Chemical Engineering Journal 429 (2022) 132278

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Chemical Engineering Journal

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Kinetic study of glycerol steam reforming catalyzed by a Ni-promoted

metallurgical residue
Alex Desgagnés, Maria C. Iliuta *
Department of Chemical Engineering, Université Laval, Québec, QC G1V0A6, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: The kinetics of the glycerol steam reforming reaction catalyzed by a nickel-promoted metallurgical residue was
Glycerol steam reforming studied in a fixed-bed reactor at atmospheric pressure. The temperature was varied between 480 ◦ C and 580 ◦ C.
Ni-based catalyst The experimental reaction rates were correlated via different heterogeneous kinetic models based on Langmuir-
Metallurgical waste valorization
Hinshelwood-Hougen-Watson mechanisms that consider single- or dual-site adsorption of the reactants. The
Kinetic modeling
Langmuir-Hinshelwood-Hougen-Watson
mechanism that provided the most mathematically accurate and thermodynamically consistent results is initi­
reaction mechanism ated by dissociative adsorption of glycerol, which cause the breaking of two C–C bonds in the glycerol molecule
upon adsorption. This model claims that the dehydrogenation of an adsorbed glycerol intermediate is the rate-
determining step of the global reaction. A macroscopic analysis of the glycerol to gas consumption rates also
validated the activation energies identified by the successful heterogeneous model by fitting the experimental
data to a straightforward power law model. The activation energy was found to be 66.1 kJ⋅mol− 1 with a partial
order with respect to glycerol of 0.63.

C3 H8 O3(g) + 3H2 O(g) ↔ 7H2(g) + 3CO2 (g) r

ΔH298K = 128kJ∙mol− 1
(R1)

1. Introduction
In the current environmental crisis in which the world finds itself, the
concern to reduce our energy dependence on fossil fuels by exploiting
more ecological and sustainable alternatives is becoming increasingly
important. The hydrogen fuel (H2) will most certainly play a pivotal role
in the global energy transition towards green and less polluting re­
sources due to some outstanding assets as an energy carrier [1].
Nevertheless, the global hydrogen production is currently being almost
entirely provided by the reforming of fossil methane [2]. Consequently,
the benefits of hydrogen as a low- (or no–) carbon energy carrier become
environmentally justified only if it is generated from sustainable re­
sources [3] such as glycerol, the main by-product in the production of
biodiesel from the transesterification process of animal or vegetable fats.
In fact, the growing worldwide production of biodiesel is generating
staggering quantities of glycerol that far exceed market demand. The
production of hydrogen by glycerol steam reforming (GSR) is therefore
an interesting avenue to recover this residual organic material while
reducing the net production cost of biodiesel [4].
The stoichiometry of the overall GSR reaction claims that 7 mol of
hydrogen can be theoretically produced per mole of glycerol (R1).
Many authors agree that this overall reaction can be broken down
into an endothermic glycerol pyrolysis step (R2) followed by the
water–gas shift reaction (R3) which converts carbon monoxide into
additional hydrogen due to the excess steam present in this process
[5–9].
C3 H8 O3(g) ↔ 3CO(g) + 4H2(g) r
ΔH298K = 251kJ∙mol− 1
(R2)
CO(g) + H2 O(g) ↔ CO2 (g) + H2 (g) r
ΔH298K = − 41kJ∙mol− 1
(R3)
Inevitably, undesirable products such as methane, which reduces the
hydrogen yield, and solid elemental carbon, that can accelerate catalyst
deactivation, are generated through secondary reactions in this process.
A variety of condensable organic compounds including formaldehyde,
acrolein, allyl alcohol, and hydroxyacetone can also be derived from the
decomposition of glycerol in the GSR process [5].
Due to the wide range of possible reaction paths in this process, the
selection of a suitable catalyst capable of converting a maximum amount
of glycerol while maintaining a high yield of hydrogen over a long
period of time is paramount. Nickel-based catalysts are widely reported
in the literature since this metal demonstrates high activity in the GSR
reaction [5,6,8,10–12], which is mainly attributed to its good ability to
cleave the C–H, O–H and C–C bonds present in glycerol [13]. Nickel

* Corresponding author.
E-mail address: maria-cornelia.iliuta@gch.ulaval.ca (M.C. Iliuta).

https://doi.org/10.1016/j.cej.2021.132278
Received 4 May 2021; Received in revised form 18 August 2021; Accepted 1 September 2021
Available online 8 September 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
A. Desgagnés and M.C. Iliuta Chemical Engineering Journal 429 (2022) 132278

Nomenclature R ideal gas constant, 8.314 J⋅mol− 1⋅K− 1

R2 regression coefficient, dimensionless
A pre-exponential factor of the Arrhenius equation (eq. (5)), T temperature, K
variable units Ts temperature at the surface of the catalyst, K
dp catalyst particle diameter, m Tb temperature in the bulk gas phase, K
DAB gas diffusivity, m2⋅s− 1 U gas superficial velocity, m⋅s− 1
De effective diffusivity, m2⋅s− 1 W catalyst weight, g
CC3 H8 O3 ,s glycerol concentration at the surface of the catalyst, X active site, dimensionless
mol⋅m− 3 XG glycerol conversion to gaseous products, dimensionless
CC3 H8 O3 ,b glycerol concentration in the bulk gas phase, mol⋅m− 3 xC3 H8 O3 glycerol feed molar fraction, dimensionless
Cpmix isobaric molar heat capacity of gas mixture, J⋅mol− 1⋅K− 1 YH2 hydrogen yield, dimensionless
Ea activation energy, J⋅mol− 1 Yl yield of liquid product l , dimensionless
F molar flow rate, mol⋅min− 1 yi,k molar fraction associated with compound i, and
F1− ϕ critical value of the Fisher distribution experimental condition k, dimensionless
G gas phase mass velocity, kg⋅m− 2⋅s− 1
Subscripts
GHSV gas hourly space velocity, std L⋅gcat-1⋅h− 1
in at the reactor inlet
h heat transfer coefficient, J⋅m− 2⋅s− 1⋅K− 1
out at the reactor outlet
k rate constant of the Arrhenius equation (eq. (5)), variable
PL associated to power law model
units
exp experimental
k’ pseudo rate constant given in the power law model (eq.
cal calculated
(10) and eq. (11)), mol⋅min− 1⋅gcat-1⋅atm-α
kc mass transfer coefficient, m⋅s− 1 Greek letters
krxj rate constant associated to heterogeneous kinetic model j, α partial order of reaction with respect to glycerol,
variable units dimensionless
KAi.j apparent adsorption constant associated with reactant i ϕ confidence interval, dimensionless
and heterogeneous kinetic model j (M1-M12), variable units ΔHr298K standard enthalpy of reaction, J⋅mol− 1
KDi.j apparent desorption constant associated with product i and ΔHAi.j enthalpy of adsorption associated with reactant i and
heterogeneous kinetic model j (M1-M12), variable units heterogeneous kinetic model j (M1-M12), J⋅mol− 1
K’Ai.j actual adsorption constant associated with reactant i ΔHDi.j enthalpy of desorption associated with product i and
derived in the development of the mechanism of heterogeneous kinetic model j (M1-M12), J⋅mol− 1
heterogeneous kinetic model j (M1-M12), variable units ΔSAi.j entropy of adsorption associated with reactant i and
K’Di.j actual desorption constant associated with product i heterogeneous kinetic model j (M1-M12), J⋅mol− 1⋅K− 1
derived in the development of the mechanism of ΔSDi.j entropy of desorption associated with product i and
heterogeneous kinetic model j (M1-M12), variable units heterogeneous kinetic model j (M1-M12), J⋅mol− 1⋅K− 1
L0 liquid flow rate of the reactant feed mixture, std mL⋅min− 1 λe effective thermal conductivity of catalyst, J⋅K− 1⋅m− 1⋅s− 1

