Renewable and Sustainable Energy Reviews 51 (2015) 13451353

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Renewable and Sustainable Energy Reviews

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

Advances in ethanol autothermal reforming

Renika Baruah, Marm Dixit, Pratik Basarkar, Dhrupad Parikh, Atul Bhargav n
Energy Systems Research Laboratory, IIT Gandhinagar, Ahmedabad, Gujarat, India

art ic l e i nf o

a b s t r a c t

Article history:
Received 4 September 2014
Received in revised form
13 May 2015
Accepted 10 July 2015

Fuel cell systems powered by bio-fuels such as ethanol are potential solutions to local, small scale
electricity needs, especially in remote, off-grid locations. In recent years, many researchers around the
world have studied the on-site autothermal reforming of ethanol to hydrogen, which can then be used in
the fuel cell. However, a comprehensive review of those efforts has not been carried out. In this paper, a
detailed literature review of experimental and numerical research is presented, with a focus on the
catalysts, reactor design, and simulation and modelling efforts that sought to understand interactions
among uid ow, heat and mass transfer and chemical kinetics. Our review indicates that although
considerable work has been carried out on the development of catalysts, relatively fewer studies report
system level experiments and simulations that are necessary before these systems can be commercially
deployed. Thereby, we also identify areas for further research in the area of ethanol autothtermal
reforming.
& 2015 Elsevier Ltd. All rights reserved.

Keywords:
Ethanol
Autothermal reforming
Catalyst
Simulation
Fuel cell system

Contents
1.
2.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Catalysts for ethanol ATR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Noble metal catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Non-noble metal catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Bi-metallic catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. Reactor design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Simulation and modelling studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Conclusion and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
International energy outlook projections indicate that with
world GDP rising by 3.6% each year, world energy use will grow
by 56% between 2010 and 2040. Since most economic growth is
expected to occur in developing countries such as China and India,
more than 50% of these increases in energy demand are expected
to be attributable to these countries [1]. With these rising energy demands and depleting conventional energy sources,

n
Corresponding author at: IIT Gandhinagar (VGEC Campus), VisatGandhinagar
Highway, Chandkheda, Ahmedabad 382424, Gujarat, India. Tel.: 91 814 030 7813.
E-mail address: atul.bhargav@iitgn.ac.in (A. Bhargav).

http://dx.doi.org/10.1016/j.rser.2015.07.060
1364-0321/& 2015 Elsevier Ltd. All rights reserved.

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non-conventional sources of energy are being sought [26].

Hydrogen as an energy carrier, and fuel cells as energy conversion
devices have gained traction recently in the context of the shift
toward more efcient and less carbon-intensive energy solutions
[79]. Broadly, the most common fuel cell systems can be
classied according to the primary fuel used: (1) hydrogen based,
(2) hydrocarbon based, and (3) solar energy (water-electrolysis)
based [10]. For each type of fuel cell system, a great number of
research efforts are underway in industry, academia and governments to overcome challenges, reduce cost and commercialize the
various technologies involved [1114].
Of these, fuel cells using pure hydrogen are currently not
suitable for auxiliary power or remote power backup, owing to
the costs associated with the transport and storage of hydrogen.

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R. Baruah et al. / Renewable and Sustainable Energy Reviews 51 (2015) 13451353

Fuel Cells running on hydrogen produced by water-electrolysis are

still not cost effective for remote off-grid applications [15]. And
thus, a lot of work has been seen recently on hydrocarbon based
fuel cell systems [1618]. There are three main reforming methods
employed to obtain hydrogen from ethanol: steam reforming,
partial oxidation and autothermal reforming.
Steam reforming involves reaction of a fuel with steam over a
catalyst. This process has the maximum theoretical yield of
hydrogen, and has been studied extensively [17,1922]. However,
it is a strongly endothermic reaction requiring external heat, and
therefore using steam reforming increases system complexity.

m
Cn Hm n H2 O2 n
H2 n CO;
2

H0reaction 4 0

Catalytic partial oxidation, on the other hand involves reaction

of an oxygen lean mixture of fuel and air for incomplete combustion. The obvious advantage is that the reaction is exothermic;
however, it has the least hydrogen yield of all the reforming
reaction. This reaction too has been actively studied in the past
decade [2327].
n
m
Cn Hm O2 2 H2 n CO;
2
2

H0reaction o 0

Autothermal reforming combines the endothermic steam

reforming reaction and the exothermic partial oxidation to get a
(nearly) thermodynamically neutral reaction. This has a lower H2yield than SR, but the thermodynamic neutral nature makes it a
better alternative for fuel reforming. This has been studied
through various theoretical and experimental studies for comparing these reactions [17,2835]
m

