Renewable and Sustainable Energy Reviews 16 (2012) 2366–2372

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Renewable and Sustainable Energy Reviews

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

A review on current status of hydrogen production from bio-oil

Shyamsundar Ayalur Chattanathan, Sushil Adhikari ∗ , Nourredine Abdoulmoumine
Department of Biosystems Engineering, Auburn University, Auburn, AL 36849, USA

a r t i c l e i n f o a b s t r a c t

Article history: Increase in energy demand and growing environmental awareness has increased interest for alternative
Received 3 June 2011 renewable energy sources over the last few years. Hydrogen produces only water during combustion,
Accepted 16 January 2012 and therefore, it is seen as an alternative fuel for locomotive application. Nonetheless, hydrogen is not an
Available online 20 March 2012
energy source; rather it is an energy carrier. Different techniques are being explored to find an economical
way of generating hydrogen from renewable resources. Hydrogen production from water using sunlight
Keywords:
is still expensive. Biomass is another alternative to produce hydrogen. Bio-oil derived from biomass
Bio-oil
using a fast pyrolysis is a potential source for hydrogen production. Although different techniques have
Catalyst
Steam to carbon ratio
been employed to produce hydrogen from bio-oil, significant effort has been put into steam reforming
Steam reforming process. This paper reviews major hydrogen production techniques with a great deal of importance given
Thermodynamic analysis to steam reforming. The important factors that are known to affect hydrogen yield are temperature, steam
to carbon ratio, and catalyst type. Literature review of bio-oil steam reforming technique has been done,
and a comparison of experimental conditions has been carried out. However, as a major shortcoming, this
technique is accompanied by the formation of carbonaceous deposits over the catalyst surface rendering
it inactive and requiring frequent regeneration. Coke formation has been cited as the major disadvantage
of bio-oil reforming, and it is more pronounced when Ni based catalysts are used.
© 2012 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2366
2. Bio-oil feedstock and characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2367
3. Hydrogen production from bio-oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2367
3.1. Steam-reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2367
4. Thermodynamic analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2367
5. Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2368
5.1. Catalysts characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2368
6. Experimental conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2369
6.1. Choice of reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2369
6.2. Temperature and S/C ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
6.3. Other methods of hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
6.3.1. Partial oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
6.3.2. Autothermal reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
6.3.3. Aqueous-phase reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2371
6.3.4. Supercritical water reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2371
6.3.5. Sequential cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2371
7. Challenges and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2371
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2372

1. Introduction

Renewable and alternative fuels have attracted significant inter-

est as a remedy for greenhouse gases emitted from fossil fuels and
∗ Corresponding author. Tel.: +1 334 844 3543; fax: +1 334 844 3530. uprising price of petroleum fossil based fuels. Among many renew-
E-mail address: sushil.adhikari@auburn.edu (S. Adhikari). able fuels investigated, hydrogen is of utmost importance because

1364-0321/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.rser.2012.01.051
 S. Ayalur Chattanathan et al. / Renewable and Sustainable Energy Reviews 16 (2012) 2366–2372 2367

of its highest energy content per weight (120 MJ/kg) [1]. Addition- Table 1
Typical properties of bio-oil.
ally, when produced from biomass, hydrogen does not pose any
environmental problems and does not increase atmospheric carbon Water content 15–30
dioxide (CO2 ) emissions [2]. Although several methods of hydro- pH 2.5
Specific gravity 1.2
gen production exist, the emphasis of this paper is on hydrogen
HHV (MJ/kg) 16–19
production from bio-oil produced from biomass fast pyrolysis. Fast Viscosity, at 500 ◦ C (cP) 40–100
pyrolysis is the degradation of biomass at around 500 ◦ C in the
absence of oxygen to yield a liquid fuel (hereafter, bio-oil), as well Elemental analysis, wt%
as solid (biochar) and noncondensable gases [3–5]. Bio-oil (also
C 54–58
called pyrolysis oil or biocrude) has an energy density of around H 5.5–7
20 MJ/m3 , which is about ten times that of biomass, making bio-oil N 0–0.2
an excellent alternative source of energy [6]. O 35–40
Bio-oil is a dark to brown organic liquid containing degradation Ash 0–0.2

