METHANOL SYNTHESIS LOOP

S12

S11

S10

REACTOR

S7
zCO(7)=52.08kmol/h
zO2(7)=36.95kmol/h
zH2(7)=244.12kmol/h
zCH4(7)=10.82kmol/h

S8
CO : a
CO2 : b
H2 : c
CH4 : d

S9
CO : 0.3a
CO2 : 0.3b
H2 : c-1.4a-2.1b
CH4 : d
CH3OH
:
0.7a+0.7b
H2O : 0.7b

CO : 0.3a
CO2 : 0.3b-0.005S13
H2 : c-1.4a-2.1b-0.003S13
CH4 : d-0.005S13

SEPARATOR

S13

The total and component flowrates S7 are calculated.

"z" represents the component flowrates.

CO2 : 0.005 x S13

H2 : 0.003 x S13
CH4 : 0.005 x S13
CH3OH
:
0.7a+0.7b
H2O : 0.7b

As the recycle loop is operated by a recycle ratio of 0.4 (ratio of dry recycle gas to dry
MUG) thus the total flowrates for S8 and S11 can be found by the equations below.
S11 = 0.4S7
S11 = 0.4 x 343.97
S11 = 137.588 kmol/h
S8 = S7 + S11
S8 = 343.97 + 137.588
S8 = 481.558 kmol/h
"S" represent total flowrate of each stream while "a", "b", "c" and "d" are terms used to
represent the component flowrates of CO, CO2, H2 and CH4 respectively in Stream 8.
The equations formed for component flowrates of other streams are termed with respect
to "a", "b", "c" and "d" as shown in the diagram above.
The recycle loop is solved by using "Solver" from Microsoft Excel.
6 equations are formed with 6 unknowns.
Unknowns set for solving are: S10, S13, a, b, c, d

Total flowrate S10:

S10 = c + d - 0.4a - 0.4b - 0.013S13 --------------(1)

Total flowrate S13:

S13= 0.7a + 1.4b + 0.013S13

Total flowrate S8:

S8 = a + b + c + d

-------------(2)

-------------(3)

Component balance at mixing point,

CO:

0.3a

S11 + ( zCO( 7 ) ) = a
S10
0.3a

137.588 + ( 52.08) = a
S10
41.2764a

+ 52.08 = a
S
10

---------------

CO2:

0.3b 0.005S13

S11 + ( zCO2 ( 7 ) ) = b
S
10

0.3b 0.005S13

137.588 + ( 36.95) = b
S10

41.2764b 0.68794 S13

+ 36.95 = b
S10

------------(5)

CH4:

d 0.005S13

S11 + ( zCH 4 ( 7 ) ) = d
S
10

d 0.005S13

137.588 + (10.82 ) = d
S10

137.588d 0.68794 S13

+ 10.82 = d
S10

--------------(6)

0.3a

S11 + sCO( 7 ) = a
S10
0.3a

137.588 + (52.08) = a
S
10
41.2764a

+ 52.08 = a
S10

(4)

All the equations derived are rearranged such that they are equated to "0".
c + d - 0.4a - 0.4b - 0.013S13 - S10 = 0 -------------(1)
41.2764a

+ 52.08 a = 0
S10
0.7a + 1.4b + 0.013S13 - S13 = 0
-------------(2)

41.2764b 0.68794 S13

+ 36.95 b = 0 a + b + c + d - S8 = 0
S
10

---------------(4)
137.588d 0.68794 S13

+ 10.82 d = 0
S10

---------------(5)

-------------(3)

----------------(6)
All the unknowns to be calculated are put into a table with an initial guess of value for
each term as shown below.
1
2
3
4
5
6
7

A
Terms
S10
S13
a
b
c
d

B
Values
200
100
65
45
340
30

Another table for functions are set. The 6 equations derived are then typed into the cells
from H1-H7 by substituting the unknowns in the equation from the variable cells (B2B7).