n
Cn Hm O2 n H2 O2
n H2 n CO2 ;
2
2

H0reaction  0

Fuel processors can work with conventional fuels like diesel,

natural gas and methanol to yield hydrogen rich mixtures that can
be directly used to drive fuel cells. However, fuels derived from
biomass, because of the additional advantages of being locally
available, carbon neutral and renewable, are the most favourable
candidates. Much work is being done to promote the use and
understanding of these fuels in reforming reactions [3638].
However among these bio-fuels, ethanol is much favoured over
others due to its availability via multiple pathways, many of which
are subjects of ongoing research [3941]. Among other advantages
of using ethanol as a fuel source are the ease of reforming, safety in
storage, handling and transportation, and its non-toxicity. Ethanol
is also preferred as a fuel source as it forms a closed carbon loop,
i.e. it adds little or no carbon to the atmosphere via the reforming
process [31].
However, in open literature it is observed that compared to
autothermal reforming, ethanol steam reforming has received
more attention due to its relatively higher conversion efciency
[22,4244]. We have not found a comprehensive literature survey
on autothermal reforming in recent years. This paper aims to
review the technological advances in autothermal reforming of
ethanol for hydrogen production in the last ve years. In this
context, we review catalyst selection, reactor design and simulation studies.
Section 2 describes in detail the catalysts developed for ethanol
autothermal reforming. It also touches on the aspect of catalyst
stability. Section 3 briey describes previous works in reactor
development, in particular for ethanol autothermal reforming.
Section 4 summairzes the simulation and modelling studies that
have been carried out to understand the process.

2. Catalysts for ethanol ATR

In the ethanol ATR process, catalysts play a very important part
in ensuring conversion and preventing coke formation. However,
each catalyst may promote the reforming reaction through distinct
pathways, and therefore catalyst selection plays an important role.
Each catalyst has different selectivity towards hydrogen and other
side products, and for fuel cell system purposes, the aim is to
maximize H2 selectivity while minimizing catalyst coking.
Very broadly, the catalysts can be divided as (1) noble metalbased, (2) non-noble metal-based and (3) bi-metallic catalysts.
During the last decade, noble metal catalysts had been the subject
of extensive research due to their high conversion efciencies and
high H2 selectivities. However, a survey of recent literature
suggests that the focus of research has now shifted to development of non-noble metal catalysts that can replace the conventional noble metal catalysts. This is primarily because of the cost
involved in noble metal catalysts which may adversely impact
market acceptability. Few research works also focus on developing
novel catalysts which involve nanostructures and composite
phases [45,46]. For instance, perovskite phase also has been
studied extensively for ethanol ATR [4751].
2.1. Noble metal catalysts
Most catalysts in this category are prepared by incipient
wetness impregnation method. Incipient wetness impregnation
(IW or IWI), also called capillary impregnation or dry impregnation, is a commonly used technique for the synthesis of heterogeneous catalysts. Typically, the active metal precursor is dissolved
in an aqueous or organic solution. The metal-containing solution is
then added to a catalyst support containing the same pore volume
as the volume of the solution that was added. Capillary action
draws the solution into the pores. The catalyst can then be dried
and calcined to drive off the volatile components within the
solution, depositing the metal on the catalyst surface. Rh, Pt, Pd,
Ru and Ir have been extensively studied for ethanol autothermal
reforming [5254].
Chen et al. used Ir/La2O3, and studied the effect of in situ
dispersion of Ir [55]. They proposed that the excellent performance of Ir/La2O3 was due to the formation of La2O2CO3 and an
in situ dispersion effect of Ir on La2O2CO3. Due to the in situ
dispersion effect, the resulting catalyst possessed enhanced ATR
performance in terms of activity and stability. Based on the insight
into the in situ dispersion mechanism of Ir over La2O2CO3-II, a
supersonic-assisted impregnation method was used to improve
the surface iridium concentration and reduce the initial Ir domain
size. This signicantly enhanced the activity and stability of Ir/
La2O3 catalysts for the ATR reaction. A systematic study for
identifying the key relationships between the catalyst morphology/structure and catalytic performance in autothermal reforming
of ethanol was carried out over a series of Ir/CeO2 catalysts by Cai
et al. [56]. They showed that the dispersion of both the ceria
support and the noble metal phase control key parameters such as
the diffusion of oxygenated adspecies along the ceria surface,
surface basicity, and the concentration of coupled sites formed at
the metal/support interface between peripheral ceria defects and
coordinately unsaturated sites on Ir particles. All of these factors
are found to be critical for ethanol conversion, selectivity toward
hydrogen production, and resistance to aging.
Rh on various supports have been independently by various
researchers [5759]. It has been reported to be a very efcient
catalyst for conversion of ethanol, generally with 100% conversion
at low temperatures with high selectivity towards hydrogen. Pt, Pd
and Ru have been similarly studied [57,58,6063]. The results for
both simple catalysts and those employed in a membrane reactor

R. Baruah et al. / Renewable and Sustainable Energy Reviews 51 (2015) 13451353

show almost 100% conversion and high hydrogen selectivity.

Efforts were also undertaken to load multiple noble metals onto
a base support [58,61]. The results from these experiments show
that having multiple noble metals improve stability of the catalyst.
Also, doping multiple noble metals has the advantage of reducing
the loading of precious metals while capturing their favourable
effect. The catalysts, reaction conditions and results have been
summarized in Tables 1 and 2. A comparison of hydrogen
selectivity is shown in Figs. 1 and 2.

