Iran. J. Chem. Chem. Eng. Research Article Vol. 40, No.

6, 2021

Modeling and Simulation of Partial Oxidation of

Methanol to Formaldehyde on FeO/MoO3 Catalyst
in a Catalytic Fixed Bed Reactor

Olatunde, Abayomi Olaniyi*+; Olafadehan, Olaosebikan Abidoye;

Usman, Mohammed Awwal
Department of Chemical and Petroleum Engineering, University of Lagos, Lagos, NIGERIA

ABSTRACT: A two-dimensional mathematical model was developed for a porous heterogeneous

catalytic fixed bed reactor. The model took into account the effect of heat generated by adsorption
of reactants on the catalyst surface and heat transfer from the fluid phase to the surroundings which
have a significant effect on reactor performance, especially at reactor hotspot. The developed model
predicted the partial oxidation of methanol to formaldehyde on FeO/MoO 3 catalyst, a complex
reaction system. Excellent agreement was achieved when the resultant simulated results were compared
with experimental data in the literature. The proposed model predicted the location of the hotspot
at a dimensionless distance of 0.4413 (= 0.0309 m) the same as the experiment value but
with a temperature of 619 K compared with an experimental value of 622 K. The conventional
heterogeneous and pseudo-homogeneous models predicted the hotspot temperature to be about 8 K
and 34 K lower than the experimental value respectively.

KEYWORDS: Heterogeneous; Pseudo-homogeneous; Non-isothermal; Orthogonal collocation;

Hotspot.

INTRODUCTION
Most of the reactions taking place in a catalytic fixed
bed reactor are complex. These can be in the form of
highly exothermic reactions or highly endothermic
reactions. Usually, when a highly exothermic reaction
takes place in a catalytic fixed bed reactor, some problems
related to the operation of the reactor always occur since
most of the chemical reaction terms are a highly non-linear
function of temperature and concentration and the value of
heat may vary in the large amount. When heat is produced
faster than the rate it leaves the reactor walls, a rapid
increase in the reactor temperature results [1]. This
excessive heat in the reactor is referred to as ‘temperature
*To whom correspondence should be addressed.
+E-mail: aolatunde@unilag.edu.ng
1021-9986/2021/6/1800-1813 14/$/6.04
runaway’, which causes some deleterious effects
in the reactor. These include the promotion of undesired
side reactions, catalyst deactivation by sintering and
productivity loss, and reduction of product selectivity.
Thus, there is a need to develop a model that predicts
the outer-tube wall temperature profile for a given set of
inputs, and the effect of heat loss through the wall on the
magnitude of hotspot temperature which will help plant
operators to reduce the risk of the reactor failure. Also,
there is continuous generation or consumption of heat due
to enthalpies of adsorption and chemical reaction. The heat
transfer that takes place during the adsorption of reactants

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 Iran. J. Chem. Chem. Eng. Olatunde, Abayomi O. et al. Vol. 40, No. 6, 2021

on the catalysts, the surface contributes to the thermal directions. It considers in addition to convection flow,
behavior of the fixed bed reactor as it increases the heat, and mass dispersion fluxes in the bulk fluid.
temperature of the reactor [2-3]. It is important to develop Mass balance:
a model that incorporates the effect of heat generated
Ci   2C 1 Ci 
2
 Ci
by adsorption of reactants on the catalyst surface in the reactor  f R Ci,T  (1)
i
uf  Dr     D e ,a x
z   r2 r r  dz
2
with a view to integrating its effect on the hotspot and  
runaway phenomena.
Several models have been proposed in the literature to Energy balance:
study the behavior of fixed bed reactors. The models
dT   2T 1  T 
are grouped into two major categories namely: the pseudo- uf f C pf  r    (2)
 2
r  r 
homogeneous and heterogeneous models. Many works dz  r
have been done on the modeling and simulation of 2
d T
catalytic packed bed tubular reactors using a two-  e,a x
2
 f  H r  R Ci,T 
dz
dimensional pseudo-homogeneous model [4-14]. They
assumed the catalyst surface to be totally exposed to the
Boundary conditions
bulk fluid conditions, that is, there is no fluid-to-particle
C  r, 0   C o ; T  r , 0   To (3)
heat and mass transfer resistance between the solid and the
fluid phases. This implies there is a negligible difference at Z0 and 0rR

between the fluid and solid phase conditions and mild

C T
radial concentration and temperature profiles. However,  0, z   0 ;  0, z   0 (4)
there are some cases when the differences between r r