n order of reaction, dimensionless μ dynamic viscosity, Pa⋅s

OF objective function calculated as (eq. (6)), dimensionless ρb catalyst bulk density, kgcat⋅m− 3 of reactor
p average partial pressure, atm ρc catalyst density, kgcat⋅m− 3 of catalyst
P total pressure in the reactor, atm ρg gas density, kg⋅m− 3
Q0 total gas flow rate introduced in the reactor, std mL⋅min− 1 υ degree of freedom, dimensionless
r consumption or formation rate, mol⋅min− 1⋅gcat-1
σ2 variance, variable units
rj glycerol to gas consumption rate calculated with
ωi,k weight factor associated with compound i, and
heterogeneous kinetic model j, mol⋅min− 1⋅gcat-1
experimental condition k, dimensionless
ri,k consumption of formation rates associated with compound
i, and experimental condition k, mol⋅min− 1⋅gcat-1

competes with noble metals such as Rh, Ru, Pt or Pd, which are also
highly active for GSR reaction and selective for hydrogen. However, Ni-
based catalysts have a head start over these precious metal-based cata­
lysts for use in industrial applications, as they are much more accessible
and less expensive. The choice of the support is also crucial since it
dictates the dispersion of the active phase, which is directly related to
the catalytic activity. The surface properties of catalytic supports or
promoters can mitigate the defects observed in some active metals. In
the case of nickel, the presence of basic promoters (e.g., MgO, CaO)
[10,14] can decrease the concentration of acidic sites conducive to coke
formation, while its vulnerability to sintering [14] can be tempered by
using lanthanoids oxides-based supports such as CeO2 [15] or La2O3
[16].
In our previous studies [5,10,17,18], interesting conclusions have
been reported regarding the use of a Fe-Mg bearing metallurgical res­
idue as a catalytic support and promoter in the GSR process. This residue
(hereinafter labeled as UGSO, abbreviation for Upgraded Slag Oxide),
which is generated in powder form at a rate of tens of thousands of tons
per year by the Rio Tinto Fer & Titane metallurgical complex in Sorel-
Tracy (Quebec, Canada), is currently stored in large mine waste sites
without marketable use. Although slightly variable, the composition of
UGSO includes mostly iron (Fe), aluminum (Al) and magnesium (Mg)
crystallized as spinel mixed oxides (MgFe2O4 and FeAl2O4) or free per­
iclase (MgO) [5]. By promoting it with Ni, UGSO can act as an effective
catalyst in the GSR process, offering a promising way to valorize the
valuable elements it contains in a sustainable development perspective.
When compared to an alumina-supported Ni-based commercial catalyst,
it has been determined that the presence of active Mg and Fe oxide
species in Ni-UGSO catalyst could favor the water gas shift reaction as
well as coke gasification [10], thus increasing the hydrogen yield and
long-term stability. In addition, a study on the effect of active metal in
UGSO-based catalysts revealed that the very slightly lower performance

2
A. Desgagnés and M.C. Iliuta
Table 1
UGSO elemental composition (wt. %) and textural properties of fresh UGSO, calcined UGSO and 5 % Ni-UGSO calcined catalyst (Data retrieved from [5,10]).
UGSO (wt. %) Fe Mg Al
31.26 17.49 5.35
Catalyst Specific surface area
2
SBET (m /g)
Fresh UGSO 29.8
Calcined UGSO 12.0
5 % Ni-UGSO 9.9
of a 5 % Ni-UGSO catalyst compared to a 1 % Rh-UGSO catalyst (both in
mass percentages) could not economically justify the use of a rhodium-
based catalyst given the low price of nickel compared to this noble metal
[18]. Without neglecting the effect of the parameters studied so far in
the GSR process using this innovative and eco-friendly catalytic mate­
rial, the reaction mechanism and kinetics component have not yet been
developed.
The study of reaction and kinetic mechanics is even more important
since it represents a further step towards the design and modeling of
reactors that could be industrially implemented. In recent years, only a
few studies have been published in the literature concerning the kinetics
of the GSR process. Although some authors have come to similar con­
clusions regarding the reaction mechanisms that best reflect reality,
others have reached quite different outcomes [19]. These discrepancies
are undoubtedly the result of differences in the properties of the studied
catalysts that lead to observable behavioural changes in surface reactive
species, and thus to different findings in the kinetic studies. Neverthe­
less, the usefulness and significance of a kinetic study is even more
justified when a new catalytic material is investigated, as is the case in
the present work. The validity of the power law empirical model has
been revealed by many authors [6–8,20–25] for estimating the kinetic
constants and activation energies of the overall GSR process reaction.
However, little attention has been paid to the mechanistic consider­
ations of the reaction.
In this work, an in-depth experimental and modelling study of the
kinetics of the GSR process over a Ni-based catalyst supported on the
UGSO metallurgical residue in a fixed-bed reactor was carried out.
Different reaction pathways were proposed to develop new or literature-
inspired expressions of reaction rates based on Langmuir-Hinshelwood-
Hougen-Watson heterogeneous kinetic mechanisms. A macroscopic
analysis was also performed by applying a power law model to correlate
the experimental rates of glycerol consumption and generation of the
main gaseous products. The reaction mechanisms developed in this
study were adjusted to the experimental data in order to obtain the ki­
netic parameters associated with each model, as well as to elucidate
which of them best reflects reality. The findings from this research will
benefit the design and operation of GSR reactors that would be operated
on a larger scale.
2. Materials and methods
2.1. Catalyst preparation
The UGSO residue was promoted with nickel following a solid-state
impregnation method described in detail elsewhere [5,10]. Briefly,
UGSO powder (previously ground and sieved to particle size less than
75 µm) was mixed and further ground by hand using an agate mortar
with the Ni precursor (Ni(NO3)2⋅6H2O, Fisher, 99.9 %) at ambient
temperature for 10 to 15 min. A few drops of acetone were also added to
the mixture to ensure good homogeneity. The resulting solid was then
calcined at 600 ◦ C under air atmosphere for 2 h. The 5 % Ni-UGSO
(weight %) catalyst was used throughout the whole kinetic study, as it
has proven to be the most efficient (higher glycerol conversion and
hydrogen yield) among other catalysts with different nickel contents
[5]. The elemental chemical composition of UGSO residue (obtained by
3
Chemical Engineering Journal 429 (2022) 132278
Ca Mn V Ti
1.05 0.98 0.92 0.61
Average pore diameter Average particle size
Dp (nm) (nm)
17.2 202
40.5 499
52.8 604
ICP-MS analysis) as well as its textural properties, alongside those of the
calcined 5 % Ni-UGSO catalyst, are shown in Table 1. It can be observed
that the heat treatment carried out during calcination is the main cause
of the decrease in the specific surface area of UGSO compared to its
initial state. The Ni incorporation has a lesser impact, but still contrib­
utes to slightly decrease the specific surface area, and to increase the size
of the catalyst particles, which is probably due to the blocking of the
UGSO pores by nickel particles [5].
2.2. Experimental setup & procedure
The experimental laboratory set-up used to perform the GSR cata­
lytic tests is schematized and described in detail elsewhere [10].
Concisely, 0.5 g of catalyst (weight used for each experiment) was put on
a grid covered with quartz wool located at the mid-length of a 40 cm
long stainless-steel tubular reactor (internal diameter = 11 mm). Prior to
the GSR reaction test, the catalyst was reduced under a 22 % vol. H2/Ar
atmosphere at 650 ◦ C for 1.5 h. Argon (carrier gas) and hydrogen
(reduction gas) flow rates were adjusted by mass flow controllers, while
temperature of the catalytic bed was controlled by an electric tubular
furnace combined with a temperature controller and a thermocouple.
Afterwards, an argon purge was carried out for 30 min to flush the
hydrogen from the lining and allow the reactor to cool down to the
desired reaction temperature (480–580 ◦ C). To begin the GSR reaction,
the liquid phase reactant solution (99.5 % pure glycerol and water) was
fed to the reactor via a high-performance liquid chromatography pump.
A water-to-glycerol feed molar ratio of 9 (steam-to-carbon feed molar
ratio of 3) was maintained for all GSR experiments. The upper part of the
reactor (the first 18 cm above the catalyst bed) was considered long
enough to evaporate all reactants before they reached the catalyst bed.
Unless stated otherwise, 52 std mL⋅min− 1 (at 298.15 K and 1 atm, i.e., at
std conditions) of Ar was mixed in the reactor with the vaporized
reactant feed mixture (liquid flow rate L0 varied from 0.05 to 0.11 std
mL⋅min− 1) during catalytic tests. At the exit of the reactor, the gas flow
passed through a cold trap used to capture the condensable products of
the reaction. A mass flow meter measured the total gas flow rate exiting
the reactor and the concentration of its components was recorded on-
line by a microGC (Agilent Technologies, 3000A) that analyzed sam­
ples taken automatically every 15 min. Liquid product analysis was
conducted using a high-performance liquid chromatograph (HPLC;
Shimadzu SPD-M20A HPLC) equipped with a refractive index detector
(RID).
Glycerol conversion to gaseous products (XG ) and hydrogen yield
(YH2 ) were determined to quantify and compare the different catalytic
activity performances observed during the study. In the present work,
the values of these parameters were obtained after 2.5 h of reaction,
when steady-state conditions were well established. Glycerol conversion
to gaseous products (eq. (1)) was calculated based on the carbon balance
of the gaseous products detected by the microGC:
XG =
FCO2 + FCO + FCH4
(1)
3∙FC3 H8 O3 in
where F is the molar flow rate of the different compounds.
The hydrogen yield (eq. (2)) was calculated based on the theoretical
and maximum amount of H2 that can be obtained by steam reforming of
A. Desgagnés and M.C. Iliuta Chemical Engineering Journal 429 (2022) 132278

