Chemical Papers (2019) 73:2619–2635

https://doi.org/10.1007/s11696-019-00840-8

REVIEW

A review of steam reforming of glycerol

Adewale George Adeniyi1   · Joshua O. Ighalo1

Received: 26 February 2019 / Accepted: 29 May 2019 / Published online: 4 June 2019
© Institute of Chemistry, Slovak Academy of Sciences 2019

Abstract
The increase in glycerol in the global market (from increased biodiesel production) has led to a glut. Of the different meth-
ods of utilising crude glycerol, steam reforming has been explored as a viable energy generation technique. Over the years,
research has explored process optimisation, process catalysis, thermodynamics analysis, kinetic modelling, exergy and energy
analyses, techno-economic analyses, environmental performance, and computational fluid dynamics (CFD) simulations in this
regard. This paper reviewed and catalogued the current state of knowledge on the production of bio-hydrogen by the steam
reforming of glycerol obtained from transesterification while revealing key knowledge gaps. It was observed that impurities
in crude glycerol have much more negative effect on the overall yield than on the product selectivity. Impurities such as water
and methanol favour the production hydrogen. The catalysts for steam reforming are usually noble and transition metals co-
precipitated together or impregnated on metal oxides and ores. Nickel is considered as the best catalyst for the process with
temperature and pressure optimal pegged around 650–900 °C and 1 atm. Gaping gaps in knowledge abound in the research
area and these are in the domain of crude glycerol use, fluidised bed use, artificial sorbent use, pilot scale studies, cost and
profitability analysis, and investigations on carbon deposition behaviour.

Keywords  Glycerol · Steam reforming · Crude · Catalyst · Hydrogen

List of symbols bl Total number of gram atoms of element l in the

APR Aqueous phase reforming reaction mixture
G Gibbs free energy M Total number of atomic elements
T Temperature n Reaction order
P Pressure E Activation energy
ni Number of moles of species i ri Reaction rate of i
K Total number of chemical species in the reaction R Universal gas constant
mixture Ci Concentration of i
R Gas constant k0 Reaction constant
𝜇i Chemical potential of species i
yi Mole fraction of species i
ΔG0i Standard Gibbs free energy of the formation of Introduction
species i
N Total number of moles of all species in the gas The global energy demand has been on the rise and fossil-
mixture fuel reserves are depleting (Koh and Ghazi 2011). These
ali Number of gram atoms of element l in 1 mol of are the consequences of global population increase and
species i industrialization (Pambudi et al. 2013). There is an unfa-
vourable mismatch in the global demand and supply levels
of fossil-based crude (Ofari-Boateng et al. 2012). Fossil-
fuel use has also exacerbated global warming and climate
* Adewale George Adeniyi changes (Averill et al. 2010). Considering all these, focus
adeniyi.ag@unilorin.edu.ng has shifted to renewable energy sources that utilises cleaner
1
Chemical Engineering Department, Faculty of Engineering
production technologies and can serve as viable alternatives
and Technology, University of Ilorin, P. M. B. 1515, Ilorin, to fossil fuels.
Nigeria

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Vol.:(0123456789)