conditions in these phases are significant mostly highly at r0 and 0zL

exothermic reactions which are common in industries,

C T
hence heterogeneous models have to be considered. The R,z  0 ; r  R , z   U w  T  T w  (5)
r r
conventional heterogeneous model developed by [11,15-18]
although caters to the defects in the pseudo-homogeneous at rR and 0zL

models but still failed to explain explicitly the effects

of heat loss from the fluid phase via the wall to the Conventional two-dimensional heterogeneous model
surrounding and the effect of heat generated by adsorption The models consider the heterogeneity of the reactor
of reactants on the catalyst surfaces both of which i.e the two-phase nature of the reactor. The models account
have effects on the location and magnitude of hotspots for the difference between the concentration and
and temperature runaway phenomena. temperature in the bulk fluid phase and inside the catalyst
This work will develop a two-dimensional heterogeneous and the catalyst surface.
reactor model that will that incorporate the effect of heat Fluid phase for concentration:
generated by adsorption of reactants on the catalyst surface 2
Cf  Cf Cf
in the reactor and also explicitly predicts the effect  D e,a x  Uf  (6)
t z
2
z
of outer-tube wall temperature profile for a given set of inputs,
and the effect of heat loss through the wall. This will be compared  1  b  3 
  k Cf  Cs  rR
with two-dimensional pseudo homogeneous and conventional    R  g
 b  
heterogeneous models. The developed models will be used to
predict the reaction process for partial oxidation of Solid-phase for concentration:
methanol to formaldehyde on FeO/MoO3 catalyst.
s D s   2  C s  n Cs
r   s  R i  C i , Ti   s (7)
r
2
r  r  i 1 t
Two-dimensional pseudo-homogeneous model
This model considers concentration and temperature
profiles in the bulk fluid phase both in the axial and radial Fluid phase for temperature:

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 Iran. J. Chem. Chem. Eng. Model and Simulation of Partial Oxidation of... Vol. 40, No. 6, 2021

 Tf
2
 Tf  Tf Cf
f Cspf   e ,a x  U f f Cspf  (8) (ii) U f C f (t)  U f C o  D e ,a x 0 t  0 (18)
z0
t z
2
z z z0

 1  b  3  Cf

 

 R  f
  Tf  Ts  (iii)  0, t  0 (19)
 b   z z zT

Solid-phase for temperature: The mass transfer effects included in the model are
intra-particle diffusion, inter-phase film diffusion, and
 s  s   2  Ts  n

r    s   H r R i  C i , Ti   (9) axial and radial dispersion. The essential assumptions are

r
2
r  r  i 1
constant pressure in the reactor because the pressure drop
 Ts is so small that the initial pressure may be used instead of
s  s C s p s
t the reactor pressure at a particular position, constant
coefficients of dispersion and diffusion, constant
Initial and boundary conditions: porosities, the constant activity in each catalytic zone,
(i) Cf  Co , t  0, zT  z  0 (10) plug flow and the spherical catalyst particles have uniform
size and homogeneous structure. Moreover, heat transfer
Cf from the fluid phase to the surrounding is included
(ii) U f C f (t)  U f C o  D e,a x  0, t  0 (11)
z0
z in the energy balance around the column.
z0
The balance for the solid phase is given thus:
Cf
(iii)  0, t  0 (12) s D s   2  C s  q
*
z z zT  r     (20)
s
r
2
r  r  t

(iv) Tf  To , t  0, zT  z  0 (13) n Cs

 s  r 'i  C i , T i    s
i 1 t
(v) U f  f C s p f Tf  U f  f C s p f To  (14)
subject to the following initial and boundary conditions
 Tf
 e ,a x  0, t  0
z z0 (i) Cs = 0, t  0, 0  r  R (21)

 Tf Cs
(vi)  0, t  0 (15) (ii)  0, 0  z  zT , t  0 (22)
z z zT r r0

THEORETICAL SECTION  Cs 

(iii) s D s    kg Cf  Cs , (23)
Mathematical models of catalytic fixed bed tubular reactor  r  rR
A material balance applied to the bulk fluid phase
0  z  zT , t  0
(macrosystem) gives the following equation:

Cf  Cf
2
Cf
The energy balance applied to the bulk fluid phase
 D e,a x  Uf  (16) (macrosystem)gives the following equation:
t z
2
z

 1  b  3  2
 Tf  Tf  Tf
  k Cf  Cs  rR
   R  g f Cspf   e ,a x  U f f Cspf  (24)
 b   t z
2
z