Table 1
Nomenclature and abbreviations.
Symbol

Description

H2O:EtOH
n,m
O2:EtOH
Pr
S H2 C2 H4
SCH3 CHO
SC H4
SCO
S H2
Tfeed
Tr
W
XEtOH
H0reaction

Steam to ethanol ratio

Stoichiometric coefcients in Eqs. (1)(3)
Oxygen-to-ethanol ratio
ATR reactor pressure
C2H4 selectivity
CH3CHO selectivity
CH4 selectivity
CO selectivity
H2 selectivity
Feed temperature
ATR reactor temperature
Catalyst weight
Ethanol conversion
Enthalpy of reaction

Acronyms
ATR
CPO
GDP
PO
SR
WGS

Autothermal reforming
Catalytic partial oxidation
Gross domestic product
Partial oxidation
Steam reforming
Watergas shift

Units

bar

1C
1C
mg
J kg  1

1347

2.2. Non-noble metal catalysts

Similar to noble metal catalysts, most non-noble metal catalysts are heterogeneous catalysts and are prepared by impregnation method as described above. However, it must be noted that in
case of non-noble metal catalyst, a majority of the reviewed
literature showed the catalyst to be of perovskite structure. It
has been seen that the perovskite structure can be stable and
catalytically active, while at the same time can allow for more
possible combinations of metals as catalysts [64]. This is due to the
fact that most of the naturally occurring metals are stable in the
perovskite type oxide structure and there is a possibility of
synthesizing multicomponent catalysts by partial substitution of
A and B in ABO3 structure of perovskite. Hence there is an increase
in the study and development of perovskite type catalysts for
autothermal reforming of ethanol. The primary ways of synthesis
of perovskite type compounds are combustion method, precipitation method and wet chemical method. A detailed study of
preparation methods is done by Galasso [65].
Chen et al. compared the impregnated Ni/La2O3 with LaNiO3
perovskite type catalyst [50]. They found the perovskite-derived
catalyst to be more active, stable and selective for H2 production.
In addition, the coke deposition is also suppressed signicantly
during ATR compared to the impregnated one. This was attributed
to possibility of the formation of highly dispersed Ni nanoparticles
from the perovskite precursor. Lima et al. also studied Ni based
catalysts derived from La12CexNiO3 perovskite type oxides [47].
They hypothesized that there are a minimum number of active
sites that are required to dissociate the CH4 for coking of the
catalyst, and that the catalyst they developed effectively dispersed
the metallic sites through the base, thereby not allowing very
many sites where CH4 could potentially dissociate to coke. Silva
et al. studied the effect of space time while analyzing Co/CeO2 as
catalysts for ethanol ATR [66]. The different space times were

Table 2
Noble metal catalysts.
Catalyst

Reaction conditions

Ir/La2O3

H2O:EtOH 3. O2:EtOH 0.83.

Tr 500700 1C

Rh/Al2O3

Rh/ZrO2, Pt/ZrO2, RhPt/

ZrO2, RhPt/ZrO2

Platinum based on
alumina sphere Pt/
Al2O3
M/Al2O3

Ir/CeO2

RhPd/CeO2
Rh catalyst supported
on CeLa solid
solution

Results

Ref

At all temperatures from 600 to 700 1C, XEtOH is observed to be 100% and the SH2 is observed as [55]
80% while SCO was 45% at 700 1C. La2O3 gets converted in to La2O2CO3 during ethanol ATR, which
helped in suppressing coking effectively
Three different catalyst were used 1%Rh/Al2O3, 1%Rh20%Ce/Al2O3 and 2%Rh20%Ce/Al2O3. The [59]
H2O:EtOH 6. O2:EtOH 0.51.
Tr 300500 1C., micro channel
product selectivity and activity of catalyst were signicantly lower on 1%Rh/Al2O3 compared to
reactor
the other two catalysts. The distribution of product and activity of Catalyst were similar in 1%
Rh20%Ce/Al2O3 and 2Rh20CeAl at higher temperature. The conversion of ethanol is slightly
higher on 2%Rh20%Ce/Al2O3 at lower temperatures. 100% conversion of ethanol is observed at
550 1C. Ethanol ATR and SR reactions on the catalysts are also compared
[58]
H2O:EtOH 2. O2:EtOH 0.2. Tr 500 Mono- (Rh and Pt) and bimetallic (RhPt) catalysts with 0.5 wt% total metal loading were
900 1C
prepared by dry impregnation and dry co-impregnation of metal precursors on ZrO2 support.
XEtOH for Rh/ZrO2, RhPt/ZrO2, and RhPt/ZrO2 is 100% while for Pt/ZrO2 is 65%. The maximum SH2
obtained was 43 mol% with Rh/ZrO2 catalyst
H2O:EtOH 13. O2:EtOH 2. Tr 400 A membrane reformer was utilized consisting of a thin wall of PdAg permeator lled with a [62]
450 1C.
Pt-based catalyst. Ethanol conversion is 100% at 450 1C. A higher hydrogen yield, up to 70%, is
obtained at temperature 450 1C, pressure 200 kPa and at lower ow rate of ethanol
(4.66 mol s  1)
H2O:EtOH 3. O2:EtOH 0.3. Tr 400 Different noble metals were used with Al2O3 to form a catalyst (Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt [57]
600 1C.
and Au). Maximum ethanol conversion was observed to be 97% for Ni, Rh, Ag and Au at 600 1C.
The highest hydrogen yield obtained was 94% for Rh based catalyst
H2O:EtOH 1.8. O2:EtOH 0.6.
Different catalyst were used, Ir/CeO2, Ir/Ce550, Ir/Ce700, and Ir/Ce850. 100% ethanol conversion [56]
Tr 400700 1C
was noted for Ir/CeO2 catalyst with sintered base at 400700 1C while for Ir/Ce850 100%
conversion is obtained at 650 1C. SH2 is 60% at 450 1C for all above catalysts except Ce850. Ce850
achieves only 40% at 650 1C. Moreover, SC H4 decreases and SCO increases with time for all except
Ce850
H2O:EtOH 2. O2:EtOH 0.5.
XEtOH is observed to be 100% and SH2 is 60.4% at 600 1C. SCO2 25.3%, SCO 9.3%, SC H4 4.9% and [61]
Tr 600 1C
SCH3 CHO 0.1%
H2O:EtOH 3. O2:EtOH 0.5. Tr 200 Ethanol conversion was greatly enhanced by doping of La in CeO2 particularly for 30 mol% of La, [48]
450 1C
100% XEtOH was achieved at 300 1C. Over the whole tested region of 200450 1C, the hydrogen
yield order of the catalyst series was Rh/CL0.3 4Rh/CL0.4 4Rh/CL0.5 4 Rh/CL0.2 4Rh/
CL0.1 4Rh/LERh/C