products of the three main components, namely cellulose, hemi-

celluloses and lignin. The composition of bio-oil varies depending
is very light, highly flammable and burns with pure oxygen pro-
on the biomass source as well as the process conditions. Nonethe-
ducing heat and water in contrast to fossil fuels which produce
less, it typically consists of water and a complex mixture of organic
CO2 on combustion [21]. It has a very high energy content of
compounds such as hydroxyaldehydes, hyroxyketones, sugars,
120 MJ kg−1 compared to that of gasoline (44.4 MJ kg−1 ). Hydrogen
carboxylic acids and phenolics from the breakdown of biomass
is considered as an energy carrier instead of an alternative fuel
carbohydrates and lignin [7]. Its main elemental constituents are
because it is not available freely [21–23]. Bio-oil comprises good
carbon (C), hydrogen (H), and oxygen (O), and hence its empirical
percentage of hydrogen and is therefore utilized in hydrogen pro-
chemical formula is given as Cn Hm Ok ·xH2 O [8]. Bio-oil can be sep-
duction. DynaMotive Energy Systems Corporation, Ensyn Group
arated into organic and aqueous phases by adding water to it and
Inc., and BTG Biomass Technology Group are three major bio-oil
volatile compounds constitute about 60% of bio-oils [9].
producers [24]. There are different techniques by which hydrogen
Bio-oil has numerous applications which includes its usage in
is produced from bio-oil but the majority of the studies are focused
boilers for heat and electricity, in engines and turbines for elec-
on steam reforming process. Therefore, in-depth review on bio-oil
tricity, in chemicals production such as phenols, organic acids,
steam reforming is presented here.
and oxygenates or in transportation fuel production [4]. However,
bio-oil derived transportation fuels require expensive upgrading
techniques, and this route is currently less attractive for motor fuels 3.1. Steam-reforming
production. To alleviate this disadvantage, reforming of bio-oil has
been proposed and employed to produce hydrogen, another viable Steam reforming is an efficient process for hydrogen produc-
fuel for the future. tion and has been in practice since 1930 [25]. Standard Oil Co., USA
This paper reviews the state-of-the-art of hydrogen production began the first steam reforming plant in 1930 with light alkanes
from bio-oil with the main focus on steam reforming. Furthermore, as feed [26]. It is an endothermic process in which the substrate is
the paper discusses the influence of different process parameters treated with steam in the presence of catalyst to produce carbon
such as temperature, steam to carbon ratio, catalysts type, reactor monoxide (CO), CO2 and hydrogen (H2 ) [27]. The chemical reactions
design and others on hydrogen yield. The paper addresses some of for steam reforming of bio-oils are given below [28]:
the challenges faced by reforming of bio-oil for hydrogen produc-
Cn Hm Ok + (n−k)H2 O → nCO + (n + m/2−k)H2 (1)
tion including possible remedies.
The CO can be further converted to CO2 by the water–gas shift
2. Bio-oil feedstock and characterization reaction (Eq. (2)).

Bio-oils have been produced from different biomass feedstocks CO + H2 O → CO2 + H2 (2)
such as corn stover [10] rice husk [11,12], saw dust [13,14], wood
Overall reaction is given as presented in Eq. (3).
[15] [16], barley straw [17], poultry litter [18] and many others. A
detailed review on bio-oil production techniques and its proper- Cn Hm Ok + (2n−k)H2 O → nCO2 + (2n + m/2−k)H2 (3)
ties can be found elsewhere [19]. Physical and chemical properties
of bio-oil are highly influenced by the composition of biomass. For The amount of biological material that contains 1 g atom of
example, Wang et al. [8] reported that sawdust has 54.5% C, 6.7% H carbon is termed as 1 mol of the biological material [29]. Table 2
and 38.7% O, while rice husk has 41% C, 7.4% H and 51.2% O and cot- summarizes a comparison of the moles of H2 produced per mole
ton stalk has about 42.3% C, 7.9% H and 49.4% O. Hydrogen yield is of the source in different methods which includes steam reform-
also affected by the chemical composition of bio-oils and therefore, ing, partial oxidation and supercritical water reforming of various
the feedstock used to generate bio-oil plays a vital role in hydrogen substrates like ethanol, ethyl lactate, glycerol, and bio-oil and its
production. Estimating the bio-oil composition is important in cal- aqueous fraction. On an average, it is found that 1 mol of bio-oil
culating the stoichiometric hydrogen (H2 ) yield, which is discussed substrate produces 2 mol of H2 .
in the next section. Typical properties of bio-oil are summarized in
Table 1 [20]. It is interesting to note that bio-oils are acidic in nature 4. Thermodynamic analysis
and the pH value is also highly dependent on the biomass type. For
example, the bio-oils generated from sawdust, rice husk and cotton The composition of an exit gas stream and important process
stalk had pH of about 2.1, 3.2, and 3.3, respectively [8]. parameters affecting H2 yield are usually predicted by the thermo-
dynamic analysis. Vagia and Lemonidou [34] performed a detailed
3. Hydrogen production from bio-oil thermodynamic analysis of H2 production via steam reforming
with ASPEN 11.1 using acetic acid, ethylene glycol, and acetone as
Hydrogen is the most abundant element in the universe and model compounds of bio-oil. Peng–Robinson property method and
the third most abundant element on the earth’s surface [21]. It RGibbs reactor were selected with equilibrium compositions being
2368 S. Ayalur Chattanathan et al. / Renewable and Sustainable Energy Reviews 16 (2012) 2366–2372

Table 2
Theoretical estimation of number of moles of H2 produced per mole of the source.

Substrate/source Technique Moles of H2 produced/mole Reference

of source (theoretical)

Bio-oil/poplar wood Steam reforming 2.2 [30]