 1  b  3  aw
The initial and boundary conditions needed to complete 
 

 R  f
  Tf  Ts   U w  Tf  Tw 
the definition of the macrosystem are:  b   b

(i) Cf  Co , t  0, zT  z  0 (17) subject to the initial and boundary conditions:

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(i) Tf  To , t  0, zT  z  0 (25) Ci T r
Ci  , T  ,   ,
 C i o To R
 Tf
(ii) U f  f C s p f Tf  U f  f C s p f To   e ,a x 0 (26)  rC , T 
z  i  z tuf
i 
Ci ,T 
i
z0 R  ,Z  , 
t  0   ri  o   C i  o , T o  zT zT

Eq. (16) in dimensionless form gives:

 Tf
(iii)  0, t  0 (27) 2
z Cf 1  Cf Cf
 1 Cf  Cs   1
z zT
  (33)
 P em  Z 2
Z
The enthalpy balance for the solid phase is given thus:
where
 s  s   2  Ts  q
*

 r    s
 H ad
 (28) zT U f
r
2
r  r  t P em  (34)
D e ,a x
n  Ts
s   H rR i  C i , Ti   s  s C s p s
i 1 t
 1  b  3  kgzT
1    (35)
   R  U
The initial and boundary conditions needed to  b   f

complete the definition of Eq. (28) are:

Subject to the transformed initial and boundary
(i) Ts = T w , t  0, 0  r  R (29) conditions:

(i) Cf 1 t  0, 1 Z  0 (36)
  Ts 
(ii) s    f  Tf  Ts  , (30)
 r  rR
1  Cf 
(ii) C f (0, )  1    0 (37)
0  z  zT , t  0 P em  Z  Z0

 Ts Cf
(iii)  0, 0  z  zT , t  0 (31) (iii) 0 , t  0 (38)
r Z
r0 Z 1

Eq. (28) is the equation that shows the effect of heat For spherical pellets, Eq. (20) for solid-phase in terms
generated by adsorption of reactants on the catalyst surface of dimensionless variables yields:
while the second term on the left-hand side of the equation
Cs 1    2C 2 Cs  
is the representation of the term.    R i  C s , Ts 
s 2
  s   (39)
 2    2
   
The energy balance around the column wall is given   
by:
where
 Tw
 w C p,w   hwaw  Tw  Tf   (32)  *
sq o  Q * 
t   1   (40)
2  C o s  C s 
a a m b  Tw  Ta m b  
U am b 
The Thiele modulus,  , is given by
Eq. (32) explicitly predicts the effect of the outer-tube
wall temperature profile for a given set of inputs, and the 
  s   ro  C o , T o   
effect of heat loss through the wall.  
  R  (41)
 D sC o 
 

Non-dimensionalization of the model equations A restatement of the initial and boundary conditions
Introducing the dimensionless variables, defined as needed to solve Eq. (39) in terms of the dimensionless
follows: variables yields:

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(i) C  0, t  0, 1   0 (42) The transformed initial and boundary conditions

s
needed to complete the definition of Eq. (52) are:
Cs (i) Ts = 1 ,   0, 0    1 (55)
(ii)  0, 0  Z  1, t  0 (43)

0
 Ts
(ii)  0, 0  Z  1,   0 (56)
 C 
4 
 Cf  Cs   1 ,
s
(iii)   (44) 0
S h s    
 1
4   Ts 
0  Z  1,   0 (iii)     Tf  Ts  , (57)
N u    
 1
Eq. (24) in dimensionless form gives:
0  Z  1,   0
2
 Tf 1  Tf  Tf
   3  Tf  Ts   (45) The linear adsorption isotherm used in computation has
 P eh  Z2 Z
the form:
 4  Tf  Tw 
*
q  aLC (58)
where
In dimensionless form, we have equations:
U f f C spf zT
P eh  (46) *
 e ,a x Q aLCo
 , (59)
Cs qo
*

 1  b   3   f zT
   (47)
3    R  C Which are used in equations (40) to obtain simple
 b   f spf U f
expressions  2 .
awU w
zT For an ideal gas, p V  nR T  p  C R T , that is
 4
 (48)
b f U f C sp f C  p RT . Using this relationship in Eq.(59) and

Subject to the transformed initial and boundary introducing dimensionless variables, we obtain:
conditions: Q
*
aLCo
 , (60)
(i) Tf  1 , t  0, 1 Z  0 (49) Cs qo
*

