A Review On Glycerol Reforming Processes Over Ni-Based Catalyst For Hydrogen and Syngas Productions

international journal of hydrogen energy xxx (xxxx) xxx
Available online at www.sciencedirect.com
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A review on glycerol reforming processes over

Ni-based catalyst for hydrogen and syngas
productions
Nurul Asmawati Roslan a, Sumaiya Zainal Abidin a,b,*, Asmida Ideris a,

Dai-Viet N. Vo c
a
Faculty of Chemical and Process Engineering Technology, College of Engineering Technology, Universiti Malaysia
Pahang, Lebuhraya Tun Razak, 26300, Gambang, Kuantan, Pahang, Malaysia
b
Centre of Excellence for Advance Research in Fluid Flow (CARIFF), Universiti Malaysia Pahang, Lebuhraya Tun
Razak, 26300, Gambang, Kuantan, Pahang, Malaysia
c
Center of Excellence for Green Energy and Environmental Nanomaterials (CE@GrEEN), Nguyen Tat Thanh
University, 300A Nguyen Tat Thanh, District 4, Ho Chi Minh City 755414, Viet Nam
highlights
A review of glycerol reforming reactions over Ni-based catalysts is presented.

Glycerol as the potential feedstocks for hydrogen and syngas productions.
Recent technologies on glycerol reforming are systematically overviewed.
Role of catalyst, supports and promoters in glycerol reforming reaction is reported.
Deactivation of Ni-based catalysts in glycerol reforming is discussed in detail.
article info abstract
Article history: The rapid increase in energy demand coupled with the depletion of fossil-based resources
Received 30 April 2019 has elevated the need for cleaner, renewable and sustainable fuels. Amongst alternative
Received in revised form energies, hydrogen-based energy solution has become a promising replacement candidate
30 July 2019 due to its clean emission, high efficiency and it is considered to be a perfect substitute to
Accepted 26 August 2019 reduce the dependency on non-renewable sources. Recently, the valorization biomass has
Available online xxx become one of the attractive routes for hydrogen production and it has received growing
attentions from worldwide researchers. Glycerol, the by-product from the biodiesel pro-
Keywords: duction faced oversupply crisis due to the high refining cost and this has affected the
Glycerol valorization economics and sustainability of biodiesel industry. Hence, the most attractive way to boost
Hydrogen and syngas the economic value of biodiesel is through the valorization of crude glycerol into value-
Reforming reaction added products, i.e., H2 and syngas. Previously, the production of H2 from glycerol has
Ni-based catalyst been carried out using various reforming processes such as aqueous phase reforming,
Catalyst deactivation pyrolysis, steam reforming, partial oxidation and dry reforming reactions. In the large scale
industrial applications, Ni-based catalyst has been reported as the most common catalyst
used in reforming reactions since this type of catalyst is readily available, inexpensive and
possesses high catalytic activity. Ni was also found to have a good intrinsic activity and
easily dispersed over the support materials. Throughout the years, various production
* Corresponding author. Faculty of Chemical and Process Engineering Technology, College of Engineering Technology, Universiti
Malaysia Pahang, Lebuhraya Tun Razak, 26300, Gambang, Kuantan, Pahang, Malaysia.
E-mail addresses: sumaiya@ump.edu.my, sumaiyaza@gmail.com (S.Z. Abidin).
https://doi.org/10.1016/j.ijhydene.2019.08.211
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Roslan NA et al., A review on glycerol reforming processes over Ni-based catalyst for hydrogen and syngas
productions, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.08.211
2 international journal of hydrogen energy xxx (xxxx) xxx
routes and catalyst design have been reported in literature; however, none of the litera-
tures are specifically focusing on benefits, constraints, limitation and challenges faced by
glycerol reforming reactions catalyzed by Ni-based catalysts. Therefore, the focus of this
review is to highlight the recent findings on Ni-based thermochemical processes of glycerol
reforming reactions and emphasis will be given on the recent advances in catalyst and
reactor designs as well as discovering the main routes of catalyst deactivation.
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
fuel for gas turbines and internal combustion engines [4,5].