Bio-oil/pine wood Steam reforming 1.73 [30]
Bio-oil/hardwood Steam reforming 2.12 [30]
Aqueous fraction of bio-oil Steam reforming 1.92 [11]
Bio-oil/sawdust Steam reforming 2.2 [8]
Bio-oil/rice husk Steam reforming 2.15 [8]
Bio-oil/cotton stalk Steam reforming 2.24 [8]
Bio-oil/poplar wood (after cold Steam reforming 2.19 [31]
storage for long time)
Bio-oil/poplar wood Partial oxidation 1.66 [31]
Ethanol Steam reforming 3 [1]
Ethyl lactate Partial oxidation 1 [32]
Glycerol Steam reforming 2.33 [27]
Glycerol Super critical water 2.33 [33]
reforming

computed by the minimization of Gibb’s free energy. The impor- suppressing the coke formation and a 90% hydrogen yield was
tant specifications fed into the software included reactant and reported for the equimolar mixture of model compounds [16].
product inlet composition, inlet temperature, pressure, reaction Pan et al. [9] employed C12A7-Mg catalyst and determined its
temperature, and steam to fuel (S/F) ratio. A study from Vagia and lifetime to be about 210 min at 750 ◦ C. Steam reforming of bio-
Lemonidou [34] showed that equilibrium concentrations of ethane, oil at 750 ◦ C using this catalyst resulted in a hydrogen yield of
ethylene, acetylene and other oxygenated compounds in the prod- 80%. Wang et al. [8] conducted reforming over three catalysts:
uct stream were negligible. It was established that H2 yield was C12A7/15% Mg, 12% Ni/gamma-Al2 O3 , and 1% Pt/gamma-Al2 O3
favored at increased temperatures and S/C (steam to carbon ratio) at 650 ◦ C and the observed hydrogen yields were 56.7%, 58.1%,
at atmospheric pressure. At optimum conditions of 627 ◦ C, atmo- and 66.8%, respectively. Yan et al. [42] reformed bio-oil with
spheric pressure and S/C = 3 (steam to carbon ratio), 0.208 kmol/s of commercial Z417 catalyst along with CO2 sequestration using
the mixture of the model compounds (acetic acid, ethylene glycol calcined dolomite and reported a hydrogen yield of about 75%.
and acetone at 4:1:1 molar ratios) yielded about 1 kmol/s of hydro- Lin et al. [14] performed catalytic reforming of bio-oil over CoZ-
gen. No coke formation was reported at temperatures higher than nAl catalyst electrochemically by passing ac current in a Ni–Cr
327 ◦ C. Vagia and Lemonidou [34] also established that bio-oil can wire entwined around the catalytic column. A detailed compari-
be thermally decomposed to form a mixture of gases containing son of different studies in reforming of bio-oil has been made in
methane (CH4 ), H2 , CO, CO2 and water (H2 O). Table 3.
Similar thermodynamic analysis was done by the same research The reactors usually used are fluidized bed, bench-scale, and
group for H2 production via autothermal reforming with the same fixed bed reactors. From the table we can observe that model com-
model compounds [35]. They reported a maximum yield at 627 ◦ C pounds are usually used, though a few of them have used aqueous
but 20% lesser than the yield obtained by the steam reform- fraction of bio-oil. This is attributed to the complex composition of
ing. Aktas et al. [36] conducted thermodynamic analysis of steam bio-oils which form residual solids on heating. A common problem
reforming using isopropyl alcohol, lactic acid and phenol as model experienced in the above cases is coking.
compounds of bio-oil at temperatures from 327 ◦ C to 927 ◦ C, S/F
ratio from 4 to 9 and total pressure of 30 bar. The fact that H2
yield increased with increasing temperature and S/F ratio was 5.1. Catalysts characterization
confirmed.
Galdámez et al. [2] characterized Ni–Al catalyst using induc-
tively coupled plasma (ICP), X-ray diffraction (XRD), nitrogen
5. Catalysts adsorption and temperature-programmed reduction (TPR) and
found the surface area of the catalyst to be 150 m2 /g. When the cat-
Steam reforming of bio-oils is usually carried out in the pres- alyst was loaded with 8% and 12% La2 O3 its surface area reduced to
ence of a catalyst which not only increases the reaction rate but 141 and 131 m2 /g, respectively. Yan et al. [42] used differential ther-
also helps achieving equilibrium faster. Catalytic reforming of bio- mogravimetric (DTG) and differential scanning calorimetric (DSC)
oils has been studied by Chornet group [6,37–41]. Galdámez et al. curves to determine the decomposition mechanism of their sorbent
[2] prepared Ni–Al catalysts by co-precipitation and studied the dolomite. Pan et al. [9] used XPS to study their catalyst before and
extent to which loading of La2 O3 onto Ni–Al catalyst affected the after steam reforming and found that there was an increase in car-
hydrogen yield while, they also conducted non-catalytic steam bon content on the surface of the catalyst after reforming. Lin et al.
reforming and confirmed that the H2 , CO2 yields were low in [14] used N2 physisorption to determine Brunauer–Emmett–Teller
the absence of catalyst. Galdámez et al. [2] also noticed that (BET) and pore volume of the catalyst. Wang et al. [8] measured
the total gas yield decreased with decrease in catalyst weight. Mg, Ni and Pt contents in the catalyst using inductively coupled
Catalysts were usually reduced for an hour at high temperature plasma (ICP) and atomic emission spectroscopy (AES). They also
with N2 /H2 before their usage in experiments to increase activ- used XRD and N2 physisorption at 196 ◦ C to determine the surface
ity. Galdámez et al. [2] reduced Ni–Al catalyst with a mixture of atomic composition, BET surface area and pore volume. A summary
H2 and N2 gas for 1 h at 650 ◦ C. Czernik et al. [40] and Kecha- of analysis techniques used is given below. BET is used to determine
giopoulos et al. [16] used nickel-based naphtha reforming catalyst the surface area of the catalyst. ICP is used to determine the metal
to produce hydrogen. Kechagiopoulos et al. [16] used C11-NK and non-metal concentrations in the catalyst while XPS is used to
catalyst which has higher potassium content compared to other determine the composition of the catalysts on the surface and dif-
Ni catalysts. The higher potassium content plays a vital role in ferent states of the metal used for catalyst. The temperature effects
 S. Ayalur Chattanathan et al. / Renewable and Sustainable Energy Reviews 16 (2012) 2366–2372 2369

Table 3
Comparison study of reforming techniques discussed in the literature.

