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u0E1Au0E17u0E17u0E35u0E48 3mass Energy
u0E1Au0E17u0E17u0E35u0E48 3mass Energy
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
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
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
297.665 kmol/hr
297.665 kmol/hr
(2)
Balance CH3COOH
n3 COOH,out
52.53 kmol/hr
=
=
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 ,
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
340.979 kmol/hr
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
+
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
n2,
n2,
n2,
= 11.757 kmol
C4H8O +H2O
C4H10 + 5/2O2
(1)
CH3COOH + H2O
(2)
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
H 2O
E x 1011
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
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
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
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
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
6,570,118.32 J
6.57 x 106 J
H298
+ HP
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
Recycle C4H10
17.049 kmol/hr
11.757 kmol/hr
323.93 kmol/hr