Renewable and Sustainable Energy Reviews 38 (2014) 428–438

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Review of recent developments in Ni-based catalysts

for biomass gasification
Fan Liang Chan, Akshat Tanksale n
Department of Chemical Engineering, Monash University, Clayton, Victoria 3800, Australia

art ic l e i nf o a b s t r a c t

Article history: Biomass gasification is recognized as one of the most promising solutions for renewable energy and
Received 6 August 2013 environmental sustainability. However, tar formation in gasifier remains as one of the main hurdles that
Received in revised form hinder commercialization. Nickel based catalyst is widely used in chemical industries and is proven as
8 May 2014
one of the most effective transition metal catalysts in biomass gasification for tar cracking and reforming.
Accepted 18 June 2014
This paper presents a review of various commercial nickel catalysts that have been evaluated for tar
elimination in biomass gasification. This review also looks at recent advancements in nickel based
Keywords: catalyst used in biomass gasification, including discussion on the effects of different support, promoter
Biomass and particle size on the catalytic performance. Future direction of biomass gasification, including
Gasification
reactive flash volatilization and steam gasification, are also discussed in this review.
Nickel catalyst
& 2014 Elsevier Ltd. All rights reserved.
Reactive flash volatilization

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428
2. Tar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
3. Biomass gasification with commercial nickel based catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
3.1. Commercial catalyst as primary catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
3.2. Commercial nickel catalyst as secondary catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
3.2.1. Synthesis gas upgrading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
3.2.2. Bio-oil steam reforming. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
4. Recent advancements in nickel based catalyst for biomass gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
4.1. Effect of support on nickel based catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
4.2. Promoted nickel based catalyst. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
4.3. Nickel nanoparticle catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434
5. Future directions of biomass gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437

1. Introduction and greenhouse gas emissions, non-renewable fossil fuels such as

coal, petroleum and natural gas can no longer be considered as the
According to the 2011 Energy White Paper by the Australian only energy sources for the meeting of our future energy needs. In
Department of Resource, Energy and Tourism, the world global the short to medium term, a versatile and diverse energy plan,
energy demand in year 2035 will be 40% higher than current comprising both renewable and non-renewable energy sources is
level [1]. However, with the growing concerns about climate change required. In the long term, there is a need for global transition to
100% renewable energy and chemical feedstock to achieve sustain-
able growth.
n
Corresponding author. Tel.: þ 61 3 9902 4388; fax: þ 61 3 9905 5686. Biomass is a renewable energy resource derived from biological
E-mail address: [email protected] (A. Tanksale). sources such as energy crops, agricultural residues, forestry

http://dx.doi.org/10.1016/j.rser.2014.06.011
1364-0321/& 2014 Elsevier Ltd. All rights reserved.
 F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438 429

residues and municipal wastes [2]. Biomass utilization is recog- efficiency. Recently, significant progress has been made in the
nized as one of the most promising solutions for our current gasifier designs coupled with the use of catalysts to overcome
energy and environmental problems. Alternative renewable these operational problems. The key focus of this paper is to
energy technologies such as solar energy and wind power, which review some of the recent developments in nickel based catalyst
often suffer from intermittent power generation issue, are less used in biomass gasification and tar removal.
reliable in term of security of supply [3]. Also, biomass is the only
renewable energy source that can be converted into liquid fuel and
utilized as feedstock in chemicals production [4].
Thermochemical processes for biomass conversion, such as 2. Tar
combustion, gasification and pyrolysis, can be used for power
generation and biofuels production [5]. Among these processes, Tar consists of more than 100 different compounds and is
biomass gasification has attracted the most attention from both produced in a series of complex thermochemical reactions. The
industrial and academic researchers due to its high conversion amount of tar produced in biomass gasification is greatly affected
efficiency [6]. Biomass gasification is a process to convert biomass by factors such as type of biomass feedstock, particle size, type of
feedstock into combustible gaseous products like hydrogen, car- gasifier, type of gasifying agent and operating conditions such as
bon monoxide and methane; however, undesirable products like temperature and pressure. Table 1 shows an overview of different
tar and char are also produced under high temperature and types of biomass gasification setups. Majority of the gasifiers
limited oxygen supply environment. are operated in a temperature range of 700–1000 1C. Generally,
Chemistry of biomass gasification is complex and yet to be fully higher operating temperatures lead to lower tar content in the
understood by researchers [7]. It is generally acceptable to say that product gas. Among the three designs listed in Table 1, gas product
the major reactions include pyrolysis, oxidation, partial oxidation, generated from entrained flow gasifier normally has the lowest tar
reduction, steam reforming and water–gas shift reactions [4,8,9]. content because they operate at the higher end of the gasification
Pyrolysis is an endothermic decomposition process which takes temperature range (1000–1400 1C) [13]. Increasing the pressure of
place at high temperature in the absence of air or steam. In gasifiers also has a positive effect in reducing or eliminating the tar
biomass pyrolysis, the feedstock is converted into gas, liquid tar formation [14]. However, it has been observed that increasing the
and solid char products [10] as shown in Fig. 1. pressure results in greater reduction of light hydrocarbons com-
In oxidation or partial oxidation reactions, carbonaceous pro- pared to the heavy hydrocarbons, therefore the fraction of poly-
ducts from pyrolysis reaction may react further with oxygen to nuclear aromatic hydrocarbons (PAH) in the tar increases with
generate more gas and release heat. In the final step of gasification, pressure [15].
product gases are upgraded through steam reforming, which In addition to the quantity of tar produced, the composition of
converts low molecular weight hydrocarbons such as CH4 into tar also depends on the type of biomass feedstock, particle size
CO and H2. Water–gas shift reaction further converts CO and steam and gasification conditions used. Fraga et al. [16] showed that the
into H2 and CO2. Side reactions such as methanation also occur in distribution of the furan derivatives in sugarcane bagasse tar was
gasification but to a lesser extent [11,12]. Using cellulose as a different from the distribution found in silver birch wood tar
model, the main chemical reactions of biomass gasification can be under the same pyrolysis conditions. Ku et al. demonstrated that
expressed in the equations below the content of PAH found in bamboo pyrolysis tar was higher than
the PAH content found in oak and pine wood tar [17]. Furthermore,
overall cellulose steam reforming Qin et al. reported that PAH concentration in tar from sawdust
ðC6 H10 O5 Þn þ 7nH2 O-12nH2 þ 6nCO2 gasification decreased as the gasification temperature increased
from 700 1C to 900 1C [18]. Therefore, it is important to understand
the composition of tar and the conditions under which different
water–gas shift types of tar compounds are formed.
CO þ H2 O’-CO2 þ H2 ΔH ¼  41 kJ=mol Definition of tar varies widely by study, but it is generally
accepted as aromatic hydrocarbons with molecular weight higher
than benzene [38]. In order to better understand the character-
methanation
istics of tar, various ways to classify tar have been suggested. The
CO þ 3H2 -CH4 þ H2 O ΔH ¼  251 kJ=mol first approach proposed by Milne et al. [39] divides tar into four
groups: primary, secondary, alkyl tertiary and condensed tertiary,
methane steam reforming based on their experimental results obtained from gas phase
thermal cracking reactions. Primary tar, which is defined as low
CH4 þ H2 O’-CO þ 3H2 ΔH ¼ 206 kJ=mol: molecular weight oxygenated hydrocarbons, is composed of com-
pounds derived from cellulose, analogous hemicellulose and
lignin. Examples of primary tar include levoglucosan and furfurals.
Biomass gasification produces condensable heavy hydrocar- Secondary tar is composed of phenolic and olefin compound,
bons, generally referred to as tar. Tar removal is a major hurdle including cresol and xylene. Alkyl tertiary tar is composed of
that hinders the commercialization of the biomass gasification [4]. methyl derivatives of aromatics such as toluene and the condensed
Accumulation of tar in the gasifier may lead to severe operational tertiary tar is composed of polynuclear aromatics hydrocarbons
problems such as corrosion, clogging and low gasification (PAH) without the branched molecular groups such as benzene
and naphthalene. Alkyl tertiary and condensed tertiary tars are
products of condensation reaction of the primary tars at high
temperature.
Tar can also be classified based on its components solubility and
condensability, as suggested by Kiel et al. [40]. It is crucial to
understand the condensability and the solubility of tar compounds
because condensation of tar in the reactor may lead to severe
Fig. 1. Pathways for biomass pyrolysis. operating issues and solubility of tar components may increase the
430 F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438