2620
Biodiesel has gained importance due to the adverse envi-
ronmental impact of petroleum fuels and because it can
be obtained from a renewable source (Blanco-Marigorta
et al. 2013; Tiwari et al. 2007). Biodiesel is defined as the
mono-alkyl esters of long-chain fatty acids derived from the
reaction of vegetable oils or animal fats and alcohol with
or without the use of a catalyst (Atabani et al. 2013). Bio-
diesel is bio-degradable, non-toxic, and environmentally
friendly (Dou et al. 2014). Biodiesel is obtained via the
transesterification reaction and the by-product of the pro-
cess is glycerol (­ C3H8O3). In converting vegetable oils into
biodiesel, approximately 10% (w/w) of glycerol is produced
as a by-product (Adeniyi et al. 2018; Adhikari et al. 2008a;
Behr et al. 2008). This glycerol is crude as it comes with
various impurities usually 10–30% (Dou et al. 2014). The
nature and volume of the impurities depends on the nature
of the feedstock and catalyst used in the process (Thompson
Fig. 1  Biodiesel and glycerol production (Bagnato et al. 2017)
Fig. 2  Percentage distribution
of the main glycerol applica- Poly-urethane
tions found in the open litera- 7%
ture (Bagnato et al. 2017) Pharmaceutical
8%
Tobacco
9%
Alkyl Resin
9%
13
Chemical Papers (2019) 73:2619–2635
and He 2006; Yang et al. 2012). The crude glycerol usually
has a dark colour and contains variable amounts of soap,
catalyst, alcohol (typically methanol), mono-glycerides, di-
glycerides, glycerol oligomers, polymers, water, unreacted
triacylglycerol, and biodiesel (Schwengber et al. 2016).
From Fig. 1, we observe the rise in biodiesel produc-
tion from year 2000 and then a steep increase in produc-
tion beyond 2005 (Bagnato et al. 2017). Europe still has the
greatest share in the global output of biodiesel. This increase
in glycerol in the market (due to increased biodiesel produc-
tion) has led to a glut in the global market (Johnson and
Taconi 2007). The glycerol price dropped by two-thirds
within the last decade (Adhikari et al. 2007b) because of
surplus amounts in the market and is still dropping in the
current decade. Currently, there are many applications of
pure glycerol and these include personal care products, food,
oral care, tobacco, and polyurethane production (Adhikari
et al. 2007a). From Fig. 2, we see that cosmetics (37%) and
food (25%) are the major applications of the product (Bag-
nato et al. 2017). Unfortunately, commercial development of
alternative processes for pure glycerol utilization has been
limited, as the price of glycerol purification has made it eco-
nomically unattractive as a feedstock chemical (Johnson and
Taconi 2007; Thompson and He 2006). Most by-product
glycerol is sent to water treatment for digestion. It can also
be purified by distillation, though this is expensive process
and uneconomic (Slinn et al. 2008). Other alternative uses
of glycerol include its conversion to of esters, ethers, acetals,
ketals of glycerol, diols, epoxides, aldehydes, ketones, and
carboxylic acids (Behr et  al. 2008). Reactions involves
hydrogenolysis (Chaminand et al. 2004; Dasari et al. 2005),
selective oxidation (Chaminand et al. 2004; Pagliaro et al.
2007; Zhou et al. 2008), etherification (Pagliaro et al. 2007),
dehydration (Pagliaro et al. 2007), pyrolysis and gasification
Others
5%
Cosmetics
37%
Food
25%
Chemical Papers (2019) 73:2619–2635 2621
(Zhou et al. 2008), and carboxylation (Zhou et al. 2008)
amongst others. Glycerol can also be utilised in biochemi-
cal conversion processes (such as fermentation) to obtain
useful biochemical like succinic acid, propionic acid, citric
acid, ethanol, dihydroxyacetone, among others (Bagnato
et al. 2017; Da Silva et al. 2009; Ito et al. 2005; Yazdani and
Gonzalez 2007). It can also be added in ruminant and non-
ruminant animal diets (Yang et al. 2012).
One viable and proven possibility is using it as a source
for the production of hydrogen via the steam-reforming
process (Behr et al. 2008). Bio-hydrogen (hydrogen gas
obtained from bio-sources and bio-processes) are viable
options for the future due to their theoretically carbon–neu-
tral and renewable nature (Adeniyi and Ighalo 2019). Bio-
hydrogen poses no environmental problem and also does not
contribute to atmospheric carbon dioxide emissions (Chat-
tanathan et al. 2012). Besides glycerol, other bio-sources
have been proved to be good feedstock for steam reform-
ing such as bio-oil (Adeniyi et al. 2019; Chen et al. 2016;
Fu et al. 2014; Remón et al. 2015; Wang et al. 1997; Xie
et al. 2016), vegetable oils (Yenumala and Maity 2011), and
other oxygenated organic compounds (Abdullah et al. 2014;
Hoang et al. 2015; Iwasa et al. 2010; Nabgan et al. 2016;
Thaicharoensutcharittham et al. 2011; Shurong Wang et al.
2015). At present, almost 95% of the hydrogen produced is
obtained from fossil-fuel-based feedstock (Adhikari et al.
2007c) and global hydrogen demand is growing due to the
technological advancements in fuel cell industry (Adhikari
et al. 2007c). Hydrogen gas possesses the highest energy
content per unit of weight (120.7 kJ/g), compared to any
of the known fuels (Haryanto et al. 2005). Other reforming
techniques includes autothermal reforming (ATR), supercrit-
ical water reforming (SCWR), partial oxidation reforming
(POR), liquid-phase reforming (LPR), and chemical looping
reforming (CLR) (Schwengber et al. 2016).
Over the years, the steam reforming of glycerol has been
studied by researchers. These studies have come in the
domain of energy and exergy analyses (Hajjaji et al. 2014),
kinetic modelling and thermodynamic analysis (Adhikari
et al. 2007a, b; Chen et al. 2009; Da Silva and Müller 2011;
Patel et al. 2013; Wang et al. 2008; Wang et al. 2010; Yang
et al. 2011; Yenumala and Maity 2011), sorption enhance-
ment techniques (Da Silva and Müller 2011; Dou et  al.
2009), catalysis and the minimisation of carbon deposition
(Adhikari et al. 2007a, c, 2008a, b, 2009; Cheng et al. 2010;
Chiodo et al. 2010; Dave and Pant 2011; Hirai et al. 2005;
Nichele et al. 2012; Pompeo et al. 2010; Profeti et al. 2009;
Zhang et al. 2007), and process simulations (Adeniyi and
Ighalo 2018; Dou et al. 2008; Dou and Song 2010). Bagnato
et al. (2017) presented a critical review of glycerol steam
reforming though with a greater emphasis on the overall pro-
duction and application of the liquid. The aim of this paper
is to review and catalogue the current state of knowledge
on the production of bio-hydrogen by the steam reforming
of glycerol and to elucidate possible knowledge gaps and
future perspectives.
Glycerol steam‑reforming theory
Glycerol ( C3 H8 O3 ) is also known as 1,2,3-propane tri-ol or
glycerine. The chemical structure is presented in Fig. 3.
Steam reforming is a high-temperature process whereby
glycerol is converted to a hydrogen-rich gaseous product
known as synthesis gas. The general expressions for the
equation of reaction of the steam reforming of any oxygen-
ated organic compound were presented by Czernik et al.
(2002):
m
( )
Cn Hm Ok + (n − k)H2 O ↔ nCO + n + − k H2 . (1)
2
The chemical reactions involved in the steam reforming
of glycerol into synthesis gas are well understood and have
been previously outlined in the literature (Dave and Pant
2011; Pompeo et al. 2010; Slinn et al. 2008; Vaidya and
Rodrigues 2009):
ΔH0r = + 250 kJ/mol . (2)
( )
C3 H8 O3 ↔ 3CO + 4H2
Overall reaction for glycerol steam (Adhikari et  al.
2007c, 2008b; Slinn et al. 2008) is presented in the follow-
ing equation:
C3 H8 O3 + 3H2 O → 7H2 + 3CO2 ΔH0r = + 128 kJ/mol .
( )
(3)
Due to excess steam in the process, the carbon monoxide is
oxidised to carbon dioxide also leading to the evolution of
more hydrogen gas. The equation is reversible, and hence,
both species do exist in the system at dynamic chemical
equilibrium. This is known as the water–gas shift reaction:
(4)
( 0 )
CO + H2 O ↔ CO2 + H2 ΔHr = − 41 kJ/mol .
At low temperatures, methanation can occur whereby some
of the hydrogen produced combines reversibly with the oxy-
genated compounds in the system to give methane:
CO + 3H2 ↔ CH4 + H2 O
( 0 )
ΔHr = − 206 kJ/mol ,
(5)
Fig. 3  Chemical structure of glycerol
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2622 Chemical Papers (2019) 73:2619–2635

Table 1  Typical composition of crude glycerol (in wt%)

( 0 )
CO2 + 4H2 ↔ CH4 + 2H2 O ΔHr = − 165 kJ/mol . Components Slinn et al. Veiga and Bussi Veiga
(6) (2008) (2016) et al.
This reaction is exothermic, and, hence, will be favoured at (2017)
low temperatures as opposed to the steam-reforming reac-
Glycerol 33% 64% 64%
tions that are endothermic and favoured by higher tempera-
Fatty matter 40% – –
tures (Adeniyi and Ighalo 2018). Similarly, higher molecular
Methanol 23% < 5% < 5%
weight hydrocarbons can be synthesised during the process
water 3.2%
especially at low temperatures and for heavier feeds. At high
Ash 3.8%
temperatures, coke formation occurs in the system and can
Inorganic salts – 5.7% 5.7%
lead to depositions on the catalyst surface and subsequent
Polyglycerol – 26% 26%
inactivation. Carbon deposition is a very serious challenge
in catalytic steam-reforming systems utilising heterogeneous
catalysts. The deposited carbon on the surface of the solid
catalyst prevents reactants from gaining access to active alongside the negative effect of the carbon source from
sites thereby reducing the catalyst activity. Possible reac- the fatty matter, then the 30% lower value is justified. The
tions leading to carbon deposition in the steam-reforming negative effect of the carbon source from the fatty matter
system (Adhikari et al. 2007b; Schwengber et al. 2016) are is because long-chain fatty acid impurities are harder to
mentioned in the following equations: reform and are more likely to form carbon. It was, however,
recommended in the study that harsher reaction conditions
(7)
( 0
such as longer residence time and higher temperatures and
)
2CO ↔ CO2 + C ΔHr = − 172 kJ/mol ,
S/C ratios should be utilised when crude glycerol is used
as feedstock to overcome the negative effect of the impuri-
(8)
( 0 )
CH4 ↔ 2H2 + C ΔHr = + 75 kJ/mol , ties. Im general, impurities such as water and methanol in
the crude glycerol favour the production hydrogen from the
steam-reforming process. Impurities such as biodiesel cata-
(9)
( 0 )
CO + H2 ↔ H2 O + C ΔHr = − 131 kJ/mol .
lyst and unreacted triglycerides contribute to the increase in
coke formation and catalyst deactivation (Veiga and Bussi
2016).
Composition of crude glycerol