Catalyst Experimental conditions Key findings Fuel type Reference

Ni–Al promoted with La Reactor: fluidized bed Use of catalyst showed an increase in total gas Model compound: acetic [2]
T = 450–700 ◦ C and H2 yield. Promotion with La did not affect acid
S/C: 5.58 H2 yield with Ni––Al catalyst. H2 yield:
Liquid feeding rate: 1.84–2.94 g/min 0.029 g/g of acetic acid at 1.84 g/min feeding
rate and 650 ◦ C
Commercial catalyst Z417 Reactor: bench-scale fixed bed Optimum temperature with CO2 capture: Aqueous fraction of bio-oil [42]
Temperature: 500–700 ◦ C 550–650 ◦ C
water: bio-oil ratio-1:1
Use of dolomite to capture CO2 showed highest
H2 yield.
H2 yield: 75% at 600 ◦ C
Ni based catalyst Reactor: fixed bed The high potassium content in the catalyst Model compounds: acetic [16]
Temperature: 600–900 ◦ C suppressed coking. A H2 yield of 60% was acid, acetone, and ethylene
H2 O/C: 2–8.2 reported when aqueous phase of bio-oil was and aqueous phase of
GC1 HSV: 300–500 h−1 reformed, but 90% yield was reported for the bio-oil
model compounds at temperatures higher
than 600 ◦ C.
Ru/Mgo/Al2 O3 Reactor: Nozzle fed reactor Role of MgO is vital in converting CO to CO2 Model compound: acetic [28]
T: 800 ◦ C and enhancing steam adsorption capacity of acid and aqueous phase of
P: 1 atm the catalyst. bio-‘oil
S/C: 7.2 The selectivity of H2 in the form of pellets was
the highest and was close to 100%
C12A7 doped with 15% Mg, Reactor: fixed-bed flow reactor C12A7/15% Mg exhibited high reforming Volatile organic [8]
12% Ni/␥-Al2 O3 and 1% T: 750 ◦ C activity, a H2 yield of 71% and carbon components of crude
Pt/␥-Al2 O3 S/C: 6.0 conversion of 93% bio-oil
GHSV: 26,000 h−1
Ni/CeO2 –ZrO2 Reactor: fixed bed Highest H2 yield of 69.7% was achieved when Aqueous fraction of bio-oil [11]
Temperate: 450–800 ◦ C T = 800 ◦ C, W/B = 4.9, Ni-12% and Ce-7.5%.
Water/bio-oil: 4.9 Under same conditions H2 yield was higher
Ni-12% than commercial Z417 catalyst
Ce-7.5%
Ni, Rh or Ir supported on Reactor: fixed bed quartz reactor Coke deposition over Ni loaded catalyst was Model compounds: acetic [43]
calcium aluminates Temperature: 550–750 ◦ C higher than that with the Rh or Ir. The Highest acid and acetone
S/C: 3 H2 yield was obtained with 5% Ni/CaO·2Al2 O3
Space velocity: 30,000 h−1 catalyst and was about 70% at 750 ◦ C for
acetone
Ni–Al catalyst modified with Reactor: fluidized bed Coke formation was reduced by decreased Aqueous fraction [44]
Mg and Ca Temperature: 650 ◦ C space velocity and increased O2 . Mg modified
GC1 HSV: 11,800 h−1 catalyst performed better than Ca modified
catalyst. A hydrogen yield of 0.1056 g/g of
organics was reported for Magnesium
modified catalyst.
Commercial catalyst C11-NK Reactor: bench-scale fluidized bed Steam reforming resulted in a H2 yield of about Whole bio-oil [45]
and NREL#20 Temperature: 850 ◦ C 70–80%
S/C: 5.8
Space velocity: 920 h−1
C12A7 doped with 18% Mg, Temperature: 200–750 ◦ C At 750 ◦ C, S/C > 4, GHSV of 10,000 h−1 Whole bio-oil [46]
C12A7 doped with 25% K, S/C: 1.5–9 C12A718% Mg showed the highest hydrogen
C12A7, C12A7 doped with Gas hourly space velocity(GSHV): yield of 80% and carbon conversion of 96%
12% Ce, C12A7 doped with 10,000 h−1
12% Mg, Al2 O3 doped with Reactor: fixed bed micro-reactor
12% Mg, Al2 O3 doped with Pressure: atmospheric pressure
18% Mg
Non-catalytic Temperature: 625–850 ◦ C The partial oxidation resulted in a hydrogen Whole bio-oil [31]
O:C (oxygen to carbon ratio): 1.4–1.6 yield of about 25%
Reactor: tubular reactor

