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MASS TRANSFER EFFECT ON STEAM REFORMING OF GLYCEROL OVER

RUTHENIUM-ALUMINA (Ru/Al 2 O 3 ) CATALYST

Article · March 2020

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 MASS TRANSFER EFFECT ON STEAM REFORMING OF GLYCEROL
OVER RUTHENIUM-ALUMINA (Ru/Al2O3) CATALYST

PETER, E.E.1,2, EDOMWONYI-OTU, L C.,1,3* ALAH, J.,4 OLAFADEHAN, O.A.2

1
Department of Chemical engineering, Ahmadu Bello University, Zaria
2
Department of Chemical engineering, University of Lagos
3
Department of Chemical and Petroleum Engineering, Delta State University, Abraka, Nigeria
4
Department of Chemical engineering, Niger-Delta University, Wilberforce Island, Bayelsa State

ABSTRACT
Diffusion plays an important role in steam reforming of glycerol over ruthenium-alumina (Ru/Al2O3). It forms a major
consideration in the proper design of the reactor for optimal conversion to hydrogen in the temperature range of 623-773K. The
size and geometry of the catalyst particles is known to influence the efficiency of diffusion. In this report, the governing equation
for reaction–diffusion rate for ruthenium-alumina (Ru/Al2O3) was solved numerically using finite element method, and the non-
linear equations were simulated with the help of COMSOL Multiphysics 4.3b. Different geometrical shapes (spherical, cylindrical
and planar) of various sizes were considered and the concentration profile of the glycerol was noted and compared to deduce the
particle shape with least mass transfer effect. The Thiele Modulus of 5, 8, 12, and 16 as well as catalyst particle sizes of 3.0 X 10 -4
m, 4.0 X 10-4 m, 5.0 X 10-4 m, 6.0 X 10-4 m were investigated. The planar catalyst of Thiele modulus 5 with a particle diameter of
3.0 X 10-4 m was observed to be the right dimension for optimal utilization of Ru/alumina for steam reforming of glycerol to
hydrogen. The parameters thus obtained will enhance optimal design and operations of steam processes for glycerol conversion to
hydrogen.

Keywords: COMSOL Multiphysics, diffusion, geometrical shapes, Glycerol, reaction, Thiele Modulus
*Correspondence: uceclce@ucl.ac.uk
*

INTRODUCTION
One of the major ways of utilizing the catalyst is to
Steam reforming of glycerol has attracted attention because add the active component of the catalyst on a support so as
of the large quantity of bio-diesel that is produced yearly [1]. to optimize its usage. The supported material may be porous
Glycerol is a large reservoir of hydrogen which has an with a large internal surface area where the active
economic potential in fuel cell technology. component of the catalyst is anchored. Only limited studies
on Ru based catalysts (Y2O3, ZrO2, CeO2, La2O3, SiO2,
C3 H8O3  3H 2 3CO2  7 H 2
kSR
'
kSR MgO) for glycerol steam reforming were reported [6]. They
1
revealed that 0.5 % wt Ru had the best results at 873K
Steam reforming of glycerol has been used successfully to
among lanthanides supported group VIII metals. Better
unlock the hydrogen with the aid of a Ru/Alumina catalyst
activity was shown by Ru on Y2O3 with a complete
[2]. Many catalysts have been investigated over different
conversion and a H2 yield of 83%. However, when Ru was
supports (Al2O3, SiO2, CeO2, CeO2-ZrO2, Y2O3, La2O3) and
supported on MgO, Al2O3 and SiO2 the conversion of
it is known that oxides with low acidity or with basic
glycerol was about 30 %. For the steam reforming, the active
properties can decrease coking. For instance, the use of a
component of the catalyst is Ruthenium anchored on
promoter (such as lanthanide) on alumina resulted in a more
alumina.
stable catalyst [3]. Supports with high oxygen storage
The pores inside the catalyst are not straight and but
capacity, such as CeO2 and CeO2-ZrO2, are also shown to be
cylindrical and passing right through the pellet from one end
efficient modifiers in decreasing coke deposition and in
to the other. Rather, the pores are tortuous, interconnecting,
promoting Water Gas Shift (WGS) reaction [4].
have dead ends, and varying cross-sectional areas. Such
It was reported that at 9000C glycerol conversion
properties cause the flux through the catalyst pellet to be less
decreased in the order Ni>Ir>Pd>Rh>Pt>Ru for alumina
than that of uniform pores, and this should be taken into
monolith-supported samples, and that the results should be
account. To account for actual flux through the catalyst
varied only on the given experimental conditions [5]. In
pellet, the diffusion coefficient factor can be obtained by
another study on La2O3 supported metals, with larger surface
introducing a term called the tortuosity factor (τ) [7] and also
area in powdered form, the activity order at 600 0C was
Ru≈Rh>Ni>Ir>Co>Pt>Pd>Fe [6]. the porosity ( ) [8] of the catalyst pellet into their equations.
The tortuosity factor accounts for the varying directions of
the pore paths and also the varying cross-sectional areas. As
a result of these, the diffusivity obtained is corrected by

