equilibrium values for
Methyl Alcohol 8.1 1,582.3 239.7 a system of methanol-ethanol at 1 atmosphere
Ethyl Alcohol 8.1 1,592.9 226.2 pressure, assuming ideal behavior.
System Pressure 760 mm Hg

Err:502 VP, mm Hg Partial Pressure

Methyl Ethyl Methyl Ethyl
X Y Temp, deg C Alcohol Alcohol Alcohol Alcohol Difference
0.00 0.00 78.298191854 1,275.42 760.00 0.00 760.00 (0.00)
0.10 0.16 76.62501972 1,200.44 711.06 120.04 639.96 (0.00)
0.20 0.30 75.030439013 1,132.40 666.90 226.48 533.52 (0.00)
0.30 0.42 73.509200873 1,070.50 626.93 321.15 438.85 (0.00)
0.40 0.53 72.056463845 1,014.03 590.65 405.61 354.39 0.00
0.50 0.63 70.667734183 962.38 557.63 481.19 278.81 0.00
0.60 0.72 69.338764978 915.01 527.49 549.00 211.00 (0.00)
0.70 0.80 68.065743233 871.47 499.91 610.03 149.97 (0.00)
0.80 0.88 66.845061452 831.35 474.62 665.08 94.92 (0.00)
0.90 0.94 65.673400907 794.29 451.36 714.86 45.14 (0.00)
1.00 1.00 64.547732539 760.00 429.92 760.00 0.00 (0.00)
quid equilibrium values for
ol at 1 atmosphere
havior.
 Antoine Constants
Problem Statement:
A B C Construct a table of vapor-liquid equilibrium values fo
Ethyl Alcohol 8.1 1,592.9 226.2 system of ethanol-water at 1 atmosphere pressure, us
Water 8.0 1,701.8 231.5 Activity coefficients from the Margules model.

Err:502 VP, mm Hg Margules

X Y Temp, deg C Ethyl Alcohol Water 1 2

0.00 0.00 100.09 1,699.09 760.00 4.964 1.000
0.03 0.23 93.65 1,355.04 601.42 4.314 1.002
0.06 0.35 89.78 1,177.22 520.02 3.781 1.008
0.10 0.44 86.60 1,046.49 460.47 3.212 1.023
0.15 0.51 84.30 959.27 420.88 2.671 1.050
0.20 0.54 82.94 910.83 398.94 2.268 1.087
0.30 0.59 81.49 861.00 376.42 1.729 1.189
0.40 0.62 80.65 833.48 364.01 1.411 1.326
0.50 0.65 79.99 812.34 354.48 1.220 1.493
0.60 0.69 79.41 794.18 346.30 1.107 1.680
0.70 0.75 78.94 779.45 339.67 1.043 1.872
0.80 0.82 78.60 769.13 335.03 1.012 2.045
0.90 0.91 78.40 763.19 332.36 1.001 2.170
1.00 1.00 78.30 760.00 330.93 1.000 2.214

Solution Model VLE Ethanol-Water Reference Line

None 1
Margules 2 X Y X Y
van Laar 3 0 0 0 0
0.056 0.366 1 1
0.091 0.448
0.189 0.539
0.286 0.582
0.323 0.6
0.331 0.605
0.419 0.627
0.512 0.666
0.62 0.712
0.704 0.759
0.715 0.764
0.798 0.818
0.843 0.851
0.847 0.854
0.849 0.856
0.884 0.886
0.908 0.907
0.922 0.92
Source:
Kurihara, K., Nakamichi, M., Kojima, K., "Isobaric Vapor-Liquid Equilibria for Methanol + Ethanol +
 Margules Parameters van Laar Parameters
ent:
of vapor-liquid equilibrium values for a A12 A21 A12 A21
-water at 1 atmosphere pressure, using 1.6022 0.7947 1.6798 0.9227
s from the Margules model.