Introduction Important chemical processes such as hydrogenation process
in food industries and hydrocracking process in petrochem-
Over decades, petroleum-based fossil fuels such as coal, pe- ical refineries also utilize H2 in their production plants. Syn-
troleum and natural gas have become the main world's energy gas, on the other hand, can be potentially used in the Fischer-
sources and nowadays, the modern life is heavily relying on Tropsch (FT) synthesis, and the production of this gas can be
this source of energy. However, in spite of the growing energy tailored by varying the conversion routes, reaction conditions
demand, the limited supply of this finite source has put a and reactant compositions.
strain to its applications. The utilization of the current oil- Currently, 95% of the global H2 production uses fossil fuels
based fuels also leads to an increase in carbon dioxide (CO2) as the raw materials, and H2 is mainly produced through the
emissions [1], especially in the power and transport industry thermochemical [6,7], electrolysis [8] and biological processes
amounting to 266.652 metric ton per year as of 2016 [2]. [9]. The first two processes are commonly employed in in-
Minimizing the carbon emissions is a crucial effort in miti- dustry since they provide the most practical conversion
gating global warming risks caused by the emissions of the routes. However, the expensive feedstock price elevates the
greenhouse gases. The concerns on the security of energy overall processing cost and makes the process uneconomical.
supply and environmental issues have also driven the energy Biological production potentially becomes the preferred
system of the world from solids to liquids and then gases as choice since the process is conducted at ambient pressure and
shown in Fig. 1. From the figure, it is expected that in 2080, temperature and requires less energy consumption. Never-
hydrogen (H2) would be responsible for 90% of the world theless, the inconsistent H2 production becomes one of the
energy. limitations for this process route. Currently, in industrial
Currently, the focus on global mitigation strategy is to scale, the conventional route to produce syngas and H2 is
utilize the H2 and synthesis gas (syngas) as the alternative through the steam reforming of methane (CH4). Since the
source of energy. These gases can be utilized in different kind methane feedstock is originated from fossil fuels, it is also
of applications, i.e. as chemical feedstocks and intermediates considered to be a non-renewable source [10,11]. In addition,
for the production of methanol, long-chained alcohols, de- the uncontrolled emissions of greenhouse gas, i.e., CO2 from
tergents, ammonia and synthetic hydrocarbon fuels and as a steam reforming reaction have contributed to global warming
Fig. 1 e Global energy system transition, 1850e2150 [3].
international journal of hydrogen energy xxx (xxxx) xxx 3
effect [12]. Therefore, there is an increasing interest to find a process could lead to equipment clogging [5]. Therefore, the
sustainable and renewable source of energy to replace fossil valorization of glycerol into other value-added chemicals
fuels. found to be the best pathway to increase the biodiesel global
Recently, glycerol has become one of the potential feed- market. Currently, glycerol has been used as the building
stocks for H2 production [13e15] and investigation on the blocks and intermediates for many chemical productions
potential utilizations of this feedstock has been extensively such as 1,3-propanediol, propylene glycol, glyceric acids, pol-
carried out by researchers worldwide. Glycerol, the by- yols and branch polyesters and these chemicals are produced
product from the biodiesel production faced oversupply through processes such as hydrogenolysis, dehydration and
crisis due to uneconomical purification process and thus, oxidation [22]. Recently, the production of H2 and syngas has
bringing down its commercial value. It is estimated about 10% become another potential route for glycerol valorization. The
of glycerol is generated from biodiesel production [16], which production of H2 from glycerol can be done using various
is about 1.05 pound of glycerol produced per one gallon of synthesis routes such as steam reforming [23,24], dry
biodiesel generated [17]. A current market study in 2013 shows reforming [25], partial oxidation [26], autothermal reforming
that nearly 1.4 million tons of glycerol were produced through [27], aqueous phase reforming [28,29], pyrolysis [30] and
the biodiesel transesterification process, which is approxi- anaerobic fermentation [31].
mately 63% of the global glycerol production. Fig. 2 shows the Over the year, extensive numbers of literatures have been
projected biodiesel and crude glycerol productions from 2003 reported on glycerol reforming processes over a diverse range
to 2020. The data used was adopted from Food and Agriculture of catalyst-support combinations. From the studies, the
Organization of the United Nations (OECD) [18]. According to feedstock conversion, product selectivity, catalyst activity and
the Figure, by 2020, 36 million tons of biodiesel will be pro- stability are significantly influenced by the catalyst-support
duced and approximately over 3 million tons of crude glycerol design, catalyst pre-treatment and preparation methods as
will be generated as the by-product. In 2014, the global market well as manipulation of reaction variables [32]. In many pro-
value of crude glycerol is approximately USD 0.12e0.15 per cesses, noble metal catalysts, i.e., palladium (Pd), ruthenium
liter while for the pure glycerol, it is between USD 0.19e0.20 (Ru), ridium (Ir), rhodium (Rh) and platinum (Pt) are always
per liter [19]. These values are expected to remain within the preferred due to their high catalytic performance. In addition,
projected range until 2020 [20]. their excellent physicochemical properties successfully sup-
The substantial production of crude glycerol not only press the coke deposition on the catalyst surface and simul-
contributes to unfeasible biodiesel production but also creates taneously prolong the lifespan of the catalysts [33,34].
environmental and disposal problems. Due to the presence of However, the utilization of noble metals leads to uneco-
impurities such as alcohol, unreacted glycerides, fatty acids, nomically feasible processes due to their limited sources and
water and catalysts, crude glycerol cannot be used directly in high price. On the other hand, catalysts based on transition
most of the applications. The purification of crude glycerol metals, i.e., nickel (Ni), cobalt (Co) and copper (Cu) are signif-
through distillation process is expensive and not economi- icantly cheaper and widely available. From the large-scale
cally feasible especially for a small-scale biodiesel plant. On industrial applications, Ni is the most conventional catalyst
the other hand, apart from the purification process, several that is widely employed in reforming reactions since this type
biodiesel plants use crude glycerol for energy generation [15] of catalyst owns a superior catalytic activity, and it is cost-
through the direct burning process. However, the process is effective and easily available. It was also found to have good
not simple since the high viscosity of the glycerol hinders the intrinsic activity and easily dispersed over the support mate-
flow, flame spray and pumping processes. The high ignition rials. The presence of Ni also helps to promote the water-gas
temperature also decreases the effectiveness of combustion shift reaction and thus, increasing the H2 production [35,36].
process and contributes to the formation of highly toxic However, the lone Ni catalysts are easily deactivated by the
acrolein. Apart from that, the residual salts produced from the coking effect and sintering of Ni clusters [37]. Therefore, the
recent works are focusing on the development of new catalyst
design through the combination of various metals to achieve
high product selectivity and good catalytic activities [38]. For
example, the development of Ni-noble metal bimetallic cata-
lyst improves the carbon resistance of the catalyst and creates
an excellence catalytic activity due to the enhancement of
metallic dispersion [35]. The physicochemical properties of
each element also significantly influenced the catalytic ac-
tivities during the reaction. The combination of Ni metals with
other transition metals, namely, Cu, Fe and Co through the
bimetallic approach results in different catalytic perfor-
mances based on their individual nature. For example, the
excellent redox properties owned by Fe have successfully
reduced the coking effect and eliminated the deposition of
carbon [39]. On the other hand, the high oxygen affinity
possessed by Co metal improves the adsorption of oxygen
Fig. 2 e Global biodiesel and crude glycerol production from species in NieCo alloys, thereby hindering the attachment of
2003 to 2020 [21]. carbon on the catalyst surface [40].
Apart from active metals and promoters, catalyst support technically proven to be less challenging. Furthermore, glyc-
is also known to be one of the important elements in the erol was found to be compatible with the existing process
catalyst design. By having a suitable morphology and physi- where only minor modifications are required on the current
cochemical properties needed for the reaction, a suitable industrial set-up [48]. Theoretically, in glycerol steam
support will be able to hinder the coke formation and yield an reforming (GSR), water vapour reacts with glycerol to produce
excellent metal dispersion. Furthermore, an appropriate mainly carbon monoxide (CO), CO2 and H2 [48,49]. The process
metal-support interaction is also needed to produce catalysts is the most favorable conversion route since the direct
with outstanding stability and reducibility properties. In order removal of H2 from water increases the selectivity and yield of
to enhance the metal-support interactions, support with a the product.
good chemical and textural properties is required to improve The valorization of glycerol via steam reforming has been
the active particles dispersion as well as prevent the catalyst one of the subjects of interest since the past 10 years. The
deactivation via the sintering and coking effects. Properties process is principally a combination between the glycerol
such as oxygen storage capacity, surface area, porosity of the decomposition as the main reaction and water-gas shift as the
materials, redox properties and thermal stability need to be side reaction [50]. This process takes place at high operating
carefully evaluated before the selection is made. Numerous temperature and atmospheric pressure and the reaction is
supports have been investigated in reforming reactions and classified as an endothermic process [43]. This process also
they cover a wide range from basic to acidic supports. On top requires substantial energy consumption for the vaporization
of all, alumina is known to be the most preferred choice due to of reactant mixtures and this condition indirectly reduces the
its high specific surface area and thermal stability. However, it energy efficiency of the process. The overall steam reforming
is also prone to deactivation due to carbon deposition and reaction is presented in Eq. (1) and notably, the process is a
catalyst sintering. The addition of alkali elements, i.e., ceria combination between the water-gas shift reaction (Eq. (2)) and
(CeO2), magnesium oxide (MgO) and zinc oxide (ZnO2) can the glycerol decomposition reaction (Eq. (3)) [51]. There is also
partially decrease the acidity of the catalysts and increase a possible occurrence of carbonaceous species, depending on
their stability [41,42]. Basic characteristic also promotes the the selected reaction conditions (Eqs. (4)e(6)) [52,53]. The
water-gas shift reaction, methane reforming and dissociation presence of other potential side reactions through methana-
of water due to the presence of oxygen lattice storage and tion (Eqs. (7)e(9)) also complicates the process.
better redox delivery [42]. Overall steam reforming reaction.
The review on catalytic conversion of glycerol to hydrogen 1
and syngas has been presented in few articles [5,7] however, C3 H8 O3 þ 3H2 O43CO2 þ 7H2 DH ¼ 123 kJ mol [1]
the scope of these reviews is focusing more on the processing Water-gas-shift (WGS) reaction:
side. Hence, in the present article, the advancement in tech-
1
nological processes for glycerol conversion into H2 and syngas CO þ H2 O4H2 þ CO2 DH ¼ 41 kJ mol [2]
will be elaborated, and major focus will be given on the role of
Decomposition of glycerol:
Ni-based catalyst in the reforming reactions. Throughout this
1
review paper, technological development, catalyst and reactor C3 H8 O3 4 3CO þ 4H2 DH ¼ 245 kJ mol [3]
designs and catalyst deactivation phenomena will be exten-
sively discussed. The role of catalysts’ supports and pro- Formation of carbon
moters will be elaborated to provide a better understanding on
1
the synergistic effect between the active metals, supports and CH4 / 2H2 þ C DH ¼ 75:6 kJ mol [4]
promoters. This understanding will subsequently help to
1
overcome the existing problems related to catalyst design and CO þ H2 4H2 O þ C DH ¼ 131 kJ mol [5]
indirectly highlights the research gap that need to be ventured
1
in the future. 2CO 4 CO2 þ C DH ¼ 172 kJ mol [6]
Methanation
Technologies of hydrogen and syngas 1
CO þ 3H2 /CH4 þ H2 O DH ¼ 206 kJ mol [7]
productions from glycerol valorization
1
2H2 þ 2CO4CH4 þ CO2 DH ¼ 247 kJ mol [8]
Glycerol steam reforming (GSR)
1
Steam reforming is the most common reaction used by the CO2 þ 4H2 4CH4 þ 2H2 O DH ¼ 165 kJ mol [9]
industry to produce H2. Commercially, 95% of the world pro- In the last decade, GSR has been actively investigated using
duction of H2 uses fossil fuels as the raw materials [43e45] and different types of catalysts, for instance transition metals (i.e.,
from this figure, 48% is generated from natural gas and the Co and Ni) and noble metals (i.e., Pt, Rh, and Ru) supported on
remainder is coming from oil and coal. As the availability of various oxides. From the literatures, Ni-based catalysts were
these conventional feedstocks is declining, biomass, particu- found to be the most preferred choice and extensively studied
larly glycerol, has become a promising replacement for the in the past few years [50,54e59]. Apart from the type of cata-
syngas and H2 productions [46,47]. Steam reforming is known lyst and support used in the reaction, the glycerol-to-water
to be an established route for H2 production. Therefore, the ratios, reaction temperature and gas hourly space velocity
diversion from the non-renewable feedstocks to glycerol is
(GHSV) are other important variables that determine the H2 between glycerol and CO2 produces H2O, CO and H2 (Eq. (10)).
yield and glycerol conversion in GSR. From the previous To ensure the reaction is thermodynamically favored, it must
studies, the yield and selectivity of the H2 production were be conducted at temperatures above ~500 C. Therefore, Eq.
found to be strongly influenced by the glycerol-to-water ra- (10) can be envisioned as the combination of reverse-water-
tios. The common glycerol-to-water ratio used in GSR varies gas shift reaction (Eq. (11)) and glycerol decomposition (Eq.
from 1/20 [60,61], 1/12 [36], 1/9 [62e64], 1/6 [6,65,66], 1/5 [67] (12)). Methane steam and dry reforming reactions are the po-
and 1/3 [68]. Theoretically, high water-to-glycerol ratio is tential side reactions that could possibly occur (Eqs. (13) and
needed to shift the equilibrium towards the production of H2. (14), respectively). Apart from that, through the decomposi-
However, too high ratios will only increase the energy and cost tion of glycerol, various chemical intermediates can be
consumptions through the substantial vaporization of water formed, for example acetaldehyde, alkanes, alcohols, acetone,
[69]. The choice of ratio used in GSR is also influenced by the ethylene, acetic acid and acrolein. At higher temperatures,
operating conditions, i.e., temperature and pressure, type of these chemicals were further converted into coke through
catalyst and support used in the system [70]. various thermal cracking processes (Eqs. (15)e(17)).
High reaction temperature is also preferred in GSR and Overall dry reforming reaction:
temperatures within the range of 525e725 C were found to 1
C3 H8 O3 þ CO2 44CO þ 3H2 þ H2 O DH ¼ 292 kJ mol [10]
give the best results [70,71]. However, high temperature is not
easily manageable and therefore, there is high possibility on Water-gas shift reaction:
the occurrence of side reactions, i.e., coking effect and sin-
1
tering of catalyst [44]. High temperature will also increase the CO þ H2 O4H2 þ CO2 DH ¼ 41 kJ mol [11]
operational costs, consumption of energy, and the cost of Glycerol decomposition:
reactor construction. On the other hand, at low operating
1
temperatures, the process experiences lower selectivity of H2 C3 H8 O3 4 3CO þ 4H2 DH ¼ 251 kJ mol [12]
due to the formation of other by-products such as CO2 and
Methane reforming:
methane (CH4). The reaction is normally conducted at atmo-
1
spheric pressure; however, vacuum pressure is more prefer- CH4 þ H2 O/CO þ 3H2 DH ¼ 206 kJ mol [13]
able as the reaction is allowed to be operated at lower 1
CH4 þ CO2 /2H2 þ 2CO DH ¼ 247 kJ mol [14]
temperatures and thus, reducing the energy consumption and
sintering of catalysts. On the other hand, the reduced GHSV is Deposition and gasification of carbon
preferred in GSR to obtain high yield of CO2 and H2 through the 1
C þ 2H2 O/CO2 þ 2H2 DH ¼ 90 kJ mol [15]
enhancement of water-gas shift reaction.
Another drawback of GSR is the significant production of 1
CO2 and CO in the generated gas. To overcome the problem, few C þ CO2 /2CO DH ¼ 172 kJ mol [16]
reaction designs have been proposed including the integrated
1
process involving the simultaneous hydrogen production with C þ H2 O/CO þ H2 DH ¼ 131 kJ mol [17]
in-situ CO2 adsorption. This process is commonly known as