Table 2 Table 3
Assessment of the absence of internal mass and heat transfer effects using the Assessment of the absence of external heat and mass transfer effects using Mears
Weisz-Prater criterion. criterion.
Transfer Massa, b Heatb, c Transfer Massa Heatb
phenomenon phenomenon
⃒( ⃒ ⃒ ⃒
Criterion (rC3 H8 O3 exp )ρc dp 2 ⃒ − ΔHr )d 2 ρ (r ⃒ Criterion (− rC3 H8 O3 exp )dp ρb n ⃒( − ΔHrxn )(− rC3 H8 O3 exp )dp ρb Ea ⃒
⃒ 298K p b C3 H8 O3 exp )Ea ⃒ < 0.15 ⃒⃒ ⃒ < 0.15
<1 ⃒ ⃒ < 0.1 2kc CC3 H8 O3 ,b 2
4De CC3 H8 O3 ,s ⃒ λe RTs 2 ⃒ 2hRTb ⃒
Calculated value 0.0033 Calculated value 0.0004 0.0002
< 1∙10− 4
a
a
De = 0.1 × DAB where DAB is calculated using equation developed by Fuller, The mass transfer coefficient kc is calculated from kc = JD ∙U∙Sc2/3 , where
( )
Shettler, and Giddings [29]. 1 0.765 0.365 μ ρ ∙U∙dp
JD = + , Sc = , Re = g μ .
b
The highest (− rC3 H8 O3 exp ) value was used to estimate both criterions in the ε Re0.82 Re0.386 ρg ∙DAB
b
worst conditions. The heat transfer coefficient h is calculated based on the J-factor Chilton and
c
λe = 10 × λg h Cpmix ∙μ
Colburn analogy: JH = JD = ∙Pr2/3 wherePr =
Cpmix ∙G λg
1 mol of glycerol according to the stoichiometry of the overall reaction
(R1): 3. Experimental results
FH 2
Y H2 = (2) 3.1. Mass and heat transfer effects
7∙FC3 H8 O3 in

The kinetic regime in which the catalytic tests were performed Heterogeneously catalyzed chemical reactions such as GSR involving
favored the conversion of glycerol to condensable products at different gas phase reactants and a solid catalyst occur through a three-phase
extents depending on the selected conditions. The yield of each of the mass transfer mechanism: (i) external diffusion of the reactants in the
detected liquid products (eq. (3)) was calculated based on the carbon gas film at the surface of the catalyst, (ii) internal diffusion of the re­
balance of the liquid products detected by HPLC: actants through the pores of the catalyst followed by the chemical re­
action on the active sites, and (iii) diffusion of the products from the
moles of C in liquid product ↕
Y↕ = (3) catalyst surface to the bulk gas phase. In a kinetic study, the influence of
3∙FC3 H8 O3 in
these mass transfer processes should be minimized to identify the
where l can be glycerol, acrolein, allyl alcohol, hydroxyacetone or intrinsic kinetic parameters of the reaction. In catalytic reactions, the
formaldehyde. particle size of the catalyst is among the most significant contributors to
The reaction rates were estimated based on the conversion to gaseous the internal mass transfer resistance. For particles smaller than 1 mm, it
products by differential analysis of the plug-flow reactor equation [26]. has been reported that the effects of internal diffusion on catalyzed gas-
Since the weight of catalyst used is very small (as is the height of the phase reactions are not significant [26,28]. In the present study, since
bed), the differential reactor model assumes that the reactant concen­ the catalyst particles were all smaller than 75 µm, the resistance due to
trations vary linearly in the bed. Therefore, a reaction rate that is internal diffusion could be expected to be negligible compared to the
spatially uniform in the bed and based on average concentrations is surface reaction. The Weisz-Prater criteria calculated from the experi­
considered. For a given conversion and reactant flow rate, the steady- mental data validated this assumption that no significant concentration
state mole balance on glycerol is similar to that for continuous-stirred gradient exists within the catalyst pellets [27]. For the same reason, a
tank reactors, and is given as follows [27]: zero-temperature gradient was expected within the particles due to their
small size, as evidenced by compliance with the calculated criterion [8].
[Flow ratein ] − [Flow rateout ] − [Rate of reaction] The criterion employed to evaluate the internal effects of mass and heat
= [Rate of accumulation] (4.1) transfer is presented in Table 2.
To ensure the absence of external diffusion effects, a preliminary test
[ ] [ ]
FC3 H8 O3 in − FC3 H8 O3 out was carried out to confirm that the total gas velocity did not influence
[(
Rate of reaction
) ] the glycerol conversion (and thus the reaction rates) achieved in steady
−
Weight of catalyst
∙(Weight of catalyst) state [30]. For the same W/FC3 H8 O3 in ratio, where W and FC3 H8 O3 in refer to
the catalyst weight and the glycerol molar feed rate, respectively, the
=0 (4.2)
conversion difference was within the experimental error range (less than
[ ] [ ]
FC3 H8 O3 in − FC3 H8 O3 out − rC3 H8 O3 ∙dW = 0, where W is the catalyst 0.5 %) between two tests performed with different argon flow rates (52
weight. and 190 std mL⋅min− 1), and therefore, different total gas flow rates Q0
By substituting FC3 H8 O3 out = FC3 H8 O3 in − FC3 H8 O3 in ∙dXG , we find: (166 and 304 std mL⋅min− 1). Since these tests were performed using the
highest temperature and the lowest W/FC3 H8 O3 in ratio values covered in
r C 3 H8 O3 =
FC3 H8 O3 in ∙dX G
(4.3) the kinetic study (580 ◦ C and 17.866 g⋅h⋅mol− 1), it was agreed that the
dW effect of external diffusion was ultimately negligible for all other tests in
With the following assumption: dX G
≈ ΔXG
when ΔW→0, we find the this work. Based on empirical data, the Mears criterion is another way to
dW
investigate whether the effect of external mass transfer from the bulk gas
ΔW
experimental glycerol to gas consumption rate (rC3 H8 O3 exp ) defined as
phase to the catalyst surface can be neglected. Similarly, Mears also
follows (eq. (4.4)):
proposes that the bulk fluid temperature will be essentially the same as
XG at the catalyst surface if the criterion associated with heat transfer is
rC3 H8 O3 exp = ( ) (4.4)
W met. These homologous versions of Mears’ criterion are presented in
FC3 H8 O3 in
Table 3.