The information in Table 2 (column 2) reveals that most

Process input and performance parameters
studies on the steam reforming of glycerol utilised pure and
analytical grade product for their study. Only three stud-
In steam-reforming studies, several parameters are used to
ies examined glycerol in its crude form (Slinn et al. 2008;
represent the nature of feed input as well as the performance
Veiga and Bussi 2016; Veiga et al. 2017). Adhikari et al.
of the process. A few of these parameters have been item-
(2007c) commented that pure glycerol was used in their
ised in other steam-reforming reviews (Adeniyi et al. 2019)
study instead of crude to avoid the complexity associated
albeit for other feedstock. In this section, we will present
with the interpretation of results. This can be an underlying
the steam-reforming indices as it applies to studies involv-
reason why most other studies followed suit. Typical compo-
ing glycerol feedstock. Key input parameters for the steam
sition of crude glycerol obtained from biodiesel production
reforming of oxygenated compounds are the steam-to-car-
is presented in Table 1. These results are only restricted to
bon (S/C) ratio, temperature, pressure, and catalyst loading:
studies where the glycerol is considered as feedstock for the
steam-reforming process. S/C =
Amount of steam
. (10)
In the study by Slinn et al. (2008), it was observed that Total amount of carbon in the feed (wet basis)
the selectivity of the chemical species in the product stream
The steam-to-carbon ratio (S/C) in mass or moles can
does not change much for pure versus crude glycerol given
be defined as the ratio of the amount of steam to the total
the same set of process conditions. However, the overall
amount of carbon in the feedstock (including the water con-
product yield from the process was observed to be 30%
tent). Several studies on glycerol steam reforming prefer a
lower when crude glycerol is used. The crude glycerol
similar term known as the water–gas feed ratio (WGFR or
composition (see Table 1) reported by Slinn et al. (2008)
WGR) (Adeniyi and Ighalo 2018; Adhikari et al. 2007b).
only contains a 55% alcohol content. If we consider this
The difference is the change in the organic basis from the

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Chemical Papers (2019) 73:2619–2635 2623

Table 2  Summary of process conditions for glycerol steam reforming

References Nature of glyc- Process parameters Catalysts
erol feed
Temperature Pressure Space time/vel Water–glycerol
molar ratio

Hirai et al. (2005) Analytical 500–600 °C 1 atm 80 L/g h S/C of 3 Ru/Y2O3

grade
Adhikari et al. Pure 327–727 °C 1–5 atm – 1–9 Ni/MgO
(2007b)
Zhang et al. (2007) Pure 250–600 °C 1 atm 11 L/g h 9 Ir/CeO2, Co/CeO2, Ni/CeO2
Adhikari et al. Pure 600–900 °C – – 3–9 Al2O3, Rh/Al2O3, Pt/Al2O3,
(2007c) Pd/Al2O3, Ir/Al2O3, Ru/
Al2O3, Ni/Al2O3, Ce/Al2O3,
Rh/Ce/Al2O3, Pt/Ce/Al2O3,
Pd/Ce/Al2O3, Ir/Ce/Al2O3,
Ru/Ce/Al2O3, Ni/Ce/Al2O3
Slinn et al. (2008) Crude and Ana- 600–900 °C – – S/C of 1.35 Pt/Al2O3
lytical grade
Adhikari et al. Pure 550–650 °C – – 6–12 Ni/MgO, Ni/CeO2, Ni/TiO2
(2008b)
Adhikari et al. Pure 550–650 °C – – 6 Ni/MgO, Ni/CeO2, Ni/TiO2
(2008a)
Dou et al. (2009) Analytical 400–700 °C 1 atm – S/C of 3 Ni/Al2O3
grade
Adhikari et al. Pure – – – – Ni/CeO2
(2009)
Pompeo et al. Pure 250–700 °C 1 atm 0.2–6 min – Pt/SiO2, Pt/γ–Al2O3, Pt/ZrO2,
(2010) Pt/Ce4Zr1α
Cheng et al. (2010) Pure 450–550 °C 1 atm 50 L/g h 30–60 wt% glycerol Co/Al2O3
in water (or S/C
of 1.1–4)
Chiodo et al. (2010) Pure 450–750 °C 1 atm 5–30 L/ml h S/C of 3 Ni/γ-Al2O3, Rh/γ-Al2O3, Ni/
MgO, Ni/CeO2
Dave and Pant Pure 600–700 °C 1 atm 0.96–1.92 kgcat h/ 10–20 wt% glycerol CeO2, ­ZrO2, ­ZrO2/CeO2, Ni/
(2011) Kmolfeed in water CeO2, Ni–ZrO2/CeO2
Nichele et al. Pure 500–650 °C 1 atm – 10 wt% glycerol in Ni/ZrO2, Ni/TiO2, Ni/SBA-15
(2012) water
Ciftci et al. (2014) Pure 130–400 °C (600 rpm, for 13,000/h 50 wt% glycerol in Pt/CeO2, Pt–Re/CeO2, Pt/Ce-
APR) water ZrO2, Pt–Re/Ce-ZrO2, Pt/
ZrO2, Pt–Re/ZrO2, Pt/TiO2,
Pt–Re/TiO2
Pairojpiriyakul Analytical 450–575 °C 25 Mpa 3.15–10.8/h 2.5–10 wt% glyc- Ni/α–Al2O3, Ni/γ–Al2O3, Ni/
et al. (2014) grade erol in water La2O3, Ni/ZrO2, Ni/YSZ
De Rezende et al. Pure 600 °C 1 atm – 9 PtMgxAl-H, PtMgxAl-O
(2015)
Gallegos-Suárez Pure 200 °C 1 atm – 10 wt% glycerol in Ni/CeO2
et al. (2015) water
Veiga and Bussi Crude 650 °C 1 atm – S/C of 3.7 Ni–Mg/AC, Ni–Y/AC,
(2016) Ni–La/AC (AC activated
carbon)
Suffredini et al. Pure 600 °C – – 12 Ni/Al2O3, ­NiAl2O4, ­NiAl2O4/
(2016) Al2O3, ­NiAl2O4 + Al2O3
Pastor-Pérez and Pure 350 °C 1 atm – 10–30 wt% glycerol Pt–Sn/C
Sepúlveda-Escrib- in water
ano (2017)
Ni et al. (2017) Pure 550 °C – 2.28/h S/C of 3 NiO/NiAl2O4, NiO/ZrO2
Bepari et al. (2017) Pure 450–550 °C 1 atm 5.62–10.84 kgcat h/ 8–14 Ni/Fly-ash
Kmolfeed

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2624 Chemical Papers (2019) 73:2619–2635

Table 2  (continued)
References Nature of glyc- Process parameters Catalysts
erol feed
Temperature Pressure Space time/vel Water–glycerol
molar ratio

