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# 2005 Institution of Chemical Engineers
Trans IChemE, Part A, February 2005
Chemical Engineering Research and Design, 83(A2): 187195
www.icheme.org/journals
doi: 10.1205/cherd.04161
1
DSM Research, Geleen, Netherlands
Department of Chemical Engineering, University of Twente, Enschede, Netherlands
he kinetics of the oxidation of toluene have been studied in close interaction with the
gas liquid mass transfer occurring in the reactor. Kinetic parameters for a simple
model have been estimated on basis of experimental observations performed under
industrial conditions. The conclusions for the mass transfer and reaction regime on basis of
experimental observations and model calculations are in good agreement: toluene oxidation
under industrial conditions can be characterized as a slow reaction with respect to mass
transfer.
Keywords: chemical reactors; kinetics; mass transfer; mathematical modelling; multiphase
reactions; reaction engineering.
INTRODUCTION
187
188
HOORN et al.
(1)
(2)
(3)
R4 k4 cBALC cO2
(4)
(5)
w . 2 J kL cA,i w
w , 0:3 J kL (cA,i cA,b )
(7)
(8)
The enhancement factor is the ratio of the flux in presence of reaction [equation (6)] and pure physical mass
transfer under identical conditions [expression is equivalent
to equation (8)].
p cA,i (cA,b )=(1 w2 )
(9)
E 1 w2
cA,i cA,b
The extremes for small and large Hatta numbers are:
w.2 Ew
w , 0:3 E 1
(10)
(11)
The Hatta number and the enhancement factor are calculated from experimental observations, respectively
included in the modelling.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 187195
189
(12)
(13)
(14)
(15)
cA,i 1 Al w2
(16)
(1 1) kL
aD
(17)
kL2
FGL
Al D VR kL a cA,i FGL
(19)
kL (water, 258 C)
s
D(toluene, 1508 C)
D(water, 258 C)
(20)
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190
HOORN et al.
Table 1. Data from a series of standard experiments.
Reactor temperature
Reactor pressure
Off-gas inert flow
Feed flow toluene
Feed flow air
Flow liquid discharge
Flow condensate
Off-gas oxygen level
Condensate
Liquid discharge
Balc
Bald
BzA
H2 O
Tol
Balc
Bald
BzA
Tol
8C
bar
Nl/h
kg/h
Nl/h
kg/h
kg/h
vol%
mol/h
mol/h
mol/h
mol/h
mol/h
mol/h
mol/h
mol/h
mol/h
Standard deviation
in reference experiments
140160
47
100300
12
100300
0.51.5
0.51.5
06
0.00030.005
0.0030.02
00.02
0.61.6
2.15.6
0.0030.05
0.030.2
0.41.1
1.510.9
0.8%
0.2%
1.1%
1.0%
0.3%
2.1%
2.3%
32.5%
12.5%
7.3%
20.8%
11.0%
4.8%
3.9%
1.8%
3.3%
1.5%
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Condensate
Liquid discharge
Balc
Bald
BzA
H2O
Tol
Balc
Bald
BzA
Tol
SSO (mol2/h2)
SSR (mol2/h2)
Standard deviation
Standard deviation
without reflux
3.24 . 1025
9.29 . 1024
4.45 . 1024
1.26 . 101
1.61 . 102
6.92 . 1023
1.53 . 1021
5.09 . 100
4.84 . 102
5.61 . 1026
1.69 . 1024
1.87 . 1024
2.23 . 1021
2.72 . 100
5.61 . 1026
1.69 . 1024
1.87 . 1024
2.72 . 100
35.5%
21.7%
34.2%
11.0%
11.0%
2.4%
3.0%
0.5%
11.0%
8.74 . 1025
1.38 . 1023
1.34 . 1024
2.57 . 1021
3.34 . 101
8.74 . 1025
1.38 . 1023
1.34 . 1024
3.34 . 101
127.5%
61.3%
37.3%
12.6%
36.1%
9.4%
8.7%
0.4%
38.5%
DISCUSSION
From Table 1 it appears that the input process parameters
are controlled with acceptable accuracy of approximately
1%. The response variables differ in accuracy in the
range of 1.5% for toluene in the liquid discharge flow to
20% for benzoic acid in the condensate flow. Benzoic
acid concentrations in the condensate flow are difficult
to analyse because at room temperature the condensate separates into a water and an organic phase. The low accuracy
for the oxygen measurement is a combination of the
analytical measurement and the length of the sample pipe
from the off-gas vessel to the instrument. The simulation
of the partial condensation in the piping to the condenser
vessel is successfully performed by modelling the reactor
part with an additional flash calculation (Figure 4) and
this is illustrated when the results in Table 2 are compared.