Table 1
Comparison of tar content in product gas of different gasification technologies.

Gasifier Feedstock Gasifying Agent Operating conditions Tar content (g/N m3 dry gas) Reference

Temp (1C) Pressure (kPa)

Fixed bed
Updraft Straw Air 400–500 –  50.0 [19]
Updraft Sawdust Air – – 8.6 [20]
Updraft Wood pellet Air and steam 650 – 90.3 [21]
Updraft Black pine wood pellet Air 1000 – 132.4 [22]

Downdraft Wood chip, municipal solid waste – – – 0.5 [23]

Downdraft Black pine wood pellet Air 900 – 32.3 [22]
Downdraft Hazelnut shell Air 821–1206 – 2.6–4.0 [24]
Downdraft Pine wood block O2 and steam 774–934 – 1.7–4.0 [25]
Air 870–1108 – 7.9–16.7
O2 and steam 910–1090 – 7.7–21.1
Air 798–910 – 1.2–2.5

Fluidized bed
Bubbling Almond shell Steam 700 – 6.0–7.0 [26]
Steam 820 – 1.0–1.5
Bubbling Pine sawdust Air 790–810 – 2.0–18.0 [27]
Bubbling Pine sawdust Steam 750  101 180.0 [28]
Steam 780  101 40.0
Bubbling Pine wood Steam 750–780  101 30.0–80.0 [29]
O2 and steam 750–780  101 4.0–30.0
Air 750–780  101 2.0–20.0
Bubbling Wood shaving/saw dust Air 780 –  2.0 [30]
Air 857 –  0.3
Bubbling Rice husk Air 750 – 6.0 [31]
Air 940 – 0.8
Circulating Mixed sawdust Air and steam 701  105 15.1 [32]
815  105 0.4
Pressurized Pine wood sawdust Air and steam 700–850 300–1000 5.6 [33]

Entrained flow
Pressurized Grapevine pruning, pine sawdust, Air 750–1050  101 Negligible [34]
de-alcoholised marc of grape
Sawdust Air 700–1000 – Negligible [35]
Coconut coir dust Air 976  101 23.6 [36]
1100  101 4.8
Sawdust from soft stem wood Oxygen 1000–1200  195 Negligible [37]

Table 2
Performance comparison of commercial nickel catalysts used as primary catalyst in biomass gasification and pyrolysis.

Catalyst NiO Support BET surface Reactor conditions Carbon conversion Reference
(wt%) area (m2/g)
Temp (1C) Pressure (kPa) To gas (%) To solid (%) To liquid, (%)

No Catalyst – – – 750 101 80.0 13.0 7.0 Baker et al. [43]

With G-90C 15 70–76% Alumina, 3–15 750 101 90.0 10.0 0.0
5–8% CaO
No catalyst – – – 728 119 89.8 6.9 3.3 Li et al. [45]
With C11-9 LDP N/A Alumina N/A 739–805 119 95.0–98.3 1.7–4.2 0.0–0.9
0.0

processing cost of the wastewater produced from the process. Based Class 5 – Heavy polyaromatic hydrocarbons (4–7 rings) which
on these two properties, Kiel et al. categorized tar into five classes: condense at relatively high temperature and low concentration,
such as pyrene and coronene.
Class 1 – GC undetectable heaviest tars which condense at high
temperature and very low concentration.
Class 2 – Heterocyclic aromatic compounds with high water A comparison of Milne's and Kiel's tar classification approaches
solubility, including phenol and cresol. is sketched out in Fig. 2. It is clear that definition of tar proposed
Class 3 – Light hydrocarbons aromatic compound (1 ring), a by Milne et al. covers a broader range of products than definition
nonissue regarding condensability and solubility, such as provided by Kiel et al. All the tar components, from class 1 to
toluene and xylene. class 5, discussed in Kiel et al.'s study fall under secondary and
Class 4 – Light polyaromatic hydrocarbons (2–3 rings) which tertiary tar categories according to Milne et al.'s definition.
condense at relatively high concentrations and intermediate Primary tar compounds lighter than heterocyclic aromatics are
temperatures, including indene and naphthalene. not included in Kiel et al.'s classification.
 F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438 431

Fig. 2. Comparison of the tar classification methods.