Buffoni et al. Pure 450 °C 1 atm 14.7/h S/C of 1.6–15 Pt/SiO2-C

(2017)
Charisiou et al. Analytical 400–750 °C 1 atm 50 L/g h 31 v.v.  % glycerol Ni/Al2O3, Ni/La2O3-Al2O3
(2017) grade
Kousi et al. (2017) Pure 400–600 °C 1 atm 0.45 mg/ml min 20 Ru/Al2O3, Ru/B2O3–Al2O3,
Ru/MgO–Al2O3
Kumar et al. (2017) Pure – – – 5 vol% glycerol in TiO2
water
(Veiga et al. 2017) Crude 500–650 °C 1 atm 20 L/g h S/C of 3.7 Ni–La–Ti
Callison et al. Pure 240 °C (1000 rpm, for – 10 wt% glycerol in Pt/Al2O3
(2018) APR) water
Jiang et al. (2018) Pure 650 °C – 250/h S/C of 3 Ni/ZrO2, Yb–Ni/ZrO2, Pr–Ni/
ZrO2, Ce–Ni/ZrO2, La–Ni/
ZrO2
Karakoc et al. Pure 650 °C 1 atm – 6–15 Ni/CeO2, Ni/Al2O3, Ni/SiO2
(2018)
Seadira et al. Analytical – – – 5 vol% glycerol in TiO2, Ni/TiO2, Cu/TiO2, Co/
(2018) grade water TiO2, Ag/TiO2, Cr/TiO2

carbon content of the glycerol to the entire moles of the Selectivity is always based on the product, while yield is
glycerol itself. This is reasonably easier to compute. It is based on the input. For more specific computations apply-
expressed in Eq. 11 in terms of moles and can be referred to ing to glycerol steam reforming, we apply the following
as water–gas molar ratio (WGMR) (Adhikari et al. 2008b): equations:
Moles of water Moles of H2 produced
WGR =
Moles of glycerol in the feed
. (11) % H2 selectivity =
C atoms produced in the gas phase
1
Temperature increase favours hydrogen selectivity until × × 100%, (14)
RR
a threshold is exceeded. The best pressure condition for the
process is ambient pressure. Higher steam-to-carbon ratio where RR is H ­ 2/CO2 reforming ratio and it is 7/3 in the case
usually increases the hydrogen selectivity too. The fac- of glycerol steam-reforming process:
tors have different ways of interacting as regards the other Moles of H2 produced
chemical species. Detailed factor-interaction studies for each %H2 yield = × 100%, (15)
Maximum moles of H2 (= 7)
chemical species have been conducted (Adeniyi and Ighalo
2018; Adhikari et al. 2007a, b; Wang et al. 2008).
Glycerol in − Glycerol out
The general performance parameters for steam reforming Glycerol conversion = × 100%.
Glycerol in
are hydrogen gas selectivity or hydrogen gas yield. It is the
(16)
percentage (%) molar or mass composition of hydrogen in
the product stream: In some studies, percentage glycerol conversion into gaseous
products was used. This was elucidated as Eq. 19:
Amount of X produced
%X selectivity = × 100%, Gly conv to gaseous products
Total amount of syn-gas (dry basis)
(12) C stoms in gaseous product (17)
= × 100%.
C atoms produced in the gas phase
Amount of X produced
%X Yield = × 100%, (13) The terms explained in this section are all widely used
Total amount of feed
in steam-reforming studies in general and glycerol steam
where X can be hydrogen ( H2 ), carbon monoxide (CO), car- reforming in particular. Even in this review, these param-
bon dioxide ( CO2 ), methane ( CH4 ), or any other chemical eters are referred to in virtually all sections. A proper reader
species present in the product stream. The ‘amount’ can be understanding of these parameters is foundational in obtain-
in moles or grams depending on the basis of calculations. ing a proper appreciation of the current work.

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Process conditions
Research work on the steam reforming of crude glycerol has
a vast array of process conditions. These conditions include
the type and nature of catalyst used, process temperature,
pressure, steam-to-carbon ratio, space time or velocity, and
the presence of a ­CO2 sorbent. In this section, an exami-
nation of these conditions and the way which they affect
the steam-reforming process are presented. Table 2 gives
a summary of the domain of process conditions examined
in empirical studies and presented in a chronological order.
Catalyst
The catalysts for steam reforming are usually noble and
transition metals co-precipitated together or impregnated
on metal oxides and ores. In most cases reported, incipient
wetness technique (Adhikari et al. 2007c, 2008a) also known
as wet impregnation technique (Adhikari et al. 2008a; Cheng
et al. 2010) was the impregnation techniques used. There
have also been reports of the use of anionic and cationic
exchange (Pompeo et al. 2010), micro-emulsion (Gallegos-
Suárez et al. 2015), homogenous precipitation (Jiang et al.
2018), sol–gel (Buffoni et al. 2017), and the deposition–pre-
cipitation method (Zhang et al. 2007) for catalyst prepara-
tion. The support is also as important as the metal catalyst
itself as it exercises a certain level of catalytic activity espe-
cially at lower reforming temperatures (Kousi et al. 2017).
The performance of the catalyst with respect to catalyst
deactivation and sintering is also affected by the nature of
the support. Adhikari et al. (2007c) was able to show that the
type of catalyst used will affect both the hydrogen electiv-
ity in the product and the over conversion of the feed. This,
of course, is one of the fundamental reasons for catalysis.
From Table 2, we can observe that the most studied metal
catalyst for the steam reforming of glycerol is Nickel. The
study by Adhikari et al. (2007c) was quite foundational to
this research trend. This will be examined in the foregoing
paragraphs.
Adhikari et al. (2007b) utilised Ni/MgO as a catalyst for
the process. The performance of the catalyst in the domain
of hydrogen production was poorer than thermodynamic
predictions. Zhang et al. (2007) tested Cobalt, Nickel, and
Iridium in a ceria oxide matrix support as catalyst for glyc-
erol steam reforming. Though the performance of all three
catalysts was considered excellent for hydrogen production,
the Ir/CeO2 was the best of the three. This was ascribed to
the better and more intimate contact between Iridium parti-
cles and Ceria based on the Ceria-mediated redox process.
The study by Adhikari et al. (2007c) was quite exhaustive
in the domain of catalysis. They studied the performance
of seven different metals on alumina support in a variety
of combinations for use in glycerol steam reforming. The
catalysts studied were A­ l2O3, Rh/Al2O3, Pt/Al2O3, Pd/Al2O3,
Ir/Al2O3, Ru/Al2O3, Ni/Al2O3, Ce/Al2O3, Rh/Ce/Al2O3, Pt/
Ce/Al2O3, Pd/Ce/Al2O3, Ir/Ce/Al2O3, Ru/Ce/Al2O3, and Ni/
Ce/Al2O3. The study revealed that Ni/Al2O3 has the best
selectivity for hydrogen compared to the other noble metals.
When the far cheaper cost of Nickel is considered in relation
to the noble metals, the extensive interest in nickel-based
catalyst observed in Table 2 is seemingly justified. Based
on their premise, most future studies continued to pay close
attention to Nickel catalysts in the steam-reforming process.
Haven earlier established the superiority of Nickel (Adhi-
kari et al. 2007c) over other metal catalysts, Adhikari et al.
(2008b) proceeded to study the performance of various metal
oxides as catalyst support for the Nickel catalyst. MgO,
­CeO2, and ­TiO2 were considered. The BET surface areas of
the developed catalyst were 67, 50.2, and 64.9 m2/g for Ni/
CeO2, Ni/MgO, and ­TiO2, respectively. The best catalyst of
the three was shown to be Ni/CeO2 (Adhikari et al. 2008a,
b). The maximum ­H2 selectivity was 74.7% with Ni/CeO2 at
a water–gas molar ratio (WGMR) of 12:1 and temperature of
600 °C. The conversion of Glycerol was over 99% at these
conditions. In a continuation of the investigations on Nickel,
Chiodo et al. (2010) studied Ni/γ–Al2O3, Rh/γ–Al2O3, Ni/
MgO, and Ni/CeO2 for glycerol steam reforming. They
observed that Rh/γ–Al2O3 is more stable than the Ni cata-
lysts and coke formation is lesser when the catalyst is used.
Dave and Pant (2011) compared C ­ eO2, ­ZrO2, ­ZrO2/CeO2,
Ni/CeO2, and Ni–ZrO2/CeO2 for glycerol steam reform-
ing. In the domain of the comparison, Ni–ZrO2/CeO2 was
observed to be the best in terms of glycerol conversion and
hydrogen yield. In recent times, a plethora of studies have
also studied different catalyst support for Nickel catalyst (see
Table 2). In light of these, it can be surmised that nickel is
the best metal catalyst for the steam reforming of glycerol.
Quite recently, Seadira et al. (2018) considered several metal
catalysts on T
­ iO2 support for the photocatalytic reforming of
glycerol. They evaluated ­TiO2, Ni/TiO2, Cu/TiO2, Co/TiO2,
Ag/TiO2, and Cr/TiO2. The ­TiO2 support was in the form of
nano-structured hollow spheres. The researchers made this
choice, because, in that form, incorporating metals reduces
the band energy gap of the material for visible light harvest-
ing and slows down the rate of electron/hole recombina-
tion, thereby increasing the photocatalytic activity. Cu/TiO2
showed highest activity for hydrogen production from the
process.
Temperature
The temperatures studied are in wide variations. This is
because studies focus on different aspects of the process,
such as catalyst performance (selectivity and activity),
carbon deposition or process optimisation, and/or product
13