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Doped
7%

Doped
17%

Noble
Metals
32%

Noble
Metal 58%

Non Noble
metal
25%

Non Noble
Metals
61%

Fig. 1. Comparison of trends in catalyst study for autothermal reforming of ethanol (a) until 2009, (b) 20092014.

effect of support on the reforming reaction has also been studied for
various catalysts [70,71]. There also have been a few studies of nonnoble metals supported on nanobers [45,46] Table 3 shows the
detailed description of the catalyst, reaction conditions and the results
for non-noble metal catalysts. A comparison of hydrogen selectivity is
shown in Fig. 3.

Ag/Al2O3
Au/Al2O3
Pd/Al2O3
Pt/Al2O3
Pt/ZrO2
1%Rh/Al2O3

Catalysts

Ru/Al2O3
Ir/Al2O3

2.3. Bi-metallic catalysts

Rh/Al2O3
Ir/La2O3
Rh/Ce-La Solution
RhPt/ZrO2
RhPd/CeO2
Rh/ZrO2
Pt/Al2O3 (MR)
2%Rh-20%Ce/Al2O3
1%Rh-20%Ce/Al2O3
0

SH2 (mol/mol of ethanol)

Fig. 2. Hydrogen selectivity for noble metal catalysts.

obtained by changing the weight of the catalyst and the ow rates

of the input stream. Increasing space time increased ethanol
conversion and hydrogen selectivity and decreased the selectivity
to acetaldehyde. A bimetallic catalyst, Co promoted over Ni/Al2O3
was studied by Andonova et al. [67]. Bimetallic loaded catalyst was
found to be more stable and having higher yields than corresponding mono-metallic catalyst. Large variation observed in H2 yield in
Ni/Al2O3 unlike in CoNi/Al2O3. Higher CO2/CO ratios are observed
in the case of bimetallic catalyst. Nawadee et al. studied the effect
of CeO2 and ZrO2 promoters in Ni/Al2O3 catalyst on product
distribution of ethanol ATR [68]. It was observed that for CeO2
ZrO2 promoted catalyst H2 yield increased with an increase in O2:
EtOH ratio, unlike unpromoted catalyst and catalysts with single
promoter. Selectivity to carbon products was also reduced for the
CeO2ZrO2 promoted catalyst, which suggests reduction in coking.
This was attributed to the presence of oxygen intermediates
positively affecting the oxygen storage capacity (OSC) of the
promoters.
Five Co, Ni and Cu oxides derived from hydrotalcite-like precursors
were prepared by urea hydrolysis and tested in the oxidative steam
reforming reaction of ethanol by Guil Lopez et al. [69]. It has been
shown that the particle size of the active metal oxide decreases upon
increasing the crystallinity of the precursor. Moreover, the small
particle sizes cause a high stabilization of the active metal phases as
they favour the strong interactions between active metals and the
amorphous matrix of Al-modifying cations. Hydrogen production
capacity of the catalysts at low temperature (575 1C) decreases in
the following the sequence: CoZnAl4CoMgAl4CoAl4NiMgAl. The

Non-noble metals are doped onto noble metal catalysts for

capturing the favorable effects of non-noble metals. Ternary
systems such as NiPdAg have been tested for ethanol ATR by
Lin et al. [77]. A PtRu/ZrO2 catalyst modied with Mg and Na was
evaluated by Wang et al. [60]. The addition of Na improved the
catalytic performance of the PtRu/ZrO2 catalyst for ethanol ATR.
The preferential PtRuNa/ZrO2 catalyst showed activity at temperatures as low as 300 1C and produced less CO ( o0.2%) at temperatures lower than 340 1C. Also, there were no C2 and C3 sideproducts in that sample. PtRuNa/ZrO2 catalyst was found to be
preferable for ATR on account of it being able to enhance the WGS
reaction at lower temperatures and reducing the coke deposits.
The details of bi-metallic catalysts are summarized in Table 4.

