2

Input-output structure
2.1 Methyl Ethyl Ketone (MEK)
Methyl Ethyl Ketone (MEK) oxidation Butane cobalt
manganese chromium acetate 200C 5.5
MPa conversion Butane 95% selectivity MEK 85%
Butane Oxidation
C4H10 + O2

C4H8O +H2O

(1)

Side - reaction
C4H10 + 5/2O2

2CH3COOH + H2O

(2)

2.2

2.2.1 Mass Balance

MEK 170,000 / 330/
170,000 ton

1000 kg

year

1 ton

n=

m
MW

)(

21,464.64
72.11

)(

1 year

1 day

)(

330 day

24 hr

) = 21,464.64 kghr

= 297.665 kmolhr

Selectivity MEK (C4H8O) acetic acid(CH3COOH) 0.85 0.15

selectivity MEK (C4H8O)

Selectivity MEK

0.85

All product

nc4 H8 o
All product
297.665kmol/hr
All product

350.197 kmol/hr

CH3COOH
n3 COOH

Selectivity CH3COOH =
0.15

n3 COOH

350.197
n3 COOH
350.197

52.53 kmol/hr

C4H8O
n
n i
out
in

Balance C4H8O
nC4 H8 O,out

nC4 H8 O,in + (1) + (0)

297.665 kmol/hr

297.665 kmol/hr

(2)
Balance CH3COOH
n3 COOH,out
52.53 kmol/hr

nCH3 ,in + (2) 2

=
=

0 + 2 2

26.265 kmol/h

n2
4 10

n4 10

Butane
Oxidation

n C 4 H8 O
nCH3

n2

n H2

n4 10 ,

Conversion = 0.95 C4H10

4 10 n410,
410

0.95

nA.re

n*A -

nC4H10,re

n*C4H10 ( 1+ 2)

1+ 2

n*C4H10 - nC4H10,re

+
1
2

0.95

410

410

4 10

v i

(297.665 kmol/hr)+(26.265 kmol/hr)

0.95

340.979 kmol/hr

C4H10 Feed C4H10 Recycle

C4H10 Feed
410 = n4 10 + 4 10,
340.979 = n4 10 + 4 10 ,

 balance 4 10
n4 10, = n4 10, + v
0

n410, +

(1) + (1)
1

n4 10,

n4 10,

297.665 + 26.265

n4 10 ,

323.93 kmol/hr

+ 2

C4H10 Recycle
340.979 = n4 10 + 4 10 ,
340.979 = 323.93 + 410,
4 10, = 17.049 kmo/hr

C4H10 Recycle =17.049 kmol/hr

balance 2
n2 , = n2 , + v
n2 , = 0 + (1) 1 + (1) 2
n2 ,

+
1

n2 ,

297.665 + 26.265

n2 ,

323.93 kmol/hr

 balance 2
n2,

n2,

n2, n2,
n2, n2,
n2, n2,

n2, + v

5
n2, + (1) + ( )
1
2 2
5
=
+
1
2 2
5
=
297.665 + (26.265)
2
=
363.32 kmol/hr

n2,
% excess O2 = 10%
stoichiometry C4H10: O2 = 1:1
n C4H10 = 340.979 kmol/hr

C4H10

nO2,in =

340.979 kmol/hr
10

% excess O2 = 10% nO2,in = 340.979 + 340.979(100)

nO2,in = 375.077 kmol/hr

n2,

375.077 363.32 kmol/hr

n2,

375.077 363.32 kmol/hr

n2,

= 11.757 kmol

2.2.2 Energy balance

Butane Oxidation
C4H10 + O2

C4H8O +H2O

C4H10 + 5/2O2

(1)

CH3COOH + H2O

(2)

200 oC (473.15 K) 5.5 MPa

Cp/R = A+BT+CT2+DT3+ET4 (J/mol.K)
Chemical

Formula

Oxygen

Cp

H,298.15

(KJ/mol)