2626
selectivity. In a study of process factors, Adeniyi and Ighalo
(2018) observed that hydrogen yield will increase with tem-
perature. And beyond an optimal temperature, the hydrogen
production gradually drops will temperature. This is as a
result of other competing reaction such as high-temperature
thermal cracking of oxygenates, reverse WGS, and some
of the coke deposition reactions. Temperature is the most
studied factor in steam-reforming systems, and its effect
on product yield and selectivity is already well understood.
Adhikari et al. (2007b) examine the effect of temperature
on the selectivity of each of the constituents in the product
stream albeit in a comparative study between experiments
and thermodynamic results. Though the same trend as that
of Adeniyi and Ighalo (2018) was observed for tempera-
ture, the study was able to pinpoint that Ni/MgO catalyst is
not effective enough as its hydrogen yield is comparatively
poorer than thermodynamic predictions. Slinn et al. (2008)
observed that high yields and hydrogen selectivity can be
obtained at higher temperatures not only for pure glycerol
but for crude glycerol too. From their study, Chiodo et al.
(2010) concluded that it is more convenient to carry out
steam reforming of glycerol at temperature not higher than
650 °C despite favourable thermodynamics due to coking
and thermal cracking of species. Encapsulating carbon is
deposited on the surface of the catalysts at higher tempera-
tures which subsequently reduces the catalyst stability.
Pressure
Thermodynamic analysis has revealed that atmospheric pres-
sure is optimum for hydrogen production, and hence, most
studies stick with this (Adeniyi and Ighalo 2018; Wang et al.
2008; Yang et al. 2011). Adeniyi and Ighalo (2018) observed
that optimal hydrogen production will be obtained at atmos-
pheric pressure, while methane production was favoured at
higher pressures. The CO and ­CO2 in the system were fairly
insensitive to pressure changes. Chemical equilibrium of the
system will shift in favour of the lighter chemical species at
lower pressures and vice versa (Adeniyi et al. 2019). Since
hydrogen is the most desired chemical species in the product
stream (and the lightest too), it would only be practical to
keep the system pressure at atmospheric conditions. This
is also desirable, considering that it is cheaper to design
systems to operate at this condition. Due to this already well-
established knowledge on steam reforming, pressure effects
is scarcely studied in empirical steam-reforming research. In
silico studies still consider pressure though.
Steam‑to‑carbon (S/C) ratio
The steam-to-carbon ratio is sometimes as weight percent
(Cheng et  al. 2010; Dave and Pant 2011; Nichele et  al.
13
Chemical Papers (2019) 73:2619–2635
2012) and molar ratio (Adhikari et al. 2007a, b, c, 2008a,
b). However, some researchers still use steam-to-carbon
ratio (S/C) (Chiodo et al. 2010; Dou et al. 2009; Hirai et al.
2005; Slinn et al. 2008) which is more popular in bio-oil and
methane reforming papers. Adhikari et al. (2007c) showed
that the higher the S/C or STGR, the higher the conver-
sion and hydrogen yield from the system. This is because a
higher amount of steam in the system will invariably favour
the water–gas shift reaction. Pairojpiriyakul et al. (2014)
expressed the S/C ratio in terms of glycerol concentration
in the feed. It should be noted that this parameter is the
opposite of S/C ratio (which is a measure of water concen-
tration in the feed). It was observed from their study that
increasing the glycerol feed concentration reduced hydrogen
yield and increased methane yield albeit for supercritical
water reforming. This also holds for the conventional steam
reforming (Bepari et al. 2017).
Spacetime and space velocity
The spacetime will always show a reverse relationship to any
space velocity effects. Higher velocities of the feed indicate
lesser space time and vice versa. That being said, increas-
ing the contact time of feedstock with catalyst (decrease the
weight hourly space velocity or increasing the space time)
will lead to a higher yield of hydrogen. Dave and Pant (2011)
elucidated an increase in glycerol conversion and hydrogen
yield with increase in spacetime. The exact same trend was
also observed by Pompeo et al. (2010) and Bepari et al.
(2017). Slinn et al. (2008) gave an interesting interpretation
of the effect of spacetime and velocity on the product selec-
tivity and yield. It was explained that the reactant molecule
will need to meet several requirements; an available active
site, contact with a water molecule for a certain period of
time, and enough energy to overcome the activation energy
barrier. If the flow rate per gram of catalyst is too fast, then
one or all of these conditions may not be met. Without these
conditions, the reactant molecules may just be pyrolysing on
the surface of the catalyst support.
Process type
The nature of the reforming process will determine the
process conditions and ultimately the yield of hydro-
gen. Besides the conventional steam reforming of glyc-
erol, studies have examined the sorption-enhanced steam
reforming (Dou et al. 2009), chemical looping reforming
(Ni et al. 2017), aqueous phase reforming (Ciftci et al.
2014), supercritical steam reforming (Pairojpiriyakul et al.
2014), and photocatalytic reforming (Seadira et al. 2018).
Sorption-enhanced processes usually have very high purity
of hydrogen in the product stream as they are used when
the product is required for highly specialised applications
Chemical Papers (2019) 73:2619–2635 2627

like for fuel cells. Photocatalytic reforming, for example,
takes place at near ambient conditions under the influ-
ence of light. Supercritical steam reforming utilises water
at its supercritical state. Aqueous phase reforming is a
high-pressure process and low-temperature process. Fur-
thermore, the use of either a fixed or fluidised bed will
invariably affect the catalyst performance, and, hence, the
product yield and quality. Table 3 gives a summary of
the different reactor and process types utilised in steam
reforming of glycerol. It is quite conspicuous that most
studies prefer to utilise fixed bed reactors for their experi-
mental studies. For a majority of the reforming process
reported, very good yield of hydrogen gas was obtained.
Some researchers presented their results in terms of yield,
percentage selectivity, non-percentage yield or selectivity,
or a combination.
Thermodynamic analyses
Before a review of the findings of thermodynamic analy-
ses is presented, a brief summary of the calculation tech-
nique utilised will first be elucidated. Thermodynamic
analysis of steam-reforming systems is by minimisation
of Gibbs free energy method. The minimisation of Gibbs
free energy method has been explicitly elucidated in the
literature (Adeniyi et al. 2019; Ashraf and Kumar 2018). If
we keep the temperature and pressure of our system con-
stant, then the equilibrium of the system can be expressed
as put in Eq. 19:
K
∑
dG = 𝜇i ni dni . (19)
i=1