Margules Model van Laar Model

Partial Pressure
Ethyl
Alcohol Water Difference 1 2 1 2
0.00 760.00 (0.00) 4.964 1.000 5.364 1.000
175.38 584.62 (0.00) 4.314 1.002 4.506 1.003
267.09 492.91 (0.00) 3.781 1.008 3.851 1.010
336.16 423.84 0.00 3.212 1.023 3.197 1.026
384.38 375.62 0.00 2.671 1.050 2.618 1.056
413.06 346.94 0.00 2.268 1.087 2.211 1.094
446.66 313.34 0.00 1.729 1.189 1.699 1.194
470.39 289.61 0.00 1.411 1.326 1.409 1.320
495.44 264.56 (0.00) 1.220 1.493 1.235 1.469
527.32 232.68 (0.00) 1.107 1.680 1.128 1.639
569.28 190.72 (0.00) 1.043 1.872 1.063 1.830
622.98 137.02 (0.00) 1.012 2.045 1.025 2.041
687.89 72.11 (0.00) 1.001 2.170 1.006 2.270
760.00 0.00 0.00 1.000 2.214 1.000 2.516
(0.00)

Vapor-Liquid Equilibrium

0.9

0.8
M ole Fraction, Vapor Phas e

0.7

0.6
Ref erence Line
Predicted
0.5
Experimental

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
M ole Fraction, Liquid Phas e
 0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
M ole Fraction, Liquid Phas e

por-Liquid Equilibria for Methanol + Ethanol + Water and the Three Constituent Binary Systems," J. Chem Eng. Data 1993, Vol 38, p 446-449.
Ref erence Line
Predicted
Experimental
 Antoine Constants
A B C Problem Statement:
Methyl Alcohol 8.1 1,582.3 239.7 Estimate the minimum reflux ratio for a binary fe
Ethyl Alcohol 8.1 1,592.9 226.2 consisting of 40 mole% methanol and 60 mole%
ethanol at its bubble point. The desired distillate
Molar Composition Bottoms Feed Distillate composition is 98 mole % methanol.
Methyl Alcohol 0.40 0.98
Ethyl Alcohol 0.60 0.02

Err:502 VP, mm Hg Partial Pressure

Methyl Ethyl Methyl Ethyl
X Y Temp, deg C Alcohol Alcohol Alcohol Alcohol Difference
0.40 0.53 72.06 1,014.03 590.65 405.61 354.39 0.00

Minimum Reflux Ratio

alpha 1.716808
Rm 3.34 Answer
ent:
mum reflux ratio for a binary feed
mole% methanol and 60 mole%
ble point. The desired distillate
mole % methanol.
 Antoine Constants
A B C Problem Statement:
n-hexane 6.8 1,112.6 218.0 Estimate the minimum reflux ratio for the tertiary
n-heptane 6.8 1,224.4 212.9 system n-hexane, n-heptane, n-octane, with the
n-octane 6.9 1,317.0 205.5 feed at the bubble point and molar composition
0.1, 0.5, 0.4 respectively. 95% of the n-heptane
should be contained in the distillate and 99% of the
n-octane in the bottoms.
System Pressure 760 mm Hg
Temperature 102 deg C

Molar Composition Feed VP, mm Hg PP i

n-hexane 0.10 1,915.450 191.545 5.12
n-heptane 0.50 837.854 418.927 2.24
n-octane 0.40 373.820 149.528 1.00
760.000
Difference 0.000

Feed Condition, q 1.00 (1 = feed at the Bubble Point)

Theta 1.30

Molar Composition Feed i xi i / (i - ) Distillate xiD i / (i - )

n-hexane 0.10 5.12 0.13 0.173 0.23
n-heptane 0.50 2.24 1.19 0.820 1.96
n-octane 0.40 1.00 (1.33) 0.007 (0.02)
0.00 2.17 = Rm + 1
Difference (0.00)

Calculation of the distillate and bottoms compositions

Moles
Recovery of
Molar Composition Feed Light Key Heavy Key Keys Bottoms Distillate
n-hexane 0.10 0.00 10.00
n-heptane 0.50 x 95% 2.50 47.50
n-octane 0.40 x 99% 39.60 0.40
42.10 57.90
:
m reflux ratio for the tertiary
heptane, n-octane, with the
oint and molar composition
vely. 95% of the n-heptane
in the distillate and 99% of the
ms.