on the catalyst are determined using DTG and DSC curves. XRD is different noble metal based catalysts for steam reforming of glyc-
done to get an idea about the crystallographic atomic structure of erol.
the catalyst.
6.1. Choice of reactor
6. Experimental conditions
Type of reactor plays a vital role in steam reforming of bio-oil.
Since bio-oil is a complex mixture of many organic compounds, Fixed reactors are not preferred for steam reforming of bio-oils,
its steam reforming has been usually studied by either using since the operating time is limited due to formation of carbona-
its aqueous fraction or by using model compounds. Chornet and ceous deposits [2]. They were prescribed to be unfit for thermally
co-workers [6] conducted experiments with aqueous fraction of unstable biomass liquids by Czernik et al. [40] who in turn used
bio-oil. Many researchers have investigated H2 production with a fluidized bed reformer. Fluidized bed on the contrary, ensured
acetic acid as a model compound [6,37,38]. Takanabe et al. [47] have continuous operation by gasification of carbonaceous deposits on
studied steam reforming of acetic acid over Pt/ZrO2 . Kechagiopou- catalyst particles [2]. Basagiannis et al. [28] established that using a
los et al. [16] used three model compounds for their investigation: nozzle-fed reactor, in which the liquid is fed into the reactor using
acetic acid, acetone and ethylene glycol. Adhikari et al. [48] tested high flow rate nozzles, decreased the carbon deposition to a great
2370 S. Ayalur Chattanathan et al. / Renewable and Sustainable Energy Reviews 16 (2012) 2366–2372

Fig. 1. Schematic representation of unique reactors used Ref. [49].

extent. Gongxuan et al. [49] performed a coupled steam reforming of the reaction was directly dependent on reactant concentration,
of bio-oil in a Y-type reactor design in which the catalyst bed was higher partial pressure resulted in higher H2 yield.
in the center and bio-oil and bio-oil mixed with steam/water were Kechagiopoulos et al. [16] reported a low hydrogen yield of
sent through the other inlets. The important factors that affect H2 about 60% by reforming the aqueous phase of bio-oil. Wang et al.
production are temperature, steam: carbon ratio, and space veloc- [8] performed reforming over three different catalysts (C12A7/15%
ity. Fig. 1 depicts the nozzle-fed and Y-type reactors used for bio-oil Mg, 12% Ni/␥-Al2 O3 , and 1% Pt/␥-Al2 O3 ), and found that at 700 ◦ C
reforming. 1% Pt/␥-Al2 O3 showed the highest H2 yield of 75%. Pan et al. [9]
reported a maximum carbon conversion and H2 yield of about
95% and 80% at 750 ◦ C, respectively which were higher than that
6.2. Temperature and S/C ratio obtained with naphtha and CH4 .

Since the steam reforming of bio-oils is accompanied by

6.3. Other methods of hydrogen production
decrease in temperature, an increase in temperature shifts the
equilibrium towards the right thereby leading to increase in H2
Apart from steam reforming, there are other techniques being
yield. Similarly, the steam to carbon ration also affects H2 yield
used for hydrogen production from bio-oil. Although not all the
to a great extent. Wang et al. [8] observed that H2 production
available processes have been tested, the paper briefly discussed
increased with increase in temperature and S/C ratio. This was
below to demonstrate techniques that are relevant to produce
accompanied with an increase in carbon conversion which was
hydrogen using bio-oil.
only 15% at 500 ◦ C but later on increased to 93% at 750 ◦ C. As
S/C was increased from 1.5 to 6, both H2 yield and carbon con-
version increased. Galdámez et al. [2] conducted studies at 650 ◦ C 6.3.1. Partial oxidation
and 13,000 h−1 space velocity using a fluidized bed reactor. Yan In this method, the substrate is oxidized with oxygen (in the
et al. [42] carried out steam reforming of bio-oil aqueous fraction presence or in the absence of catalyst), resulting in high temper-
in a fixed bed reactor with CO2 capture (using CaO and dolomite). ature which in turn balances the energy required for the process.
Interestingly, they found out that H2 production decreased at high However, excess air leads to complete oxidation of the substrate
temperatures with the capture of CO2 . The optimal temperature as resulting in formation of CO2 and water [27].
reported by them for H2 production with CO2 capture is between
(Substrate) Cn Hm Ok + air → carbonoxides + H2 + N2 (4)
550 ◦ C and 650 ◦ C. Kechagiopoulos et al. [16] observed an increase
in H2 yield with increase in H2 O/C ratios and decrease in pressure. Marda et al. [31] conducted non-catalytic partial oxidation of
They also found that the maximum yield for their experimental bio-oil, while Rennard et al. [32] performed autothermal catalytic
conditions was between 600 and 750 ◦ C. Czernik et al. [40] car- partial oxidation of bio-oil using esters and acids as model com-
ried out steam reforming at temperatures 800–850 ◦ C, S/C range of pounds over platinum and rhodium based catalysts. Marda et al.
7–9 and space velocity of 700–1000 h−1 . Pan et al. [9] conducted [31] reported a low H2 yield of about 25% while Rennard et al. [32]
steam reforming of bio-oils in a fixed bed micro-reactor where in have concentrated on synthesis gas production.
the vaporized bio-oil was fed into the reactor at a space velocity of
10,000 h−1 . They performed experiments in the temperature range
6.3.2. Autothermal reforming
550–750 ◦ C at S/C 4.0.
It is a combination of steam reforming and partial oxidation
The effect of liquid feed rate has been well addressed by
techniques in which the substrate is reformed in the presence of
Galdámez et al. [2] with respect to their experimental conditions.
air and water to produce H2 .
The residence time decreases as the liquid feed rate increases which
should eventually result in lower H2 yield. But, the result obtained (Substrate) Cn Hm Ok + air + steam → CO + H2 + N2 (5)
indicated higher H2 yield. This was due to the increase in partial
pressure in the reaction bed with higher liquid feed rate. The typi- The advantage lies in the fact that the process does not require
cal residence time used was in the range 0.56–0.44 s. Since the rate energy ideally because all heat produced during the oxidation step
 S. Ayalur Chattanathan et al. / Renewable and Sustainable Energy Reviews 16 (2012) 2366–2372 2371