The objective is to find the set of ni values that will

Sorption enhancement minimize the value of G (Adhikari et al. 2007a, b). This
can be done by two approaches:
Sorption usually encompasses adding a heterogeneous
chemical species in the reacting system to preferentially 1. Stoichiometric approach.
combine with C ­ O 2 in situ and reduce its concentration 2. Non-stoichiometric approach.
in the product stream. In most cases, quicklime (CaO) is
used (Wang et al. 2018). This is possible, because it reacts In the first approach, the system is described by a set of
reversibly with ­CO 2 to form calcium tri-oxo-carbonate stoichiometrically independent reactions which are typically
­(CaCO3) according to the following stoichiometry: chosen arbitrarily from a set of possible reactions. The non-
stoichiometric approach involves finding the equilibrium
(18)
( 0 )
CaO + CO2 ↔ CaCO3 ΔHr = − 178 kJ/mol . composition by the direct minimization of the Gibbs free
energy for a given set of species. There are several advan-
In some systems, dolomite is used (Dou et al. 2009).
tages of non-stoichiometric approach over the former: a
Dolomite contains several metal oxides majorly MgO
selection of the possible set of reactions is not required,
and CaO. Once calcined to a very high temperature, the
divergence does not occur during computation, and an accu-
MgO is no longer able to carbonate; hence, only CaO
rate estimation of the initial equilibrium composition is not
remains as a sorbent. Other natural sorbents are huntite
necessary (Adhikari et al. 2007a, b). The non-stoichiometric
and hydrotalcite (Dou et al. 2014). Synthetic sorbents
approach is the more applied technique in the open literature:
include lithium orthosilicate ­(Li4SiO4), lithium zirconate
­( Li 2ZrO 3), and sodium zirconate ­( Na 2ZrO 3) (Dou et al. K
2014). Ni et al. (2017) considered potassium promoted
∑
G= 𝜇i ni . (20)
lithium zirconate ­( Li 2ZrO 3) considered as a ­CO 2 sorb- i=1
ent in the chemical looping reforming of glycerol. The
study concluded that the sorbent was very effective in its To find the value of ni that will minimize the value of G,
intended purpose and the presence of Nickel oxides as then it is important that the value of ni be in mass balance:
oxygen transfer materials was of help in reducing coking K
and carbon deposition. In general, hydrogen from steam
∑
ali ni = bl , l = 1, … , M. (21)
reforming is difficult to use in energy generation via fuel i=1
cells due to its high ­CO2 and CO content; therefore, sorp-
tion technology is applied to remove these chemical spe- The above expression can then be further expressed by
cies from the product stream and obtain hydrogen gas of the following equation:
high purity (Esteban-Díez et al. 2016; Gil et al. 2016; Ni K K K
et al. 2017; Xie et al. 2016).
∑ ∑ ∑
G= ni ΔG0i + RT ni Inyi + RT ni InP. (22)
i=1 i=1 i=1

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2628 Chemical Papers (2019) 73:2619–2635

Table 3  Summary of hydrogen production levels obtained for different studies

References Reactor Optimal hydrogen yield or selectivity Process type

Hirai et al. (2005) Fixed bed About 90% maximum H ­ 2 yield Steam reforming
Adhikari et al. (2007b) – About 0.65 mol fraction of H ­ 2 (dry basis) Steam reforming
in the feed
Zhang et al. (2007) Fixed bed 94.1% maximum ­H2 selectivity (Ir/CeO2, Steam reforming
550 °C)
Adhikari et al. (2007c) Fixed bed 80% maximum ­H2 selectivity Steam reforming
Slinn et al. (2008) – About 62% maximum H ­ 2 selectivity Steam reforming
Adhikari et al. (2008b) Fixed bed 74.7% maximum ­H2 selectivity (Ni/CeO2, Steam reforming
600 °C)
Adhikari et al. (2008a) – 66.69% maximum ­H2 selectivity (Ni/CeO2, Steam reforming
550 °C), 56.51% maximum ­H2 yield (Ni/
MgO, 650 °C)
Dou et al. (2009) Fixed bed About 80% maximum H ­ 2 selectivity and Steam reforming (sorption enhanced)
maximum purity of 97% after sorption
Adhikari et al. (2009) Fixed bed – Steam reforming
Pompeo et al. (2010) Fixed bed About 65% maximum H ­ 2 selectivity Steam reforming
Cheng et al. (2010) Fixed bed 65% maximum ­H2 selectivity Steam reforming
Chiodo et al. (2010) Fixed bed 4.5 mol ­H2 per mol glycerol Steam reforming
Dave and Pant (2011) Fixed bed 82.6% maximum ­H2 selectivity Steam reforming
Dave and Pant (2011); Nichele et al. (2012) Fixed bed About 90% H ­ 2 yield (Ni/ZrO2, 5 h, 500 °C) Steam reforming
Ciftci et al. (2014) Fixed bed About 35% glycerol conversion Aqueous phase reforming
Pairojpiriyakul et al. (2014) – 3.8 mol of ­H2 per mol glycerol Supercritical steam reforming
De Rezende et al. (2015) Fixed bed 68.2% maximum ­H2 selectivity Steam reforming
Gallegos-Suárez et al. (2015) Fixed bed – Steam reforming
Veiga and Bussi (2016) Fixed bed Up to 90% ­H2 yield Steam reforming
Suffredini et al. (2016) Fixed bed 70% maximum ­H2 selectivity (600 °C, Steam reforming
­NiAl2O4/Al2O3)
Pastor-Pérez and Sepúlveda-Escribano Fixed bed 45% maximum ­H2 selectivity Low-temperature Steam reforming
(2017)
Ni et al. (2017) Fixed bed 87.9% maximum ­H2 selectivity (NiO/ Chemical looping reforming (sorption
NiAl2O4) enhanced)
Bepari et al. (2017) Fixed bed 5.8 mol of ­H2 per mol glycerol (550 °C) Steam reforming
Buffoni et al. (2017) Fixed bed 5.8 mol of ­H2 per mol glycerol Steam reforming
Charisiou et al. (2017) Fixed bed Up to 85% maximum ­H2 selectivity Steam reforming
(700 °C, Ni/LaAl) and 55% ­H2 yield
(750 °C, Ni/LaAl)
Kousi et al. (2017) Fixed bed 70% ­H2 yield Steam reforming
Kumar et al. (2017) Fixed bed – Photocatalytic reforming
Veiga et al. (2017) Fixed bed Up to 88% ­H2 yield Steam reforming
Callison et al. (2018) – 34% glycerol conversion and 5.5% H ­ 2 yield Aqueous phase reforming
Jiang et al. (2018) Fixed bed Up to 90% maximum ­H2 selectivity (Ce–Ni/ Chemical looping reforming
ZrO2)
Karakoc et al. (2018) Fixed bed 4.82 mol of ­H2 per mol glycerol (Ni/CeO2, Steam reforming
650 °C)
Seadira et al. (2018) – – Photocatalytic reforming