1
2
3
4
5
6
7

G
Function
F1
F2
F3
F4
F5
F6

H
Equations

Objective cells are then typed in with the formula

=(H2^2)+(H3^2)+(H4^2)+(H5^2)+(H6^2)+(H7^2)
Open "Solver" and set all the parameters. In the set objective column the objective cell is
inserted then setting the value of "0". The cells from B2-B7 are taken for the column "By
Changing Variable Cells" in the solver parameter. Cells from H2-H7 are then taken for
the column "Subject to the Constraints" where all the constraints are set to "= 0".

After it is solved, the values for all the unknown terms will be shown in the variable cells.
1
2
3
4
5
6
7

A
Terms
S10
S13
a
b
c
d

B
Values
219.0879
109.4874
64.1696
45.1038
344.1224
28.1622

The component flowrates for stream 8 are directly taken from the variable cells.

Component
CO
CO2
H2
CH4
Total

Stream 8
Flowrate
(kmol/h)
64.1696
45.1038
344.1224
28.1622
481.558

Mole
Fraction
0.133254
0.093662
0.714602
0.058481
1

The component flowrates for S9, S10 and S13 are then calculates by substituting the known
values of S10, S13, a, b, c, d into the equation in the diagram above.
Stream 9
Component
Equations
Flowrate
(kmol/h)
CO
= 0.3a
19.2509
CO2
= 0.3b
13.5311
H2
= c - 1.4a - 2.1b
159.567
CH4
=d
28.1622
CH3OH
= 0.7a + 0.7b
76.4914
H2O
= 0.7b
31.5727
Total
328.5752

Component
CO
CO2
H2
CH4
Total

Stream 10
Equations
= 0.3a
= 0.3b - (0.005S13)
= c - 1.4a - 2.1b - (0.003S13)
= d - 0.005S13

Flowrate
(kmol/h)
19.2509
12.9837
159.239
27.6148
219.0879

Mole Fraction
0.05859
0.04118
0.4856
0.08571
0.2328
0.09609
1

Mole
Fraction
0.087868
0.059263
0.726825
0.126044
1

Stream 13
Component
Equations
Flowrate
(kmol/h)
CO2
= 0.005S13
0.5474
H2
= 0.003S13
0.3285
CH4
= 0.005S13
0.5474
CH3OH
= 0.7a + 0.7b
76.4914
H2O
= 0.7b
31.5727
Total
109.4874

Mole Fraction
0.005
0.003
0.005
0.6896
0.2884
1

The composition of S10, S11 and S12 are the same.

Thus the component flowrates for Stream 11 can be calculated by the relationship,
[xY(10)]S11 = zY(11)
Where, "xY(10)" represents the mole fraction of component "Y" in Stream 10
while "zY(11)" represents the component flowrate "Y" in Stream 11
Stream 11
Component
Equations
Flowrate
(kmol/h)
CO
=0.087868 x S11
19.2509
CO2
=0.059263 x S11
13.5311
H2
=0.726825 x S11
159.567
CH4
=0.126044 x S11
28.1622
Total
137.588

Mole Fraction
0.087868
0.059263
0.726825
0.126044
1

At purge point, S10 = S11 + S12

S12 = S10 - S11
S12 = 219.0879 - 137.588
S12 = 81.4999 kmol/h
Component flowrates for Stream 12 are also calculated the same way as Stream 11,
[xY(10)]S12 = zY(12)

Where "xY(10)" represents the mole fraction of component "Y" in Stream 10 while "zY(12)"
represents the component flowrate "Y" in Stream 12.
Component
CO
CO2
H2
CH4
Total

Equations
=0.087868 x S12
=0.059263 x S12
=0.726825 x S12
=0.126044 x S12

Stream 12
Flowrate
(kmol/h)
7.16128
4.829903
59.23612
10.27256
81.49986

Mole Fraction
0.087868
0.059263
0.726825
0.126044
1

Methanol Distillation
S17

S15
Light Gas

S13
CH3OH
:
76.4914kmol/h
H2O : 31.5727kmol/h
CO2 : 0.5474kmol/h
H2
: 0.3285kmol/h
CH4 : 0.5474kmol/h