Answer

Mole Fraction

Bottoms Distillate
0.00 0.173 Feed 100 moles
0.06 0.820
0.94 0.007
 Antoine Constants
A B C Problem Statement:
Find the number of stages for a me
Methyl Alcohol 8.1 1,582.3 239.7
column, with 40 mole% methanol in
Ethyl Alcohol 8.1 1,592.9 226.2 % methanol in the distillate, an 1%
bottoms, given a reflux ratio of 5.0
Molar Composition Bottoms Feed Distillate Bottoms
Methyl Alcohol 0.40 0.98 0.01
Ethyl Alcohol 0.60 0.02 0.99
System Pressure 760

Err:502 VP, mm Hg Partial Pressure

X Y Temp, deg C Methanol Ethanol Methanol Ethanol Difference
0.01 0.02 78.13 1,267.58 754.87 12.68 747.32 (0.00)
0.40 0.53 72.06 1,014.03 590.65 405.61 354.39 0.00
0.98 0.99 64.77 766.65 434.07 751.32 8.68 (0.00)
0.00
Minimum Reflux Ratio
alpha 1.679202
Rm 3.52

Minimum Number of Stages at Infinite Reflux

Fenske Equation

Nm 14.64

Molkanov Equation

Y = 1 exp[(1 + 54.4X)(X 1) / ((11 + 117.2X)(X0.5)]

Y = (N Nmin) / (N + 1)
X = (R Rmin) / (R + 1)

For R = 5.0
X= 0.25

N= 26.09 Answer
Y= 0.42

RHS = 0.42
Difference (0.00)
em Statement:
he number of stages for a methanol-ethanol
n, with 40 mole% methanol in the feed, 98 mole
hanol in the distillate, an 1% methanol in the
ms, given a reflux ratio of 5.0

i
1.679
1.717
1.766
 Antoine Constants
Problem Statement:
A B C Construct a McCabe-Thiele Diagram for a system
Ethyl Alcohol 8.1 1,592.9 226.2 water at 1 atmosphere pressure, using Activity coe
Water 8.0 1,701.8 231.5 from the Margules model.

Err:502 VP, mm Hg Margules

X Y Temp, deg C Ethyl Alcohol Water 1 2

0.00 0.00 100.09 1,699.09 760.00 4.964 1.000
0.03 0.23 93.65 1,355.04 601.42 4.314 1.002
0.06 0.35 89.78 1,177.22 520.02 3.781 1.008
0.10 0.44 86.60 1,046.49 460.47 3.212 1.023
0.15 0.51 84.30 959.27 420.88 2.671 1.050
0.20 0.54 82.94 910.83 398.94 2.268 1.087
0.28 0.58 81.72 869.00 380.04 1.824 1.164
0.40 0.62 80.65 833.48 364.01 1.411 1.326
0.50 0.65 79.99 812.34 354.48 1.220 1.493
0.60 0.69 79.41 794.18 346.30 1.107 1.680
0.70 0.75 78.94 779.45 339.67 1.043 1.872
0.80 0.82 78.60 769.13 335.03 1.012 2.045
0.90 0.91 78.40 763.19 332.36 1.001 2.170
1.00 1.00 78.30 760.00 330.93 1.000 2.214

Molar Composition Bottoms Feed Distillate

Ethyl Alcohol 0.02 0.40 0.88
Water 0.98 0.60 0.12

Reflux Ratio 6
Feed, q 0.999

Reference Line Stripping Feed Rectification

Slope 1.00 Slope 1.18 Slope 999.00 Slope
Intercept 0.00 Intercept (0.00) Intercept (399.20) Intercept
X Y X Y X Y X
0.00 0.00 0.02 0.02 0.40 0.40 0.88
1.00 1.00 0.40 0.47 0.40 0.47 0.40