3. Reactor design
While scientic literature focuses on catalyst development and
analysis of catalysts for ethanol ATR, a few efforts are seen in
development of reactors for system scale set-up of reforming
process. Many reactor patents have been awarded ATR of fossil
fuels like gasoline, diesel, JP-8 and renewable fuels like methanol
and glycerol. A good review of the recent patents is carried out by
recently by Nahar and Dupont [78].
Ahmed et al. developed a three-segmented conguration
system for studying ATR of dodecane and hexadecane [79]. They
have a two zone reactor, the initial zone loaded with an oxidation
catalyst, while the downstream zone loaded with a reformer
catalyst. This helps in initiation of the ATR reaction, by achieving
the temperatures required for ATR by partial oxidation of the feed,
as shown in Fig. 4. They also incorporate different supports to
achieve uniform temperature by transferring the heat from the
exothermic PO zone to the pre-reforming zone and the endothermic SR zone. The support for pre reforming zone is essentially a
metallic foam that helps in distributing the feed ow, as well as to
heat the incoming feed from the heat of the CPO reaction. The
substrates in the latter two zones are coated with an oxidation and
a reforming catalyst.
Yamazaki et al. devised an innovative way to capture the heat
of the CPO reaction for initiation of the ATR reaction [80]. They

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Table 3
Non-noble metal catalyst.
Catalyst

Reaction conditions
H2O:EtOH 2. O2:
EtOH 0.98. Tr 500
700 1C

Results

The XEtOH for LaMnO3, LaFeO3, LaCoO3 and reduced LaNiO3 is 100% and drops
with decreasing O2:EtOH ratio. Unreduced LaNiO3 however only gives around
60% conversion. SH2 reaches a maximum of 80% and decreases in the order
LaNiO3 4LaFeO3 4LaCoO3 4LaMnO3. The bed temperatures for all catalysts
reduce with decreasing O2:EtOH ratios
W/Q test has been carried out for the catalyst to see the effect of space time on
H2O:EtOH 3. O2:
Co/CeO2
the catalyst. For W/Q40.01 g s mL  1, XEtOH is 100%. SH2 shows an increasing
EtOH 0.5. Tr 500 1C
trend with W/Q and levels off for values more than 0.06 g s mL  1 to  65%.
SCH3 CHO and SC2 H4 reduce to zero with increasing W/Q while SC H4 , SCO and SCO2 all
show reducing trends with W/Q
Co/CNF
H2O:EtOH 3. O2:
The effect of the cobalt particle size in the ethanol ATR was investigated. 2.6
EtOH 0.5. Tr 500 1C
16 nm were tested in the ATR of ethanol reaction to produce hydrogen. XEtOH
(4 85%) were obtained, however at the expense of SH2 . Less carbon was
observed. The catalysts with the lowest Co particle size deactivated most likely
due to oxidation of surface atoms by oxygen from the feed whereas the catalysts
with large Co particle size ( 44 nm) remained quite stable
CoAL, CoZnAL, CoMgAl, NiMgAl, CuMgAl
H2O:EtOH 2.28. O2:
XEtOH for all the catalysts in all the temperature ranges is found to be 100%.
EtOH 0.36. Tr 575
Highest production is obtained for CoMgAl catalyst. Co- and Ni-catalysts show a
similar performance in this reaction, although, there are slight differences
675 1C
between the Co- and Ni ex-LDHs catalytic behaviour. Thus, Co-catalyst reached a
higher H2 production level at lower temperatures compared to the Ni-catalyst
Nanorod alumina is used as a support for these catalysts. Ni/Al2O3 and NiZrFe/
Ni/Al2O3, NiFe/Al2O3, NiZr/Al2O3, and NiZrFe/ H2O:EtOH 3. O2:
Al2O3
EtOH 0.5. Tr 600 1C
Al2O3 show 100% XEtOH for over 30 h. NiZr/Al2O3 and NiFe/Al2O3 show 100%
conversion initially but drop over time. SH2 however decreases radically for Ni/
Al2O3 but remains stable for all other catalysts at  80%
NiCu/-Al2O3, NiCu/-Al2O3, NiCu/Ce0.6Zr0.4O2, H2O/EtOH 10. O2:
XEtOH was maximum for NiCu/-Al2O3being 100% and reducing as NiCu/
NiCu/Nb2O5 and NiCu/ZnO
EtOH 0.8. Tr 400 1C
ZnO4NiCu/Nb2O5 4NiCu/-Al2O3 4 NiCu/Ce0.6Zr0.4O2. Highest SH2 was
observed for NiCu/Ce0.6Zr0.4O2. The presence of oxygen inhibits catalytic
deactivation by oxidation of coke deposited on the catalyst surface, which is
associated with the high stability of ethanol conversion
Co/CeO2
H2O:EtOH 3. O2:
Cerium oxide was prepared by (i) calcination of cerium ammonium nitrate at
EtOH 0.5. Tr 500 1C
800 1C (CeO2LS) and (ii) addition of an aqueous solution of cerium ammonium
nitrate to an ammonium hydroxide solution (CeO2HS). Cobalt (10 wt%) was
added to the CeO2 support. These supports were then compared for ethanol ATR.
Both catalysts observed show 100% XEtOH. However Co/CeO2LS catalyst showed
higher and more stable SH2 . However, carbon deposits were observed on the LS
catalyst and not on the HS catalyst. This was attributed to higher O2/OH group
mobility
H2O:EtOH 3. O2:
La1  xCexNiO3 (x 0, 0.05, 0.1, 0.4, 0.7 and 1.0)
All catalysts show 90100% XEtOH for a 30 h run. SH2 is observed to be around 50%
EtOH 0.5. Tr 500 1C
for almost all the catalysts. Signicant formation of acetaldehyde occurred
during OSR over La1  xCexNiO3 with x 0.4 and 0.7. However, there is no clear
correlation observed between product distribution and Ce content.
La0.90Ce0.10NiO3 is stated to be the best catalyst because of the absence of carbon
deposition
Ni/Al2O3 (NAM00), NiMn/Al2O3 [Mn loading: 5% H2O:EtOH 3. O2:
NAM00, NAM10, NAM15 and AM15 show 100% XEtOH initially, however, only
(NAM05), 10% (NAM10) and 15% (NAM15)], Mn/ EtOH 0.5. Tr 600 1C
NAM10 sustains the conversion for 30 h. SH2 also shows a similar trend with a
Al2O3 (AM15)
maximum selectivity of  35%. AM15 shows the least selectivity of  10%
OMCo refers to the mixed oxide obtained at the end of the catalyst calcination
OMCo, OMCo3Ce, OMCo3Pr, and OMCo2.5Ce2.5Pr H2O:EtOH 3. O2:
EtOH 0.5. Tr 550 1C
from hydrotalcite type precursors. All catalysts show XEtOH 100%. SH2 6568%
for all catalysts. The introduction of redox promoters such as Ce and/or Pr
improves the basicity reducibility and reduces the carbon formation. The
catalytic results exhibit a high selectivity to H2 and chemical stability producing
the complete transformation of ethanol into H2 and CO2-rich gas mixtures
LaNiO3
H2O:EtOH 3 and O2:
XEtOH is found to be 100% and SH2 55% at 700 1C. A stability test was carried out
EtOH 0.5. Tr 500700 1C for 50 h and it was observed that H2 selectivity decreased from 60% to 55%,
SCO 8% was constant for the whole run and SCH3 CHO increased up to 7%
XEtOH is found to be 44% at 350 1C & 78% at 400 1C and SH2 55% at 700 1C. The
H2O:EtOH 0.2 & 0.6. O2:
LaCo0.7Cu0.3O3
EtOH 1.8 & 2.6. Tr 350 comparison among the behaviour of the samples treated at different
400 1C
temperatures and the analyses of the spent catalysts suggest that all the
elements play a signicant role in determining the reactivity with respect to ATR
of ethanol
Co/NiAL2O3
H2O:EtOH 3. O2:
XEtOH is found to be 100% at 500 1C and SH2 increases up to 70% and drops to 60%
EtOH 0.5. Tr 170500 1C at 500 1C. SCO is observed to be 32% while SCO2 20% at the highest temperature
H2O:EtOH 3. O2:
CuOCeO2
XEtOH is found to be 81% for Rh/CeO2 and 70% for Rh/20CuCe. The SH2 is observed
EtOH 0.5. Tr 250450 1C to be 1.44 mol mol  1(EtOH) for Rh/20CuCe and 1.32 mol mol  1(EtOH) for Rh/
CeO2. The results conrmed that CuOCeO2 catalysts may be suitable for low
temperature hydrogen production from ethanol
LaNiFeO3
H2O:EtOH 3. O2:
The reaction was been carried out for 4 h at 650 1C and the XEtOH is found to be
EtOH 0.5. Tr 650 1C
100% for LN, LNF5, LNF10 & 75.592% for LNF20. The LaNiO3 catalyst had a H2
yield around 2.6 mol H2/mol EtOH, while the iron-doped catalyst produced good
stability and a higher H2 yield of about 3.0 mol H2/mol EtOH
10% Ni/YSZ, 15% Ni/YSZ, 20% Ni/YSZ
H2O:EtOH 3 and O2:
In all the three cases XEtOH was observed to be higher than 99%. SH2 decreases
EtOH 0.5. Tr 300400 1C with increase in loading of Ni. An increase in the reaction temperature and a
decrease in Ni particle size favored the yield to H2
LaMnO3, LaFeO3, LaCoO3 and LaNiO3