DC1

xCH3OH(17) : 0.9972

S14

DC2

S16
xCH3OH(16) : 0.001

Distillation Column 1
We assume all the gases (CO2, H2 and CH4) are distilled out from the crude methanol at
the first distillation column. Thus, component flowrates for CO2, H2 and CH4 in Stream 13

and Stream 15 are the same while the component flowrates for CH3OH and H2O in
Stream 13 and Stream 14 are the same.
Component
CO2
H2
CH4
Total

Component

Stream 15
Flowrate
(kmol/h)
0.5474
0.3285
0.5474
1.4233
Stream 14
Flowrate
(kmol/h)
76.4914
31.5727
108.064

Mole Fraction
0.3846
0.2308
0.3846
1

Mole Fraction

CH3OH
0.7078
H2O
0.2922
Total
1
Distillation Column 2
The design specification given is 0.28 mole % impurities thus 99.72 mole % methanol
produced from S17. The flowrates for S16 and S17 are calculated using 2 equations
simultaneously,
Overall mass balance: S14 = S16 + S17 -----------(7)
Component mass balance : zCH3OH(14)=[xCH3OH(16)]S16 + [xCH3OH(17)]S17 ----------(8)
Where, "xCH3OH(16)" represents the mole fraction of CH3OH in Stream 16;
"xCH3OH(17)" represents the mole fraction of CH3OH(in Stream 17;
while "zCH3OH(14)" represents the CH3OH flowrate in Stream 14.
From equation (7),
S16 = S14 - S17

------------(9)

Substitute equation (9) into (8),

zCH3OH(14) = [xCH3OH(16)]( S14 - S17 ) + [xCH3OH(17)]S17 -----------(10)
76.4914 = 0.001 ( 108.064 - S17 ) + ( 0.9972 ) S17
76.4914 = 0.108064 - ( 0.001 ) S17 + ( 0.9972 ) S17
76.4914 - 0.108064 = ( 0.9962 ) S17
S17 = 76.675 kmol/h
Substitute S17 = 76.675 kmol/h into equation (7),
S16 = S14 - S17
S16 = 108.064 - 76.675
S16 = 31.389 kmol/h
Component flowrates for CH3OH in Stream 16 and Stream 17 are calculated by

multiplying stream flowrate with mole fraction of CH3OH for the same stream.
zCH3OH(16) = [xCH3OH(16)]( S16 )
= 0.001 ( 31.389 )
= 0.3139 kmol/h
zCH3OH(17) = [xCH3OH(17)]( S17 )
= 0.9972 ( 76.675 )
= 76.4603 kmol/h
Component flowrates for H2O in Stream 16 and Stream 17 are calculated by subtracting
flowrate of CH3OH from stream flowrate.
zH2O(16) = S16 - zCH3OH(16)
= 31.389 - 0.3139
180000tonnes 1000kg
kmol
year
= 31.358 kmol/h
=

year
tonne 32.0007 kg 8000hours
zH2O(
17) = S17 - zCH3OH(17)
kmol
= 703.1089
= 76.6747 - 76.4603
hour
= 0.3137 kmol/h

Scale Up
Mr (CH3OH) = 32.04 kg/kmol
Mr (H2O) = 18.016 kg/kmol
Average molecular mass of crude methanol,
= [ xCH3OH(17) x Mr(CH3OH)] + [xH2O(17) x Mr(H2O)]
= (0.9972 x 32.04) + (18.016 x 0.0028)
= 32.0007 kg/kmol
Methanol production,
(CH3OH)T

Scale up Factor, k
(CH3OH)T = k [zCH3OH(17)]
703.1089 = k (76.4603)
k = 9.1958
All the stream and componenet flowrates obtained from the basis are then multiplied by
the scale up factor to get the scaled up figures.
For Stream flowrates,
e .g: S1
= 100 kmol/h (basis)

= 100k
= 100 x 9.1958
= 919.58 kmol/h (scaled up)
For component flowrates,
e.g: zCH4(1)
= 84.8725 kmol/h (basis)
= 84.8725k
= 84.8725 x 9.1958
= 780.4682 kmol/h (scaled up)