At high temperatures and low pressure, the system is con-
sidered to be ideal (Adhikari et al. 2007a, b). Equation 22 is
known as the objective function. It can be solved on mathe-
matical softwares like Mathcad (Adhikari et al. 2007a, b) and
Matlab (Wang et al. 2008) by Lagrange Multiplier method.
Microsoft Excel has been used to solve the set of linear equa-
tions by the solver function (Da Silva and Müller 2011).
Process simulation softwares like ASPEN Plus (Adeniyi and
Ighalo 2018; Goicoechea et al. 2015; Montero et al. 2015;
Patcharavorachot et al. 2018; Vagia and Lemonidou 2007,

13
Chemical Papers (2019) 73:2619–2635 2629
2008; Yang et al. 2011) and ASPEN Hysys (Gallegos-Suárez
et al. 2015) also utilise this objective function in the mini-
misation of Gibbs free energy calculation method to obtain
thermodynamically accurate results. It should be noted that
Eq. 10 does not apply when carbon is incorporated in the
study, because the free energy of formation of solid carbon
is zero and it has no vapour pressure (Adhikari et al. 2007b).
The key information from thermodynamic analyses is the
prediction of product composition at different levels of the
different input parameters. This can be used in comparison
with experimental systems to determine efficiency and in
optimisation and factor-interaction studies.
Adhikari et al. (2007a) showed that high temperatures,
low pressures, and high WGFRs favour the production
of hydrogen. The study revealed that the optimum condi-
tions for hydrogen yield are at > 900 K temperature and 9:1
molar ratio of water to glycerol. The formation of carbon is
thermodynamically inhibited at these conditions. The find-
ings of this study were quite similar to those of Wang et al.
(2008). Adeniyi and Ighalo (2018) combined the thermo-
dynamic analyses with response surface optimisation. The
study showed a 900 °C optimum temperature, 15.75 mol/mol
steam-to-glycerol ratio (STGR), and 1 atm as the optimum
conditions. At these conditions, hydrogen yield was 66.72%
and there was no methanation in the system.
The thermodynamic analysis of Ashraf and Kumar (2018)
was for a hydrazine-assisted reforming process. Their stud-
ies showed that reforming with increased hydrazine in the
system did not lead to zero coke formation or incomplete
conversion and an increase in hydrogen production was also
observed. The analysis by Chen et al. (2009) involved the
enhancement of the process by the sorption of carbon diox-
ide. Apart from the improvement of the product purity, it
was observed that the sorption enhancement also increases
the glycerol conversion to hydrogen. The study by Yang
et al. (2011) was for an oxidative steam-reforming process. It
was revealed that the process preferred moderate S/C ratios
to compensate between hydrogen yield and energy con-
sumption. The comparison of glycerol steam reforming and
ethanol SR showed that ethanol will give a higher hydrogen
yield under the same basis because of the more oxygenated
composition of glycerol.
Kinetic modelling
The kinetics of glycerol steam-reforming reactions have
been studied (Adhikari et al. 2009; Bepari et al. 2017; Dave
and Pant 2011; Yang et al. 2018). Both the power law model
and the Langmuir–Hinshelwood–Howgen–Watson (LHHW)
model has been employed to study the kinetics of glycerol
steam reforming, though the former is more used. The power
law model is in the following form:
E [ ]n
( )
ri = k0 Exp − Ci . (23)
RT
The given form of the rate model does not include the
water concentration, because water was present in excess
compared to the concentration of glycerol. In kinetic studies,
it is sacrosanct that ideal reactor conditions be maintained.
Mass transfer limitations can be minimized by selecting an
appropriate particle-size range for the catalyst. Film diffu-
sion in the reaction system can be minimized by selecting
suitable flow rates. The reactor flow conditions (plug or
mixed) must be carefully monitored to ensure that they are
according to standards (Levenspiel 1999; Perry and Don
1999). The key information obtained from the kinetic mod-
elling is the activation energy and the reaction order for the
reforming reaction. Table 4 gives the results obtained by
different researchers. The results of Adhikari et al. (2009)
showed that the activation energy and the reaction order for
the glycerol steam-reforming reaction over Ni/CeO2 cata-
lyst were found to be 103.4 kJ/mol and 0.233, respectively,
based on a power model. These results were estimated with
nonlinear regression analysis using the Marquardt algorithm
using SAS 9.1 software and proposed to be in line with those
of other researchers. Dave and Pant (2011) utilised curve-
fitting tool box from MATLAB for their study and obtained
an activation energy with the reaction order of 43.4 kJ/mol
and 0.3, respectively, based on a power model.
Exergy and energy analyses
Studies have been conducted on the energy and exergy anal-
yses of steam reforming (Hajjaji et al. 2014; Rabbani and
Dincer 2015). Hajjaji et al. (2014) investigated the chemi-
cal reactions, design, and simulation of the steam-reforming
process on ASPEN Plus, and used it to study the energetic
and exergetic performances and perform parametric analyses
(using intuitive and design of experiment-based methods).
In studying and optimizing the chemical reaction of steam
glycerol reforming and its associated input parameters, their
study revealed the optimal conditions for maximizing hydro-
gen production as a temperature and a water-to-glycerol feed
ratio (WGFR) of 677 °C and 9, respectively. The thermal and
exergetic efficiencies of the resulting process are 66.6% and
59.9%, respectively. These findings by Hajjaji et al. (2014)
were lower than those of other reformates (methane, etha-
nol, and methanol) but higher butanol (Da Silva and Mül-
ler 2011). The parametric investigation indicates that the
performance of the process (energetic and exergetic) could
be increased using a judiciously selected combination of
the reactor conditions. Based on the investigations, WGFR
of 6 and 827 °C appear to be the exergetic optimal for the
entire glycerol-to-hydrogen process. For this recommend
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2630
Table 4  Kinetic parameters for References Model
the catalytic steam reforming of
glycerol
Adhikari et al. (2009) Power law
Cheng et al. (2010) Power law
Dave and Pant (2011) Power law
Bepari et al. (2017) LHHW
Bepari et al. (2017) Power law
configuration, the thermal and exergetic efficiencies are
78.1% and 66.1%, respectively.
Rabbani and Dincer (2015) studied a glycerol steam-
reforming system coupled with a combined power plant for
co-generation of hydrogen and electricity. Parametric and
optimisation studies were conducted to investigate the effects
of varying operating conditions and state properties on energy
and exergy efficiencies of the system. Their results showed
that an increasing steam-to-glycerol ratio increases the hydro-
gen production, but, due to an increase in energy input, it
decreases the efficiency of the overall system. Increasing the
combustion temperature also increases the efficiency, while an
increasing reformer pressure reduces the hydrogen production
and decreases the overall efficiency of the system.
Techno‑economic performance
Cormos and Cormos (2017) evaluated from the conceptual
design, thermal integration, and techno-economic and envi-
ronmental performances point-of-view hydrogen and power
generation using glycerol (as a biodiesel by-product) on a
large scale with and without carbon capture. Conventional
steam reforming and oxygen autothermal reforming were the
processes considered. The evaluated hydrogen plant was to
conceptually produce 100,000 Nm3/h hydrogen. The power
plant was to conceptually generate about 500 MW net power
output. Similar designs without carbon capture were devel-
oped to quantify the energy and cost penalties for carbon
capture. The various glycerol-reforming cases were modelled
and simulated to produce the mass and energy balances for
quantification of key plant performance indicators (e.g., fuel
consumption, energy efficiency, ancillary energy consump-
tion, specific ­CO2 emissions, capital and operational costs,
production costs, cash flow analysis, etc.). The designs were
energy optimized by heat and energy integration analysis.
The evaluations show that glycerol reforming is promising
concept for high energy efficiency processes with low ­CO2
emissions. The technical and environmental results showed
that the conventional steam reforming is slightly more energy
efficient than the autothermal reforming with or without car-
bon capture. On the other hand, the autothermal reforming has
higher carbon capture rates than the conventional reforming.
13
Chemical Papers (2019) 73:2619–2635
Catalyst Activation energy Reaction order
(kJ/mol)
Ni/CeO2 103.4 0.233
Co/Al2O3 67.20 –
Ni-ZrO2/CeO2 43.4 0.3
Ni/Fly-ash 29.0 –
Ni/Fly-ash 30.0 –
The economic analysis underlines also the slightly better per-
formance of conventional steam reforming than autothermal
reforming in terms of specific capital investment costs, opera-
tional and maintenance costs, and hydrogen and power pro-
duction costs. The slightly higher carbon capture rate of auto-
thermal reforming than the conventional reforming is reflected
­ O2 capture cost. Hydrogen and power co-generation
in lower C
is surmised as a promising option to further increase the over-
all energy efficiency and to improve the plant flexibility.
Computer simulations
Process simulation studies involving glycerol steam reform-
ing have been reported and most are in the domain of com-
putational fluid dynamics (Dou et al. 2008; Dou and Song
2010; Wang et al. 2018), energy and exergy analyses (Hajjaji
et al. 2014), thermodynamic analysis (Gallegos-Suárez et al.
2015; Patcharavorachot et al. 2018; Yang et al. 2011), process
comparisons (Patcharavorachot et al. 2018), factor-interaction
studies (Adeniyi and Ighalo 2018), and sorption enhancement
(Wang et al. 2018). Dou et al. (2008) prepared a computa-
tional fluid dynamics simulation of gas–solid flow in a fluid-
ized bed reactor to investigate the steam reforming of glycerol
using a three-step reaction scheme. The Eulerian–Eulerian
two-fluid approach was adopted to simulate hydrodynam-
ics of fluidization, and chemical reactions were modelled by
the laminar finite-rate model. Their results revealed that the
gas–solid system exhibited a more heterogeneous structure.
Clusters were observed to fall and stack together along the
wall, and the process of wall slug formation was very evident
in the represented visualisations of gases and solids velocities
with vector plots. Figure 4a and b gives a better representa-
tion of the kinetic findings of Dou et al. (2008) in the regards
of both solids and gases. The heterogeneity of the systems
is quite apparent. They also observed that the solid and gas
velocities in the core region are much higher than those in the
annulus region, whereas solid and gas velocities near the wall
are decreasing and downward. This observation is an expla-
nation for any potential back-mixing and internal circulation
behaviour in the system.
Dou and Song (2010) also prepared a simulation to
study the relationship of hydrodynamics with hydrogen
Chemical Papers (2019) 73:2619–2635 2631
production. They used a similar fluidisation and reaction
model to that of Dou et al. (2008). Their results showed
that the core-annulus structure of gas–solid flow led to
back-mixing and internal circulation behaviour, and, thus,
resulted in a poor velocity distribution. The conversion
of glycerol and the subsequent production of hydrogen
decreased with increasing inlet gas velocity. H­ 2 concen-
trations in the bed were shown to uneven and increased
downstream with higher concentrations found on walls.
Their model effectively demonstrated a relationship
between hydrodynamics and hydrogen production. The
computer simulations on glycerol steam reforming have
helped to reveal helpful data needed to design and operate
a bench-scale catalytic fluidized bed reactor.
Knowledge gaps and future perspectives
Based on the review of glycerol steam-reforming research,
several knowledge gaps have been identified which can
open up more opportunities for future perspectives in those
areas. Very few studies have utilised crude glycerol from the
Fig. 4  Solids (a) and gases; (b)
velocity vector plots; velocity
coloured by magnitude, m/s
(Dou et al. 2008)
transesterification process itself as most researchers prefer
to use pure glycerol. Beyond the fact that an ease of inter-
pretation is afforded, the impurities in the crude glycerol
possess a significant effect on the process (in a diversity of
ways) which, at this current time, has not been extensively
explored. Most empirical studies have been done on a labo-
ratory scale. Pilot studies have not been examined in this
regard. The large-scale evaluations have only been done on
in silico platforms. CFD simulations have predicted possible
internal circulations and back-mixing in pilot systems. The
dynamics of mass and heat transfer in the system will be a
very interesting study. Design, budgeting, cost, and energy
considerations can be very different and more realistic in
pilot studies. This is also a great perspective for future
research.
For biomass bio-oil, for example, Adeniyi et al. (2019)
observed that most researchers have now moved focus to
the use of fluidised bed in steam reforming, especially in
recent times. This has not yet been observed in glycerol-
reforming studies. Majorly, fixed bed reactors have been
utilised and there are little reports on fluidised bed reac-
tors. Due to a more rigorous and effective contacting, the
surface area of the catalyst is harnessed to the fullest. It
13