Ref
[50]

[66]

[45]

[69]

[46]

[70]

[71]

[47]

[72]

[73]

[51]

[74]

[67]
[75]

[49]

[76]

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R. Baruah et al. / Renewable and Sustainable Energy Reviews 51 (2015) 13451353

Table 3 (continued )

Ni/Al2O3, 15 wt%Ni/8 wt%CeO2/Al2O3, 15 wt%Ni/

8 wt%ZRO2/Al2O3, 15 wt%Ni/4 wt%CeO24 wt%
ZrO2/Al2O3

Reaction conditions
H2O:EtOH 3. O2:
EtOH 0.060.36
Tr 550 1C700 1C

devised an annular cylindrical reformer to form a fourfold circular

tube structure. The oxidation takes place inside the inner tubes,
while the heat is conducted to the outer tube for the SR reaction.
The schematic of this reactor is shown in Fig. 5. It is worth
mentioning here that a novel system was also proposed and tested
by Du et al. [81]. They carried out ethanol ATR by laval nozzle arc
discharge. In this case, the vaporized reactant feed is passed
through a nozzle and near the throat an electric discharge is
initiated to carry out the ATR reaction. Although there are some
ongoing studies to determine whether this process can be commercially viable, results show over 85% ethanol conversion and
good hydrogen selectivity. Schematic of the setup of this experiment is given in Figs. 6 and 7. Martin et al. [34] and Chiu et al. [82]
experimented with complete fuel cell systems.