Step Data
X Y
M cCabe-Thiele Diagram
0.02 0.02
0.02 0.17
0.15 0.17 1.00

0.15 0.50
0.90
0.44 0.50
0.44 0.63
0.80
n, Vapor Phas e

0.70

0.60

0.50
 1.00

0.90

0.80
0.59 0.63
0.59 0.69

M ole Fraction, Vapor Phas e

0.70
0.66 0.69
0.66 0.72 0.60
0.70 0.72
0.70 0.75 0.50
0.73 0.75
0.73 0.77 0.40
0.75 0.77
0.75 0.78 0.30
0.76 0.78
0.76 0.79 0.20
0.78 0.79
0.78 0.80 0.10
0.79 0.80
0.79 0.81 0.00
0.80 0.81 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90
0.80 0.82 M ole Fraction, Liquid Phase
0.81 0.82
0.81 0.83
0.82 0.83
0.82 0.83
0.83 0.83 M cCabe-Thie le Diagram
0.83 0.84
0.84 0.84 1.00
0.84 0.85
0.84 0.85 0.90
0.84 0.85
0.85 0.85 0.80
0.85 0.86
0.86 0.86
0.86 0.87 0.70
Mole Fraction, Vapor Phase

0.87 0.87
0.87 0.87 0.60
0.87 0.87
0.87 0.88 0.50
0.88 0.88
0.88 0.89
0.40
0.89 0.89
0.89 0.90
0.90 0.90 0.30
0.90 0.90
0.91 0.90 0.20
0.91 0.91
0.92 0.91
0.10
0.92 0.92
0.93 0.92
0.93 0.93 0.00
0.94 0.93 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.9
0.94 0.94 Mole Fraction, Liquid Phase
 0.10

0.00
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.9
Mole Fraction, Liquid Phase

0.95 0.94
0.95 0.95
0.97 0.95
0.97 0.97
0.98 0.97
0.98 0.98
1.00 0.98
1.00 1.00
1.02 1.00
1.02 1.02
1.04 1.02
1.04 1.04
1.07 1.04
1.07 1.06
1.09 1.06
1.09 1.09
1.12 1.09
1.12 1.11
1.15 1.11
1.15 1.14
1.18 1.14
1.18 1.16
 Margules Parameters van Laar Parameters
ent:
be-Thiele Diagram for a system of ethanol- A12 A21 A12 A21
here pressure, using Activity coefficients 1.6022 0.7947 1.6798 0.9227
model.

Margules Model van Laar Model

Partial Pressure
Ethyl
Alcohol Water Difference 1 2 1 2
0.00 760.00 (0.00) 4.964 1.000 5.364 1.000
175.38 584.62 (0.00) 4.314 1.002 4.506 1.003
267.09 492.91 (0.00) 3.781 1.008 3.851 1.010
336.16 423.84 0.00 3.212 1.023 3.197 1.026
384.38 375.62 0.00 2.671 1.050 2.618 1.056
413.06 346.94 0.00 2.268 1.087 2.211 1.094
440.72 319.28 (0.00) 1.824 1.164 1.787 1.170
470.39 289.61 0.00 1.411 1.326 1.409 1.320
495.44 264.56 (0.00) 1.220 1.493 1.235 1.469
527.32 232.68 (0.00) 1.107 1.680 1.128 1.639
569.28 190.72 (0.00) 1.043 1.872 1.063 1.830
622.98 137.02 (0.00) 1.012 2.045 1.025 2.041
687.89 72.11 (0.00) 1.001 2.170 1.006 2.270
760.00 0.00 0.00 1.000 2.214 1.000 2.516
(0.00)