2632
would be interesting to study how crude glycerol will per-
form under fluidised catalyst conditions and in what ways
the impurities will affect the catalyst. There is a lack of in-
depth stand-alone studies on carbon deposition behaviour in
glycerol steam reforming as regards the numerous catalysts
already employed. Sorption enhancements involving some
more novel and efficient artificial sorbents have not been
examined for glycerol reforming. This is another excellent
perspective for future studies. Some other novel-reforming
techniques such as partial oxidation and autothermal reform-
ing have been scarcely examined (at least within the domain
of this review). Besides the recent techno-economic analysis
by Cormos and Cormos (2017), few researchers have delved
into the cost and profitability studies of hydrogen production
from crude glycerol as it compares to other feedstock.
Conclusion
This paper reviewed and catalogued the current state of
knowledge on the production of bio-hydrogen by the steam
reforming of glycerol obtained from transesterification.
Key domains of research over the years explored process
optimisation, catalysis, thermodynamics analysis, kinetic
modelling, exergy and energy analyses, and computational
fluid dynamics (CFD) simulations. From the review, it was
observed that the selectivity of the chemical species in
the product stream does not change much for pure versus
crude glycerol reforming given the same set of process
conditions. However, the overall product yield from the
process is lower when crude glycerol is used. Impurities
such as water and methanol in the crude glycerol favour
the production hydrogen from the steam-reforming pro-
cess. Impurities such as biodiesel catalyst and unreacted
triglycerides contribute to the increase in coke forma-
tion and catalyst deactivation. Nickel is probably the best
catalyst for the steam reforming of glycerol based on the
agreement of many studies. Temperature optimal is always
somewhere around 650–900 °C, while pressure is always
kept at atmospheric condition. 827 °C is considered as the
exergetic optimal of the entire process, while 677 °C is
the exergetic optimal for hydrogen selectivity alone. Gap-
ing gaps in knowledge abound in the research area and
these are in the domain of crude glycerol use, fluidised
bed use, artificial sorbent use, pilot scale studies, cost and
profitability analysis, and studies on carbon deposition
behaviour. It can be surmised that glycerol is a very good
feedstock for the steam-reforming process and a good yield
of hydrogen can be obtained. In view of the impending
global energy crisis, commercialising this technology will
be invaluable for energy sustainability in years to come.
13
Chemical Papers (2019) 73:2619–2635
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