3. Biomass gasification with commercial nickel based catalyst in-situ, no downstream reactor or extra heating is required, which
results in lower plant capital and operating cost [6,44].
Significant efforts have been put into developing a cost effec- Nonetheless, little work has been reported on using commer-
tive method to eliminate tar in gasification. Among all the cial nickel catalyst as primary catalyst in biomass gasification. One
proposed solutions, the use of catalysts in gasification in-situ is study by Baker et al. [43] examined the performance of G-90C
the most promising approach [6,8]. Catalyst used in biomass catalyst used as primary and secondary catalysts in biomass steam
gasification can be categorized into three types, they are natural gasification (Table 2). In a fluidized bed experiment with G-90C as
mineral catalyst, alkali metal catalyst and transition metal catalyst primary catalyst, synthesis gas yield of 1.8 m3/kg was obtained in
[8,41]. Dolomite and olivine are two of the most commonly used the first 5 h of run. However, gas yield started to decline after 5 h
natural mineral catalysts in biomass gasification. Although the and the catalyst was completely deactivated after 7 h. For compar-
quality of the gaseous product can be improved substantially with ison, the maximum theoretical gas yield with a H2/CO ratio of
these catalysts, additional gas clean-up step is still needed as the 2.0 is 2.4 m3/kg. Similar behavior was observed in the experiments
quality of the end product is inadequate for direct use in other end with G-90C used as a secondary catalyst. The initial activity was
user applications, such as fuel cell [42]. Alkali metals, such as high but gradually reduced thereafter. After 16 h of on stream
lithium, sodium, potassium, and rubidium, have been widely used testing, synthesis gas yields of the secondary fixed bed reactor and
as catalysts in biomass gasification [41]. Despite the fact that these the secondary fluidized bed reactor stabilized at 1.25–1.30 m3/kg
catalysts provide a considerable increase in initial reaction activity, and 1.50 m3/kg respectively. The G-90C catalyst performed better
they are susceptible to loss of activity at high temperature due to as secondary catalyst over longer time period because of lower
particle agglomeration. Alternatively, transition metal-based cata- carbon fouling (1/3rd) compared to the primary catalyst.
lysts, particularly nickel, are excellent for biomass gasification due Li et al. [45] also conducted a study using commercial nickel
to their high activities in tar elimination and ability to improve catalyst as primary catalyst in biomass gasification (Table 2). The
producer gas quality. main focus of their studies was to investigate the impact of
A large number of studies have been conducted and reported in operating parameters on the final gaseous product composition
the literature using commercial nickel based catalysts in biomass in a circulating fluidized bed gasifier and to develop a model for
gasification to promote steam-reforming, water–gas shift reactions the air-blown circulating fluidized bed biomass gasification. They
and to eliminate tar. These studies can be categorized into two reported that tar yields in two of the runs with Sud-Chemie
groups. The first group focuses on using nickel catalyst as the catalyst C11-9 LDP were substantially lower when compared with
primary catalyst in the gasifiers and the second group concen- the runs with no catalyst added under the same operating
trates on using it as the secondary catalyst in post gasification or temperature. The tar yield reduced from 10.26 g/N m3 to 2.35 g/
post pyrolysis reactor. N m3 and 0.04 g/N m3 respectively. However, no further investiga-
tion and characterization was conducted on the spent catalyst and
deactivation of the catalyst was not reported.
3.1. Commercial catalyst as primary catalyst Both Baker and Li studies demonstrated the advantages and
limitations of commercial nickel catalyst used as primary catalyst
There are several benefits of using nickel catalyst as the in biomass gasification. The catalysts were effective in increasing
primary catalyst. First, nickel is one of the most effective transition the gaseous product yield and reducing tar yield. However, the
metals for tar cracking and reforming [43]. In addition to reducing catalysts suffered from rapid deactivation. The deactivation of
the tar content, nickel catalyst improves the quality of the gaseous nickel catalyst in in-situ gasification is commonly caused by carbon
product in biomass gasification. Second, it is economically attrac- formation on the catalyst surface and nickel sintering [46].
tive. Because both gasification and gas clean-up processes occur The deactivation of catalysts in gasification may be minimized
432 F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438

through the use of additives and promoters, which is discussed in temperature range of 780–830 1C. These findings agree with the
Section 4. result reported by Pfeifer et al. [7].
Pfeifer et al. [7] tested six commercial nickel catalysts, also
made for heavy and light hydrocarbons reforming, in toluene
3.2. Commercial nickel catalyst as secondary catalyst
steam reforming reaction with a fixed bed quartz reactor. They
found that heavy hydrocarbons steam reforming catalysts were
Secondary catalysts are used in post gasification or post
more effective in converting tars and ammonia into gaseous
pyrolysis reactor to improve the quality of the product gas or to
product than light hydrocarbons reforming catalysts. High conver-
reform the bio-oil produced in the primary reactor. Secondary
sion of tar (98%) and ammonia (40%) was achieved at a space
catalysts are active for longer duration because coke formation on
velocity of 1200 h  1 and operating temperature of 850–900 1C.
the catalyst surface is minimized in a downstream reactor. In this
Selectivity toward CO formation was higher with heavy hydro-
review, studies using nickel catalysts as secondary catalyst will be
carbons reforming catalysts. No deactivation of catalyst was
discussed for upgrading synthesis gas and bio-oil in separate
reported from the 12 h test which implies that these catalysts
sections. Comparison of the results from literature is listed in
were able to suppress coke deposition.
Table 3.
One of the catalysts, G-90B, studied by Pfeifer was also used by
Kinoshita et al. [52] in sawdust gasification investigation. Using in
3.2.1. Synthesis gas upgrading an indirectly heated fluidized bed catalytic reformer, they noticed
Studies conducted by Caballero et al. [47] and Aznar et al. [48] that carbon conversion, tar conversion and gas yield, particularly
looked into the feasibility of using commercial nickel catalyst as carbon monoxide and hydrogen yield, increased as the tempera-
secondary catalyst in biomass gasification. Four out of eight ture and space time increased. Complete conversion of tar was
catalysts used in their studies were made for heavy hydrocarbons achieved at 700–800 1C at space velocity 4 1.2 s. Hydrogen to
steam reforming, while the remaining were made for light hydro- carbon monoxide ratio also improved by increasing steam to
carbons steam reforming. Catalysts were tested in a reactor set up biomass ratio. However, increasing the steam to biomass ratio
shown in Fig. 3 for pine wood chips gasification. It was found that lowers the heating value of the product gas due to high vapor
catalysts made for heavy hydrocarbons steam reforming were content in the product gas.
more effective in eliminating tar, promoting hydrogen and carbon In summary, commercial catalysts used in heavy hydrocarbons
monoxide productions and suppressing the formations of the reforming performed better in converting tar and supressing coke
undesired methane and carbon dioxide [49–51]. No catalyst formation. The nickel loading of the heavy hydrocarbons reform-
deactivation was reported after 45 h of on-stream testing in a ing catalysts is typically 5–10 wt% higher than light hydrocarbons

Table 3
Comparison of the properties of commercially available nickel based catalyst.