1   Tf  Which are used in Eq. (53) to obtain an expression for  5 .

(ii) Tf ( 0 ,  )  1    , 0 (50)
P eh  Z  Z0
The dimensionless energy balance equation around
the column wall is given by:
 Tf
(iii)  0, 0 (51)
Z  Tw h w a w zT
Z 1
   Tw  Tf   (61)
Eq. (28) in dimensionless form yield Eq. (52):   w C p,w U f

U am ba am bzT
 Ts 1    2T 2  Ts  n 
 Tw  Ta m b 
 R i  C i , Ti  
s 2
  s     (52)  w C p,w U f
 5   2    
  i 1


where
Application of the model to partial oxidation of methanol
H q
*
Q
* to formaldehyde
ad o
 5  s  (53)
C p s To  Ts In this study, the exothermic reaction chosen was from
the pilot plant experimental work of Windeset al. [19],
D s    H rxn  C o which involves the partial oxidation of methanol to
s  (54) formaldehyde accompanied by a side reaction of formaldehyde
 s To

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Table 1: The geometric, kinetic and parameters used for the partial oxidation of methanol to formaldehyde.
Physical properties and bed characteristics value unit
Fluid density 1000 [kg/m3]
Catalyst density 2000 [kg/m3]
Wall density 7800 [ kg/m3]
Specific heat of the fluid 952 [J/kg-K]
Specific heat of the catalyst 1904 [J/kg-K]
Thermal conductivity of the fluid 2.0 [W/m-K]
Superficial velocity 2.47 [m/s]
Feed temperature 523 [K]
Methanol in feed 1.7 [mol/m3]
Oxygen in feed 34 [mol/m3]
Fluid Temperature 523 [K]
Wall temperature 523 [K]
Ambient temperature 523 [K]
Reactor tube radius 0.0133 [m]
Particle diameter 0.0046 [m]
Thermal conductivity of the catalyst 2.0 [W/(m.K)]
Thermal conductivity of the bulk fluid 0.08 [W/(m.K)]
Void fraction in the bed 0.5
Void fraction in particles 0.57
Length of the reactor 0.7 [m]
Particle effective diffusivity 4.910-6 [m2/s]
Effective axial diffusivity 0.2619 [m2/s]
Ratio of mean surface area to volume of the column
Wall 270.0 [m-1]
Ratio of internal surface area to volume of the column
Wall 300.0 [m-1]
Heat transfer coefficient from wall to ambient 7.092 [W/(m2.K)]
Heat transfer coefficient from the fluid to solid phase 400 [W/(m2.K)]
Heat transfer coefficient of the wall 528 [W/(m2.K)]
Overall heat transfer coefficient of the wall 220 [W/(m2.K)]
Inlet pressure 1.55 [atm.]
Outlet pressure 1.3 [atm.]
Kinetic parameters
Heat of reaction for reaction 1 -158700 [J/mole]
Heat of reaction for reaction 2 -158700 [J/mole]
Heat of adsorption - 8368 [ J/mole]
Dimensionless number
Peclet number (mass) 6.6
Peclet number (heat) 8.6
Sherwood number 11.0
Biot number 5.5

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 Iran. J. Chem. Chem. Eng. Model and Simulation of Partial Oxidation of... Vol. 40, No. 6, 2021

to carbon monoxide and water. This is a consecutive side Where

reaction over an iron oxide/molybdenum oxide catalyst.
The chemical reaction is as follows:    H rxn  D sC o E1 H2
1  ; 1  ; 2 
 s To R g To R g To
1
C H 3O H  O 2  H C H O  H 2O (62)
2  b k 1o
s  R e x p   1 
0 .5
with the rate expression: D sC o

0 .5     1  C   
k 1C M  79496 
  rM  D E N 1  1  k 2 o e x p    2  C o e x p
2 2 s
 Cs 
0 .5 0 .5
 ;
7
k1  1 2 5 1 0 e x p   (63) 
 ;
  1   2 1  C s   
0 .5
1 K 2C M  RT 
   

 8368 
K 2
 1 .1 2 ex p   
 RT  Methods for the numerical solution
The numerical method adopted for the solution
This is accomplished with an undesirable side reaction.
of the mass and enthalpy balance equations is the method
1 of orthogonal or optimal collocation. The orthogonal
C H 2O  O 2  C O  H 2O (64)
2 collocation method is applied by first choosing a new set
0 .5 of dimensionless variables, which have values lying
k 2C C H
r C H 2O  
O
2
; k2  (65) between 0 and 1.
0 .5
1 0 .2 C C H 2O When the method of orthogonal collocation is applied
5  8368 to the space variables Z and then substituting u=2,
54 10 exp 
 RT  Eq. (33) becomes:

These values of constants and parameters were taken d C fj N 1 NR

from the experimental work of Windeset al. [19] and to

  W j, k C f k   A N  1, k C p k  (68)
d k2 k 1
which the simulation results were compared.
 1 1   6  C fj  P em
Rendering the rate Eq. (63) for the partial oxidation of
methanol to formaldehyde in dimensionless forms, and using Where
the resulting expressions in Eq. (39), we have:
B 
1
W j, k  A 1, k  B j, N  2 A 1, k  B j, k (69)
Cs P em
j,1
 (66)


    1  C   
A j,1
  A
A 1, k j, N  2
  A
A 1, k j, k 
 exp 
1 1 s
 C 0 .5 
 1   1  C s  
s
   2C 
2 CS   P e 
1
1
 s 2    P em  B  P e m B (70)
    s
1
m j,1 j, N  2
 2 P em
  
s
2  D E N1 
 
 
   P e m
A j,1
 P e m A j, N  2 
 

Introducing dimensionless reaction term to Eq. (52), P em

 Ts A 1, N  2
 (67) P e m 
 P em A 1,1 A N  2 ,1
 
A 1, N  2 A 1, N  2 A
    1  C    N  2,N  2
1 1 s
 exp   Cs 
0 .5

 1   1 1  C s  
A 1, k A
1    2T
s 2  Ts  2  


N  2 ,k
 s     1 s  A 1, N  2 A
5    2
   D E N1  N  2,N  2
   
A 1,
 
k
P em A 1,1 A N  2 ,1
   
A 1, N  2 A 1, N  2 A N  2,N  2

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 Iran. J. Chem. Chem. Eng. Olatunde, Abayomi O. et al. Vol. 40, No. 6, 2021

B 
P em A 1, k A N  2 ,k 1
 H j, k
 j,1
A 1,k  B j, N  2 A 1, k  B j, k (76)
A 1,1  P e m A 1,1  P e m A N  2 ,1 P eh
P e m  ; A 1, k 
A N  2,N  2

A 1, N  2 A N  2,N  2

A 1, N  2
A j,1
  A
A 1, k j, N  2
A 1, k  A j, k 
A N  2 ,1 A 1,1  P e m A N  2 ,1 A 1,1  P e m

6 
1
; A N  1, k 
4
A N  1, k 9
U j, k
 4u
 j B j, k
 B j, N  1 A
*
N 1  (77)
4 Shs
1
 
A N  1, N  1 *
S hi 6 A j, k
 A j, N  1
A N 1

Also, by applying orthogonal collocation to the system

 P e B 
1
model equations for the spherical particle radial direction, P eh  h j,1
 P e h B j, N  2
(78)
P eh
we have
 P e A h j,1
 P e h A j, N  2 
 Csj
 (71)


 7  4 u j B j, N  1  6 A j, N  1  (79)


   1 C
   

exp 
1 1 sj 0 .5
C
 1   1  C
   
sj
 NR
 Peh
1   1 sj


2
s  F j, k C s k   6  7 C f j    s
2   k 1  D E N1  A 1, N  2
  P e h 
  Peh A 1,1 A N  2 ,1
   
A 1, N  2 A 1, N  2 A N  2,N  2
Where
A 1, k A N  2 ,k

B 
A 1, N  1 A
F j, k   4 u  B j, N  1 A N  1, k (72) k 
A 1,
N  2,N  2
 j j, k
A 1,1 A
Peh N  2 ,1
 
6 A j, k
 A j, N  1
A N  1, k  

A 1, N  2 A 1, N  2 A N  2,N  2

Peh

 7  4 u j B j, N  1  6 A j, N  1  (73) A 1,1  P e h
P e h 
A N  2,N  2 A 1, N  2

Following the same development of the collocation A A 1,1  P e h
N  2 ,1
points for the concentration profiles in the bulk fluid phase
A 1, k A N  2,k
and solid phase, the resulting expressions for the 
A 1,1  P e h A N  2 ,1
temperature profiles in these phases are presented thus: A 1, k 
A N  2,N  2 A 1, N  2

d Tf j N 1 NR A N  2 ,1 A 1,1  P e h
 
*
 H j, k
Tf k  A T
N  1, k s k
 (74)
d k2 k 1 1 * 4
8  ; A N  1, k  A N  1, k  8
 3   3 8   4  Tf j  P e h   4 Tw 1
4
A N  1, N  1
Nus
Nus