O2

3.630

-1.794

0.658

-0.601

0.179

MEK

C4 H 8 O

-238.5

6.349

11.062

4.851

-6.484

2.469

Butane

C4H10

-147.6

5.547

5.536

8.057

-10.571

4.134

-438.1

4.375

-2.397

6.757

-8.764

3.478

-241.8

4.395

-4.186

1.405

-1.564

0.632

Acetic acid CH3COOH

Water

H 2O

B x 103 C x 105 D x 108

E x 1011

General energy balance

473.15
H

473.15

HP =

Cp dT

298.15

H,298
+ HP

B
C
D
E
[AT + ( ) T2 + ( ) T3 + ( ) T4 + ( ) T5 ]473.15
298.15
2
3
4
5
473.15

473.15
H

= H,298
+ ( Cp dT)
298.15

473.15
= (Hrxn
i )

product

473.15
+ (Hrxn
i )

reactant

= CPi H

HP

Enthalpy change
H

H298
+ HP

5 Heat of Formation Standard Heat of Formation j [2]

i

C4H9OH

o
Hf,298.15

(J/mol)
j
1
2

C4 H 8 O

H2

C8H18O

H 2O

-292290

-238360

-360660 -241800

292290
584,580

-238360
0

0
0

0
0
-360660 -241800

H298
= (70 kmol) (53,930, 000

Enthalpy change of product

=

CPo H

53,930
-17,880

J
J
) + (3.684 kmol) (17,880,000
)
kmol
kmol

H298
= 3.71 109 J

HP

H298,j

CPo H (T 298.15)
o
i ni CPi
H

 T = 773.15 K (500C)
o
CPi H

773.15

Cp dT

B
C
D
E
[AT + ( ) T 2 + ( ) T 3 + ( ) T 4 + ( ) T 5 ]773.15
298.15
2
3
4
5

298.15

6 Heat Capacity of Gas i, CPio H [2]

Cp = A+BT+CT2+DT3+ET4
Chemical

Formula

2-Butanol

C4H9OH

22.465

3.5134x10-1

-1.2858x10-4

-1.1931x10-8

1.2940x10-11

MEK

C4 H 8 O

37.369

2.3045x10-1

5.7387x10-6

-8.8168x10-8

2.9637x10-11

Hydrogen

H2

25.399

2.0178x10-2

-3.8549x10-5

3.1880x10-8

-8.7585x10-12

C8H18O

-50.577

1.1014

-9.940x10-4

5.1326x10-7

-1.1304x10-10

H 2O

33.933

-8.4186x10-3

2.9906x10-5

-1.7825x10-8

3.6934x10-12

Di-sec-butyl
ether
Water

o
CP,C4H9OH
H

(22.465)(773.15-298.15) + (3.513x10-1/2) (773.152-298.152)

+ (-1.2858x10-4/3)(773.153- 298.153) + (-1.1931x10-8/4) (773.154298.154) + (1.2940x10-11/5)(773.155- 298.155)

o
CP,C4H9OH
H

81.05809 kJ/mol

Chemical

Formula

2-Butanol

C4H9OH

81.05809

MEK

C4 H 8 O

71.13961

Hydrogen

H2

13.90551

Di-sec-butyl ether

C8H18O

150.505

Water

H 2O

16.96434

o
CPi
H

(kJ/mol )

CPo H

o
H
ni CPi
i

o
i ni CPi
H

(70 kmol)(71,139.61 J/kmol) + (70 kmol)(13,905.551 J/kmol)

+ (3.684 kmol)(150,505 J/kmol) + (3.684 kmol)(16,964.34 J/kmol)

6,570,118.32 J

6.57 x 106 J

H298
+ HP

(3.71 109 ) + (6.57 106 )

3.71 10 J

Input-output structure

C4H10
323.93 kmol/hr
O2
375.077 kmol/hr

*C4H10
340.979 kmol/hr
*C4H10

O2
Butane
Oxidation
5.5MPa, 200oC

C4H8O

297.665 kmol/hr

CH3COOH 52.53 kmol/hr

H2O

Recycle C4H10
17.049 kmol/hr

11.757 kmol/hr

323.93 kmol/hr