Catalyst NiO content (wt%) Support Surface Area (m2/g) Reactor temp (1C) Initial tar conversion (%) Reference

Heavy hydrocarbons reforming

BASF
G1-25/1 25 CaO–Al2O3–SiO2–K2O 16.4 785–850 98–99 [7,50]
G1-50 20 MgO–CaO–Al2O3–SiO2–K2O 19.9 660–800 89–99 [50,51]
Haldor Topsoe
R-67 15 MgAl2O4–SiO2–K2O 17 780–840 95–100 [50,51]
ICI Katalco
46-1 22 MgO–CaO–Al2O3–SiO2–K2O 16.2 700–875 73–100 [43,50,51,53,55]
Sud Chemie
C11-NK 20–25 MgO–CaO–SiO2–Al2O3 8.8 600–900 – [7,53,56]

Light hydrocarbons reforming

BASF
G1-25S 12–15 2.5 785 88–97 [47,48]
V1693 10.2 – 850–900 – [7]
Haldor Topsoe
RKS-1 15 MgAl2O4–SiO2–K2O 6.8 785–800 92 [47,48,50,51]
R-67-7H 16–18 MgAl2O4 12–20 690–780 99 [57]
ICI Katalco
57-3 12 CaO–Al2O3–SiO2 2.9 – 69 [47,48,50,51]
Sud Chemie
G-90LDP 14 CaO–Al2O3 – 850–900 99 [7]
G-90EW 14 CaO–Al2O3 – 850–900 99 [7]
G-90B 14 CaO–Al2O3 5-7 650–900 99 [7,52]
United Catalyst
C11-9-061 10–15 Al2O3 2.9 725–800 – [47,48,50,51]

Fig. 3. Simplified reactor setup used in [47,48].

 F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438 433

reforming catalysts. The catalyst BET surface area of the heavy A comparison of catalysts reviewed in this section can also be
hydrocarbons reforming catalyst was on average 3 times the found in Table 3.
surface area of the light hydrocarbons reforming catalysts. High
BET surface area along with higher metal loading would provide
large metal surface area which is one of the reasons for better 4. Recent advancements in nickel based catalyst for biomass
activity of heavy hydrocarbon catalysts. Another reason is the gasification
presence of magnesium compounds in the heavy hydrocarbons
reforming catalysts. Oxides of magnesium play a key role in Various catalyst supports, metal additives and synthesis meth-
suppressing coke formation in gasification [53,54]. ods have been developed by researchers to improve stability and
activity of nickel catalysts. These studies can be divided into the
effect of support material, the effect of promoter and the effect of
3.2.2. Bio-oil steam reforming particle size. Some of the most commonly used support materials
Steam reforming of bio-oil with commercial nickel catalyst is a include olivine, dolomite [59], alumina [59–61], silica [59–61] and
well-studied approach for synthesis gas production [53,55,56]. magnesium oxide [60]. Promoter such as platinum [62,63], palla-
Bio-oil is produced by fast pyrolysis of biomass and steam dium [62], rhodium [62], ruthenium [62], cobalt [63,64], iron [63]
reforming of bio-oil produces synthesis gas rich in hydrogen. and copper [65] are widely used in catalyst synthesis to improve
Composition of bio-oil depends upon biomass type and pyrolysis catalyst performance.
conditions, however, typical compounds found in bio-oil are
saccharides, anhydrosugars, aldehydes, furans, ketones, alcohols, 4.1. Effect of support on nickel based catalysts
carboxylic acids and aromatics (pyrolytic lignin) [57]. The com-
mercial catalysts are used in the secondary reactor to facilitate bio- One of the prominent issues with using nickel catalyst in
oil steam reforming reaction. All the published work reviewed in biomass gasification is rapid loss of catalytic activity due to carbon
the paper conclude that the nickel catalysts suffers from rapid deposition. Varying degree of success has been achieved in
deactivation [53,55,56]. suppressing coke formation by changing the type of support
Three commercial catalysts were investigated by Wang et al. [55], material. Srinakruang et al. [59] studied the effectiveness of three
including G-90C, G-91 from United Catalyst and a dual catalyst catalyst supports, alumina, silica–alumina mixed oxide and dolo-
46-1/46-4 from ICI Katalco. By using rapid catalyst screening mite, in suppressing carbon deposition in gasification. Ni/Al2O3
method, they found that all catalysts were efficient in conver- and Ni/SiO2–Al2O3 catalysts were synthesized using impregnation
ting model compounds like methanol, acetic acid, an aqueous method while Ni/dolomite catalyst was prepared by precipitation–
solution of hydroxyl-acetaldehyde, a methanol solution of 4-allyl- deposition method with aqueous solution of nickel nitrate hex-
2,6-dimethoxyphenol and a mixture model compounds of 67% ahydrate. Detailed catalyst preparation parameters are listed in
acetic acid, 16% m-cresol, and 16% syringol into hydrogen rich Table 4. Catalytic activity of toluene conversion in a fixed bed
gaseous products (499%). The dual catalyst 46-1/46-4 was more reactor decreased in the following order Ni/Al2O3 4Ni/SiO2–
effective in inhibiting carbonaceous deposition than G-90C and Al2O3 4Ni/dolomite. However, Ni/dolomite catalyst was stable
G-91 because the former catalysts contained MgO additive in the for the longest duration (7 h). Results from thermogravimetric
support. Further investigation carried out by Garcia et al. [53] analysis (TGA) showed that the amount of coke formation was in
demonstrated that similar performance was achieved with com- the following order Ni/dolomiteo Ni/Al2O3 oNi/SiO2–Al2O3, mea-
mercial catalysts G-91, C11-NK and 46-1/46-4 in steam reforming sured at 0.0 wt%, 1.7 wt% and 7.2 wt% respectively. Srinakruang
of poplar wood pyrolysis bio-oil into gaseous product. Carbon et al. attributed the better performance of Ni/dolomite catalyst to
conversion into CO and CO2 started at 85–90% and gradually the basicity of the dolomite support. Basic oxides, such as MgO and
decreased to 75–85% in 25 min. Decrease in hydrogen and carbon CaO found in dolomite, help to promote forming of surface oxide
dioxide yields was accompanied by the increase of carbon mon- ions which assist in gasifying of deposited carbon.
oxide, methane, benzene and other aromatics yields during the Kong et al. [60] conducted a study on carbon dioxide reforming
run which indicated catalyst deactivation. of toluene in a fluidized bed reactor with nickel catalyst on various
Deactivation of C11-NK catalyst, used in a bio-oil steam support materials, including alumina, silica, zirconium oxide and
reforming, was also reported by Kechagiopoulos et al. [56]. They magnesium oxide. All the catalysts were prepared by impregna-
reported complete conversion of model compounds including tion method. From their studies, they found that Ni/MgO and
acetone, ethylene, glycol, and acetic acid at temperatures higher Ni/α-Al2O3 were more stable than other supported catalysts for up
than 600 1C, gas hourly space velocity of 1500 h  1 and steam to to 400 min on stream. Nickel catalyst supported on acidic supports
carbon ratio higher than 3. Hydrogen yield in product gas was as were least coke resistant and the synthesis method play a big
high as 90%. However, steam reforming of aqueous-phase beech role in catalyst stability. Ni/SiO2 catalyst made by the sol–gel
wood pyrolysis bio-oil produced lower hydrogen yield at around method had the highest surface area (765 m2/g), gas yield (54 wt%)
60%. The real bio-oil led to substantially higher coke formation and coke deposition (19.4 wt%) compared to Ni/SiO2 made by
compared to the model compounds which led to rapid deactiva- incipient wetness method (136 m2/g, 49.8 wt% and 3.7 wt%,
tion and lower hydrogen yield. respectively) [61].
The catalysts reviewed in this paper suffered significantly faster Support material plays an important role in defining the
deactivation due to coke formation in bio-oil steam reforming activity and service life of the catalyst. Studies reviewed here have
compared to synthesis gas upgrading. Hydrogen yield from bio-oil concluded that catalyst with high surface area support generally
steam reforming using ICI-46 series catalyst and UCI G-91 exhibits higher catalytic activity. However, the catalyst support
decreased from 80% to 60% in 300 min and from 75% to 70% in acidity is important for stability. Basic supports such as dolomite
150 min of run, respectively [55]. Garcia et al. [53] also reported an and MgO are better at inhibiting carbon fouling [47,48,59,60].
average drop of 20% in hydrogen yield in 25 min, while the C11-NK
catalyst used by Kechagiopoulos et al. [56] deactivated completely 4.2. Promoted nickel based catalyst
after 17 h of run. Coke formation was identified as the primary
cause of deactivation. Section 4 reviews the advancements in Another method to improve the activity and coke resistance of
gasification using nickel catalysts to overcome the coke deposition. nickel supported catalysts is to dope it with noble metals [62,63],
434 F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438