is consumed by steam reforming step. However, low H2 yield com-

pared to steam reforming process is a disadvantage of autothermal
reforming.
Vagia et al. [35] performed thermodynamic analysis of autother-
mal reforming of selected components of aqueous bio-oil fraction
to determine the optimum amount of oxygen required to carry out
an energy neutral process. They also studied the effect of tempera-
ture and pressure on H2 production. They reported that at optimum
operating conditions, 1 kmol of H2 is produced from 0.245 kmol of
bio-oil, which is 20% lower than the H2 yield obtained by steam
reforming method.

6.3.3. Aqueous-phase reforming

This process which was developed by Dumesic and his co-
workers is carried out at high pressure (at around 60 bar) and low
temperature (at around 270 ◦ C) [50]. The advantages of this pro-
cess are it produces low amount of CO and the process takes place
Fig. 2. TGA results for bio-oil produced from pine wood.
in liquid phase (while the others take place in gas phase) so there
is no need to vaporize the substrate used for producing hydrogen.
The effect of catalyst size with pure and crude glycerol was studied H2 g−1 as compared to 20 and 37 mmol H2 g−1 (at 2.5 and 10 H2 O/C
by Claus and Lehnert [51] and the study revealed that H2 selectiv- ratios) productivities in steam reforming method. The operating
ity was higher for larger particles. Iriondo et al. [52] used different temperature was 700 ◦ C and H2 yield observed was 40%.
promoters and found that Ni catalyst does not work very well for
glycerol due to severe deactivation. 7. Challenges and conclusions

6.3.4. Supercritical water reforming Coking is a major problem that is encountered in steam reform-
Water when heated and compressed to its critical tempera- ing process. It results from thermal decomposition of organic
ture (374 ◦ C) and pressure 22.1 MPa becomes supercritical water. compounds onto the catalyst resulting in its deactivation [16].
Supercritical water possesses characteristics of both liquid water Cn Hm Ok → Cx Hy Oz + Gas (H2 , CO, CO2 , CH4 . . .) + Coke (8)
and vapor which includes densities, viscosities, high diffusivity and
good transporting properties [53,54]. Penninger and Rep [55] con- Thermogravimetric analysis (TGA) revealed that there is a
ducted supercritical water reforming of aqueous wood pyrolysis maximum weight loss at 125 ◦ C, which could be mainly due to
condensate obtained from moist beech wood saw dust at 650 ◦ C vaporization of water. At temperatures higher than 400 ◦ C, the
and 28 MPa. They found that, there was no plugging at 28 MPa weight loss decreased gradually and when the temperature reached
pressure and a small percentage of soda (0.1%) promoted hydro- 600 ◦ C there was no weight loss observed. From the TGA graph
gen production. A hydrogen yield of 36.6 vol% was observed at a (Fig. 2), it can be seen that there is a total weight loss of 73.07%
residence time of 12.5 s and a total feed flow of 690 g/h. Byrd et al. at 600 ◦ C, which means that 26.93% of the bio-oil fed into the
[56] studied hydrogen production from switchgrass biocrude by reactor did not vaporize, and hence would result in clogging of
catalytic gasification in supercritical water. The Ni, Co, Ru catalysts catalyst’s pores and the reactor. Bio-oil cannot be completely vapor-
supported on TiO2 , ZrO2 and MgAl2 O4 were tested and among them ized, and when heated, leads to the formation of residual solids.
Ni/ZrO2 exhibited highest hydrogen yield of 0.98 mol H2 /mol C at To overcome this operational difficulty while feeding, Basagiannis
600 ◦ C and 250 bar. Yu et al. [57] and Antal et al. [58] reformed wet et al. [28] used a nozzle injection system to spray bio-oil into the
biomass to hydrogen, carbon dioxide and carbon monoxide using reactor. This problem can also be avoided by increasing the temper-
supercritical water at 600 ◦ C and 35 MPa. Gupta and co workers ature so that gasification of the carbonaceous deposits takes place
carried out supercritical water reforming of glycerol over Ru/Al2 O3 thereby resulting in regeneration of the catalyst. Rennard et al. [30]
catalyst which yielded 6.5 mol of H2 /mol of glycerol [33]. established that high steam to carbon ratio helps decreasing coke
formation. However, the heat load increases, since more steam has
6.3.5. Sequential cracking to be supplied. Coke formation is also reduced by blending of bio-oil
It is a two step process in which the bio-oil is first catalytically [30]. Oxidation of coke also helps in alleviating coking, although the
cracked/reformed without addition of water followed by subse- presence of oxygen results in decreased experimental and theoret-
quent regeneration of the catalyst with oxygen [59]. Reactions to ical H2 yields [66–70]. Medrano et al. [44] reported that the coke
demonstrate the technique are given below taking methane as an formation decreased from 149 mg C/g catalyst to 73 mg C/g catalyst
example [60–65]: with an addition of 4% oxygen. The use of Ce1−x Nix O2−y as catalyst
is also known to decrease the formation of carbonaceous deposits
Cracking : CH4 → C + 2H2 (6) due to Ce, O, Ni interaction [71]. A catalyst (Ce0.8 Ni0.2 O2−y ) prepared
using adapted micro emulsion method proved to be an excellent
Regeneration : C + O2 → CO2 (7)
catalyst for ethanol steam reforming. It was not only less expen-
Davidian et al. [59] used two Ni based catalyst and found them to sive than Rh/CeO2 catalyst, but also has a higher catalytic activity
be performing very well for producing hydrogen from bio-oil. Iojoiu [72].
et al. [66] used Pt and Rh catalysts supported in ceria–zirconia for H2 Estimating the world’s current energy demands and foresee-
production from bio-oil obtained from beech wood residues. From ing the demands in the upcoming years we realize the need for
the heat balance calculations, they also established that sequential a pollution-free alternative source of energy. Hydrogen obtained
cracking process could be operated auto-thermally. The possibil- from bio-oil would serve as a versatile energy carrier in this regard.
ity of removing large carbon deposits by catalyst regeneration is The purpose of this review is to give a comprehensive update of
a great advantage of this method despite the reported sintering various developments in the field of hydrogen production from
of ceria–zirconia support. The H2 productivity was only 18 mmol bio-oil. Though we have specifically documented an overview of
2372 S. Ayalur Chattanathan et al. / Renewable and Sustainable Energy Reviews 16 (2012) 2366–2372