Studies on GDR have been conducted using different types
sorption-enhanced glycerol steam reforming (SEGSR) where
of catalysts, i.e., Ni, Rh, Ru, Ir, Pd, and Pt supported on various
the reaction and purification processes take place in the same
oxides such as CeO2, Al2O3, ZrO2, MgAl2O4, CaO and SiO2
reactor. Few researchers have explored the potential of SEGSR
[75,78e81]. Wang et al. [26] conducted the thermodynamics
for hydrogen production [72e74] and the production of high H2
study of GDR for syngas and H2 productions. Using the Gibb
purity was reported with negligible coke formation. Advances
free energy minimization approach, the optimum conditions
on the reactor design have led to the development of SESGR
were achieved at CO2-to-glycerol (CGR) ratios of 0e1 with re-
coupled with subsequent CO2 desorption/methanation pro-
action temperatures higher than 702 C. Reaction at high
cess by Iliuta and Iliuta [74]. The is an integrated process where
pressure and CO2 loading also gives negative impact to the H2
the glycerol valorization via SESGR and CO2 conversion via
and syngas yields. Comparison study with other conventional
catalytic hydrogenation were carried out in the same reactor.
processes, i.e., GSR, GDR and microwave-assisted pyrolysis
The findings show that the proposed technology could be a
shows that the reforming processes assisted with oxidizing
potential alternative to glycerol valorization; however, in-
agents (CO2 or H2O) could yield higher glycerol conversions
depth investigation needs to be carried out as various factors,
than the lone thermal decomposition [82]. Study by Siew et al.
i.e., temperature, pressure, adsorbent, catalyst, and reactant
[78] found that the dominating reaction in GDR is the glycerol
ratios could significantly affect the process.
decomposition. Although initially the addition of CO2 seems
to increase the production rate of syngas consistent with the
Glycerol dry reforming (GDR)
reaction proposition, the glycerol conversion and hydrogen
yield production rates dropped with CGR above 1.67, which
Glycerol dry reforming (GDR) is recently getting attention
ascribed to the shift of reaction mechanism. This shifting
worldwide as one of the potential reforming routes for H2 and
process was also supported by the data of CH4 production.
syngas productions. GDR offers an attractive pathway for the
Initially the production rate of CH4 declined before plateauing
H2 production since this process utilizes biodiesel waste
at CGR of 1.67 indicating the possible CH4 production directly
(crude glycerol) and unwanted greenhouse gas (CO2) as its
from glycerol decomposition. Previous study by Lee et al. [83]
feedstocks [75]. The overall GDR process is represented by Eq.
also confirms that the glycerol decomposition is the primary
(10) [76,77]. GDR is an endothermic process where the reaction
reaction in GDR and the presence of CO2 initiated the reverse controlling the catalyst temperature and the unavoidable
water-gas shift reaction yielding H2:CO of less than 2.0, which occurrence of intermediate products decreasing the purity of
makes the process suitable for Fischer-Tropsch (FT) synthesis. the main products [86,87]. Besides that, this reaction requires
Apart from the process, catalyst and support, the H2 yield and oxygen which could contribute to the high production cost.
glycerol conversion are also directly influenced by the CO2-to- The production of syngas and H2 through the partial
glycerol ratio and gas hourly space velocity (GHSV). Previous oxidation of ethanol and methane has been extensively
studies show that an increase of CO2-to-glycerol ratio de- investigated [88e93]. In contrast, there are only few works
creases the deposition of carbonaceous species over the conducted on the partial oxidation of glycerol. Wang [94].
catalyst surface due to the equilibrium nature of GDR reaction. conducted a thermodynamics study of glycerol partial oxida-
On the other hand, an increase in GHSV reduces the glycerol tion using Gibbs free energy minimization method. From the
conversion which is possibly influenced by the coke deposi- optimization study, the highest glycerol conversion of 78.93%
tion onto the catalyst's surface [25,80]. and H2 yield of 78.93e87.31% were achieved under the
The major obstacle hindering the application of this tech- following reaction conditions: reaction temperature in the
nology is mainly due to the coke accumulation and sintering range of 727e827 C and oxygen-to-glycerol molar ratio of
of catalyst particles, which eventually cause a rapid catalyst 0.4e0.6 at atmospheric pressure. This mathematical study
deactivation. In most of the reforming reactions, the sufficient also proved that the coking effect is inevitable at low tem-
ratio of CGR is required to prevent the coking effect. Since GDR peratures and low oxygen-to-glycerol molar ratios.
normally produces a lower H2:CO ratio, the severity of coke The latest advances in glycerol partial reforming are the
deposition from this process is higher compared to other introduction of chemical looping reforming of glycerol (CLRG)
reforming processes. Thus, the development of carbon- [95]. In this process, instead of having air as the reaction
resistance catalysts should be extensively carried out to medium, the oxidation process of CLRG is carried out by the
ensure the viability of the process. solid oxygen carrier. It normally consists of two continuous
reactors, i.e., air reactor and reformer (preferably fluidized
Glycerol partial oxidation bed). The function of the air reactor is to regenerate the oxy-
gen carrier (in solid form) before being introduced to the
Partial oxidation is a reaction when a sub-stoichiometric reformer. This method produces harmless gases, i.e., N2 and
number of oxygen was reacted with glycerol to create the traces of O2 as the products while most of the H2 gas stream is
partial combustion [23]. It is an exothermic reaction and does concentrated in the solid carrier. CLRG also prevents the direct
not require any additional external heat to drive the reaction contact of glycerol with air which could possibly lead to ex-
once the reaction has been started. Eqs. (18)e(20) show the plosion or hot spot. A thermodynamic investigation on CLRG
equations for the glycerol partial oxidation. was carried out by Wang [96]. Catalysts such as CuO, NiO and
CoO were found to be excellent oxygen carriers and through
1 the mathematical simulation, these catalysts have success-
C3 H8 O3 þ O2 /2CO þ CO2 þ 4H2 O [18]
2 fully achieved the complete conversion. In CLRG reaction,
higher temperature promotes the H2 formation; however,
3 higher pressure was found to inhibit the production. These
C3 H8 O3 þ O2 /3CO2 þ 4H2 [19]
2 results give a bright future to the application of CLRG in
glycerol valorization as it is considered to be relatively low-
7
C3 H8 O3 þ O2 /3CO2 þ 4H2 O [20] priced and safer.
2
The products from partial oxidation can also be selectively Glycerol autothermal reforming
produced by varying the oxygen inputs. Due to the exothermic
nature of oxidation reaction, partial oxidation has a faster Autothermal reforming is a combination process between
start-up time compared to steam reforming [19] and thus of- partial oxidation and steam reforming reactions, in which the
fers a lower energy consumption. In addition, unlike the feedstocks including water and oxygen are charged simulta-
steam reforming, a long-time operation is allowable as the neously into the reactor. The chemical equation of glycerol
oxidative environment produced by this process prevents the autothermal reforming is written as follows [97]:
formation of coke. Nevertheless, the rapid oxygen consump-
tion and high reaction temperature promote various side re- 1
C3 H8 O3 þ 2H2 O þ O2 /3CO2 þ 6H2 [21]
actions [84]. Although this reaction can be performed without 2
the presence of catalysts, it requires a very high reaction This reaction does not require additional or external heat
temperature (>1200 C) to produce syngas. Thus, Carettin et al. supply due to the exothermic nature of oxidation reaction [29].
[85] and Rennard et al. [86] reported that high conversion and Hence, by choosing the best reaction conditions, autothermal
equilibrium compositions could be achieved with the pres- reforming can occur automatically [30,31]. According to Qi
ence of catalysts, where Ni, Pt and Rh are the most favorable et al. [98], in autothermal reforming, the reaction temperature
catalysts found from the previous literatures. However, the could be optimized by adjusting the reactant compositions
presence of local hotspots in the catalytic bed could possibly and thus preventing the catalyst deactivation. The addition of
deactivate the catalyst through the exothermic conditions oxygen during the initial reaction stage helps to increase the
initiated by the glycerol partial oxidation [38]. The high pro- H2 production favoring the glycerol reforming reaction
duction of energy during the process also leads to difficulty in [27,97,99,100]. The oxidative environment also reduces the
likelihood of coke formation and this condition could prolong GAPR is presented in Eq. (22). During the reaction, two parallel
the lifespan of the catalyst [7]. reactions which produce hydrogen was initiated as presented
Wang et al. [26] conducted a thermodynamics study on in Eq. (23) and Eq. (24). Initially the GAPR reaction starts with
autothermal reforming of glycerol for H2 production. Through the decomposition of glycerol by the cleavage of CeC and CeH
the Gibbs free energy minimization method, most favorable bonds to form adsorbed species (i.e. CO) as an intermediate.
conditions for H2 production are achieved at the oxygen-to- Then, WGS reaction took place by converting CO into H2 and
glycerol ratios of 0.0e0.4, steam-to-glycerol ratios of 9e12 CO2. Unfortunately, the competing side reactions such as
and reaction temperatures of 627e727 C. Under the proposed dehydration reaction could decrease the H2 yield through the
conditions, methanation and carbon formation are expected formation of intermediate compounds, namely, hydroxides
to diminish to a negligible level. In 2014, Liu and Lin [27] and CO [104,105]. The cleavage of CeC and CeH bonds is very
investigated the potential of two perovskite (LaNiO3 and important in GAPR reaction as these cleavages promote the
LaMnO3) catalysts for autothermal reforming of glycerol. This production of desired gases such as H2 and CO2 [106]. How-
work has successfully produced H2 from glycerol and it was ever, the occurrence of undesirable reactions including hy-
found that LaMnO3 performed better in the autothermal re- drogenation reaction is also unavoidable since the cleavage
action as it is more active, generates more heat to maintain also initiates the CO formation.
the reaction, and stable during the 24 h reaction time [24].
C3 H8 O3 þ 3H2 O/3CO2 þ 7H2 [22]
Sabri et al. [101] studied the performance of Ni-based catalysts
supported on combined metal oxides (Ce0.5Zr0.33M0.17O2-
C3 H8 O3 / 3CO þ 4H2 [23]
d where, M ¼ Ca, Mg, La, Gd and Y) in the glycerol autothermal
reforming. In this study, the oxygen-to-glycerol ratio of
CO þ H2 O/CO2 þ H2 [24]
0.2e0.8, reaction temperature of 400e700 C, and steam-to-
glycerol ratio of 6e12 were varied to obtain the best reaction The addition of catalyst in GAPR reaction helps to assist the
condition. The results indicated that the glycerol conversion splitting process of CeC bond and facilitate the displacement
and H2 selectivity increased with the increase of reaction of CO with water vapour to the catalyst's surface. This step
temperature and oxygen-to-glycerol ratio. In contrast, steam- will simultaneously increase the selectivity of H2 and from
to-glycerol ratio did not portray any significant increases in most of the GAPR literatures, platinum was found to be the
glycerol conversion, which possibly due to the dilution effect most stable catalyst [107e110]. The selection of the catalyst
of the stream whereas higher steam-to-glycerol ratio lowers must be carefully made as the oxidation of the catalyst could
the H2 production in the reformate product. Statistical anal- possibly contribute to higher surface acidity and facilitate the
ysis done by Ghani et al. [102] on the production of H2 from CeO bond cleavage. This condition results in higher selectivity
crude glycerol using 5%Ni/Ce0.5Zr0.33M0.17 (where M ¼ Gd, Ca of liquid products and alkanes [111]. According to Lin [7], GAPR
and Mg) catalysts revealed that the reaction temperature is is a structure-sensitive process and normally, transition
the most influential parameter followed by oxygen-to-glycerol metals such as Co and Ni are often used as catalysts. In most
ratio, steam-to-glycerol ratio and catalyst calcinations tem- cases, these metals are catalytically promoted with noble and
perature. The H2 selectivity was also highly influenced by the rare earth metals [112,113]. Recent advances in catalyst design
oxygen-to-glycerol and steam-to-glycerol ratios. also lead to the application of bimetallic and perovskite cat-
Autothermal reforming was also found to have a low en- alysts and their performance was found to be superior
ergy usage and able to reduce the effect of coke deposition. In compared to monometallic catalyst. GAPR is considered to be
addition, the adjustment of the product outlet-stream can be a cost-effective process because i) it does not require high
done by the modification of inlet composition. However, operating temperature as the reaction is conducted in liquid
autothermal reforming is not gaining much interest among phase, ii) the cost of the reactor is reduced due to high fluid
the researchers due to the low yield of H2 production. Ac- density, iii) the low energy requirement as it doesn't need
cording to Yang et al. [37], high reaction temperature (>700 C) additional steam to initiate the reaction and iv) the efficient
and steam-to-carbon ratio are needed to improve the yield heat recovery since pre-vaporization of reactants is not
and selectivity of H2. Nevertheless, these steps could decrease required [114]. Unlike other available reforming technologies
the glycerol conversion. The reasoning behind this phenom- in which the processes occur in the gas phase, the ability of
enon is yet to be discovered since none of the literatures is GAPR to be conducted in liquid phase provides huge benefits
focusing on the mechanism of glycerol autothermal reform- especially to biomasses with higher boiling point and longer
ing. This is probably due to the complexity of simultaneous carbon chain. As a comparison to steam reforming, the dis-
side reactions (viz., oxidation, glycerol pyrolysis and steam advantages of GAPR are due to its lower H2 selectivity resulted
reforming) in autothermal system. from lower reaction temperatures, which initiate the alkanes
formation [115]. Apart from that, the presence of inorganic
Glycerol aqueous phase reforming (GAPR) compounds in crude glycerol promotes the isomerization and
condensation reactions and further effecting the overall per-
The glycerol aqueous phase reforming (GAPR) process is formance of the reaction [7]. Therefore, future work in GAPR
another potential route for the production of fuels and H2. should be focusing on the development of catalysts to obtain
GAPR is usually conducted in a continuous stream at moder- high selectivity of H2 production and to suppress the forma-
ate temperature (200e260 C) and high pressure (20e50 bar), tion of CH4. Precious noble metals are known to be the most
where the transformation to aqueous state did not involve any favorable choice as they have high resistance towards the
pre-vaporization steps [103]. The overall reaction scheme for carbonaceous species and produce high catalytic activity.
However, their low availability and high cost limit their suffer from deactivation due to coke formation on the catalyst
application and usage [112]. Ni is an attractive and alternative surface which blocks the Ni active sites. A large number of
catalyst; however, the presence of this catalyst encourages the researchers have considered Ni monometallic and bimetallic
production of CO and methanation reactions. Additionally, systems supported on various metal oxides for glycerol
this catalyst can be easily deactivated by the deposition of reforming, aiming for high selectivity of targeted products and
carbonaceous species. The development of bimetallic (i.e., exceptional stability.
PteNi and CueNi) and perovskite catalysts has found to be an The performance of various active metals (Ni, Co and Cu)
attractive solution towards these problems. Rahman et al. has been evaluated for GSR aiming for high H2 production
[116] studied the potential of bimetallic PteNi composites [122]. Ni metal supported on SiO2 was found to be the most
supported on CeO2 doped alumina as catalyst in GAPR. active for GSR with the highest H2 selectivity (~70%) and the
1Pte6Ni/3CeAl was found to be the superior catalyst due to its highest glycerol conversion to gaseous products (~90%). The
favorable physicochemical characteristic, i.e., smaller crys- catalyst produced less liquid products compared to the Co/
tallite size, greater electronic interaction degree and higher SiO2 and Cu/SiO2 catalysts. Additionally, the H2 yield of the Ni/
metal dispersion onto the support. The presence of Pt also SiO2 almost reached to the theoretically maximum value
reduces the severity of coke deposition and prolongs the predicted by thermodynamics. Compared to Co/SiO2 and Cu/
lifespan of the catalyst. SiO2, the formation of CO2 was higher compared to the CO
formation, suggesting that WGS reaction was more favorable
when using Ni-based catalyst. In an earlier work by the same
Application of Ni-based catalysts and the roles of group [120], Ni/Al2O3 catalyst had a higher glycerol conversion
catalyst supports and promoters in glycerol to gaseous products than the Co/Al2O3 and Cu/Al2O3 catalysts.
reforming Ni/Al2O3 catalyst also exhibited the highest H2/CO with the
lowest CO/CO2 ratio. The excellent catalytic activity of Ni has