Reference
alkali metals [65], rare earth metals [62] or transition metals [63–65].
Table 5 compares the experimental parameters and catalyst synthesis

[58]

[59]

[60]
methods and Table 6 compares catalysts properties based on chemis-
orption measurements.
deposition

Nishikawa et al. [62] examined the effect of noble metals,

including Pt, Pd, Rh and Ru, on the performance of Ni/CeO2–Al2O3
(wt%)
Coke

19.4c
0.0b

0.3b

3.4b
3.8b
4.1b

3.7c
b

7.2b

1.2b
1.7
catalyst in cedar wood biomass steam gasification with a labora-

–
–
tory scale continuous feeding dual bed reactor. The Ni/CeO2–Al2O3
Gas yield

was prepared by co-impregnation method, whereas, the noble

(wt%)

metal promoter was impregnated later. Although the addition of

49.5

49.8
54.0
47.6
–

–
–

–
–
–
–
–
noble metals, especially Pt, was effective in promoting steam
gasification, these additives had minimal effect in inhibiting coke
Conversion of

formation. Nonetheless, high catalytic activity of Pt promoted

toluene (%)

catalyst was the result of the strong interaction between the

platinum and nickel metals. They also noted that unreduced
92.0a

90.0a
99.0

32.8
74.2
67.2
91.0

platinum catalyst had the same catalytic performance as the

11.1

–
–

–
–
reduced catalyst, which suggested that hydrogen pre-treatment
may not be required.
temp (1C)
Reduction temp (1C) Reaction

Chaiprasert et al. [63] studied Pt, Fe and Co as promoter for Ni

catalysts in a fluidized bed coconut shell gasification. Catalysts
600
600
600
600
600
700

700
700

760
760

760
760

were prepared by impregnation and co-precipitation methods

with 1 wt% promoter and 10 wt% Ni loading on dolomite sup-
700 (2) follow by

ported catalysts. XRD analysis suggested that catalysts synthesized

by these two methods had similar crystalline structure. Gasifica-
No reduction
770 (0.25)

tion results indicated that the addition of Pt promoter enhanced

(time, h)

700 (1)

steam reforming and water–gas shift reactions. Product gas

generated had higher concentration of hydrogen, carbon mon-
oxide and carbon dioxide. Fe promoted catalyst was only effective
in promoting water–gas shift reaction, which increased the pro-
Calcination temp

duction of hydrogen and carbon dioxide. Cobalt promoted catalyst

(1C) (time, h)

was more effective in promoting methanation and reforming of

methane. While all the three promoters reduced coke deposition,
(6)
(6)
(6)
(6)
(6)
750 (2)

750 (2)
750 (2)

450 (3)
450 (3)

450 (3)
450 (3)

Pt promoted catalyst exhibited the highest coke resistance.

700
700
700
700
700
Comparison of nickel catalysts with different support materials used in pyrolysis and steam reforming of bio-oil.

T amount of coke deposited onto the Pt, Fe, Co promoted catalysts,

and non-promoted catalysts were 6.5, 8.3, 9.3 and 16.5 wt%
Drying temp (1C)

respectively.
The effect of cobalt concentration on the performance of nickel
120 (  12)

120 (  12)
120 (  12)

105 (  12)
105 (  12)

105 (  12)
80 (  12)
(time, h)

catalyst in steam reforming of toluene was investigated by Wang

(6)
(6)
(6)
(6)
(6)

et al. [64]. Catalysts were prepared by co-impregnating Co up to

120
120
120
120
120

12 wt% onto 12 wt% Ni/Al2O3 catalyst. The catalytic activity initially

improved with the increase of Co loading up to 3 wt% but later
Ni(NO3)2  6H2O, SiO2–Al2O3

dropped with higher Co loadings. Similar trend was observed

Ni(NO3)2  6H2O, citric acid,
Ni(NO3)2  6H2O, dolomite,

PD¼ precipitation–deposition, IWI ¼incipient wetness impregnation, SG ¼sol–gel.

in the study of Cu promoted catalytic steam reforming of acetic

Ni(NO3)2  6H2O, Al2O3

Ni(NO3)2  6H2O, Al2O3

Ni(NO3)2  6H2O, SiO2

acid [65]. This behavior can be explained by lowering of nickel

(NO3)3  6H2O, Al2O3
Ni(NO3)2  6H2O, Ce

ethanol, SiC8H20O4
α-Al2O3
γ-Al2O3

surface area at high promoter loading. Nevertheless, Co and Cu

MgO

ZrO2
SiO2

promoted nickel catalysts were more effective than non-promoted

Measured by thermogravimetric analyzer after reaction for 7 h.
(NH4)2CO3

Measured by X-ray photoelectron spectroscopy after reaction.