 Ts 1   NR

  s   U j, k
Ts k   7  8 Tf j   (75) RESULTS AND DISCUSSION
 3   k 1 
The results of the reaction network investigated
   1  C   
exp 
1 1 s
 C sj 
0 .5 is presented and discussed in this section.
 1   1 1  C s   
The effects of heat generated by adsorption of the
2  
1 s 
D E N1  reactants on the catalyst and heat loss by the wall on the

 magnitude of hotspot temperature using partial oxidation of
methanol to formaldehyde on FeO/MoO3 catalyst
Where
were discussed.

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 Iran. J. Chem. Chem. Eng. Model and Simulation of Partial Oxidation of... Vol. 40, No. 6, 2021

Temperature and concentration profiles in the reactor 660

Figs. 1 and 2 show the temperature and concentration 640

profiles for the experimental work, the simulated model, 620

Temperature(K)
the conventional heterogeneous model without the effect 600

of heat generated by adsorption of reactants on the catalyst 580

surface, and the pseudo-homogeneous model in the axial 560

direction of the reactor for the partial oxidation of 540 experimental data
proposed model
methanol to formaldehyde and water. In Fig. 1, excellent 520 heterogeneous model
pseudo-homogeneous model
agreement was achieved between the experimental data for 500
the partial oxidation of methanol to formaldehyde on 0 0.2 0.4 0.6 0.8 1 1.2

FeO/MoO3 catalyst and simulated results. The proposed Dimensionless axial distance
model predicted the location of the hotspot at the same
dimensionless distance of 0.4413 (= 0.0309 m) as the Fig. 1: The axial temperature profiles of different models
experimental value but with a temperature of 619 K as developed in the reactor.
compared with the experimental value of 622 K having
2
an Absolute Average Deviation (AAD) 0.48%. The conversion

Methanol concentration (mol/m3)

1.8 experimental data
proposed model
of methanol for the models shows a faster conversion 1.6 heterogeneous model
of the methanol to formaldehyde even before reaching 1.4 pseudo-homogeneous model

the half of the reactor as a result of high temperature. 1.2

The conventional heterogeneous model predicted the
magnitude of the hotspot temperature to be about 8 K
lower than the experimental value at the same location
with the experimental result. This thus shows that heat
generated by adsorption of the reactants on the catalyst
surface has a major effect on the magnitude of the hotspot.
A temperature difference of such magnitude will lead to a
runaway effect which can lead to deleterious effects in the
reactor like undesired side reactions, catalyst deactivation
by sintering and productivity loss, and reduction of
product selectivity. The pseudo-homogeneous model
predicted the magnitude of the hotspot temperature to be
34K lower than the experimental value. The model shows
a gradual conversion of methanol with a prolonged
reaction which is normally the point of runaway condition
but was been predicted as a steady temperature variation.
Fig. 2 shows the concentration profiles of the methanol
conversion for the experimental work, the simulated
model, and the conventional heterogeneous model without
the effect of the heat of adsorption isotherm and the
pseudo-homogeneous model in the axial direction of the
reactor. Just like in the temperature profiles, the experimental
work, simulated model, and conventional heterogeneous
model showed that complete conversion takes place
at a dimensionless distance of 0.4413 at the location
of the hotspot. This shows that at the hotspot temperature,
the methanol concentration is almost zero, and at this point
1
0.8
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1
Dimensionless axial distance
Fig. 2: The axial concentration profiles of different models
developed in the reactor.
the undesired product is being produced as the reaction is
a consecutive one. The formaldehyde produced is converted
to carbon monoxide and water. The pseudo-homogeneous
model predicted a stretched concentration profile up to
a dimensionless concentration of about 0.8 very close
to the exit of the reactor [14].
Effect of change in wall temperature and wall heat
transfer coefficient on hotspot
Fig. 3 shows the effect of change in the wall
temperature on the magnitude of hotspot temperature as
predicted from the developed model Eq. (61). As the wall
temperature decreases from 523 K to 493 K the hotspot
temperature drops from 622 K to 589.12 K. This shows
that 1 K decrease in wall temperature leads to 1.1 K drop
in hotspot temperature. Fig. 4 depicts the effect of change
in the heat transfer coefficient of the wall on the