The differences between model predictions and experimental observations are clearly reduced with respect to the situation where there is no liquid recycle. When compared
to the indication of experimental errors in Table 1, the
model describing the partial condensation has a scatter in
the model predictions that is much closer to the
0.015 + 0.004
1.35 + 0.36
3.9 + 1.0
Reactions
3
m /mol/s
m3/mol/s
m3/mol/s
Tol ! Balc
Tol ! Bald
Bald ! BzA
Balc ! Bald
Correlation matrix
k12
k3
k4
k12
1
0.98
0.99
k3
k4
1
0.98
7.2 . 10
7.2 . 1022
9.6 . 1023
2.4 . 1021
7.5 . 100
Model SSR
4.3 . 101
1.8 . 1023
1.4 . 1024
1.7 . 1023
1.6 . 1023
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 187195
192
HOORN et al.
Figure 9. Comparison between experimental values and model calculations for the oxygen concentration in the off-gas.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 187195
193
CONCLUSIONS
Experiments performed in a reactor that was operated
under industrial conditions have been successfully applied
in the estimation of kinetic parameters in a model with
inclusion of the description of mass transfer phenomena.
Analyses of the mass transfer characteristics reveal that
toluene oxidation under industrial conditions is a slow reaction with respect to mass transfer.
Figure 11. Residuals between experimental and model values as function
of the experimental observed oxygen concentration in the off-gas;
(W) benzyl alcohol; (A) benzaldehyde; () benzoic acid.
NOMENCLATURE
a
Al
c
cA,b
cA,i
cO2,sat
cO2,out
D
E
F
FGL
J
k
k
kfo
kL
kL a
n
p
Ptot
R
VR
w
x
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 187195
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HOORN et al.
xO2,sat
y
z
Greek symbols
1
x
f
fV
w
rmol,L
s
tL
Sub/superscripts
i
BALC
BALD
BzA
H2O
N2
O2
TOL
F
G
L
V
R
Abbreviations
ACM
SSO
SSR
REFERENCES
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The manuscript was received 2 June 2004 and accepted for publication
after revision 13 December 2004.
APPENDIX
Overall pseudo first-order rate constant for oxygen
k fo
3
1
k12 cTOL k3 cBALD k4 cBALC
2
2
p
kfo D
kL
FGL J VR a
p cO2,sat (cO2 )=(1 w2 )
E 1 w2
cO2,sat cO2
J kL cO2,sat cO2 E
Reaction rate expressions (according to Figure 1)
R1 k12 cTOL cO2
R2 k12 cTOL cO2
R3 k3 cBALD cO2
R4 k4 cBALC cO2
RBALC R2 R4
RBALD R1 R3 R4
RBzA R3
RH2O R1 R4
1
RO2 R1 (R2 R3 R4 )
2
RTOL R1 R2
Definition for toluene conversion
FF,TOL FL,TOL FG,TOL
x
FF,TOL
Definition for benzoic acid, benzaldehyde and benzyl
alcohol selectivity
si P
FL,i FG,i
P
j FL,j
j FG,j
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 187195
FG,O2
FG,N2 FG,O2
195
fL,i xi fV,i zi
fG,i yi fR,i wi
FF,i FR,i V Ri FL,i FV,i
FV,i FG,i FR,i
Mass balances for oxygen
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 187195