Murphree Tray Efficiency: 1

Segment 1 Origin Segment 2 Origin

Murphree
Rectification Step X Y X Y
0.86 Reboiler 0.02 0.02 0.02 0.17
0.13 1 0.15 0.17 0.15 0.50
Y 2 0.44 0.50 0.44 0.63
0.88 3 0.59 0.63 0.59 0.69
0.47 4 0.66 0.69 0.66 0.72
5 0.70 0.72 0.70 0.75
6 0.73 0.75 0.73 0.77
7 0.75 0.77 0.75 0.78
8 0.76 0.78 0.76 0.79
e Diagram
9 0.78 0.79 0.78 0.80
10 0.79 0.80 0.79 0.81
11 0.80 0.81 0.80 0.82
12 0.81 0.82 0.81 0.83
13 0.82 0.83 0.82 0.83
14 0.83 0.83 0.83 0.84
 15 0.84 0.84 0.84 0.85
16 0.84 0.85 0.84 0.85
17 0.85 0.85 0.85 0.86
18 0.86 0.86 0.86 0.87
19 0.87 0.87 0.87 0.87
20 0.87 0.87 0.87 0.88
21 0.88 0.88 0.88 0.89
22 0.89 0.89 0.89 0.90
23 0.90 0.90 0.90 0.90
24 0.91 0.90 0.91 0.91
25 0.92 0.91 0.92 0.92
26 0.93 0.92 0.93 0.93
27 0.94 0.93 0.94 0.94
28 0.95 0.94 0.95 0.95
29 0.97 0.95 0.97 0.97
30 0.98 0.97 0.98 0.98
0.50 0.60 0.70 0.80 0.90 1.00 31 1.00 0.98 1.00 1.00
on, Liquid Phase 32 1.02 1.00 1.02 1.02
33 1.04 1.02 1.04 1.04
34 1.07 1.04 1.07 1.06
35 1.09 1.06 1.09 1.09
36 1.12 1.09 1.12 1.11
Thie le Diagram 37 1.15 1.11 1.15 1.14
38 1.18 1.14 1.18 1.16

Referenc e
Line
VLE Curve
Stri pping
Feed
Rec tific ation
T ray Steps
M urphree
VLE

0 0.60 0.70 0.80 0.90 1.00

Liquid Phase
0 0.60 0.70 0.80 0.90 1.00
Liquid Phase
Solution Model
None 1
Margules 2
van Laar 3

VP, mm Hg Margules Partial Pressure

Temp, deg Ethyl Ethyl
VLE Y C Alcohol Water 1 2 Alcohol Water Difference
0.17 95.42 1,443.10 641.88 4.516 1.001 130.35 629.65 (0.00)
0.50 84.36 961.35 421.82 2.687 1.049 383.19 376.81 0.00
0.63 80.36 824.27 359.85 1.320 1.392 480.25 279.75 0.00
0.69 79.47 795.77 347.02 1.115 1.662 523.92 236.08 0.00
0.72 79.13 785.21 342.26 1.065 1.791 550.11 209.89 0.00
0.75 78.95 779.73 339.80 1.044 1.868 568.23 191.77 0.00
0.77 78.84 776.36 338.28 1.033 1.919 581.89 178.11 0.00
0.78 78.76 774.06 337.25 1.026 1.956 592.81 167.19 0.00
0.79 78.71 772.37 336.49 1.021 1.985 601.91 158.09 0.00
0.80 78.66 771.06 335.90 1.017 2.009 609.75 150.25 0.00
0.81 78.63 770.00 335.42 1.015 2.028 616.70 143.30 0.00
0.82 78.60 769.12 335.03 1.012 2.045 623.00 137.00 0.00
0.83 78.58 768.37 334.69 1.011 2.060 628.82 131.18 0.00
0.83 78.55 767.71 334.39 1.009 2.073 634.29 125.71 0.00
0.84 78.53 767.13 334.13 1.008 2.085 639.51 120.49 0.00
0.85 78.52 766.60 333.89 1.007 2.096 644.57 115.43 0.00
0.85 78.50 766.11 333.67 1.006 2.106 649.53 110.47 0.00
0.86 78.49 765.65 333.46 1.005 2.116 654.47 105.53 0.00
0.87 78.47 765.22 333.27 1.004 2.125 659.43 100.58 0.00
0.87 78.46 764.80 333.08 1.004 2.134 664.47 95.53 0.00
0.88 78.44 764.41 332.91 1.003 2.143 669.65 90.35 0.00
0.89 78.43 764.02 332.73 1.003 2.151 675.03 84.97 0.00
0.90 78.42 763.64 332.56 1.002 2.160 680.68 79.32 0.00
0.90 78.41 763.26 332.39 1.002 2.168 686.67 73.33 0.00
0.91 78.39 762.89 332.22 1.001 2.176 693.08 66.92 0.00
0.92 78.38 762.51 332.06 1.001 2.184 700.01 59.99 0.00
0.93 78.37 762.13 331.88 1.001 2.191 707.57 52.43 0.00
0.94 78.36 761.75 331.71 1.000 2.198 715.90 44.10 0.00
0.95 78.34 761.35 331.53 1.000 2.205 725.14 34.86 0.00
0.97 78.33 760.93 331.34 1.000 2.210 735.46 24.54 0.00
0.98 78.31 760.48 331.14 1.000 2.213 747.05 12.95 0.00
1.00 78.30 760.00 330.92 1.000 2.214 760.09 (0.09) 0.00
1.02 78.28 759.44 330.67 1.000 2.210 774.72 (14.72) 0.00
1.04 78.26 758.78 330.38 1.000 2.201 790.98 (30.98) 0.00
1.06 78.23 757.95 330.00 0.999 2.184 808.70 (48.70) 0.00
1.09 78.19 756.89 329.53 0.999 2.158 827.37 (67.37) 0.00
1.11 78.15 755.55 328.93 0.997 2.120 846.07 (86.07) 0.00
1.14 78.10 753.96 328.21 0.994 2.073 863.48 (103.48) 0.00
1.16 78.04 752.26 327.45 0.990 2.020 878.28 (118.28) 0.00
Difference
Total 3,916.90
 Problem Statement:
Determine a column pressure that fits within available
steam and cooling water temperatures