In glycerol conversion for H2 and syngas productions, the se- been associated with its remarkable ability for breaking the
lection of catalysts, supports and promoters for Ni-based CeC bonds. Nevertheless, a drastic drop within the first 7 h
catalysts plays a crucial role in determining the reaction was observed in Ni/Al2O3 activity during 20 h of a prolonged
pathways, gas-liquid products distributions and minimizing reaction when the Ni/Al2O3 deactivated at a higher rate
the catalyst deactivation. Reaction pathways and product compared to the Co/Al2O3 and Cu/Al2O3 catalysts, which has
distribution are closely related to the catalyst's catalytic ac- been associated with coke deposition. Therefore, as Ni-based
tivity towards CeC, OeH and CeH bonds cleavages as well as catalysts are widely investigated so far for GSR due to their
the acid-basic properties of the catalyst. Catalysts with high economic potential and high effectiveness in breaking the
catalytic activity for cleavages of CeC, OeH and CeH bonds, CeC, CeH, and CeO bonds, however, the challenges on the
yet with minimum cleavage of CO and facilitation of WGS are stability and coke-resistance of Ni-based catalysts are still
highly preferable for glycerol reforming [28,117,118]. Mean- inevitable. The performance of transition metals (Ni, Cu, Co
while, the selections of the supports and promoters are crucial and Fe) supported on attapulgite (ATP) clay were investigated
as they will affect the physicochemical properties, particularly for GSR [123]. Among the catalysts, Ni/ATP and Co/ATP were to
acid-base surface properties of the catalysts, thus greatly in- be more active for GSR than the Cu/ATP and Fe/ATP catalysts.
fluence the H2 yield, H2/CO ratio of gaseous products and It is suggested that both Ni and Co showed a higher capacity to
liquid products distribution [24,119]. Additionally, the surface promote the cleavages of CeC and CeH and enhance the WGS,
acidity and basicity of the catalyst are also responsible for giving the H2/CO molar ratios of these catalysts at the
minimizing catalyst deactivation as coke deposition is re- following order: Ni/ATP > Co/ATP > Cu/ATP > Fe/ATP. Addi-
ported to be highly formed on strong acid sites [120]. Similar to tionally, both Ni/ATP and Co/ATP were stable over the 24 h of
glycerol oxidation process, factors that significantly influence GSR reaction with formation of filamentous carbon on the
the glycerol conversion, product distribution and catalyst catalysts’ surface. Encapsulated carbon was found on Cu/ATP
long-life stability are (1) applications of mono-metallic and bi- and Fe/ATP catalysts, with severe deactivation occurred on
metallic catalysts, (2) basic or acidic characteristics of support, the Fe/ATP catalyst [123].
and (3) modification of metal catalysts [121]. These factors will The application of bimetallic catalysts combination in the
be elaborated further in the following sections upon discus- glycerol reforming is a promising practice to enhance glycerol
sing the role of catalyst, catalyst supports and promoters in conversion, product selectivity and catalytic stability of Ni-
glycerol reforming of Ni-based catalysts. based catalysts. Bimetallic system consists of a combination
between transition and noble metals have raised much at-
Application of Ni-based catalysts in glycerol reforming tentions due to their predominant catalytic activities. Glycerol
reactions adsorption on Ni and Pt-based systems have been theoreti-
cally evaluated where bimetallic (PteNiePt and NiePtePt),
Ni-based catalysts have attracted a considerable attention for Pt3Ni bulk alloy and Pt3NiPt surface alloy surfaces were
glycerol reforming due to their low cost and wide availability investigated for glycerol reforming reactions [124]. The activ-
compared to the noble metal catalysts. Additionally, Ni has ities of the systems have been evaluated on probe reactions of
been reported to have an outstanding catalytic activity for the glycerol reforming and resulted in the following order of
cleavage of CeC, OeH and CeH bonds and own an excellent reforming yield; NiePtePt > PtNiePtePt3Ni > Ni > Pt3-
intrinsic activity especially when it is highly dispersed over Ni > Pt > PtePtNiePt3Ni > PteNiePt. Although NiePtePt and
the support. Nevertheless, Ni-based catalysts commonly PtNiePtePt3Ni show a higher activity in the glycerol
reforming, the catalyst surfaces are non-stable thus expected catalyst for GSR. The prepared support possessed high surface
to be applicable for low temperature glycerol reforming pro- area and small crystallite size. Increasing the Ni loading up to
cesses such as GAPR that is normally performed at 200e260 C. 15 wt% Ni on the g-Al2O3 support has increased the total
The estimation of reforming yield using fundamental surface conversion of glycerol, and further increase in the Ni loading
science study is applicable as a guide for designing Ni and Pt- gave an adverse effect on the total conversion of glycerol [61].
based bimetallic catalysts for glycerol reforming. Ni-aluminate-based catalysts has been explored for GSR
Experimental work on the effect of bimetallic NieCo, where Ni/Al2O3 and NiAl2O4 have been compared with NiAl2O4
NieCu and NieZn catalysts supported on ATP has been con- supported on Al2O3 (NiAl2O4/Al2O3) and NiAl2O4 that was
ducted to attain more stable Ni-based catalysts during GSR. physically mixed with Al2O3 (NiAl2O4 þ Al2O3). Despite high
The addition of second metals to Ni has altered the crystal global glycerol conversion observed in all catalysts, only
size, the reducibility and the metal-support interaction of the NiAl2O4 and Ni/Al2O3 converted all glycerol into gaseous
catalysts where the bimetallic catalysts have shown higher products. On the other hand, NiAl2O4/Al2O3 presented a lower
glycerol conversions and H2 yields compared to the mono- conversion to gaseous products, giving the other parts of
metallic Ni catalyst. The second metals are also believed to glycerol is converted into condensable liquid by-products. H2
change the reaction pathways for GSR. With higher H2/CO and CO2 are the main products produced over all catalysts and
ratios and lower CO/CO2 ratios, it is suggested that the bime- NiAl2O4/Al2O3 was found to be the most resistant towards
tallic catalysts have improved the steam reforming reaction coke formation. Catalyst deactivation due to coke deposition
and WGS for GSR. Additionally, the bimetallic NieZn/ATP is highly affected by catalyst formulation (bulk, supported or
catalyst has demonstrated an outstanding stability for 30 h of physically mixed) and it is suggested that the assembly of
GSR reaction. This has been related to superior metal-support catalyst metal and acid-base sites is a critical factor for
interaction which has suppressed the coke formation and designing a coke-resistant catalyst [36].
sintering of active metals on the bimetallic catalyst [125]. In a The nature of the catalyst support also greatly influences
previous work aiming for more stable and optimal catalyst the surface acidity-basicity of the catalyst and thus affecting
using bimetallic NieSn/CeMgAl, the formation of NieSn alloy the reaction pathways and gas-liquid product distribution in
has successfully enhanced the stability of the bimetallic glycerol reforming. In GSR reforming using Pt catalyst, Sad
catalyst, yet with a slight decrease in the catalytic activity et al. [118] found that when the catalyst was supported on
during the GSR. This activity loss upon Sn addition is due to acidic supports such as Al2O3 and TiO2, significant amounts of
coverage of Sn species on the Ni active sites which has pre- glycerol were consumed in the dehydration-dehydrogenation
vented the adsorption of glycerol on the metallic Ni surface. reactions and hence promoting the formation of more unde-
The Sn addition, nevertheless, inhibits the reaction of coke sirable liquid products. In a study using Ni-based catalysts
formation and improves the catalyst durability during GSR for where the Ni metal was supported on various metal oxides
24 h [126]. Bimetallic NieRu/Al2O3e5CeO2 has been utilized for with different acid-base characteristics (Al2O3, SiO2, and ZrO2),
APR of glycerol and the catalyst was found to be the most Ni/Al2O3 was presented by medium to strong acid sites while
selective towards H2 with the least amount of by-products; CO Ni/ZrO2 composed of high population of weak acid sites. High
and CH4. It is suggested that Ru has promoted the utilization total neutrality was observed on NieSiO2 catalyst when it
of CO and CH4 through WGS and methane reforming, composed of both acid and basic surface sites. Ni/SiO2 and Ni/
respectively. The highest stability over 24 h under APR also ZrO2 catalysts show high H2 selectivity and low CO/CO2 ratio
observed on the bimetallic catalyst, suggesting that Ru has suggesting that catalysts with good neutrality and high weak
improved the metallic dispersion, thus contributed to the acid sites facilitate WGS reaction, producing a gas mixture
anti-coking tendency of the catalyst [35]. with a high H2/CO ratio. Meanwhile on liquid products dis-
As a conclusion, Ni has been applied as an active metal in tribution, dehydration of glycerol for formations of acrolein
most published works on glycerol reforming. Compared to and acetol, the coke precursors are favored on Ni/Al2O3 and
other metals, Ni-based catalyst exhibited the highest H2 Ni/ZrO2 catalysts, due to their acidic sites. NieSiO2, on the
selectivity with the lowest by-products; CO and CH4 in other hand, is a stable catalyst with less condensed liquid by-
gaseous products. To circumvent the effects of coking and products, attributed to its neutrality. Additionally, Ni/Al2O3
sintering of active metal on Ni catalyst in glycerol reforming, catalyst showed the most drastic deactivation due to its sur-
bimetallic system has been employed. Ni bimetallic system face acidity which is responsible for initiating coke formation
has resulted in a better catalytic activity and improved cata- [128].
lyst stability. In an aqueous phase reforming (APR) of glycerol using bulk
nickel aluminate (NiAl2O4) spinel catalyst, reduction temper-
Role of catalyst supports in Ni-based glycerol reforming ature has a significant effect on the surface acidity-basicity of
the catalyst, thus remarkably influenced the liquid product
Ni supported on alumina (Ni/Al2O3) is a predominant catalyst distribution [28]. Strong acid sites of the NiAl2O4 spinel cata-
for glycerol reforming. In a study using NieAl2O3 catalyst for lyst has been decreased with the increase of reduction tem-
glycerol reforming, the catalyst satisfactory activity towards perature causing the catalyst surface to be enriched with
acceptable glycerol conversion and H2 yield has been related medium strength acid sites. H2 is the main gaseous product in
to its nano-size Ni particles, high dispersion and catalytic all reduction temperatures applied and the gaseous products
surface area and strong interaction between Ni nanoparticles selectivity did not vary with the reduction temperature.
and the Al2O3 support [127]. Mesoporous nanocrystalline g- Nevertheless, the distribution of liquid by-product was
Al2O3 support has been synthesized and employed with Ni extensively modified. It is suggested that through reduction
temperature, surface acid-base properties would allow the activation of hydroxyl species of glycerol and 3) the presence
tuning of glycerol reforming's reaction pathways and product of various active magnesium and iron oxide species in the Ni-
selectivity. The work also suggested that accessible metallic UGS catalyst which have stimulated the WGS and coke gasi-
sites and medium strength acidic sites have contributed to the fication [132].
overall reaction scheme. Similarly, Kamonsuangkasem et al.
[129] argued that favorability towards the reaction pathways Role of promoters in Ni-based glycerol reforming
and product distribution is dependent on the bifunctional ef-
fect of metal-acid properties of the supported catalysts. GSR Surface acidity is a crucial factor in determining the coke
has been investigated on Ni/CeO2eAl2O3 catalyst using sup- deposition on the catalyst surface. The higher the acidic na-
port prepared from a single-step sol-gel method. The support ture of the catalyst, the higher the affinity of the catalyst for
produced is a well-developed mesoporous structure in CeAlO3 coke deposition. Ni catalysts have shown the highest degree of
perovskite form, which gives the high number and dispersion activity but were deactivated quickly due to coke deposition
of active sites of the catalyst. Additionally, the occurrence of [133]. Efforts have been conducted by researchers to overcome
CeAlO3 phase has resulted in the Brønsted acid sites which the problems associated with undesirable products and coke
represent the moderate acid sites on the Ni/CeO2eAl2O3 formation through the addition of additives or promoters to
catalyst. The combination of Brønsted acid sites and high Ni the Ni-based catalysts. Ni catalyst supported on Al2O3 modi-
active sites on the Ni/CeO2eAl2O3 catalyst has promoted the fied with La2O3 (Ni/La2O3eAl2O3) has been reported for GSR.
GSR reaction pathways towards hydrogenolysis and Based on conversion of glycerol to gaseous products, NieLa2-
dehydrogenation-dehydration, thus converting the interme- O3eAl2O3 catalyst was obviously more active compared to the
diate liquid compounds into more gaseous products; H2, CO, bare alumina catalyst (NieAl2O3). This is attributed to that role
CH4 and CO2. of La2O3 as a metal dispersant, thus facilitated the dispersion
The selection of support is also crucial in alleviating the of Ni in Ni-alumina system. Additionally, the presence of
effect of catalyst deactivation due to coke deposition. GSR La2O3 has reduced the acidic nature of the Al2O3 on Ni/La2-
based on Ni/Al2O3 is commonly hindered by catalyst deacti- O3eAl2O3 catalyst and favored the production of gaseous
vation due to coke deposition. This is associated to the fact products with better selectivity of H2. The addition of basic
that acidic property of Al2O3 support promotes coke formation La2O3 to Al2O3 supports was responsible for improving the
where the cleavage of CeC bonds through decomposition of stability of Ni catalyst [134].
liquid by-products occurred over the acidic sites. Nonetheless, The addition of CeO2 as a promoter to Al2O3 support has
WGS is active on catalysts supported on acidic oxides such as been investigated where Ni catalyst supported on Al2O3
Al2O3. The support offers the sites for dehydration to occur on modified with CeO2 (Ni/AlCeO3) was applied for GSR [135]. The
the acidic oxide support, producing more H2 and CO2 with less modification of Ce has increased the basicity of Al2O3 support
CO [130]. Lee et al. [83], has employed the cement clinker and improved the dispersion on Ni catalyst which has led to a
support which is composed of a basic oxide, CaO in GDR. It is high conversion of glycerol to gaseous products (60%e80%),
reported that there is a presence of strong acid-basic sites on mainly H2 and CO2, through the enhancement of WGS reac-
the Ni/CC catalyst with the concentration of basic sites 15 tion. Additionally, the Ni/AlCeO3 was more stable during 20 h
times than that for the acid sites. These strong basic sites are of GSR compared to the Ni/Al2O3 as the catalyst was more
known to be the effective coke-deposition-resistance agents. resistant towards coke deposition. A lesser amount of coke
Similarly, Arif et al. [131] found that CaO support has reduced was deposited on Ni/AlCeO3 with formation of more easily
the accumulation of coke on Ni/CaO catalyst in GDR. Basic oxidized carbon on Ni/Al2O3. Ni supported on SiO2-doped ZrO2
functional group of CaO support encourages CO2 adsorption, (Ni/SiO2eZrO2) also has been applied where the SiO2 doping
thus improves coke gasification on catalyst surface. Effect of on ZrO2 has removed the weak acidic sites of the ZrO2 support
ceria (CeO2) and zirconia (ZrO2) supports has been evaluated [134]. The doping of SiO2 also has influenced the distribution
for GDR on catalytic activity and stability. Catalyst supported gaseous of products of Ni/SiO2eZrO2 catalyst by improving H2
on ZrO2 exhibited a higher conversion and H2/CO ratio production yet not favouring the conversion of CO2 to CO.
compared to catalyst supported on CeO2. Even though CeO2 Meanwhile in liquid products analysis, acetone and acetal-
support has resulted in a lower catalytic activity, it exhibited a dehyde were the key liquid products in Ni/ZrO2 whereas Nie
superior as compared to one with ZrO2 support. The excellent SiO2/ZrO2 produced only allyl alcohol. Importantly, Ni/SiO2-
stability in the presence of CeO2 has been related to the in- eZrO2 catalyst has a higher resistance towards catalyst
hibition of coking on the catalyst surface by the mobility of O2 deactivation than the Ni/ZrO2 catalyst. In fact, the total
species and formation of oxygen vacancies on the CeO2 do- amount of deposited carbon on Ni/SiO2eZrO2 was lower by
mains [76]. Uncommon support has been also applied for GSR half to that of Ni/ZrO2 catalyst.
when Ni catalyst has been supported on upgraded titania-rich
slag (UGS). The UGS support composed of a spinel groups of
MgFe2O4 and FeAl2O4 with mutually co-exist in a Mg(AlxFe2-x) Catalyst deactivation
O4 solid solution. The catalytic activity of Ni/UGS was greater
than the activity of Ni/Al2O3, with a stable performance Catalyst deactivation is a degradation process where the
throughout 48 h of reforming reaction. The excellent feature catalyst loses its activities over time-on-stream, particularly
on this unconventional Ni/UGS has been attributed to 1) a high in chemical processes with various operating parameters.
dispersion of Ni particles due to the formation of (Ni,Mg)O Practically, the cost for catalyst replacement and procedure
solid solution, 2) basic nature of MgO which is responsible for shutdown of industrial catalytic processes could be up to
billions of dollars annually [136]. The major challenges for

