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WePoPo.1
I. INTRODUCTION
A. Reaction kinetics
The reactions of EO with water and EG can be expressed
as:
k1
EG
EO + H 2O
456
dCDEG
=
k2CEO CEG k3CEO CDEG
dt
dCTEG
=
k3CEO CDEG k4CEO CTEG
dt
dCPEG
= k4CEO CTEG
dt
dl
F
F
dCH 2O
rH 2O R 2 r1 R 2
=
=
dl
F
F
2
( r r ) R 2
dCDEG
r R
=
DEG
=
2 3
dl
F
F
2
dCTEG
r R
(r r ) R 2
=
TEG
3 4
dl
F
F
2
dCPEG
r R
r R2
=
PEG
=
4
dl
F
F
Where r1 ~ r4 are reaction rates of the reactions in Eqs (3).
(5)
(r1H1 + r2 H 2 + r3 H 3 + r4 H 4 ) R 2 =
0
X T YY T X is a 3 3 dimensional symmetric matrix and the
dl
rank of the matrix is l. So there are 2 orthonormal eigenvectors
Where is the density of the reaction mixture, c p is
which eigenvalue equals 0. Take these 2 orthonormal
specific heat capacity of the reaction mixture, H is reaction eigenvectors as column vector, we can get a 3 2
heat.
dimensional matrix B = (b1 , b2 ) . In this way, we get
In general, the flow is relatively stable, F is almost
biT X T YY T Xbi = 0 , so (b1 , b2 , Y T X ) must be a 3 dimensional
constant. The value of c p is dependent upon temperature and
orthonormal basis.
components.
The vector which consists of independent variable matrix
X and is perpendicular to dependent variable matrix Y can
III. THE REACTION RATE CONSTANT REGRESSION
be denoted by H = XA . Then we have Y T XA = 0 . So A
The value of the preexponential factor has an uncertainty consists of orthocomplement space of Y T X . Then A can be
of 10% in the literature [8]. According to the experimental expressed by a linear combination about the columns of
data in the literature [9], the reaction rate constants can be
B that can be denoted by A = BD . Next step we need to find
worked out by regression analysis. And thus the the D that can make the variance of XBD reaches the
macro-kinetics model can be proposed.
maximum, so the useless information between independent
We applied improved partial least squares regression variable and dependent variable can be removed as much as
457
k=
1.0795 107 4.5102 104 Tx + 1.4350Tx 2 + 0.1129Tx 3
4
Where Tx is absolute temperature in Kelvin, ki is in
Lmol 1 min 1 .
Using the 5 groups of experimental data and another 2
groups of experimental data to verify the reliability of the
model, the absolute value of average relative error between
the predicting data and the experimental data is 5.92%. Using
the same data to calculate the model which established based
on the method in literature, the absolute value of average
relative error is 8.56%. There was a 30.84% decrease. So this
model proved effective.
k1 ' = a1k1
k2 ' = a2 k2
(10)
k3 ' = a3 k3
k4 ' = a4 k4
1) Input the real-time operation conditions, including the
inlet temperature, pressure, flow and components of the
reactor. According to the input conditions, we can calculate
the outlet components of the reactor when taking the value
of k1 , k2 , k3 , k4 as initial value.
n ( y
EG ,i z EG ,i ) + ( y DEG ,i z DEG ,i )
(11)
min
2
2
i =1 + y
( TEG ,i zTEG ,i ) + ( yPEG ,i z PEG ,i )
Boundary conditions: ki > 0, i =
1, 2, 3, 4 , C j 0
Initial value: a=
1,=
i 1, 2, 3, 4
i
Where C j is the concentration of the components in the
reaction mixture, yEG ,i is the calculating value of EG, z EG ,i is
the actual value of EG.
3) Using the correcting reaction rate constants to calculate
the model, we can get the simulation results which are more
suitable for the operation conditions.
V. THE CALCULATED RESULTS AND RESULTS ANALYSIS
A. The calculated results of the model
The reactions of ethylene oxide with water are irreversible
and exothermic. The conversion rate of EO can reach to 100%
in industry control. The model can preferably reflect the
performance of EO hydration reactor after the parameter
calibration. Using 10 groups of field data to verify the
reliability of the model, the absolute value of average relative
error is 4.82%. The model calculating components are
compared with the designed conditions in Table I.
TABLE I
Mass Fraction
Reactor
Inlet
(designed)
EO
H2O
EG
DEG
TEG
PEG
Total Flow(Kg/hr)
0.0999
0.8985
0.0016
0.0000
0.0000
0.0000
260377.5
Reactor
Outlet
(designed)
Reactor
Outlet
(calculated)
0.0000
0.8600
0.1269
0.0123
0.0007
0.0001
260377.5
0.0000
0.8595
0.1281
0.0117
0.0006
0.0001
260377.5
458
460
450
T(K)
440
430
420
410
400
20
40
60
80 100 120
l(m)
140 160
xEO
20
32992.4
3305.6
188.9
33.7
179.8
0.8
21
22
33174.9
33345.5
3174.5
3051.4
172.9
157.8
30.8
28.1
177.7
175.7
23
33502.5
2936.4
145.1
25.8
173.8
24
33649.2
2829.6
133.1
23.7
172.2
25
33777.1
2730.8
122.4
21.8
170.9
0.6
0.4
0.2
0
20
40
60
80 100
l(m)
120
140
160
x 10
2
yEO
yH2O
yEG
yDEG
yTEG
yPEG
1.5
0.5
20
40
60
80
l(m)
100
120
140
160
TABLE II
PRODUCT DISTRIBUTIONS AT DIFFERENT WATER/EO MOLAR RATIOS
Outlet
Water/E
DEG
TEG
PEG
EG
Temperat
O Molar
(kg/h)
(kg/h)
(kg/h)
(kg/h)
ure (C)
Ratios
TABLE III
2500
yDEG
yTEG
yPEG
2000
Inlet
Temperat
ure (C)
1500
1000
500
0
20
40
60
80
l(m)
100
120
140
160
EG
(kg/h)
DEG
(kg/h)
TEG
(kg/h)
PEG
(kg/h)
Outlet
Temperat
ure (C)
127
33352.3
3041.2
157.3
28.0
172.9
128
129
33350.2
33347.8
3044.6
3078.0
157.5
157.7
28.0
28.0
173.8
174.8
130
33345.5
3051.4
157.8
28.1
175.7
131
33343.2
3054.7
158.0
28.1
176.6
132
33340.8
3057.9
158.2
28.1
177.7
133
33338.5
3061.3
158.3
28.1
178.6
459
[9]
[10]
[11]
[12]
[13]
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REFERENCES
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460