Composition of Methanol-

Water Batch Distillation

September 20, 2005
Prepared by: Jason Hixson
Don Scott
Michael Hickey
 Objective
Determine the composition of liquid
methanol-water binary system at
equilibrium based on temperature in a
distillation column.
Vapor-Liquid Equilibrium Diagram
Antoine Equation

B B
ln p A *
ln pw A
*

C T C T
m

pm* , w Vapor Pressure in mmHg of methanol and water.

T is the absolute temperature

A, B, and C are constants.
 Antoine Constants
Are calculated using using the known
temperatures and vapor pressures from
Perrys Chemical Engineers Handbook.
p*(mmHg) T(C ) p*(mmHg) T(C )
1.00 -44.00 1.00 -17.30
5.00 -25.30 5.00 1.20
10.00 -16.20 10.00 11.20
20.00 -6.00 20.00 22.10
40.00 5.00 40.00 34.00
60.00 12.10 60.00 41.50
100.00 21.20 100.00 51.60
200.00 34.80 200.00 66.50
400.00 49.90 400.00 83.00
760.00 64.70 760.00 100.00

Methanol Water
 Antoine Constants
B
ln p *
A
C T
m,w

Arbitrary values are then chosen for A, B, and C giving an

incorrect vapor pressure.
Excel solver is then used to find values of A, B and C for
both methanol and water which gives the correct pressure.

METHANOL A 18.5875
B 3626.5500
C -34.2900
WATER A 18.3036
B 3816.44
C -46.13
 Van Laars Model
Ptotal xm * m * p (1 xm ) * w * p
*
m
*
w

Gamma correction factors for non-ideal system.

 Gamma Correction Factor
A
m exp[ A and B are constants
Axm 2
RT (1 )
Bxm
Ideal Gas Constant = 1.987 cal/K*g-mol

A
w exp[
Axw 2
RT (1 )
Bxw
Temperature (K)
 ym * P yw * P
m,actual *
w,actual *
xm * pm xw * pw
Using data from Perrys where P is 760 mmHg the
constants A and B can be calculated using solver in Excel
T (C) xa ya
100 0 0
96.4 0.02 0.134
93.5 0.04 0.23
91.2 0.06 0.304
89.3 0.08 0.365 VAN LAAR A= 585.6215111
87.7 0.1 0.418
84.4 0.15 0.517 Gives LIQ MODEL B= 375.733096
81.7 0.2 0.579
78 0.3 0.665
75.3 0.4 0.729
73.1 0.5 0.779
71.2 0.6 0.825
69.3 0.7 0.87
67.5 0.8 0.915
66 0.9 0.958
65 0.95 0.979
64.5 1 1
 Raoults Law

ya xa * p / Ptotal
*
a

Vapor Liquid
 Set Up
Xa yA T(C) T(K) pA (mmHg) pB (mmHg) G A CALC G B CALC P DIF
0.020 0.133 96.591 369.751 2384.780601 672.2824004 2.114262724 1.000486141 760 0.001905382

Set arbitrary temperature = (Pcalc-Pactual)

Use Solver to minimize DIF

cell by changing T(C).
 VLE Diagram
METHANOL- WATER

95.000
Vapor
90.000
Temperatur (C)

85.000

80.000

75.000

70.000
Liquid
65.000
0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 1.000
xm, ym
 Composition Calculation Using
WFIT Program

0.38652+0.39727*B2-0.012737*B2^2+0.00013528*B2^3-(0.00000048036)*B2^4)+1%
 Reboiler Composition vs Time
Time Vs Composition Time Vs Composition

20 20
xMethanol (%)

xMethanol (%)
15 15

10 10

5 5

0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W

Initial xm: 23% Initial Vm: 16.86 L

 Tray # 12 Composition vs Time
Time Vs Composition Time Vs Composition

100 35
90 30
80
xMethanol (%)

xMethanol (%)
70 25
60 20
50
40 15
30 10
20
10 5
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 11 Composition vs Time
Time Vs Composition Time Vs Composition

100 25
90
80 20
xMethanol (%)

xMethanol (%)
70
60 15
50
40 10
30
20 5
10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 10 Composition vs Time
Time Vs Composition Time Vs Composition

100 25
90
80 20
xMethanol (%)

xMethanol (%)
70
60 15
50
40 10
30
20 5
10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 9 Composition vs Time
Time Vs Composition Time Vs Composition

100 25
90
80 20
xMethanol (%)

xMethanol (%)
70
60 15
50
40 10
30
20 5
10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 8 Composition vs Time
Time Vs Composition Time Vs Composition

25
100
90 20

xMethanol (%)
80
xMethanol (%)

70 15
60
50 10
40
30 5
20
10 0
0
0 10 20 30 40 50 60 70 80 90
0 10 20 30 40 50
Time (minutes)
Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 7 Composition vs Time
Time Vs Composition Time Vs Composition

100 25
90
80 20
xMethanol (%)

xMethanol (%)
70
60 15
50
40 10
30
20 5
10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 6 Composition vs Time
Time Vs Composition Time Vs Composition

100 40
90
80
xMethanol (%)

xMethanol (%)
70 30
60
50 20
40
30 10
20
10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 5 Composition vs Time
Time Vs Composition Time Vs Composition

100 40
90 35
80
xMethanol (%)

xMethanol (%)
70 30
60 25
50 20
40 15
30 10
20
10 5
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 4 Composition vs Time
Time Vs Composition Time Vs Composition

100 60
90
80 50
xMethanol (%)

xMethanol (%)
70 40
60
50 30
40
30 20
20 10
10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 3 Composition vs Time
Time Vs Composition Time Vs Composition

100 70
90 60
80
xMethanol (%)

xMethanol (%)
70 50
60 40
50
40 30
30 20
20
10 10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 2 Composition vs Time
Time Vs Composition Time Vs Composition

100 100
90 90
80 80
xMethanol (%)

xMethanol (%)
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Tray # 1 Composition vs Time
Time Vs Composition Time Vs Composition

100 100
90 90
80 80
xMethanol (%)

xMethanol (%)
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
 Reflux Composition vs Time
Time Vs Composition Time Vs Composition

100 100
90 90
80 80
xMethanol (%)

xMethanol (%)
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Time (minutes) Time (minutes)

75% Reflux 0% Reflux

2500 W
Collected 1.69 L Collected 6.38 L
 Conclusions
At 0% reflux the amount of distillate
collected was larger than 75% reflux.
At 75% reflux the purity of methane was a
much higher quality.
If quality is more important then a high
reflux percentage is needed.
If quantity and timeliness is more
important then a low reflux is needed.
QUESTIONS
?