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 Iran. J. Chem. Chem. Eng. Olatunde, Abayomi O. et al. Vol. 40, No. 6, 2021

hotspot temperature at the prevailing condition. A ten 625

times increase in the magnitude of hw from 528.0 W/m2K 620

Hotspot temperature (K)

tau=0.5
to 5280.0 W/m2K leads to about 8 K drop in hotspot 615
temperature showing that hw has a major effect on the 610
amount of heat transfer through the wall. As the value 605
of hw increases the reaction being exothermic loses heat 600
to the surroundings through the bed wall thus reducing 595
the temperature in the reactor column. 590

585
Response of the reactor to change in feed temperature, 490 500 510 520 530

wall temperature, and feed concentration. Wall temperature (K)

Fig. 5 shows the response of the reactor to change
in the feed temperature from 503 K to 523 K. There is
an increase in the hotspot temperature from about 593 K to Fig. 3: Effect of change in wall temperature on hotspot
622 K with the location of the hotspot moving closer to temperature (time is 3mins)
the entrance of the reactor. This means an increase in feed
temperature leads to an increase in the reaction rate leading 623
622
to methanol being consumed very close to the entrance Hotspot temperature (K)
621 Tw= 523.116 K
of the reactor compared to feed temperature of 503 K 620
which has its location of the hotspot at a dimensionless 619
axial distance of 0.667 which is closer to the exit [20]. 618

Figs. 6 and 7 show the response of the reactor to changes 617

616
in the wall temperature and feed concentration (methanol)
615
from 503 K to 523 K and 1.74 mol/m3 to 1.914 mol/m3 614
respectively. There is an increase in the temperature 613
throughout the reactor with the greatest effect at the location 0 1000 2000 3000 4000 5000 6000

of the hotspot with little or no change in the position Wall heat transfer coefficient (W/m2K)
of the hotspot for the two changes.

Variation of the temperature inside the catalyst pellet and Fig. 4: Effect of change in wall heat transfer coefficient on
hotspot temperature.
with time along the reactor
Fig. 8 depicts the variation of the temperature inside
the catalyst pellet. The reaction being exothermic leads
to decrease in temperature from the center of the pellet to 640
To = 523 K

the outer surface of the catalyst as heat is released 620 To = 503 K

Temperature (K)

to the surroundings. Although the increase in the feed 600

temperature leads to an increase in the temperature inside 580
the catalyst pellet [14]. Fig. 9 shows the transient change 560
in the reactor. There is an initial increase in the temperature
540
inside the reactor after which the temperature becomes
520
steady as time goes on [14, 21].
500
0 0.2 0.4 0.6 0.8 1

CONCLUSIONS Dimensionless axial distance

A detailed and feasible mathematical model for a
porous heterogeneous catalytic fixed bed tubular reactor Fig. 5: Response of the reactor to change in feed temperature
has been developed. The model consists of hyperbolic from 503 K to 523 K.

Research Article 1809

 Iran. J. Chem. Chem. Eng. Model and Simulation of Partial Oxidation of... Vol. 40, No. 6, 2021

640 660
To= 523 K
620 640
To= 503 K

Temperature (K)
600 620
Temperature (K)

600
580
580
560
560
540
540
Tw= 503 K
520
Tw= 523 K 520
500 500
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Dimensionless axial distance Dimensionless radial distance

Fig. 6: Response of the reactor temperature to change in wall Fig. 8: Temperature profiles inside the catalyst pellet at
temperature from 503 K to 523 K. different feed temperatures (503K and 523K).

750 640
Co=1.74 mol/m3

Co= 1.914 620

700
mol/m3 Temperature (K)
Temperature (K)

600
650
580

600 560

540
550
520

500 500
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Dimensionless axial distance Dimensionless time

Fig. 7: Response of the reactor temperature to change in feed Fig. 9: Temperature variation with time in the reactor.
concentration (methanol).