4
A. Desgagnés and M.C. Iliuta
Fig. 1. Experimental glycerol conversion to gaseous products (XG ) and hydrogen yield (YH2 ) as a function of reaction temperature and liquid flow rate of feed
reactants (L0 ). The total conversion of glycerol considers the combined effect of thermal decomposition (XG,thermal ) and catalytic conversion (XG,cat ). For each L0 is
associated a standard feed gas flow (Q0 ), a space–time (W/FC3 H8 O3 in ), a gas hourly space velocity (GHSV) and a glycerol feed molar fraction (xC3 H8 O3 in ).
3.2. GSR kinetic data
The experimental data of the kinetics study are presented in Fig. 1.
Reaction temperatures ranging from 480 ◦ C to 580 ◦ C were tested for
different space time values defined as the W/FC3 H8 O3 in ratio (g⋅h⋅mol− 1).
These were adjusted by varying the liquid feed rate of the glycerol and
water solution. As expected, at a given temperature, glycerol conversion
to gas and hydrogen yield increased significantly alongside the W/
FC3 H8 O3 in ratio. Similarly, for a constant value of L0 , the increase in re­
action temperature resulted in increases in XG and hydrogen yield,
confirming that the endothermic (R1) reaction is indeed prevailing in
the reaction system. Given the temperatures of the reforming process
and the high thermal instability of glycerol, some decomposition to
gaseous products is likely to occur before reaching the catalytic bed
[31,32]. Therefore, the total XG includes the combined effect of thermal
decomposition and catalytic conversion. From Fig. 1, it can be noticed
that the formation of gaseous products via the thermal route is naturally
amplified as the temperature increases. However, the latter remains
modest compared to the catalytic contribution. Glycerol conversion to
gaseous products ranged from 23.51 % to 98.99 %, while hydrogen
yields varied from 17.17 % to 77.07 % across the range of flow rates and
temperatures tested in the study. For the test performed at 580 ◦ C with a
liquid flow rate of 0.05 std mL⋅min− 1, the hydrogen yield obtained
contradicted the general trend since it was slightly lower than that ob­
tained at 555 ◦ C. The analysis of the reaction products led to the hy­
pothesis that the reverse water–gas shift reaction could be favored above
555 ◦ C, which could results in a direct decrease of the hydrogen yield,
and an increase in CO concentration [33]. However, this phenomenon
was not observed in the tests performed with lower space times.
Tests carried out at temperatures below 555 ◦ C led to the formation
of liquid products including glycerol (unconverted), acrolein, allyl
alcohol, hydroxyacetone, and formaldehyde. Other undetectable prod­
ucts (such as glyceraldehyde, 3-hydroxypropionaldehyde or acetalde­
hyde) are possibly present in trace amounts. Fig. 2A reports the yields of
5
Chemical Engineering Journal 429 (2022) 132278
each detected liquid by-products for the investigated temperatures,
while the reaction scheme shown in Fig. 2B illustrates the possible
routes taken to achieve the formation of these compounds. As expected,
the yield of liquid products is higher when the reaction temperature is
lower since the energy supplied to the system is not sufficient to convert
glycerol completely to the desired gaseous products (i.e., H2 and CO2). It
can also be observed that most of the glycerol that is not converted into
CO2, CO or CH4 is not transformed into other liquid products either,
since it is the primary component of the liquid condensate.
As shown in Fig. 3, the experimental rate of reaction is influenced by
the reaction temperature and the partial pressure of glycerol. For a
similar variation in pC3 H8 O3 , the increase in reaction rate is more pro­
nounced at higher reaction temperatures. At first sight, the experimental
consumption rates do not appear to align linearly with glycerol partial
pressure, as evidenced by the y-intercept of the trend curves, which
deviates progressively from zero as the temperature increases. This
observation allows us to exclude the possibility that the reaction system
investigated here is of order 1 with respect to glycerol, as it was the case
for other authors who studied the GSR reaction [6,7,23]. Moreover, we
can assume that this partial order is greater than zero since the reaction
rate increases with the partial pressure of glycerol. The methods used for
the identification of the order of the reaction as well as the other kinetic
parameters are addressed in detail in the following section.
4. Kinetic modeling
4.1. Estimation of kinetic parameters methodology
The establishment of an appropriate kinetic model requires the
identification of the parameters that most accurately fit the experi­
mental data. Most often, in heterogeneous kinetic modeling, these pa­
rameters include rate or adsorption constants that are valid only for
specific reaction conditions. In most laboratory and industrial reactions,
the rate constants are assumed to be a function of temperature only [27]
A. Desgagnés and M.C. Iliuta Chemical Engineering Journal 429 (2022) 132278

Fig. 2. Liquid by-products analysis: A) Yield of liquid products for the investigated temperatures (GHSV = 12.444 std L⋅gcat-1⋅h− 1) and B) Possible reaction pathways
in glycerol steam reforming.