Precursor

Ni/Al2O3 catalysts in reforming oxygenates and inhibiting coke

Ni(NO3)2,
Ni(NO3)2,
Ni(NO3)2,
Ni(NO3)2,
Ni(NO3)2,

formation.
In summary, bimetallic catalysts, especially with the noble
metal additive such as Pt, performs significantly improves catalytic
activity and suppresses coke deposition during gasification.
Synthesis
method

IWI
IWI

IWI
IWI
IWI
IWI
IWI

IWI
IWI

IWI

4.3. Nickel nanoparticle catalyst

PD

SG

A nanoparticle catalyst is defined as a catalyst with a particle

Data extracted from the figures.
BET surface
area (m2/g)

size in the range of 1–100 nm [66]. Nanoparticle catalysts can be

either unsupported or supported on alumina [67,68], carbon
152.7

319.4

nanotubes [69] and other types of support material. Li et al. [70]

10.8

31.8
27.1
322
362

765
136
147
111
8.1

conducted several studies supported and unsupported nickel

(wt%)

nanoparticle catalyst for biomass pyrolysis. The catalyst used in

Ni,

20
20

20
20
15

15
Ni/SiO2–Al2O3 15

this study was synthesized using homogenous-precipitation

5
5
5
5
5

method and had a specific surface area of 187.98 m2/g and cubic
Ni/dolomite

crystals size of 7.5 nm. Performance of this nanoparticle catalyst

Ni/α-Al2O3
Ni/γ-Al2O3

Al2O3
Ni/CeO2–
Ni/Al2O3

Ni/Al2O3
Catalyst

Ni/MgO

Ni/ZrO2
Ni/SiO2

Ni/SiO2
Ni/SiO2

and a commercial nickel based microparticle catalyst was evalu-

Table 4

ated in a TGA, measured from ambient temperature to 900 1C. The

b
a

results showed that the cellulose pyrolysis onset temperature with

Table 5
Comparison of promoted nickel catalysts used in pyrolysis and steam reforming of biomass.

Catalyst Ni Promoter Synthesis method Precursor Drying Calcination Reaction temp C based Coke deposition Reference
(wt%) (wt%) temp temp (1C) gas (wt%) per min of
(1C) (time, (1C) (time, h) yield (%) run
h)

Ni/CeO2–Al2O3 4 0 Incipient wetness Ni(NO3)2  6H2O, Ce(NH4)2(NO3)6, Al2O3 110 (12) 500 (3) 550–650 65–82 0.33 [61]
Pt–Ni/CeO2– 4 0.1 Incipient wetness Ni(NO3)2  6H2O, Ce(NH4)2(NO3)6, Al2O3 Pt 110 (12) 500 (3) 550–650 70–82 40.33
Al2O3 (NO2)2(NH3)2
Pd–Ni/CeO2– 4 0.1 Incipient wetness Ni(NO3)2  6H2O, Ce(NH4)2(NO3)6, Al2O3, Pd(NO3)2 110 (12) 500 (3) 550–650 40.33
Al2O3
Rh–Ni/CeO2– 4 0.1 Incipient wetness Ni(NO3)2  6H2O, Ce(NH4)2(NO3)6, Al2O3, Rh(NO3)3 110 (12) 500 (3) 550–650 67–83 40.33
Al2O3

F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438
Ru–Ni/CeO2– 4 0.5 Incipient wetness Ni(NO3)2  6H2O, Ce(NH4)2(NO3)6, Al2O3, Ru(NO) 110 (12) 500 (3) 550–650 70–82 40.33
Al2O3 (NO)3

Pt–Ni/dolomite 15 1 Precipitation and Ni(NO3)2  6H2O, dolomite, (NH4)2CO3, H2PtCl6 120 (  12) 600 800 79.19 0.05 [62]
Fe–Ni/dolomite 15 1 impregnation Ni(NO3)2  6H2O, dolomite, (NH4)2CO3, FeCl3 120 (  12) 600 800 78.12 0.07
Co–Ni/dolomite 15 1 Ni(NO3)2  6H2O, dolomite, (NH4)2CO3, Co(NO3)2 120 (  12) 600 800 49.53 0.08
Pt–Ni/dolomite 15 1 Co-precipitation Ni(NO3)2  6H2O, dolomite, (NH4)2CO3, H2PtCl6 120 (  12) 600 800 50.51
Fe–Ni/dolomite 15 1 Ni(NO3)2  6H2O, dolomite, (NH4)2CO3, FeCl3 120 (  12) 600 800 57.46
Co–Ni/dolomite 15 1 Ni(NO3)2  6H2O, dolomite, (NH4)2CO3, Co(NO3)2 120 (  12) 600 800 41.82

Co–Ni/Al2O3 12 0.72–12 Co-impregnation Ni(NO3)2  6H2O, Co(NO3)2  6H2O, Al2O3 110 (12) 500 (3) 550 54–68 0.01 [63]

Table 6
Comparison of chemisorption results of various research based nickel catalysts.

Catalyst Ni content Promoter content BET surface Reduction degree Particle size H2 adsorption Dispersion H2 consumption Metal surface Reference
(wt%) (wt%) area (m2/g) (TPR) (%) of Ni (nm) @298 K (10  6 mol/gcat) in TPR (10  3 mol/gcat) area (m2/g)

Ni/MgO 5 0 31.8 8 Not determined [59]

Ni/α-Al2O3 5 0 27.1 76 9.9
Ni/γ-Al2O3 5 0 152.7 11 7.9
Ni/ZrO2 5 0 8.1 97 20.7
Ni/SiO2 5 0 319.4 101 22.1

Ni/CeO2–Al2O3 4 0 15 149 40 5.8 1.02 [61]

Pt–Ni/CeO2–Al2O3 4 0.1 14–15 142 57 8.4 0.97
Pd–Ni/CeO2–Al2O3 4 0.1 18 138 55 8.0 0.95
Rh–Ni/CeO2–Al2O3 4 0.1 16 144 61 9.0 1.0
Ru–Ni/CeO2–Al2O3 4 0.5 15 146 62 9.0 1.1

Pt–Ni/dolomite 15 1 6.74 77 0.97 [62]

Fe–Ni/dolomite 15 1 5.76 364 0.20
Co–Ni/dolomite 15 1 11.18 2671 0.03
Pt–Ni/dolomite 15 1 5.33 166 0.06
Fe–Ni/dolomite 15 1 4.77 1532 0.05
Co–Ni/dolomite 15 1 8.76 2715 0.02

Co–Ni/Al2O3 12 0.72–12 N/A 25–34 47–57 2.7–4.7 2.1–4.9 [63]