and parabolic partial differential equations took into model developed herein is useful in the design and analysis
account intra-particle and inter-particle diffusion of a catalytic packed bed tubular reactor, where mass and
resistances; heat generated by adsorption of reactants heat transfer resistances are accounted for.
on the catalyst surface and the heat transfer from the fluid
phase to the surroundings was included in the energy Acknowledgments
balance as it has a significant effect on the reactor We acknowledge the contribution of the Reaction
performance, especially reactor “hotspot”. The model Engineering and Energy Research group of the Chemical
shows that heat generated by adsorption of reactants on the and Petroleum Engineering Department of the University
catalyst surface has an effect on the magnitude of the hotspot of Lagos, Nigeria.
and reducing the temperature of the column wall leads
to a decrease in the magnitude of the hotspot. An increase Nomenclature
in the value of the wall heat transfer coefficient leads aamb Ratio of mean surface area to volume
to an appreciable reduction in the magnitude of the of the column wall, m-1
hotspot. It also shows that the model was able to accurately aF Freundlich adsorption isotherm constant, m3/kg
predict the experimental result of the reaction system, aL Langmuir adsorption isotherm constant, m3/kg
suggesting that the developed model represents the aw Ratio of internal surface area to volume
essential features of the real system. The comprehensive of the column wall, m-1

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 Iran. J. Chem. Chem. Eng. Olatunde, Abayomi O. et al. Vol. 40, No. 6, 2021

Aj,k Constant generated in the orthogonal Rg Universal gas constant, kJ/(kmol K)

collocation method Ri(Ci,Ti) Reaction rate of solute, kg/(m3 s)
AAD Absolute average deviation r Radial distance in the pellet, m
bL Langmuir adsorption isotherm constant, m3/kg Shs Sherwood number of solute in catalyst pellet,
Bj,k Constant generated in the orthogonal dimensionless
collocation method Ta Ambient temperature, K
Cf Concentration of solute in fluid phase Tf Temperature of solute in the fluid phase, K
of the column, mol/m3 Ts Tmperature of solute in the catalyst pellet, K
Cf Dimensionless concentration of solute in the bulk To Inlet temperature of solute in the reactor, K
fluid phase of the reactor, Cf /Co Tf Dimensionless temperature
Cs Concentration in the solid phase, mol/m3 *
Ts Catalyst surface temperature in equilibrium
Csp Specific heat capacity, J/(kg K)
with pore-fluid phase, K
Co Inlet concentration of solute in the bulk
Tw Temperature at reactor wall,K
fluid phase of the reactor, mol/m3
t Time, s
De,ax Effective axial diffusivity of solute
Uanb Heat transfer coefficient from wall
in the fluid phase, m2/s
to ambient, W/(m2 K)
Ds Effective diffusivity of solute in catalyst
Uf Interstitial velocity,m/s
pellet, m2/s
Uw Overall heat transfer coefficient
EA Activation energy, J/mol
of the wall, W/(m2 K)
H Heat of reaction, J/mol Vi Stoichiometric coefficient of component i
Had Heat of adsorption, J/mol in reaction i, dimensionless
kg Mass transfer coefficient from the fluid z Axial distance in the column, m
to pore-fluid phase, m/s zT Total length of reactor, m
ko Frequency (or pre-exponential) factor, s-1 Z Dimensionless length of reactor, z / zT
hfs Heat transfer coefficient from the fluid
to pore-fluid phase, W/(m2 K) Greek Letters
hw Heat transfer coefficient from the fluid f Heat transfer coefficient from the fluid
to the wall, W/(m2 K) to the solid phase, W/(m2 K)
Kp Adsorption rate coefficient, s-1
b The void fraction in the bed (i.e. volume of
n Freundlich adsorption isotherm exponent
voids per unit volume of bed), dimensionless
N Number of interior collocation points
s The void fraction in particles (i.e. volume of pores
in the axial direction
NR Number of collocation points in the in the pellet per unit volume of pellet), dimensionless
radial direction  Effective thermal conductivity
Nu Nusselt number, 2  f R  p  Effectiveness factor, dimensionless
 Density, kg/m3
Peh Peclet number (heat), U f z T  f C spf f
 Dimensionlessradius, r/R
Pem Peclet number (mass), , dimensionless
U f zT D e ,ax
(tau) Dimensionless time, tUf / zT
*
q Concentration of solute in the solid (or adsorbed)  Thiele modulus
phase, mol/m3
*
qo adsorbed solute concentration at equilibrium with Superscript
*
fluid phase concentration, Co, mol/m 3 Equilibrium value
*
Q Dimensionless concentration of solute
in the solid (or adsorbed) phase, q*/q*o Subscript
R External radius of the pellet, m f Fluid phase

Research Article 1811

 Iran. J. Chem. Chem. Eng. Model and Simulation of Partial Oxidation of...
i, j, k Integer values
s Solid phase
w Wall
Received :May 1, 2020 ; Accepted : Aug. 3, 2020
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Research Article 1813