reforming reactions are the potential occurrence of coke for-
mation inducing catalyst deactivation, especially on the for-
mation of carbon filaments from amorphous carbon [137].
Table 1 summarizes the inherent mechanisms of catalyst
deactivation involving fouling (i.e. coke deposition), poisoning
and sintering [138e140]. This review will be particularly
focusing on the deactivation mechanism through coke depo-
sition and sintering of metal species as poisoning rarely oc-
curs in glycerol reforming processes. This is because glycerol
itself does not contain sulfur compound or any other con-
taminants that could contribute to poisoning effect. Poisoning
generally occurs when fossil fuels i.e. diesel used as the
feedstock in reforming processes.
Catalyst deactivation via fouling/coke deposition
Fouling is a physical type of deactivation and reflects the loss

of the catalyst active surface area due to deposition of species
resulting in the blockage of sites and pores [136]. In many re-
Fig. 3 e Visual illustration of carbon deposition due to pore
action involving biomass decomposition, the phenomena are
plugging, crystallite encapsulation and fouling of a
also termed as coking. Coke deposition found to be the major
supported metal catalyst [141].
problem for the Ni-catalyzed reforming reactions due to
methane cracking and the Boudouard reactions, leading to
loss of adsorption sites on the catalyst surface. This carbon The mechanism of coke formation from CO and hydro-
lay-down has become the main complexity problem that carbons was further discussed by Kaczmarczyk and Gurgul
hinders the commercial application of reforming reaction. As [140], and Fig. 4 represents the simplified illustration for the
illustrated in Fig. 3, the chemisorption and physisorption of mechanism. The Ca is formed via hydrocarbon decomposition
the carbon results in encapsulation of the metallic active sites and CO dissociation before transforms into polymeric Cb. This
and further blocked the support pores. This blockage pro- amorphous carbon is more reactive and favored at low tem-
motes the pressure build-up in the reactor and contribute to perature and further converts into less reactive graphitic CC
loss of products which eventually resolved through the costly after a prolonged exposure at high temperature [140]. Addi-
plant shutdown. tionally, other type of carbon such as carbide, Cg and whisker-
According to Bartholomew [139], there are three types of like or vermicular carbon, Cv, formed due to the dissolution of
carbon deposition that could exist on the Ni catalyst during carbon into the bulk metal.
the steam reforming of hydrocarbon i.e. encapsulating film, Numerous studies on catalyst deactivation due to coking
whisker-like and pyrolytic carbons. The formation of these effect have been investigated but the real challenge for the
carbons occurs at certain temperature range and causes ef- complex nature of coke is always inevitable [142]. Undeniably,
fects such as breakdown of catalyst, formation of carbon the carbon formation has brought disruptive effects and
encapsulated catalyst and contribute to high DP during the hence, minimizing carbon deposition especially in industrial
reaction. Table 2 presents different types of carbon formation reactors is crucial. The increase in catalyst basicity could
that possibly occurred on Ni catalyst through the steam possibly suppress the carbon deposition due to the enhance-
reforming of hydrocarbon. ment of CO2 chemisorption of catalyst, and the reaction are
Table 1 e Types of catalyst deactivation mechanisms.