6
A. Desgagnés and M.C. Iliuta
Fig. 3. Experimental glycerol to gas consumption rate as a function of glycerol partial pressure at different temperatures. Trend lines have been added to highlight
the lack of proportionality of the relationship near the origin.
and their dependence can be defined by the Arrhenius equation (eq. (5)):
(5)
− Ea
k = Ae
RT
where k is the rate constant, A is the pre-exponential factor, Ea is the
activation energy of the reaction, and R is the ideal gas constant. Other
constants, such as a reaction order, can be identified through modelling
as is the case in the power law model. The glycerol reforming rate as well
as the formation rates of the main gas products were first fitted to a
power law model. The estimation of the model parameters (i.e., reaction
orders and rate constants) was performed using a non-linear regression
program to minimize an objective function (OF) inspired by the
Levenberg-Marquardt algorithm, which is based on the sum of the
squares of the relative residues (eq. (6)):
( )2
∑n ∑ q rexpi,k − rcali,k
OF = ωi,k ∙ (6)
i=1 rcali,k
k=1
where rexp and rcal are, respectively, the experimental and calculated
consumption or formation rates associated with n different compounds i
(C3H8O3, H2, CO2, CO, and CH4, excluding water, which was not
quantified at the reactor’s outlet) and q experimental conditions k. The
weight factors (ωi,k ) are included to give equal importance to the rates of
each product. These vary in inverse proportion to the molar fraction of
each compound at the given conditions (yi,k ), and are calculated as fol­
lows [34,35] (eq. (7)):
1 variance, ϕ = 0.1 and the F-value was calculated using tabulated data
ωi,k = (7)
yi,k
For modeling heterogeneous kinetic expressions, the objective
function to be minimized is essentially the same as for the power law
model but does not include the product formation rates since the
developed expressions describe the overall reaction rate, i.e., the rate at
which glycerol is reformed to gaseous products based on the rate-
determining steps. By varying the values of the kinetic parameters
present in the heterogeneous rate expressions (rate, adsorption, and
7
Chemical Engineering Journal 429 (2022) 132278
desorption constants), the program minimized an OF function value
separately for each heterogeneous model. The more the value of the
function OF is minimized, the higher the regression coefficient R2 should
be on the parity plot of the calculated and experimental reaction rates.
As a primary criterion, models that had a R2 ≤ 0.98 were rejected. The
validity of the mathematical solutions respecting this first criterion was
then verified by a residual analysis. Solutions whose relative residuals
(calculated according to equation (eq. (8))) showed a trend or were not
normally distributed around a mean of zero were deemed invalid and
were discarded.
( )
rexp − rcal
Relative residuals = (8)
rexp
For the models that were able to meet the two criteria listed above,
an analysis of variance (ANOVA) was performed using Fisher’s law test
on the residuals of the models. The ANOVA was performed to compare
two models, model A having a higher sum of squares of residuals than
model B (SSRB < SSRA ). The Fisher’s law test states that the improve­
ment brought by model B is significant with a percentage of confidence
of 100⋅(1 − ϕ) if the following condition is met (eq. (9)):
SSRA /zA σ2 A
FA− B = = > F1− ϕ (υA , υB ) (9)
SSRB /zB σ2 B
∑
where SSR = qk=1 (rexp,k − rcal,k )2 ,υ is the degree of freedom, z is the
number of parameters to determine in the corresponding model, σ2 is the
for Fisher distribution [36].
Subsequent analysis of the remaining solutions was then performed
to ensure that they were thermodynamically realistic. Indeed, the so­
lutions provided by the resolution algorithm were acquired on a math­
ematical basis. It is therefore essential to ensure that the rate and
adsorption constants of the retained models have positive values and
present logical trends in relation to the temperature variation. For
instance, the rate constants should always increase with temperature
according to Arrhenius’ law in contrast to the adsorption equilibrium
A. Desgagnés and M.C. Iliuta
constants which should decrease as stated by Van’t Hoff’s relation due to
the exothermic nature of adsorption. The selection of models that best
reflect reality is detailed and justified in the Discussion section.
4.2. Proposed kinetic models
The parameters and expressions in this kinetic study were estab­
lished from experimental data obtained or calculated in the well-
established steady state only. Therefore, under the assumption that
the partial pressures of the compounds vary linearly over the length of
the catalyst bed, the average partial pressures in the catalytic bed were
considered to adjust the rate law expressions for all the proposed kinetic
models.
4.2.1. Power law model
The experimental glycerol to gas consumption rates were first
adjusted to a power law model. Due to the large stoichiometric excess of
water over glycerol in the feed solution for all tests carried out in this
study (steam/glycerol molar ratio of 9), a zero-order reaction with
respect to water was assumed. The power law model can therefore be
defined as follows (eq. (10)):
rPL− = k’ ∙pαC3 H8 O3 (10)
C 3 H 8 O3
where rPL− C3 H8 O3 is the calculated glycerol to gas consumption rate
(mol⋅min− 1⋅gcat-1), k’ is the pseudo rate constant (mol⋅min− 1⋅gcat-1⋅atm-
α
) of the reaction, pC3 H8 O3 is glycerol partial pressure (atm) and α is the
reaction order. At first sight, a α-value between 0 and 1 was expected
after observing the results in Fig. 3. An analogous power law expression
was also used to model the experimental formation rates of the main
gaseous products i (H2, CO2, CO, and CH4) (eq. (11)).
rPL− i = k’ ∙pαC3 H8 O3 (11)
4.2.2. Heterogeneous kinetic models
To date, the glycerol steam reforming reaction has been studied
using several different catalytic systems, which is probably the reason
why no consensus has yet been reached on which reaction mechanism
actually prevails. For Adesina et al. [22], who used a bimetallic cobalt/
8
Chemical Engineering Journal 429 (2022) 132278
nickel-based catalyst, a dual-site molecular adsorption of steam and
glycerol with a rate-determining surface reaction was the most adequate
representation of the reaction mechanism. In comparison, dissociative
adsorption of steam was considered more adequate in the work of Cheng
et al.[8] who studied the reaction catalyzed by nickel on an alumina
support. The results supported that dissociative adsorption of water
occurred preferentially on acidic sites, while molecular adsorption of
glycerol occurred on basic sites, also present on the catalyst surface.
Sundari et al. [7] and Vaidya et al. [37] who used Ru-based catalysts,
hypothesized a single-site molecular adsorption of glycerol followed by
its reaction with water to form an intermediate complex. The decom­
position of this complex was considered the rate-determining step in the
reaction.
In this study, mechanisms involving the reversible adsorption of
water and glycerol, surface reactions as well as the desorption of prod­
ucts were developed and derived into Langmuir-Hinshelwood-Hougen-
Watson-type kinetic expressions to correlate the experimental data.
Molecular or dissociative adsorption of the reactants on identical single
or dual sites were considered to establish different reaction mechanisms.
A partial first order with respect to each respective reactant was
considered for all the elementary steps involved in each mechanism. In
more than three quarters of heterogeneous reactions that are not limited
by mass transfer effects, the rate-determining step is a surface reaction
[27]. In light of this statement, in this work, eight different rate law
expressions were developed assuming that surface bimolecular reactions
involving the reactants (or intermediates of their decomposition) were
the limiting steps (M1-M8). In the mechanism developments detailed
below, the active sites are represented by X , while the main and sec­
ondary gaseous products are labeled in red and orange, respectively. In
models where dual-site adsorption is considered, X1 are the active sites
for glycerol while X2 represent the active sites for water. The presence of
CH4 and CO in non-negligible quantities in the gaseous products was
considered by the presence of secondary reaction pathways in the
development of all mechanisms. We also highlight that it is possible to
retrieve the global reaction of GSR (R1) by doing the stoichiometric
balance for each elementary step.
Model (M1): Single-site molecular adsorption of glycerol and
dissociative adsorption of steam
A. Desgagnés and M.C. Iliuta Chemical Engineering Journal 429 (2022) 132278