steam reforming of bio-oil, we have also discussed other meth- [30] Rennard D, French R, Czernik S, Josephson T, Schmidt L. Int J Hydrogen Energy
ods like partial oxidation, autothermal, aqueous phase reforming 2010;35:4048–59.
[31] Marda J, DiBenedetto J, McKibben S, Evans R, Czernik S, French R, et al. Int J
and supercritical water reforming to show their differences. Quite Hydrogen Energy 2009;34:8519–34.
a lot of work has been reported in the literature on steam reform- [32] Rennard D, Dauenhauer P, Tupy S, Schmidt L. Energy Fuels 2008;22:1318–27.
ing of bio-oil though, to the best of our knowledge, very few have [33] Byrd A, Pant K, Gupta R. Fuel 2008;87:2956–60.
[34] Vagia E, Lemonidou A. Int J Hydrogen Energy 2007;32:212–23.
been reported on aqueous phase reforming of bio-oils. Experiments [35] Vagia E, Lemonidou A. Int J Hydrogen Energy 2008;33:2489–500.
have been conducted to check the change in H2 yield with different [36] Aktas S, Karakaya M, AvcI. A. Int J Hydrogen Energy 2009;34:1752–9.
catalysts, reactors at wide range of temperatures. Further empha- [37] Wang D, Montane D, Chornet E. Appl Catal A: Gen 1996;143:245–70.
[38] Marquevich M, Czernik S, Chornet E, Montané D. Energy Fuels 1999;13:1160–6.
sis must be given to the catalyst deactivation issue and ways to
[39] Garcia L, French R, Czernik S, Chornet E. Appl Catal A: Gen 2000;201:225–39.
overcome the coking challenge during bio-oils reforming must be [40] Czernik S, French R, Feik C, Chornet E. Ind Eng Chem Res 2002;41:4209–15.
explored. [41] Wang D, Czernik S, Chornet E. Energy Fuels 1998;12:19–24.
[42] Yan C, Hu E, Cai C. Int J Hydrogen Energy 2010;35:2612–6.
[43] Vagia E, Lemonidou A. Appl Catal A: Gen 2008;351:111–21.
References [44] Medrano J, Oliva M, Ruiz J, García L, Arauzo J. Energy; 2010.
[45] Czernik S, Evans R, French R. Catal Today 2007;129:265–8.
[1] Haryanto A, Fernando S, Murali N, Adhikari S. Energy Fuels 2005;19:2098–106. [46] Wang Z, Pan Y, Dong T, Zhu X, Kan T, Yuan L, et al. Appl Catal A: Gen
[2] Galdámez J, García L, Bilbao R. Energy Fuels 2005;19:1133–42. 2007;320:24–34.
[3] Babu B, Biofuels. Bioprod Biorefin 2008;2:393–414. [47] Takanabe K, Aika K, Seshan K, Lefferts L. J Catal 2004;227:101–8.
[4] Bridgwater A, Meier D, Radlein D. Org Geochem 1999;30:1479–93. [48] Adhikari S, Fernando S, Haryanto A. Catal Today 2007;129:355–64.
[5] Lu Q, Li W, Zhu X. Energy Convers Manage 2009;50:1376–83. [49] Gongxuan H. Int J Hydrogen Energy 2010;35:7169–76.
[6] Wang D, Czernik S, Montane D, Mann M, Chornet E. Ind Eng Chem Res [50] Cortright R, Davda R, Dumesic J. Nature 2002;418:964–7.
1997;36:1507–18. [51] Lehnert K, Claus P. Catal Commun 2008;9:2543–6.
[7] Sipilä K, Kuoppala E, Fagernäs L, Oasmaa A. Biomass Bioenergy [52] Iriondo A, Barrio V, Cambra J, Arias P, Güemez M, Navarro R, et al. Top Catal
1998;14:103–13. 2008;49:46–58.
[8] Wang Z, Dong T, Yuan L, Kan T, Zhu X, Torimoto Y, et al. Energy Fuels [53] Loppinet Serani A, Aymonier C, Cansell F. ChemSusChem 2008;1:486–503.
2007;21:2421–32. [54] Kobe Steel L, Characteristics and uses of supercritical water 2011.
[9] Pan Y, Wang Z, Kan T, Zhu X, Li Q. Chin J Chem Phys 2006;19:190. [55] Penninger JML, Rep M. Int J Hydrogen Energy 2006;31:1597–606.