Results

Ref

Addition of promoters increased as well as hydrogen selectivity; 64% for CeO2

promoted catalyst. Increasing the O2:EtOH favoured hydrogen yield for CeO2
ZrO2 promoted catalyst as well as a decrease in coke formation. Ethanol
conversion increased with increasing temperature for all catalyst, and reached
100% at 700 1C

[68]

Ni-Cu/Ce0.6Zr0.4O2
La0.90Ce0.05NiO3
10% Ni/YSZ
Co/CNF
Co/CeO2
10%Mn-Ni/Al2O3
Catalysts

Catalyst

Cuo-CeO2
LaNiFeO3
Co-3Ce
LaNiO3
Co-2.5Ce-2.5Pr
Co-3Pr
LaNiO3

4. Simulation and modelling studies

0

Relatively fewer researchers have studied ethanol ATR through

modelling and simulations. Braga et al. developed a model for ethanol
ATR using the commercially available COMSOL suite [83]. They have
used a multichannel approach to model the behaviour of ATR
Monolith reactor showing radial temperature gradient as a consequence of heat losses present on the reactor. Monolith reactor is
divided into three zones of homogeneous temperature with 2-D
axisymmetric model for each monolith channel. Each zone was
modelled separately for 1D, slightly compressible, laminar ow in
steady state. The inlet conditions were: ethanol ow rate 0.0221 g s  1,
O2:EtOH0.11, H2O:EtOH 1.02, and inlet temperature350 1C. In
order to estimate heat losses to the surroundings, heat ux condition
is applied at the lateral monolith walls. At the wash coat (where the
reactions occur), the boundary condition corresponds to the heat
generated by reactions. The chemical reactions model is dened by the
following reactions:

Ethanol decomposition
Partial oxidation
Methane incomplete steam
reforming
Watergas shift reaction

Fig. 3. Hydrogen selectivity for non-noble metals.

decomposition and partial oxidation, while H2 concentration

decreases along the length of the reaction as a result to consumption of H2 in reverse WGS reaction. The above results appear to be
in good agreement with experimental data they referred.
Jin et al. worked on sequential simulation of dense oxygen
permeation membrane reactor for hydrogen production from ethanol
ATR using ASPEN PLUS [84]. The Dense Tubular Membrane Reactor is
divided into multiple-sub-reactors, and the Gibbs free energy minimization sub-model in ASPEN PLUS is employed to achieve thermodynamic equilibrium locally and simulate the ATR process in the subreactors. A FORTRAN sub-routine is integrated into ASPEN PLUS to
simulate the oxygen permeation through membranes in the sub-

C2 H5 OH-H2 CH4 CO
C2 H5 OH 2O2 -3H2 O 2CO
CH4 H2 O23H2 CO

H298 K 49.6 kJ mol  1

H298 K  517.3 kJ mol  1
H298 K 206.2 kJ mol  1

H2 O CO-H2 CO2

H298 K  41 kJ mol  1

As expected, a radial temperature gradient was observed inside

the monolith reactor with the inner channels comparatively hotter
than the outer channels because of the heat losses to the
surrounding. There is also a temperature gradient across the axial
direction, where at the inlet sections the temperature is high due
to exothermic partial oxidation reaction being favoured at 350 1C
and then the temperature drops on the onset of steam reforming
reaction, which is endothermic.
H2 production and O2 consumption was seen to be very fast at
the entrance of the reactor, mainly for the two reactions, ethanol

SH2 (mol/mol of ethanol)

separators, such that each sub-reactor consists of an O2 permeation

tubular membrane and a Gibbs sub-reactor. At each section, the ow
of gas is considered as a plug ow.
Their goal was to optimize the length of the reactor and
determine operating conditions for H2 and CO maxima.
Simulations indicated that the optimal number of sub-reactors
is 55. There is negligible effect on H2 production for number of sub
reactors greater than 55. For H2O:EtOH 0.5, the 100% conversion
of ethanol is observed for a temperature range of 700850 1C. H2
yield increases with the length of the reactor for temperature

R. Baruah et al. / Renewable and Sustainable Energy Reviews 51 (2015) 13451353

1351

Table 4
Doped metal catalysts detailed.
Catalyst

Reaction conditions

NiPdAg ternary
alloy membrane

[77]
H2O:EtOH 1 or 3. O2:EtOH 0.2 or 0.7. XEtOH increases with increase in temperature. Increasing H2O:EtOH ratio and the O2:EtOH also
Tr 320450 1C. Pr 310 atm
increases XEtOH. Maximum conversion is recorded to be around 80%. Increase in pressure however
reduces the conversion of ethanol
H2O:EtOH 4.86. O2:EtOH 0.26.
PtRuNa/ZrO2 shows 100% XEtOH for all ranges of temperatures with above 70% SH2 , and less than 4% [60]
Tr 300400 1C
SCO and SC H4 . PtRu/ZrO2 reaches maximum around 350 1C and then drops to 95% at 400 1C with
SCO going higher than 4%. PtRuMg/ZrO2 shows maximum conversion at 400 1C with SCO and SC H4
ranging from 6 to 10%

PtRuNa/ZrO2,
PtRuMg/ZrO2,
PtRu/ZrO2

Fuel Steam

Results

Ref

Oscilloscope
+
Transformer

Air
Electrode
Air

Fuel + Steam

Metallic Foam
Oxidation
Catalyst

Reforming
Catalyst
Reformate
GC

Fig. 6. Schematic arrangement of ethanol ATR though laval nozzle arc discharge.