Model (M2): Single-site dissociative adsorption of glycerol and

steam

Model (M3): Single-site dissociative adsorption of glycerol and mo­

lecular adsorption of steam

9
A. Desgagnés and M.C. Iliuta Chemical Engineering Journal 429 (2022) 132278

Model (M4): Single-site molecular adsorption of glycerol and steam

Model (M5): Dual-site molecular adsorption of glycerol and disso­

ciative adsorption of steam

10
A. Desgagnés and M.C. Iliuta Chemical Engineering Journal 429 (2022) 132278

Model (M6): Dual-site dissociative adsorption of glycerol and steam

Model (M7): Dual-site dissociative adsorption of glycerol and mo­

lecular adsorption of steam

11
A. Desgagnés and M.C. Iliuta
Model (M8): Dual-site molecular adsorption of glycerol and steam
The reaction mechanisms presented so far consider the rate-
determining step of the reaction to be the bimolecular reaction be­
tween the adsorbed species derived from water and glycerol. However,
several studies performed on reforming processes have shown that the
decomposition of hydrocarbons or oxygenated hydrocarbons is often the
rate-determining step in the reaction [7,38–41]. In this respect, models
(M9) to (M12) were developed considering the decomposition of glycerol
in various forms as the rate-determining step of the reaction. In each of
these mechanisms, it is possible to separate the reaction into two sub­
sequent stages, i.e., i) the decomposition and dehydrogenation of glyc­
erol on the catalyst surface that ultimately leads to the formation of
adsorbed CO species, followed by ii) the water–gas shift (WGS) reaction
between adsorbed water and CO species to form the reaction products
(CO2 and H2). The aforementioned two-phase reaction sequence was
first assumed and validated by Byrd et al. [41] using a Ru-based catalyst,
and then was later verified by Pant et al. [40] using a nickel-based
catalyst. The difference between models (M9) to (M12) lies in the
behavior of glycerol upon its dissociative adsorption to the surface of the
active site, and in the considered rate-determining step. First, model
12
Chemical Engineering Journal 429 (2022) 132278
(M9) suggests an elementary first step of dehydrogenation of glycerol to
form adsorbed CHOH-COH-CH2OH, followed by its decomposition
initiated by two simultaneous C–C bond cleavage that is considered as
the rate-determining step. Model (M10) proposes that cleavage of the
first C–C bonds occurs upon glycerol adsorption. The rate determining
step in model (M10) is considered to be the dehydrogenation of adsorbed
CH2OH, which releases the first H2 molecules. Model (M11) suggests a
molecular adsorption of glycerol on a single active site. The breaking of
a first C–H bond within this adsorbed glycerol molecule is considered as
the rate-determining step. Finally, model (M12) is similar to model (M9)
but proposes a dissociative adsorption of glycerol on two active sites,
which detach a single H from the initial glycerol molecule (compared to
two for model (M9)). The subsequent breaking of the first C–C bond is
considered to be the rate-determining step of the reaction in model
(M12). In models (M9) to (M12), it is assumed that the adsorbed water
reacts almost immediately with adsorbed CO species via the water–gas
shift reaction. This causes the rate expressions developed for these
models to be unaffected by the partial pressure of water. The de­
velopments of these reaction mechanisms are detailed below.
Model (M9): Single-site dissociative adsorption of glycerol (no C–C
bond cleavage) and molecular adsorption of steam, first and second C–C
bond breaking as rate-determining step
A. Desgagnés and M.C. Iliuta Chemical Engineering Journal 429 (2022) 132278

Model (M10): Single-site dissociative adsorption of glycerol (with

C–C bond cleavage) and molecular adsorption of steam, adsorbed Model (M12): Single-site dissociative adsorption of glycerol and
CH2OH dehydrogenation as rate-determining step molecular adsorption of steam, first C–C bond breaking as rate-

determining step

Model (M11): Single-site molecular adsorption of glycerol and mo­

lecular adsorption of steam, first C–H bond breaking as rate-determining
step

13
A. Desgagnés and M.C. Iliuta Chemical Engineering Journal 429 (2022) 132278

to gas consumption rates (rj ) as a function of the rate constants krxj , the
The rate law expressions developed from the 12 different reaction apparent adsorption and desorption constants (KAi.j and KDi.j , respec­
scenarios are presented in Table 4. These equations provide the glycerol tively) and the partial pressures (p) of the individual compounds. The

Table 4
Rate expressions developed for proposed heterogeneous kinetic models.
Model Rate expression Hypothesesa

(M1) 1
krx1 pC3 H8 O3 pH2 O 2
r1 =
1
( )2
1 + KA1.1 pC3 H8 O3 + KA2.1 pH2 O 2 + KD3.1 pCO2
(M2) 1 1
krx2 pC3 H8 o3 2 pH2 O 2
r2 =
1 1
( )2
1 + KA1.2 pC3 H8 o3 2 + KA2.2 pH2 O 2 + KD3.2 pCO2
(M3) 1
krx3 pC3 H8 o3 2 pH2 O
r3 =
( 1 1 )2
pCO2 pH2
1 + KA1.3 pC3 H8 o3 2 + KA2.3 pH2 O + KD3.3 + KD5.3 pH2 2
pH2 O
(M4) krx4 pC3 H8 O3 pH2 O
r4 =
( 1 )2
pCO2 pH2
1 + KA1.4 pC3 H8 O3 + KA2.4 pH2 O + KD3.4 + KD5.4 pH2 2
pH2 O
(M5) 1
krx5 pC3 H8 O3 pH2 O 2
r5 =
1
( )( )
1 + KA1.5 pC3 H8 O3 + KD3.5 pCO2 1 + KA2.5 pH2 O 2 + KD4.5 pCO2
(M6) 1 1
krx6 pC3 H8 o3 2 pH2 O 2
r6 =
1 1
( )( )
1 + KA1.6 pC3 H8 o3 2 + KD3.6 pCO2 1 + KA2.6 pH2 O 2 + KD4.6 pCO2
(M7) 1
krx7 pC3 H8 o3 2 pH2 O
r7 =
( 1 1 )( 1)
pCO2 pH2
1 + KA1.7 pC3 H8 o3 2 + KD3.7 + KD5.7 pH2 2 1 + KA2.7 pH2 O + KD6.7 pH2 2
pH2 O
(M8) krx8 pC3 H8 O3 pH2 O
r8 =
( 1 )( 1)
pCO2 pH2
1 + KA1.8 pC3 H8 O3 + KD3.8 + KD5.8 pH2 2 1 + KA2.8 pH2 O + KD6.8 pH2 2
pH2 O
(M9) 1
krx9 pC3 H8 o3 3
r9 =
1
( )3
1 + KA1.9 pC3 H8 o3 3 + KD3.9 pCO2
(M10) 2
krx10 pC3 H8 o3 3
r10 =
1
( )2
1 + KA1.10 pC3 H8 o3 3 + KD3.10 pCO2
(M11) krx11 pC3 H8 O3
r11 = ( )2
1 + KA1.11 pC3 H8 o3 + KD3.11 pCO2
(M12) 1
krx12 pC3 H8 o3 2
r12 =
1
( )2
1 + KA1.12 pC3 H8 o3 2 + KD3.12 pCO2
Colors: , ; S: Single-site adsorption; D: Dual-site adsorption
a
: ●: Molecular adsorption; : Dissociative adsorption; : Bimolecular surface reaction is determining the reaction rate, : A step included in the decomposition of
glycerol is determining the reaction rate