[10] Mullen C, Boateng A, Goldberg N, Lima I, Laird D, Hicks K. Biomass Bioenergy [56] Byrd AJ, Kumar S, Kong L, Ramsurn H, Gupta RB. Int J Hydrogen Energy
2010;34:67–74. 2011;36:3426–33.
[11] Yan C, Cheng F, Hu R, Fu P. Int J Hydrogen Energy 2010;35:2612–6. [57] Yu D, Aihara M, Antal MJ. Energy Fuels 1993;7:574–7.
[12] Tsai WT, Lee MK, Chang YM. Bioresour Technol 2007;98:22–8. [58] Antal Jr M, Manarungson S, Mok W, Bridgwater A. Advances in thermochemical
[13] Torri C, Reinikainen M, Lindfors C, Fabbri D, Oasmaa A, Kuoppala E. J Anal Appl biomass conversion, vol. 2; 1994. p. 1367–77.
Pyrolysis 2010;88:7–13. [59] Davidian T, Guilhaume N, Iojoiu E, Provendier H, Mirodatos C. Appl Catal B:
[14] Lin S, Ye T, Yuan L, Hou T, Li Q. Chin J Chem Phys 2010;23:451. Environ 2007;73:116–27.
[15] Agblevor FA, Mante O, Abdoulmoumine N, McClung R. Energy Fuels [60] Choudhary TV, Goodman DW. J Catal 2000;192:316–21.
2010;24:4087–9. [61] Choudhary T, Sivadinarayana C, Chusuei C, Klinghoffer A, Goodman D. J Catal
[16] Kechagiopoulos P, Voutetakis S, Lemonidou A, Vasalos I. Energy Fuels 2001;199:9–18.
2006;20:2155–63. [62] Aiello R, Fiscus J, Zur Loye H, Amiridis M. Appl Catal A: Gen 2000;192:227–34.
[17] Mullen C, Boateng A, Hicks K, Goldberg N, Moreau R. Energy Fuels [63] Takenaka S, Kato E, Tomikubo Y, Otsuka K. J Catal 2003;219:176–85.
2009;24:699–706. [64] Villacampa JI, Royo C, Romeo E, Montoya JA, Del Angel P, Monzón A. Appl Catal
[18] Mante OD, Agblevor FA. Waste Manage 2010;30:2537–47. A: Gen 2003;252:363–83.
[19] Mohan D, Pittman Jr CU, Steele PH. Energy Fuels 2006;20:848–89. [65] Odier E, Schuurman Y, Barrai K, Mirodatos C. In: Xinhe B, Yide X, editors. Studies
[20] Mohan D, Pittman CU, Steele PH. Energy Fuels 2006;20:848–89. in surface science and catalysis. 2004. p. 79–84.
[21] Armaroli N, Balzani V. ChemSusChem 2011;4:21–36. [66] Iojoiu E, Domine M, Davidian T, Guilhaume N, Mirodatos C. Appl Catal A: Gen
[22] Rand D, Dell R, Dell R. Hydrogen energy: challenges and prospects. Royal Society 2007;323:147–61.
of Chemistry; 2008. [67] Domine M, Iojoiu E, Davidian T, Guilhaume N, Mirodatos C. Catal Today
[23] In: Borgschulte A, Zuttel A, Schlapbach L, editors. Hydrogen as a future energy 2008;133:565–73.
carrier Weinheim; 2008. [68] Kechagiopoulos P, Voutetakis S, Lemonidou A, Vasalos I. Ind Eng Chem Res
[24] Svoboda K, Pohorelý M, Hartman M, Martinec J. Fuel Process Technol 2008;48:1400–8.
2009;90:629–35. [69] van Rossum G, Kersten S, van Swaaij W. Ind Eng Chem Res 2007;46:
[25] Navarro R, Pena M, Fierro J. Chem Rev 2007;107:3952–91. 3959–67.
[26] Rostrup-Nielson J. In: Anderson JR, Boudart M, editors. Catalysis, Science and [70] Rioche C, Kulkarni S, Meunier F, Breen J, Burch R. Appl Catal B: Environ
Technology, vol. 5. Berlin: Springer; 1984. pp. 1–117. 2005;61:130–9.
[27] Adhikari S, Fernando S, Haryanto A. Energy Convers Manage 2009;50:2600–4. [71] Barrio L, Kubacka A, Zhou G, Estrella M, Martiı̌nez-Arias A, Hanson JC, et al. J
[28] Basagiannis A, Verykios X. Catal Today 2007;127:256–64. Phys Chem C 2010;114:12689–97.
[29] Shuler M, Kargi F. Bioprocess engineering. NJ: Prentice Hall Upper Saddle River; [72] Zhou G, Barrio L, Agnoli S, Senanayake S, Evans J, Kubacka A, et al. Angewandte
2002. Chemie 2010;122:9874–8.