Nigerian Journal of Scientific Research, 17 (2): 2018; March - April; njsr.abu.edu.ng 165
Peter et al. (2018); Mass transfer effect on steam reforming of glycerol

multiplying it by the ratio of porosity to tortuosity to give a Where rA' is the rate of reaction per unit mass of catalyst
new diffusivity called effective diffusivity. Bulk or ordinary
diffusion occurs when the pores are large and the gases are [=] mol/(kg cat s) and rA" is the rate of reaction per unit
relatively dense. The collisions of the molecules with the surface area [=] mol/(m2 s).
pore wall of the catalyst are unimportant compared to the Assume that the surface reaction is of nth order in the gas
molecular collisions in the free space of the pore [9]. phase concentration of G within the pellet, then
When Thiele [10] developed the concept of
effectiveness factor, he introduced a dimensionless number,
 rG   k n CGn 5
called the Thiele modulus to account for the regime if Substituting equations 3 to 5 into equation 2 gives;
reaction is controlled by diffusion or by chemical reaction.
d 2 CG 2 dCG k n S a  p n
Recent advances in computer technology and   CG  0
software development has offered fast particle dr 2 r dr De 6
characterization and near accurate prediction of particle
The boundary conditions are:
diffusion in catalyst studies. Such modelling and predictive
(i) the concentration of G remains finite at the centre of the
software include COMSOL Multiphysics, ANSYS,
CosmosWorks, LS-DYNA, Nastran, RFEM among others. pellet: CG is finite at ro so symmetry requires
They have found wide application both in the industry and
state-of-the-art research in science and engineering [11].
dCG
dr 0 at r  0 (von Neumann boundary condition)
Despite the overwhelming research on steam(ii) At the external surface of the catalyst pellet, CG  CGS at
reforming of glycerol, no detailed study has been carried out
on the effect of diffusion on yield of hydrogen from steam r  R (Dirichlet boundary condition)
 CG
reforming of glycerol over Ru/Al2O3 catalyst. This work
Introducing dimensionless variables: CG  and
reports the use of COMSOL Multiphysics software for the CGS
modelling and simulation of steam reforming of glycerol.
r
The result of this work will give better insight into the effect  , the boundary conditions become;
of particle size and diffusion on steam reforming of glycerol R
as well as offer optimal design parameters for the Ru/Al 2O3
CG is finite at   0 so symmetry requires 0
dCG
catalyst. (i) d at
 0 .
MATERIALS AND METHODS 
(ii) C G  1 at   1 .
In order to discretize the modelling equations, the effective The dimensionless form of equation (6) describing diffusion
diffusivity coefficient of the mixture and the optimized and reaction in a single catalyst pellet for nth order reaction
kinetic parameters were calculated using MATLAB and is given by;
2 dCG k n S a  p R CGs
POLYMATH 6.0 software respectively. These parameters 2 n 1
d 2 CG
and the boundary conditions were used as input in the   CGn  0
COMSOL Multiphysics software. d 2
 d De 7
A material balance was taken on the physical process of 2
d CG 2 dCG
diffusion-reaction at equilibrium on a cross section of a
  n2 CGn  0
cylindrical catalyst resulting to equation 2. d 2
 d 8
d 2 CG 2 dCG  rG Ai
  0 k n S a  p R 2 CGs
n 1

dr 2 r dr De n 
2
2 De
The internal surface area of a catalyst is given by: 9
The square root of the coefficient of  is n , is called the
2
Ai  S a  p n
3
where Sa is the internal surface area per unit mass of catalyst Thiele modulus. The quantity  2
n is a measure of the ratio
[=] m2/kg cat,  p the density of the pellet [=] kg/m3 cat. of a surface reaction rate to a rate of diffusion through the
catalyst pellet:
Also,
 rG    rG Sa 4
kn Sa  p R C 2 n 1
k n S a  p RCGs
n
" a" surface reaction rate
n2  Gs
 