Mechanism Type Description
Fouling Mechanical Physical attachment of foreign species originated from fluid (i.e. liquid or
gas) onto the catalysts' surface and pores.
Poisoning Chemical Blockage of active sites due to the strong chemisorption bonding on the
catalytic surfaces.
Thermal degradation Thermal Loss of active phase-support reactions, support and catalytic surface areas
through the thermal degradation process.
Vapour formation Chemical Formation of volatile compound from the reaction between fluid reactants
and catalysts.
Solid-solid and vapour-solid reactions Chemical The occurrence of inactive phase from the reaction between fluid, support
or promoter with catalytic phase.
Attrition/crushing Mechanical Loss of active sites and internal surface area of the catalyst due to
mechanical activities i.e. abrasion and crushing.
further shifted towards the reverse Boudouard (or CO
Pressure build up in the reactor causes by the

disproportionation) reaction [143]. In fact, the ensemble size
required for carbon formation is larger than the reforming
Diffusion of carbon through the catalyst

reactions and thus, controlling the metal particle size could be
active sites that further contribute to

Whisker-like Carbon considered as alternative way to suppress the carbon depo-
nucleation and whisker growth.

sition [137]. Catalyst stability is also one of the main concern
Negligible adsorption of H2O

associated with coke deposition and till date, only few litera-
breakdown of the catalyst.
High reaction temperature

tures reported on the high stability of Ni-based catalyst i.e.
Low catalytic activity

more than 15 h time-on-stream [144e146]. The addition of
Low H2O:CnHm ratio

catalyst promoters such as noble metals, rare earth metals
[137] and other transition metals [25] was proven to improve
the resistance of Ni catalyst towards the coking effect. The
selection of support also plays an important role to hinder/
> 450
minimize the coking effect. Supports with good oxygen

transfer properties such as SBA-15 and MCM-41 were found to
be more stable compared to the conventional supports i.e.
alumina [147]. Apart from that, supports with excellence
textural properties and molecular composition also creates a
good metal-support interaction which further lead to reduc-
Formation of encapsulated catalyst particles
tion of coke deactivation rate [148e150]. Charisiou et al. [24]

Deposition of carbonaceous species on the
and deactivation of the catalyst; pressure
studied the doping effect of SiO2 on the Ni/ZrO2 catalyst for

catalysts' surface as the result from the
the GSR reaction. The fresh and spent catalysts were analyzed
using high angle annular dark field scanning electron micro-
thermal cracking of hydrocarbon
Pyrolytic Carbon
scopy (STEM-HAADF) as presented in Fig. 5. From the images,

the surface of both catalysts (Ni/Zr and Ni/SiZr) were clearly
High reaction temperature
High catalyst void fraction
covered with substantial amount of carbon, presented in a

Table 2 e Types of carbonaceous species in steam reforming of hydrocarbon on Ni catalyst [139].
build-up in the reactor.
form of crystalline carbon allotrope structures. Verification

Low H2O:CnHm ratio
from the temperature programmed oxidation (TPO) confirmed

Acidic catalyst
that Ni/SiZr is more resistance to coking effect as the

High pressure
accumulated carbon for Ni/Zr was found to be doubled

(0.51gcoke/gcatalyst) as compared to Ni/SiZr (0.24 gcoke/gcatalyst).
> 600
Sanchez and Comelli [151] studied on the deactivation of

Ni-supported alumina catalyst from GSR reaction. Through
the study, they found that the catalyst deactivation was
significantly influenced by the carbonaceous deposits on the
surface of the catalyst. To overcome the limitation, they pro-
posed a sequential regeneration steps involving oxidation
process to recover the catalyst active sites. The result shows
The formation of encapsulated carbon
that most of the coke deposits has successfully removed

Encapsulated Carbon Film
however, the strongly adsorbed coke was not completely

polymerization of CnHm radicals
eliminated even when the reaction is conducted at the opti-

film on Ni-surface through the
mum condition.
Low reaction temperature
The nature of supports and promoters also give significant

Progressive deactivation
influence to the level of coke deposition during the reaction