435
436 F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438

the nanoparticle catalyst was slightly lower than the onset velocity (mol C/Lreactor h) and high carbon mass flow rate
temperature with the microparticle catalyst, measured at 294 1C (g C/gcat h), reactive flash volatilization reactors can be economical
and 303 1C respectively. Lower onset temperatures were also at a small scale, which is important for decentralized biomass
observed in hemicellulose and lignin pyrolysis with nanoparticle gasification [74]. Small scale gasification plants can be placed
catalyst, which indicated that the nanoparticle catalyst help to closer to the feedstock source which minimizes transportation
lower the activation energy required for pyrolysis reaction. cost of low energy density biomass.
Supported nanoparticle catalysts, Ni/Al2O3 and Ni–La–Fe/Al2O3, In Salge et al.'s study, synthesis gas was produced with Rh–Ce
were developed by Li et al. [67,68,71] using the deposition– catalyst where non-volatile feed are decomposed into hydrogen
precipitation method and tested for sawdust pyrolysis reaction. and carbon monoxide in less than 50 ms without the production of
Both the catalysts demonstrated excellent tar conversion (4 99%) carbon [73]. The formation of carbon was avoided by rapidly
at a temperature of 800 1C, significantly improving in the quality of oxidizing the decomposition products into gases. The heat gener-
the product gas, especially CO, CO2, CH4 and C2 yields. Similar ated from oxidation reaction prevented condensation reactions
results were reported by Liu et al. [71] and Feng et al. [72] who that might lead to rapid carbon formation. 99% conversion of the
studied the nano-NiO/γ-Al2O3 in municipal solid waste and feed at 70% hydrogen selectivity was achieved without catalyst
sawdust steam gasification. Li et al. reported that the nanoparticle deactivation of at the end of 20 h run. Lower C/O ratio led to higher
Ni/Al2O3 and the Ni–La–Fe/Al2O3 catalysts negligible to no deac- catalyst bed temperature, feed conversion, and hydrogen and
tivation, respectively, in the 10 h sawdust pyrolysis life test studies. carbon monoxide selectivities.
It is known from literature that nickel based catalyst with smaller Cellulose gasification using reactive flash volatilization was
active metal particle size and high degree of dispersion exhibits conducted by Colby et al. [44]. This is a more complex process
higher catalytic activity [62]. Since nano-particle catalysts have compared to the liquid feeds because it involves pyrolysis, partial
higher number of active sites per gram, these catalysts should have oxidation, steam reforming, and water–gas shift reactions. 2 wt%
better performance than micro-particle catalysts on the mass basis in Rh–2 wt% Ce/Al2O3 catalyst was used for microcrystalline cellulose
gasification as stated by Li et al. However, more study is also needed gasification which produced C1 products within 24–33 ms resi-
to validate if there is any size effect per unit active site of the catalyst. dence time temperature of 600–825 1C. Increasing the C/O ratio
increased the hydrogen and CO yield. Whereas, increasing the S/C
(steam to carbon) ratio increased the hydrogen yield and
5. Future directions of biomass gasification decreased the CO yield, which is attributed to forward water–gas
shift reaction. Selectivity of hydrogen was 14–47% and selectivity
Conventional biomass gasification is commonly performed by of carbon monoxide was 21–38%.
using one of the following reactor setups: Reactive flash volatilization with Rh based catalyst is a promis-
ing method for high quality syngas production but it is impractical
 fluidized bed gasifier with downstream catalytic tar cleaning for larger than bench scale application due to the high cost of the
reactor; Rh–Ce catalyst. Moreover, lignocellulose feedstock must be used
 fast pyrolysis reactor with downstream catalytic steam reformer; instead of purified microcrystalline cellulose to make this process
 catalytic fluidized bed gasifiers. commercially viable. Gasification of lignocellulose feedstock will
be a greater challenge for the catalysts. Therefore, it is necessary to
Fluidised bed reactors are capital intensive and hence large develop a cost effective and robust catalyst for reactive flash
scale reactors are required to make it economical. According to a volatilization of lignocellulose. Further research is required to
study conducted by Leung et al., cost of the gasifier and gas study the effectiveness of this process in raw biomass gasification.
cleaning system can account for 66.7–85.5% of the total capital In this regard, nickel catalysts discussed in this paper (supported,
cost [54]. This is particularly true for fluidized bed gasifier due to unsupported, promoted, nanoparticles etc.) may play a vital role.
the high cost of blower, continuous feed systems and control
systems. In comparison, capital cost of fixed bed reactors for
biomass gasification is significantly lower. Therefore, a novel
approach called as reactive flash volatilisation, was recently 6. Conclusion
proposed for cellulose gasification [44]. Reactive flash volatilisa-
tion uses a fixed bed gasifier with carbon space velocity and Nickel catalyst has been widely employed in various chemical
carbon mass flow rate significantly higher than fluidised bed processes for decades. It has been proven as one of the most cost
reactors. effective transition metal catalyst, especially in eliminating tar and
Reactive flash volatilization, which combines pyrolysis and improving the quality of the product gas of biomass gasification.
partial oxidation, was first introduced by Salge et al. for synthesis However, various reports have pointed out that these catalysts
gas production from non-volatile fuels such as refined soy oil, suffer rapid deactivation as a primary catalyst in the gasification
biodiesel and aqueous sugar solution [73]. As illustrated in Fig. 4, due to carbon fouling, sintering and morphological changes.
one of the biggest advantages of this reactor is lower amount of Nonetheless, nickel based catalyst is still very effective in tar
catalyst used per unit mass of carbon feedstock compared to the steam reforming and adjusting the CO–H2 ratio when used as
fluidised bed gasifiers. According to Colby et al. [44], conventional secondary catalyst in a downstream reactor.
biomass gasification setup-up, such as fluidized bed gasifier with Key factors that define the catalytic activity of the nickel based
downstream catalytic tar cleaning reactor or catalytic fluidized bed catalyst are the metal particle size and its dispersion. Small
gasifier, has carbon mass velocity of 0.8–9.0 h  1. In comparison, crystallite size and high degree of dispersion of nickel on the
reactive flash volatilization has carbon mass velocity of 50.0– supports lead to high catalytic activity. Catalytic activity can also
80.0 h  1. Although similar carbon mass velocity can be achieved be improved by the addition of metal promoter, such as Pt, Co and
with fast pyrolysis reactor with downstream catalytic steam Cu. These metal promoters improve the reaction activity through
reformer, size of the reactive flash volatilization reactor is at least enhancing the nickel metal reducibility by forming strong inter-
an order of magnitude smaller than other reactors (Fig. 4). Carbon action with nickel metal. Metal promoters also enhance dispersion
space velocity of 100–300 mol L  1 h  1 can be easily attained with of the nickel metal on the support and provide higher resistance to
reactive flash volatilization. Because of its high carbon space coke formation.
 F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438 437

Fig. 4. Comparison of the space velocity, mass flow rate, amount of catalyst required and reactor size of various reactor setups.
Source: (Adapted from [44]).