14
A. Desgagnés and M.C. Iliuta Chemical Engineering Journal 429 (2022) 132278

Fig. 4. Confirmation of the validity of the power law model: calculated versus experimental reaction rate of glycerol to gas consumption, Arrhenius plot and
identified kinetic parameters.

subscript j indicates the associated model number while the subscript i
refers to the compound involved in the adsorption or desorption (glyc­
erol: i = 1, water: i = 2, carbon dioxide: i = 3 or 4, hydrogen: i = 5 or 6).
The presence of two possible subscripts associated with CO2 and H2 in
the dual-site models means that desorption of these products can occur
on either type of site.
5. Discussion
The kinetic parameters identified for the power law model for
glycerol reaction rates are shown in Fig. 4, which clearly demonstrates
the validity of this method due to the high R2 coefficient between the
experimental and calculated rate values as well as the compliance with
Arrhenius’ law. An activation energy of 66.1 kJ⋅mol− 1 and an order of
reaction of 0.63 were identified for the temperature range (480–580 ◦ C)
tested in this study. Keeping in mind that a catalyst provides an alter­
native pathway for the reaction with a lower activation energy, it is
logical to encounter distinct activation energy values from one publi­
cation to another in the literature since several parameters such as the
catalyst used, the method of preparation, or the tested temperature
range can change the rate-determining step of a reaction. Despite this
statement, similarities can be seen between the Ea values obtained in this
study and those from the work of Cheng et al. [8] (59.8 kJ⋅mol− 1 over a
15 % Ni/Al2O3 catalyst, between 450 and 550 ◦ C), Foo et al. [21] (67.2
kJ⋅mol− 1 over a 15 % Co/Al2O3 catalyst, between 450 and 550 ◦ C) and
Adesina et al (63.3 kJ⋅mol− 1 over a 5%Co-10 %Ni/Al2O3 catalyst, be­
tween 500 and 550 ◦ C) . However, the overall reaction orders identified
being different (0.82 for Cheng et al. [8] and 0.47 for Foo et al. [21])

Fig. 5. Confirmation of the validity of the power law model: calculated versus experimental reaction rate of product formation, and identified kinetic parameters.