Low H2O:CnHm ratio
Low H2:CnHm ratio
[117,126]. The addition of metal with specific physicochemical

properties helps to improve the coke resistance and sintering
of Ni species. Menezes et al. [117] studied on the deactivation
of Ni-based catalyst supported on niobia, alumina and com-
< 500
bination of both. Fig. 6 shows the scanning electron micro-

scopy (SEM) images of the spent catalysts i.e. NiNbAl, NiAl and
NiNb after the reaction. Theoretically, higher amount of fila-
mentous carbon results which normally presents at lowest
oxidation temperature causes less severe deactivation
compared to surfaces with high amount of amorphous car-
Temperature ( C)
Critical variables
bon, which normally presents at higher oxidation tempera-

ture [152,153]. From the figure, an amorphous sponge-like
Formulation
coke is observed especially on the surface of NiNb and NiAl

catalysts. On the other hand, NiNbAl surface shows significant
Effect
presence of filamentous coke, indicating that the catalyst ex-

periences less severe deactivation compared to NiNb and NiAl
Fig. 4 e The formation and transformation of carbonaceous species from hydrocarbons onto the metal surfaces [139].
Fig. 5 e Morphology of the spent (a) Ni/Zr, and (b) Ni/SiZr catalysts. The red dashed circles represent the encapsulated Ni
particles [24]. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of
this article.)
spent catalysts. The finding was verified by the differential alumina and alumina-lanthana carriers in glycerol steam
thermal analysis (DTA) and thermogravimetric (TGA) analyses reforming was investigated and examination on the spent
where lower maximum oxidation temperature was observed catalyst was carried out to understand the effect of coke
on NiNbAl (~450 C) whereas for NiNb and NiAl spent cata- deposition on the activity of the catalyst. Results from SEM,
lysts, the maximum oxidation temperature of 600 C was ob- TPO and Raman analyses show the presence of different car-
tained, indicating a major presence of amorphous coke. bon structure which significantly influenced by the nature of
Overall, the addition of niobia as the support has improved the catalyst-support combination. The addition of lanthana in the
reduction degree of Ni species, Ni dispersion and successfully catalyst combination has successfully hinders the formation
reduced the coke formation. of coke precursors, oxygenates and olefins. Ni/LaAl was
The exploration on the potential of rare earth oxides i.e. mainly covered with amorphous carbon whereas for Ni/Al, the
lanthana as the catalyst support was conducted by Charisiou presence of graphitic carbon is quite apparent. The carbon
et al. [134]. In this study, the utilization of Ni supported on was mainly deposited on the support instead of the Ni
Fig. 6 e SEM images of the spent catalysts: (a) NiAl, (b) NiNb and (c) NiNbAl [117].
particles, and therefore, the catalytic performance remains steam reforming. The investigation on the effect of two
after 20 h time-on-stream. Another study by Charisiou et al. preparation methods i.e. wet impregnation and sol-gel
[128] examined the influence of support on the catalytic ac- methods were carried out and the catalyst was named ac-
tivity of Ni based catalyst for the glycerol steam reforming cording to the types of preparation method i.e. NiCeAl_IC,
reaction. The lowest carbon accumulation was surprising NiCeAl_IS and NiCeAl_SS. From the analysis on the spent
belong to the most rapidly deactivated catalyst, Ni/Al2O3 while catalysts, the amount of graphitic carbon for NiCeAl_IC is
the other two catalysts, Ni/ZrO2 and Ni/SiO2 yielded compa- found to be higher, indicating that the catalyst prepared by
rable amount of carbon. A thorough analysis was conducted wet impregnation method was severely deactivated by coke
via the Raman analysis through the calculation of graphiti- formation. Catalyst prepared by the single-step sol gel method
zation degree (ID/IG) and the results was in accordance with was pronounced as the most remarkable catalyst with the
the catalytic performance as it follows the order of Ni/Al2O3 highest catalytic activity and lowest carbon formation,
>Ni/ZrO2 >Ni/SiO2. This result brings an indication that the approximately 5e28 times lesser. Higher content of CeAlO3
quality of carbon deposited on the catalyst significantly in- was also contributed to low carbon yield since the surface
fluence the catalysts’ deactivation. Eventhough the amount of oxygen atoms of CeO2 helps to oxidize the carbon from the
graphitic carbon presented on the catalyst surface is low, they catalyst's surface.
are harder to be oxidized and in certain cases, able to totally In few special cases, whisker carbon does not directly
encapsulate the active Ni particles. The presence of rare earth contribute to the loss of catalytic activity. However, their
oxides and mixed metal oxides as the catalyst supports also presence could break the catalyst particles and block the gas
help to reduce the formation of graphitic carbon and yielding flow in a fixed bed reactor. Yus et al. [59] investigated the
carbon with lower crystallinity i.e. amorphous carbon which feasibility of using a two-zone fluidized bed reactor (TZFBR) in
are more easily oxidized [119,154]. Acidity and basicity of the GSR. This reactor was divided into 2 zones; the upper zone
support materials helps to produce high stability catalyst mainly focuses on the reforming reaction while the lower
which further helps to increase the activity and selectivity of zone is employed for the catalyst regeneration activities. The
the reaction and products. performance of TZFBR was compared with the conventional
The catalyst preparation method also plays an important fixed bed reactor under the employment of low steam/glycerol
role to create catalyst that exhibit strong resistance towards ratios. From the results, the bed plugging via coke deposition
the phase transformation, coke formation and Ni sintering. was observed in the conventional fixed bed reactor whereas in
Kamonsuangkasem et al. [129] studies the catalytic perfor- TZFBR, a longer time-on-stream was achieved without expe-
mance of Ni catalyst supported on CeO2eAl2O3 in the glycerol riencing the effect of bed plugging in spite of the coke
formation. Few regenerating gases has been tested to remove Morales-Marin et al. [28] studied on the effect of reduction
the coke deposition and it was found that water and CO2 is the temperature on the performance of nickel aluminate spinel-
best regenerating gases. derived catalyst (NiAl2O4) for the glycerol aqueous phase
The possible treatment for coke deposition is commonly reforming reaction. Based on the characterization of spent
through the oxidative catalytic treatment [132,155]. Veiga et al. catalyst, they found that the deactivation of the catalyst was
[155] conducted a regeneration study on spent Ni-promoted mainly due to Ni sintering and re-oxidation while the effect of
Fe/Mg containing metallurgical waste (Ni-UGS) catalyst ob- coke formation and metal leaching on the catalytic activity
tained from the glycerol steam reforming reaction. The was minimal. The re-oxidation of Ni species caused an
treatment condition was selected based on the results from initially fast activity decay during the initial stage of APR and
TG-MS analysis conducted on spent Ni-UGS in air atmosphere. this finding was proven by the XRD analysis of the spent
Result from TG/DTG analysis shows a total removal of carbon catalyst, where 43% of initial Ni was re-oxidized. The re-
after the regeneration process and the findings was supported oxidation of metallic Ni was also found to be greater at
by X-ray Diffraction (XRD) study as spent Ni-UGS shows higher reduction temperature and simultaneously modified
comparably similar results to the fresh Ni-UGS, indicating a the distribution of intermediate liquid and gases products.
complete recovery of the initial crystalline phase. The per- The interaction between catalyst and its support plays an
formance of the regenerated catalyst was also tested in GSR important role in producing anti-sintering catalyst. Recently,
for 4 h and similar level of catalyst performance was achieved most of the researches focus on the synthesis of new catalysts
using the regenerated Ni-UGS. through the modification on support combination and devel-
opment of bimetallic and promoted catalysts. Wang et al. [125]
Sintering (aging) studied on the catalytic performance of bimetallic Ni-M
(M ¼ Co,Cu, Zn) catalysts supported on attapulgite for the
Sintering is a process of losing the catalytic activity due to hydrogen production through glycerol steam reforming. The
structural changes in the crystals on the catalyst surface and study shows that the deactivation process was mainly due to
extensive exposure of high temperature. It is generally trig- the presence of carbonaceous elements on the catalyst sur-
gered by excessive temperatures and this irreversible process face and sintering of active species. The ability of NieZn/ATP
leads to the formation of crystal structures with lower surface catalyst to present an excellence catalytic stability during the
area [156,157]. One of the factors that contribute to the catalyst 30 h of GSR reaction was due to the unique metal-support
deactivation via sintering is the concentration of main reac- interaction that suppress the sintering of Ni species and
tant stream. In the case of supported metal catalysts, sintering inhibited the coke formation. The image representation by
process occurred due to the loss of active sites through the TEM and results from the particle size distribution also shows
deposition of metals on the supports and agglomeration of negligible difference between the mean particle size of
catalyst crystal, which narrowing the pores within the catalyst reduced and spent NieZn/ATP, indicating the outstanding
structure. There are two model descriptions for sintering anti-sintering ability of this catalyst.
mechanism, crystallites migration and atomic migration Studies on the possible deactivation routes though the
models as seen in Fig. 7. The atomic migration (see ‘A’ in Fig. 7) utilization of different types of supports was also conducted
involves the detachment of molecular metal clusters or metal by Li et al. [158]. They investigated the physicochemical
atoms from crystallites and larger crystallites forms through properties and catalytic activity of sol-gel Ni catalyst sup-
the migration of these atoms over the support surface. On the ported on TiO2, ZrO2 and Ta2O5 in the supercritical water
other hand, a sintering mechanism involving the migration of gasification of glycerol. They found that the possible factors
entire crystallites over the support surface is known as crys- that lead to the deactivation of the catalyst were probably due
tallite migration, as shown in Fig. 7 (B). This type of migration to the sintering of the supports, sintering of Ni species with
will subsequently follow by the collision and coalescence of the support and leaching of the metal catalyst. Catalyst in-situ
crystallite particles [138]. activation technique was found to successfully enhanced the
catalytic activity and coking resistance of the as-prepared
catalysts.
Examination on the possible occurrence of Ni sintering was
also conducted by Charisiou et al. [154]. Fig. 8 shows the TEM
images and histograms of particle size distribution (PSD) of Ni/
YZr and Ni/Zr reduced and spent catalysts. From the figure,
the presence of substantial amount of carbon can be clearly
seen as the images are showing different carbon morphol-
ogies i.e. carbon nanotubes (CNT) amorphous carbon and
nanofibers (CNF). Apart from that, the effect of Ni nano-
particles sintering process was also detected in Ni/Zr catalyst
as the main diameter increased form an initial value of
48.2 ± 16.2 nm to 67.9 ± 22.9 nm. The addition of Y2O3 onto the
ZrO2 support has significantly reduced the Ni sintering since
Fig. 7 e Conceptual illustration of the crystallite growth via there were only minimal increment of mean particle diameter
sintering effect: (A) atomic migration, and (B) crystallite detected.
migration [141].
Fig. 8 e TEM image and PSD analysis of the (i) reduced catalysts of Ni/YZr and Ni/Zr, (ii) spent catalysts of Ni/YZr and Ni/Zr
[154].
Apart from the selection of catalyst, the catalyst prepa- catalysts, Ni chloride/CeO2 and Ni nitrate/CeO2 were pre-
ration method also gives significant impact to the level of pared using a wetness impregnation method and the pre-
coke deposition and particle sintering during the reaction. cursors were decomposed by either glow discharge plasma
Wang et al. [159] conducted a study on the influence of technique or thermal calcination. Glow discharge plasma
preparation method for Ni/CeO2 catalyst used in glycerol treatment was found to remarkably improve the Ni disper-
steam reforming. In this study, two types of Ni-based sion and the catalyst deactivation was only found on the
calcined catalyst. The sintering effect was reportedly more zone was initially packed with Ni/Al2O3 catalyst and further
severe on NiCl/CeO2eC than NieN/CeO2eC. However, the fed with the reacting gases to initiate the reaction. The desired
coke deposition was lower on the former catalyst. Since the reaction producing hydrocarbon gases took place in the upper
activity of NieN/CeO2eC is higher compared to NiCl/CeO2eC, part of the reactor while the catalyst regeneration process
the finding shows that the deactivation behavior was signif- occurred at the lower section. During the regeneration pro-
icantly influenced by the level and type of carbon deposited cess, a regenerating gas was introduced from the bottom of
on the catalysts’ surface. the reactor. The performance of this reactor was compared
with the conventional fluidized bed and packed bed reactors.
From the results, packed bed reactor was found to experience
Reactor design severe coke deposition leading to high pressure drop and
plugging of reactor's bed. TZFBR on the other hand was
Reactor designs, geometry and configurations play an impor- operated at longer time-on-stream as compared to the con-
tant role in improving the efficiency of a process. Currently, ventional fluidized bed reactor with negligible coke formation.
packed bed reactor is known to be the most conventional These results proved that the regeneration activities have
design that is widely used for reforming of glycerol as well as successfully eliminated the coking effect. CO2 and water were
many other catalytic reactions, owing to its relatively simple found to be the most effective regenerating gases to eliminate
structure and inexpensive structure. However, this conven- the deposited carbon.
tional design suffers with the high pressure drop due to the Membrane reactors coupled with the production and
backflow of the gases associated with the accumulation of separation in one step have been the subjects of many
carbon in the system [25]. Over the decades, few researchers studies. In many reforming reactions, this type of reactor
have extensively investigated the potential of new reactor offers the capability to selectively remove one of the products
designs to improve the conversion and selectivity of the (i.e., hydrogen) from the reaction zone through the gas
product such as fluidized bed reactor [59], membrane reactor permeation concept. Chang et al. [67] studies the steam
[65] and microchannel reactor [53]. reforming of glycerol in an electroless plated Pd/Ag alloy
Yus et al. [59], studied the feasibility of two-zone fluidized membrane reactor packed with Ni/CeO2/Al2O3 catalyst. The
bed reactor (TZFBR) for GSR reaction. The design of the reactor schematic diagram of the reaction is presented in Fig. 10. The
is shown in Fig. 9. The reactor is separated into two zones process is divided into two parts, the GSR and gas permeation
including the reaction and regeneration zones. The reaction measurement. The reactor can be converted to a conven-
tional packed bed reactor by sealing the exit port of the
membrane tube. In this study, the performance of membrane
reactor is compared with the conventional reactor design. At
the optimal condition of T ¼ 800 C, weight hourly specific
velocity (WHSV) ¼ 5 h1 and water glycerol molar ratio
(WGMR) ¼ 5, the conventional reactor results in 96.24% of
glycerol conversion. Comparison between these two reactors
are made at higher pressure, i.e., 5 atm and the glycerol
conversion for membrane reactor was found to be 10e15%
higher compared to the traditional reactor. This finding will
potentially lead to massive energy saving as this type of
reactor could achieve the same extent of reaction at lower
operating temperature.
Microreactors are usually used in multiphase reactions
because of their extremely large surface to volume ratio and
excellent mass and heat transfer performances. Koc and Avci
[53] investigated the performance of non-oxidative and
oxidative glycerol steam reforming (GSR and OGSR) over Ni-
based catalyst in a microchannel reactor. The effect of
composition, reaction temperature, flow rate of the feed
mixture and metal loading was investigated through the
parametric approach to determine the best glycerol conver-
sion and product distribution. The results show that the high
amount of inlet steam has successfully reduced the coke
deposition through the gasification and WGS reactions;
however, the condition initiates the sintering of Ni particles.
Product yield and glycerol conversion for OGSR were also
notably higher compared to GSR. The use of microchannel
reactor was also found to produce higher productivities
despite using less catalyst loading and shorter reaction
Fig. 9 e Illustration of two-zone fluidized bed reactor [59]. period.
Fig. 10 e (1) computer, (2) mass flowmeter, (3) metering pump, (4) gas chromatography, (5) six-port valve, (6) preheater, (7)
soap-bubble flowmeter, (8) de-water tube, (9) cooling device, (10) back-pressure regulator, (11) membrane module, and (12)
furnace [67].
widely used in industry and only minimal alteration is