De De CGs  0 R " a" diffusion rate 10

Nigerian Journal of Scientific Research, 17 (2): 2018; March - April; njsr.abu.edu.ng 166
 Peter et al. (2018); Mass transfer effect on steam reforming of glycerol

For a first order reaction, equation (8) becomes; Celeron(R) Dual-core CPU T3300@ 2.00GHz processor,
2
d CG 2 dCG 4.00GB RAM capacity and 500GB hard drive disk (HDD).
  12 CG  0 The simulation output was displayed using the inbuilt
d 2
 d 11 graphics (post-processing) module that has graphical editing
capability. The Thiele modulus of 8, 12, and 16 was chosen
k1 S a  p
1  R for this research work based on the fact that particle within
De this particle size is known to be less controlled by diffusion.
12

RESULTS AND DISCUSSION
with the boundary conditions: C G is finite at   0 and

C G  1 at   1 Chemical reaction due to diffusion was checked to see the
effect on concentration gradient in the internal portion of the
The dimensionless equation 11 was discretized using finite catalyst of different shapes and the results are shown in
element method which was implemented using COMSOL Figures 1, 2 and 3.
Multiphysics 4.3b installed in an HP 620 laptop which runs
on window 8.0, 64-bit operating system. The laptop has a
Normalized concentration of glycerol

Spherical

Normalized catalyst radius

Figure 1: Concentration profile of glycerol at various Thiele modulus value for spherical catalyst

Nigerian Journal of Scientific Research, 17 (2): 2018; March - April; njsr.abu.edu.ng 167
 Peter et al. (2018); Mass transfer effect on steam reforming of glycerol
Normalized concentration of glycerol

Cylindrical

Normalized catalyst radius

Figure 2: Concentration profile of glycerol at various Thiele modulus value for cylindrical Ru/Alumina.

Planar
Normalized concentration of glycerol

Normalized catalyst radius

Figure 3: Concentration profile of glycerol at various Thiele modulus value for planar Ru/Alumina

The result in Figures 1, 2 and 3 show the concentration from the surface of the catalyst towards zero near the centre
gradient of glycerol inside the spherical, cylindrical and of the spherical catalyst. At a Thiele modulus of 5, the
planar catalyst particle respectively. In Figure 1, it can be concentration decreases gradually towards the centre of the
observed that the concentration of the glycerol drops steeply catalyst. With increase in the Thiele modulus, there is a

Nigerian Journal of Scientific Research, 17 (2): 2018; March - April; njsr.abu.edu.ng 168
 Peter et al. (2018); Mass transfer effect on steam reforming of glycerol

progressive drop in the concentration of the reactant towards
the centre of the catalyst. In Figure 2, the concentration
gradient shows a significant pattern as the Thiele modulus
increases. At a Thiele modulus of 5, the concentration
gradient of glycerol shows a shallow curve that is almost
linear. At a Thiele modulus of 8, 12 and 16, the graph
gradually changes to a curve. In the vicinity of the centre of
the catalyst, the five Thiele modulus tends to converge.
In Figure 3, the concentration gradient of glycerol in planar
catalyst shows a diverging pattern as the Thiele modulus
increases in the direction towards the centre of the catalyst.
It can also be observed that a Thiele modulus of 5 shows that
the reactant penetrates into the entire catalyst volume with
the highest concentration in comparison with a Thiele
modulus of 8,12 and 16. A Thiele modulus of 16 shows the
least concentration of the reactant towards the centre of the
catalyst.
In a similar pattern, the concentration of glycerol at
various positions was also studied with different catalyst
diameter. The relationship is shown in Figures 4, 5 and 6 for
spherical, cylindrical and planar respectively.
As the particle diameter increases, there is concentration
drop of the reactant towards the centre of the catalyst as
shown in Figure 4. The concentration of glycerol closed to
the surface shows similar pattern. Gradually, the
concentration of the reactant shows a clear and distinct
pattern in the interior of the catalyst until the pattern
becomes indistinguishable towards the centre of the catalyst.