Antoine Constants
A B C
Light n-Pentane 6.8 1,059.0 231.4
Heavy n-Octane 6.9 1,317.0 205.5
Water 8.0 1,701.8 231.5

Pressure, mm Hg
Pressure Temperature Maximum Minimum
LP Steam Pressure 1 bar (gauge) 121 C 652.3
MP Steam Pressure 5 bar (gauge) 159 C 1,703.8 Therefore, to operate this c
HP Steam Pressure 15 bar (gauge) 202 C 4,020.2 atmospheric pressure (760
Results
MP or HP steam for the reb
Tower Water Temp. 30 C 370.5
water for the condenser.
Chilled Water Temp. 5 C 108.4
Reboiler approach 15 C
Condenser approach 10 C

Err:502 VP, mm Hg Partial Pressure

Bubble Point Maximum
X Y Temp, deg C Pressure n-Pentane n-Octane n-Pentane n-Octane Difference
Bottoms 0.05 0.38 105.7 652.3 4,993.14 423.78 249.66 402.59 0.00
0.05 0.31 144.3 1,703.8 10,493.08 1,241.17 524.65 1,179.12 0.00
0.05 0.25 186.7 4,020.2 20,252.38 3,165.84 1,012.62 3,007.55 0.00

Err:502 VP, mm Hg y/P*

Dew Point Minimum
X Y Temp, deg C Pressure n-Pentane n-Octane n-Pentane n-Octane Difference
Distillate 0.95 40.0 370.5 866.33 31.20 0.00109658 0.00 0.00
0.95 15.0 108.4 348.28 7.69 0.00272770 0.01 0.00
Therefore, to operate this column at close to
atmospheric pressure (760 mm Hg), choose
MP or HP steam for the reboiler, and tower
water for the condenser.
 Antoine Coefficients Mol Wt
A B C MW
Methyl Alcohol 8.08097 1582.271 239.726 32.042
Water 8.01352769 1701.78587 231.466749 18.015
Methane 6.61182948 389.926958 265.99 16.043
Ethane 6.80265848 656.401366 255.99 30.07
Propane 6.95916997 857.736201 252.414186 44.097
Toluene 7.05282866 1397.197 224.2974 92.141
Acetic Acid 7.49044999 1604.16592 229.902701 60.052
Isobutane 6.74811109 882.803422 240 58.124
n-Butane 6.96820966 1000.63935 245.310958 58.124
Isopentane 6.78967307 1020.01442 233.1 72.151
n-Pentane 6.83902998 1059.01668 231.448959 72.151
n-Hexane 6.76098367 1112.56081 218.029908 86.178
n-Heptane 6.81342209 1224.41518 212.94937 100.21
n-Octane 6.85804739 1316.95574 205.523542 114.232
Ethyl Alcohol 8.1122 1592.864 226.184 46.069