Conclusions required when the conventional feedstocks, i.e., fossil fuels
are replaced with glycerol. It produces high selectivity of H2
Challenges faced by the world on energy crisis due to the and in the same time, releases the greenhouse gas, CO2 as the
depletion of fossil fuels have led to the utilization of renew- by-product. Catalyst from GSR is also susceptible to coke for-
able sources as replacement. H2 has become one of the mation at lower operating temperature. On the contrary, GDR
attractive renewable energy sources capable of solving most reaction is considered to be more environmental friendly
of the problems related to energy crisis and environmental since it utilizes CO2 as the gasifying agent and releasing H2O as
pollution. Currently in industry, H2 is produced through the the by-product. However, due to the low H2:CO ratio and
methane steam reforming and this route is considered to be a absence of oxidation process in the reaction, the severe coke
non-renewable process as methane is derived from fossil fuels deposition is notable in GDR reaction. The utilization of oxy-
sources. Glycerol, due to its abundant availability and sus- gen in glycerol partial oxidation and glycerol autothermal
tainable nature has become one of the best substitutes for reforming has led to higher production cost although these
fossil fuel sources. Over a decade, the growing number of lit- processes are more favorable due to the low energy con-
eratures on the valorization of glycerol has been published. sumption. GAPR is the most interesting route to be explored as
The valorization of glycerol can be achieved through various the reaction is conducted in liquid phase. However, due to
routes such as GSR, GDR, glycerol partial oxidation, glycerol high pressure requirement, it significantly elevates the pro-
autothermal reforming and GAPR reactions. Each of the production and material of construction costs.
cess has its own advantages and limitations and depending on A number of technologies have been proposed to overcome
the process conditions used in the reaction, the glycerol con- all the issues related to the glycerol reforming reaction. One of
version and H2 selectivity may be varied. GSR has become the them is through the development of autothermal dry
most efficient route as steam reforming process has been
reforming of glycerol. It is a combination between the dry the conversion and selectivity of the product such as fluidized
reforming and partial oxidation processes to produce syngas bed reactor, membrane reactor and microchannel reactor.
with a high product selectivity. A thermodynamic study Recently, study on the feasibility of TZFBR in glycerol steam
shows that this process could potentially maximize the reforming reaction has been conducted and the introduction
desired product formation and diminish the formation of of regeneration zones in the reactor was found to help the
methane and carbon deposition. In most of the glycerol reforming activities, resulting in longer time-on-stream with
reforming reactions, the decomposition of glycerol was found negligible coke formation. Conventional packed bed reactor,
to be the main reaction that determines the H2 yield and on the other hand, found to experience a severe coke depo-
glycerol conversion. Through this idea, recent works on glyc- sition leading to high DP and plugging of reactor's bed.
erol valorization focus on the catalytic pyrolysis of glycerol,
where only glycerol decomposition takes place in the reaction.
The process successfully produces the desired products; Acknowledgment
however, the formation of carbon is still inevitable.
Extensive work on reforming reaction involving Ni-based The authors would like to acknowledge Ministry of Education,
catalysts shows that suitable metal combination leads to the Malaysia for awarding the FRGS research grant vote FRGS/1/
high dispersion of Ni particles and simultaneously reduces the 2018/TK02/UMP/02/12 (RDU190197) and FRGS/1/2017/TK02/
accumulation of carbonaceous species on the catalyst's sur- UMP/02/18 (RDU170119) and Universiti Malaysia Pahang
face. The use of lone Ni catalyst in glycerol reforming reaction (RDU1803118) for financial support.
could lead to severe coke deposition and sintering of Ni par-
ticles. Therefore, an in-depth study is needed to 1) improvise
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A Review On Glycerol Reforming Processes Over Ni-Based Catalyst For Hydrogen and Syngas Productions

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international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

A review on glycerol reforming processes over

Nurul Asmawati Roslan a, Sumaiya Zainal Abidin a,b,*, Asmida Ideris a,

A review of glycerol reforming reactions over Ni-based catalysts is presented.

article info abstract

fuel for gas turbines and internal combustion engines [4,5].

Fig. 1 e Global energy system transition, 1850e2150 [3].

billions of dollars annually [136]. The major challenges for

Catalyst deactivation via fouling/coke deposition

Fouling is a physical type of deactivation and reflects the loss

Table 1 e Types of catalyst deactivation mechanisms.

further shifted towards the reverse Boudouard (or CO

Pressure build up in the reactor causes by the

Diffusion of carbon through the catalyst

active sites that further contribute to

nucleation and whisker growth.

Negligible adsorption of H2O

breakdown of the catalyst.

High reaction temperature

Low catalytic activity

Low H2O:CnHm ratio

minimize the coking effect. Supports with good oxygen

tion of coke deactivation rate [148e150]. Charisiou et al. [24]

and deactivation of the catalyst; pressure

studied the doping effect of SiO2 on the Ni/ZrO2 catalyst for

scopy (STEM-HAADF) as presented in Fig. 5. From the images,

covered with substantial amount of carbon, presented in a

build-up in the reactor.

form of crystalline carbon allotrope structures. Verification

from the temperature programmed oxidation (TPO) confirmed

that Ni/SiZr is more resistance to coking effect as the

accumulated carbon for Ni/Zr was found to be doubled

Sanchez and Comelli [151] studied on the deactivation of

that most of the coke deposits has successfully removed

however, the strongly adsorbed coke was not completely

eliminated even when the reaction is conducted at the opti-

The nature of supports and promoters also give significant

influence to the level of coke deposition during the reaction

Low H2:CnHm ratio

[117,126]. The addition of metal with specific physicochemical

bination of both. Fig. 6 shows the scanning electron micro-

bon, which normally presents at higher oxidation tempera-

coke is observed especially on the surface of NiNb and NiAl

presence of filamentous coke, indicating that the catalyst ex-

widely used in industry and only minimal alteration is

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