Spherical
Normalized concentration of glycerol

Normalized catalyst radius

Figure 4: Effect of varying the particle size on the concentration of glycerol within the cylindrical catalyst particle

Nigerian Journal of Scientific Research, 17 (2): 2018; March - April; njsr.abu.edu.ng 169
 Peter et al. (2018); Mass transfer effect on steam reforming of glycerol

Cylindrical
Normalized concentration of glycerol

Normalized catalyst radius

Figure 5: Effect of varying the particle size on the concentration of glycerol within the cylindrical catalyst particle

Planar
Normalized concentration of glycerol

Normalized catalyst radius

Figure 6: Effect of varying the particle size on the concentration of glycerol within the planar catalyst particle

In Figure 5, the concentration gradient for a particle
diameter of 3 X 10-4 m is almost linear. As the particle
diameter increases, the curve becomes more pronounced for
a particle of size 6 X10-4 m. This observed drop in reactant
concentration was more pronounced when using a planar
catalyst as shown in Figure 6. The concentration gradient of
glycerol was significantly close to the centre of the catalyst
with a planar catalyst compared to other shapes with the
sphere having the least concentration of reactant.

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 Peter et al. (2018); Mass transfer effect on steam reforming of glycerol

The comparison of the various particle shape at diameter of
3.0 X 10-4 m is shown in Figure 7. The concentration
gradient of glycerol was significantly close to the centre of
the planar catalyst, while that of the cylinder lies between
the planar and the spherical catalyst with the sphere having
the least concentration of the reactant.
Normalized concentration of glycerol
To account for the actual rate of reaction of the glycerol
within the catalyst which is vital for the design of a fixed
bed reactor, the effectiveness factor of the catalyst was
established within the specified experimental condition as
shown in Figure 8.

Normalized catalyst radius

Figure 7: Concentration profiles of various geometrical shapes of particle size

0.035

0.03
Effectiveness factor

0.025

0.02
Planar
0.015
Cylindrical
0.01
Spherical
0.005

0
0 5 10 15 20 25

Thiele Modulus
Figure 8: Effect of Thiele Modulus on effectiveness factor for Ru/Al2O3

Nigerian Journal of Scientific Research, 17 (2): 2018; March - April; njsr.abu.edu.ng 171
 Peter et al. (2018); Mass transfer effect on steam reforming of glycerol
Normalized rate of reaction
Normalized catalyst radius
Figure 9: Rate profile of various geometrical shapes on particle size
The effectiveness factor for the three particle shapes were
compared. It was observed that the planar catalyst shape has
a higher value than those of the cylinder and sphere.
The rate at which glycerol is disappearing within the catalyst
of different sizes was also investigated as shown in Figure 9.
It can be observed that the rate of disappearance of glycerol
is high as the reactant diffuses within the pore space of the
catalyst. The rate of glycerol reactant was almost linear
when a cylindrical catalyst was used and the spherical
catalyst recorded the least mass transfer with almost no
glycerol reactant towards the symmetrical point of the
catalyst. This implies that the rate of reaction was very high
in such a way that the reactant gets consumed immediately
near the surface of the catalyst while the centre of the
catalyst was deprived of reactant.
However, little or no investigation has been
reported on varying the sizes and shapes of a support
catalyst from literature. In the mass–transfer analysis, [12]
reported that gas-phase dehydration of glycerol to acrolein
over supported silicotunstic acid catalyst was under diffusion
regime for a particle size of less than 1 µm. The effect of a
support particle size in steam reforming of ethanol over
Co/CeO2 catalyst was also reported [13]. The cobalt catalyst
was on a Ceria support with two different particle sizes, one
in the micro and the other in the nano-range with no mention
of the precise dimension of the support. The Authors also
investigated the effect of varying the cobalt sizes on carbon
nano-fibre for steam reforming of ethanol and concluded
that particle size of smaller dimension have lower effect on
mass transfer. This was corroborated in the current work.
CONCLUSION
Nigerian Journal of Scientific Research, 17 (2): 2018; March - April; njsr.abu.edu.ng
Different shapes and sizes of the catalyst were investigated
to see the effect of reaction to diffusion on the rate. It was
observed from the different Thiele modulus used that the
reaction was controlled by diffusion. The effect was more
pronounced with planar catalyst when compared with
cylindrical and spherical. The Thiele modulus for the three
different sizes of a planar Ru/alumina showed that the
reactant penetrated the entire volume of the catalyst. Using a
Thiele modulus of 5 with planar catalyst for steam reforming
of glycerol will be more economical because the catalyst has
the highest effectiveness factor of the various shapes
studied .This simply means that the reactant will be present
in the same concentration in the entire volume of the
catalyst.
ACKNOWLEDGEMENTS
The Authors wish to acknowledge the support of the LG
Laboratories, University of Lagos, Nigeria for the provision
of the COMSOL Multiphysics software used for this work.
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors
.
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