15
A. Desgagnés and M.C. Iliuta
Table 5
ANOVA results for discrimination of models (M10), (M11) and (M12).
Relation(A → B) (M10)→(M12)
a
F1− ϕ (υA , υB ) 3.45
FA− B 8.59
Model A significantly improves the goodness of fit compared to B Yes
a
: ϕ = 0.1 was chosen for this study
may suggest that the mechanisms involved or the rate-determining step
may also be different [19].
The kinetic parameters describing the formation rate of the gaseous
products were also determined through power law modeling using (eq.
(11)) and are presented in Fig. 5. It can be noticed that the Ea values for
H2, CO2 and CO are close to the value of 66.1 kJ⋅mol− 1 calculated for
glycerol, which proves that the formation of these products comes
mainly from the consumption of glycerol via reactions (R1) and (R2). As
for CH4, a higher activation energy of 90.7 kJ⋅mol− 1 and significantly
slower formation rates were observed. This observation is not surprising
since the 5 % Ni-UGSO catalyst has shown very low selectivity towards
methane at temperatures below 630 ◦ C in our previous studies [5].
Positive values of reaction orders for all compounds indicate that their
rate of formation is directly favored by the partial pressure of glycerol
during the reaction. While H2 and CO2 exhibit α approaching that of
glycerol consumption, higher values for CO and CH4 suggest that their
formation rates are more strongly influenced by the presence of glycerol.
According to the heterogeneous kinetic model analysis, models (M1),
(M2), (M4), and (M8) were rejected since they could not significantly
minimize the objective function OF compared to the other models (R2 ≤
0.98 on the parity plot). The residual analysis allowed the rejection of
model (M3), (M5), (M6) and (M7) since the residuals were either biased
by a trend or not averaged near zero. Model (M7), for instance, exhibits
both flaws: the residuals associated with the tests performed at 505 ◦ C
are biased by an observable trend and those calculated at 480 ◦ C are not
averaged near zero (Fig. S1).
As a result, models (M9), (M10), (M11) and (M12) were the only four
that met the two criteria stated above. It can be noted that the activation
energies calculated for models (M9) and (M11) (78.6 kJ⋅mol− 1 for M9 and
50.4 kJ⋅mol− 1 for M11) are farther than the Ea acquired from the
macroscopic power law analysis (66.1 kJ⋅mol− 1), while Ea values for
(M10) and (M12) are closer (62.8 kJ⋅mol− 1 for M10 and 58.4 kJ⋅mol− 1 for
M12). Further statistical analysis based on the variance of the estimated
rates of models (M9), (M10), (M11) and (M12) was performed using the
condition of (eq. (9)) to assess whether their results were significantly
different. Analysis by Fisher’s law test showed that models (M9), (M10)
and (M11) significantly improved the goodness of fit compared to model
(M12). The latter was therefore rejected. However, model (M10), which
showed the lowest SSR, was not able to significantly improves the
goodness of fit according to the calculated criteria when compared to
model (M9) and model (M11). The ANOVA results are presented in
Table 5. Note that F1− ϕ (υA − υB ) is the same for all relations since models
(M9), (M10), (M11) and (M12) each had 5 degrees of freedom (υ9 = υ10 =
υ11 = υ12 = 5).
Further investigation was therefore needed to identify which
mechanism was more realistic. An analysis of the adsorption and
desorption constants was performed using the Van’t Hoff relation (eq.
(12a) for adsorption and eq. (12b) for desorption) to validate the
calculated values for models (M9) to (M11). Here, the analysis was per­
formed on the actual adsorption and desorption constants. These, which
are directly obtained from the development of the mechanisms in
elementary steps, differ from the apparent constants which appear in the
rate expressions of Table 4. The relations between actual and apparent
constants are showed below:
( ) − ΔH ΔSAi.j
(12a)
Ai.j
ln K’Ai.j = + decomposition/dehydrogenation of glycerol followed by the WGS
RT R
16
Chemical Engineering Journal 429 (2022) 132278
(M11)→(M12) (M9)→(M12) (M10)→(M11) (M10)→(M9) (M11)→(M9)
3.45 3.45 3.45 3.45 3.45
6.94 3.97 1.24 2.16 1.75
Yes Yes No No No
where K’Ai.j : actual adsorption constant with respect to reactant i and
model j,
K’A1.9 = 4∙KA1.9 3 (model M9)
K’A1.10 = KA1.10 3 (model M10)
K’A1.11 = KA1.11 (model M11)
( ) − ΔH
ln K’Di.j =
Di.j
+
ΔSDi.j
(12b)
RT R
where K’Di.j : actual desorption constant with respect to product i and
model j,
K’D3.9 = KD3.9 − 3 (model M9)
K’D3.10 = KD3.10 − 3 (model M10)
K’D3.11 = KD3.11 − 3 (model M11)
( )
By plotting ln K’A1.j as a function of 1/T, it is possible to assess the
glycerol adsorption enthalpy (ΔHAi.j ) and entropy (ΔSAi.j ) variation of
the system. Yet, since adsorption is an exothermic process, the slope of
this graph should be positive (ΔHAi.j < 0). We also know that the value
of the y-intercept should be negative since the adhesion of gas molecules
to the surface decreases the randomness, and thus the entropy of the
system. To ascertain the validity of the desorption constants associated
with CO2, a similar procedure, but with an opposite reasoning, was
performed. Positive enthalpies and entropies were then expected.
Through this exercise, a negative entropy value was determined from
the Van’t Hoff plot of the constant associated with carbon dioxide
desorption in the (M9) model (ΔSD3.9 < 0). As this observation was
found to be unrealistic, the (M9) model had to be rejected. For all the
reasons mentioned above, models (M10) and (M11) were considered the
most realistic.
The accuracy of these last two models (M10 and M11) in estimating
the experimental data is clearly observable in the parity plot shown in
Fig. 6. The Arrhenius and Van’t Hoff plots showing the dependencies of
the rate and adsorption constants on temperature do not reveal any
obvious anomaly at first sight. The kinetic and thermodynamic param­
eters calculated from the trend curves of the latter plots are also pre­
sented in Fig. 6. Although the sign of the calculated values respects the
thermodynamic logic, it can be noticed that the enthalpies as well as the
entropies of adsorption and desorption identified are quite different for
model (M10) and (M11). According to model (M11), it would mean that
an energy of 197.4 kJ would be released from the system per mole of
glycerol adsorbed. This value, which seems rather extreme, is in fact
much higher than the one identified in the kinetic study of Cheng et al.
using a Ni-Co based catalyst (-39.93 kJ⋅mol− 1) [22]. As for CO2
desorption, the high enthalpy value of 297.1 kJ⋅mol− 1 also seems un­
likely when compared to other values reported in the literature for
materials known to have better affinities with CO2 than our catalyst,
such as CD-MOF-2 (113.5 kJ⋅mol− 1) [42] or 5A zeolite (44.0 kJ⋅mol− 1)
[43]. For these reasons, although models (M10) and (M11) were able to
predict the experimental data almost equally well, it may be concluded
that model (M10) is more plausible since the associated kinetic and
thermodynamic parameters are more realistic, and therefore, quite
possibly more reliable. Table 6 provides a summary of the reasons for
rejecting each kinetic model.
In terms of the mechanics of the GSR process, (M10) model suggests
that the reaction process occurs in two distinct stages including the
A. Desgagnés and M.C. Iliuta
Fig. 6. Parity plot of the calculated versus the experimental rates of glycerol to gas consumption for model (M10) and (M11), Arrhenius plot, Van’t Hoff plot (filled
symbols refer to desorption constants, empty symbols refer to adsorption constants) as well as the identified kinetic and thermodynamic parameters.
Table 6
Justification to accept/reject each of the heterogeneous kinetic models.
Model (M1) (M2) (M3) (M4) (M5)
Reason to reject 1 1 2 1 2 2
Legend: 1: The model failed to fit the experimental data with R2 > 0.98
2: The residuals exhibited a noticeable trend or are not averaged near zero
3: ANOVA revealed a significant difference in goodness of fit compared to other models
4: The model presented thermodynamic anomalies (ΔSdes < 0)
5: The model presented kinetics parameters whose values are unlikely
X: Selected model.
reaction between adsorbed water and CO species. In relation to the
conclusions drawn in our previous work [5], the first step could be
attributed to the active nickel phase owing to its good ability to break
the C–C and C–H bonds present in the glycerol molecule. The second
phase, on the other hand, could be favored by the presence of Fe in the
UGSO support which enhances the hydrogen yield of the reaction by
promoting the conversion of adsorbed CO species via the WGS pathway.
It is also assumed that the rate-determining step of the reaction is the
dehydrogenation of the adsorbed CH2OH intermediate, which initially
originates from the primary decomposition of the glycerol molecule
occurring upon its adsorption. As mentioned earlier, other studies
published in the literature have already reported that the rate-
determining step in the reforming reaction was found to include the
decomposition of an oxygenated hydrocarbon intermediate [7,38–41].
Moreover, the activation energies of the glycerol steam reforming re­
action calculated in the work of Cheng et al. [8] (59.8 kJ⋅mol− 1), Ade­
sina et al. [22] (63.3 kJ⋅mol− 1), and Foo et al. [21] (67.2 kJ⋅mol− 1) are
found to be very close to those identified in this study, either by the
power law model (66.1 kJ⋅mol− 1) or by the best heterogeneous kinetic
17
Chemical Engineering Journal 429 (2022) 132278
(M6) (M7) (M8) (M9) (M10) (M11) (M12)
2 1 4 X 5 3
model (62.8 kJ⋅mol− 1). This suggest that the mechanisms involved or
the rate-determining steps of the reaction could have similarities,
although divergent conclusions have been reported in each case.
6. Conclusions
In this study, the kinetics of the glycerol steam reforming reaction
catalyzed by a nickel-promoted metallurgical residue (5 % Ni-UGSO)
were experimentally investigated in a fixed-bed reactor at atmospheric
pressure wherein the reaction temperature was varied between 480 and
580 ◦ C and the reactant feed solution between 0.05 and 0.11 std
mL⋅min− 1. Langmuir-Hinshelwood-Hougen-Watson reaction mecha­
nisms were developed to establish detailed heterogeneous kinetic
models that incorporate single- or dual-site adsorption of reactants as
well as desorption of products on the catalyst surface. The modeling
results suggested that the reaction mechanism of the GSR process de­
velops in two stages: i) glycerol decomposition and dehydrogenation,
which could be favored by the active Ni phase, followed by ii) WGS
reaction with water in the gas phase, which could be enhanced by the
A. Desgagnés and M.C. Iliuta
presence of Fe in the catalytic support. According to the selected model,
the reaction is initiated by a dissociative adsorption of glycerol which
leads to the cleavage of a two C–C bond on the surface of the 5 % Ni-
UGSO catalyst. The rate-determining step, considered as the dehydro­
genation of an adsorbed glycerol intermediate, will ultimately lead to
the formation of adsorbed CO species, which will react with adsorbed
steam to produce the main reaction products, H2 and CO2. Glycerol and
steam adsorption are assumed to occur on identical single sites. Our
model was able to estimate the reaction rates with high accuracy while
presenting realistic kinetic parameters that exhibited logical trends with
the tested temperatures according to the laws of thermodynamics. An
activation energy of 62.8 kJ⋅mol− 1 was calculated as well as a pre-
exponential factor of 77.4 mol⋅min− 1⋅gcat-1⋅atm− 2/3 in relation with
the Arrhenius relation. The dissociative adsorption of glycerol is quan­
tified by an enthalpy of − 34.1 kJ⋅mol− 1 and an entropy of − 39.3 J⋅mol-
1⋅K− 1, while the desorption of CO2 features an enthalpy of 41.1 kJ⋅mol− 1
and an entropy of 12.1 J⋅mol-1⋅K− 1. A macroscopic analysis was also
performed by applying a power law model to correlate the experimental
rates of glycerol to gas consumption and generation of the main gaseous
products (H2, CO2, CO, CH4). A pre-exponential factor of 31.4
mol⋅min− 1⋅gcat-1⋅atm-α, a reaction order of 0.56 with respect to glycerol
as well as an activation energy of 64.7 kJ⋅mol− 1 were determined as the
kinetic parameters associated with the consumption of glycerol rate.
This Ea value is very close to that identified for the agreed heterogeneous
model, which confirms the validity of the methods used.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
Financial support provided by the Natural Sciences and Engineering
Research Council of Canada (NSERC), the Alexander Graham Bell Can­
ada Graduate Scholarships Master’s program (NSERC CGS M), and the
Centre for Innovation and Research on Carbon Utilisation in Industrial
Technologies (CIRCUIT) is gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2021.132278.
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