Reformate

Air

Fig. 4. Schematic of the reactor patented by Ahmed et al. [79].

O2

C2H5OH+H2O
Air

O2

Air/Oxidant

Fig. 7. Dense membrane reactor.

Oxidation Catalyst

SR Catalyst
Heat Transfer Material

Fuel + Steam Inlet

Reformate Out

Fig. 5. Schematic of the reactor patented by Yamazaki et al. [80].

700 1C. But for other temperatures (750850 1C), the H2 yield
increases with length of the reactor, reaches a maximum and then
decreases along the reactor. Similar trends are observed for CO as
that for H2, while CO2 yields increases with increasing operating
temperature. H2 yield for H2O:EtOH 0, 0.5 and 1 ratio, increase
up to a certain length of the reactor and then decreases; while for
H2O:EtOH 2 and 5 ratios, it follows a decreasing trend. The

amount of H2 generated is more at higher ratios. CO2 follows an

increasing trend with increasing H2O:EtOH ratios. CO follows a
similar trend as for H2 for different values of H2O:EtOH ratios and
CH4 follows a decreasing trend with less CH4 being consumed at
lower ratios.
Markova et al. used experimental data combined with mathematical analysis to optimize the reactor performance [85]. They
carried out experimental studies on ethanol ATR using a commercial monolith catalyst for various H2O:EtOH and O2:EtOH ratios,
reactant entry temperature, reactor pressure and temperature.
Using these primary results they obtained regression models for
the most critical dependent variables such as SH2 , SCO and SCO using
a statistics program STATGRAPHICS Plus for Windows 2.1. The
obtained regression model was then used to optimize the reactor
performance for maximum hydrogen yield.
Wutthithanyawat et al. use the principle of Gibbs free energy
minimization to study the steady state compostion of ethanol
autothermal reforming process. They examine the effect of varying
O2:EtOH and H2O: EtOH ratio on the performance of the reformer
to determine the optimal operating condition for maximum
hydrogen yield [86,87]. In another very recent work, Wutthithanyawat et al. open loop responses of the feed and ATR temperatures (Tfeed and Tr) are simulated by the dynamic models of ATR
system [88]. In this study they have assumed complete ATR of

1352

R. Baruah et al. / Renewable and Sustainable Energy Reviews 51 (2015) 13451353

ethanol and minimization of Gibbs free energy method to simplify

mass balance dynamics of gas production in the ATR. Transient
energy balance around the preheater and the ATR reactor was
done using energy balance equations. Step inputs were given to
the air, ethanol and the water ow rates to observe their effect on
the feed temperatures and the temperature of the ATR reactor. An
idea of a control system design strategy, based on this, is also
proposed in this paper. Based on their results, they suggest that
the air ow rate can be used to control the ATR temperature. Feed
temperatures can also be designed as another control variable, and
the fraction of heating power in the furnace should be a function
of this parameter.

5. Conclusion and perspectives

The production of hydrogen through ATR of ethanol still
continues to be an area of active research, and much progress
has been achieved in the eld of catalysts development. However,
many problems still remain to be solved. This review focuses on
ATR of ethanol to produce hydrogen for PEMFC systems, and
documents new ndings on catalyst development, reactor design
and simulation and modelling efforts. The use of a bio-fuel such as
ethanol constitutes an important option for hydrogen production
via reforming reactions by catalytic reactors, especially in remote
locations in developing countries where ethanol is available.
However, there has been relatively limited work on reactor and
system development. We have found very few studies that report
integration of ethanol fuel processor with fuel cell and balance-ofplant components.
Also, there is wide variety of materials and system designs for
micro-reactors as well as large scale systems. Therefore, there is a
need of bridging the gap between the small-scale experimental
reactors and full-blown integrated units. Also, coking studies for
catalysts have been limited, and little work has been carried out to
assess catalyst durability over expected life time of a commercial
product.
In this paper, we have reviewed ethanol autothermal reforming
from the perspectives of catalyst selection, reactor design and
simulation studies. ATR has been carried out over a wide range of
catalyst like noble metals, non noble metals and doped catalyst.
Noble metals prove to be better catalyst than their non-noble
metal counterparts. Rh and Ni show better activity in terms of
Ethanol conversion, selectivity and stability. It has also been
observed that non-noble metals are doped onto noble metal
catalysts for capturing the favourable effects of non-noble metals.
Despite limited literature, the design of a novel, millisecond
contact time autothermal reactors which helps initiating ATR
reactions and maintaining uniform temperature throughout the
reactor hold promises for an effective way of reforming ethanol.
While many studies have concentrated on developing catalytic
reactions, optimizing operating parameters through experimental
set-ups, relatively fewer have focused on modelling and simulation under steady state or transient operation. Coupling detailed
chemical kinetic mechanisms (such as those developed by) with
CFD analysis of the uid ow and heat and mass transfer processes
may yield further insights into the design and optimization of
ethanol ATR systems.

Acknowledgement
The authors acknowledge support received from the Ministry
of Human Resource Development, Government of India, and the
Ministry of Science & Technology, Government of India through
grant SR/S3/CE/078/2012.

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