Coke deposition on catalyst, which results in deactivation, is [16] Fraga AR, Gaines AF, Kandiyoti R. Characterization of biomass pyrolysis tars
the primary concern in catalytic biomass gasification and pyrolysis. produced in the relative absence of extraparticle secondary reactions. Fuel
The amount of coke deposition is associated with the types of 1991;70:803–9.
[17] Ku CS, Mun SP. Characterization of pyrolysis tar derived from lignocellulosic
supports used. Basic supports are more coke resistant than acidic biomass. J Ind Eng Chem 2006;12:853–61.
supports. Carbon deposition can be reduced by addition of alkaline [18] Qin Y, Huang H, Wu Z, Feng J, Li W, Xie K. Characterization of tar from
earth metals and effective use of catalyst supports such as dolomite sawdust gasified in the pressurized fluidized bed. Biomass Bioenergy
and MgO. 2007;31:243–9.
[19] Pedersen K. Catalytic hydrocracking of tar from gasification of straw. In:
Bridgwater AV, editor. Advances in thermochemical biomass conversion.
Netherlands: Springer; 1993. p. 246–64.
Acknowledgment [20] Wang D, Yuan W, Ji W. Char and char-supported nickel catalysts for secondary
syngas cleanup and conditioning. Appl Energy 2011;88:1656–63.
[21] Nagel FP, Ghosh S, Pitta C, Schildhauer TJ, Biollaz S. Biomass integrated
The authors are grateful for the financial support from the Rural gasification fuel cell systems – concept development and experimental results.
Industries Research and Development Corporation (RIRDC) project Biomass Bioenergy 2011;35:354–62.
grant PRJ-004758. [22] Ueki Y, Torigoe T, Ono H, Yoshiie R, Kihedu JH, Naruse I. Gasification
characteristics of woody biomass in the packed bed reactor. Proc Combust
Inst 2011;33:1795–800.
References [23] Hos JJ, M.J. Groeneveld, W.P.M. van Swaaij. Gasification of organic solid wastes
in cocurrent moving bed reactors. Energy from Biomass and Wastes 4. Lake
Buena, FL, USA: Institute of Gas Technology, Chicago, USA; 1980 p. 333–49.
[1] Draft Energy White Paper 2011: Strengtheningmumullen the foundations for [24] Dogru M, Howarth CR, Akay G, Keskinler B, Malik AA. Gasification of hazelnut
Australia's energy future. Department of Resources, Energy and Tourism; 2011.
shells in a downdraft gasifier. Energy 2002;27:415–27.
[2] Ni M, Leung DYC, Leung MKH, Sumathy K. An overview of hydrogen
[25] Lv P, Yuan Z, Ma L, Wu C, Chen Y, Zhu J. Hydrogen-rich gas production from
production from biomass. Fuel Process Technol 2006;87:461–72.
biomass air and oxygen/steam gasification in a downdraft gasifier. Renew
[3] Kirkels AF, Verbong GPJ. Biomass gasification: still promising? A 30-year
global overview Renew Sustain Energy Rev 2010;15:471–81. Energy 2007;32:2173–85.
[4] Huber GW, Iborra S, Corma A. Synthesis of transportation fuels from biomass: [26] Rapagnà S, Jand N, Kiennemann A, Foscolo PU. Steam-gasification of biomass
chemistry, catalysts, and engineering. Chem Rev (Washington, DC, US) in a fluidised-bed of olivine particles. Biomass Bioenergy 2000;19:187–97.
2006;106:4044–98. [27] Narváez I, Orío A, Aznar MP, Corella J. Biomass gasification with air in an
[5] Kumar A, Jones DD, Hanna MA. Thermochemical biomass gasification: a atmospheric bubbling fluidized bed. Effect of six operational variables on the
review of the current status of the technology. Energies (Basel, Switz) quality of the produced raw gas. Ind Eng Chem Res 1996;35:2110–20.
2009;2:556–81. [28] Delgado J, Aznar MP, Corella J. Biomass gasification with steam in fluidized
[6] Devi L, Ptasinski KJ, Janssen FJJG. A review of the primary measures for tar bed: effectiveness of CaO, MgO, and CaO–MgO for hot raw gas cleaning. Ind
elimination in biomass gasification processes. Biomass Bioenergy 2003;24:125–40. Eng Chem Res 1997;36:1535–43.
[7] Pfeifer C. Development of catalytic tar decomposition downstream from a dual [29] Gil J, Corella J, MaP Aznar, Caballero MA. Biomass gasification in atmospheric
fluidized bed biomass steam gasifier. Powder Technol 2008;180:9. and bubbling fluidized bed: effect of the type of gasifying agent on the
[8] Sutton D, Kelleher B, Ross JRH. Review of literature on catalysts for biomass product distribution. Biomass Bioenergy 1999;17:389–403.
gasification. Fuel Process Technol 2001;73:155–73. [30] Czernik S, Koeberle PG, Jollez P, Bilodeau JF, Chornet E. Gasification of residual
[9] Wang Y, Kinoshita CM. Kinetic model of biomass gasification. Sol Energy biomass via the biosyn fluidized bed technology. In: Bridgwater AV, editor.
1993;51:19–25. Advances in thermochemical biomass conversion. Netherlands: Springer;
[10] Shafizadeh F. Introduction to pyrolysis of biomass. J Anal Appl Pyrolysis 1993. p. 423–37.
1982;3:283–305. [31] Van den Aarsen FG, Beenackers AACM, van Swaaij WPM. Performance of a rice
[11] Kumar A, Eskridge K, Jones DD, Hanna MA. Steam–air fluidized bed gasifica-
husk fueled fluidized bed pilot plant gasifier. In: Proceedings of the first
tion of distillers grains: effects of steam to biomass ratio, equivalence ratio and
international producer gas conference. Colombo, Sri Lanka; 1983.
gasification temperature. Bioresour Technol 2009;100:2062–8.
[32] Li XT, Grace JR, Lim CJ, Watkinson AP, Chen HP, Kim JR. Biomass gasification in
[12] Haryanto A, Fernando SD, Pordesimo LO, Adhikari S. Upgrading of syngas
a circulating fluidized bed. Biomass Bioenergy 2004;26:171–93.
derived from biomass gasification: A thermodynamic analysis. Biomass
[33] Kurkela E, Ståhlberg P. Air gasification of peat, wood and brown coal in a
Bioenergy 2009;33:882–9.
[13] Milne TA, Evans RJ, Abatzaglou N Biomass gasifier “Tars”: their nature, pressurized fluidized-bed reactor. I. Carbon conversion, gas yields and tar
formation, and conversion. Other Information: PBD: 1 Nov 19981998. p. formation. Fuel Process Technol 1992;31:1–21.
Medium: ED; Size: vp. [34] Hernández JJ, Aranda-Almansa G, Bula A. Gasification of biomass wastes in an
[14] Devi L, Ptasinski KJ, Janssen FJJG. A review of the primary measures for tar entrained flow gasifier: effect of the particle size and the residence time. Fuel
elimination in biomass gasification processes. Biomass Bioenergy 2003;24: Process Technol 2010;91:681–92.
125–40. [35] Zhao Y, Sun S, Zhou H, Sun R, Tian H, Luan J, et al. Experimental study on
[15] Bridgwater AV. The technical and economic feasibility of biomass gasification sawdust air gasification in an entrained-flow reactor. Fuel Process Technol
for power generation. Fuel 1995;74:631–53. 2010;91:910–4.
438 F.L. Chan, A. Tanksale / Renewable and Sustainable Energy Reviews 38 (2014) 428–438

[36] Senapati PK, Behera S. Experimental investigation on an entrained flow type [56] Kechagiopoulos PN, Voutetakis SS, Lemonidou AA, Vasalos IA. Hydrogen
biomass gasification system using coconut coir dust as powdery biomass production via steam reforming of the aqueous phase of bio-oil in a fixed
feedstock. Bioresour Technol 2012;117:99–106. bed reactor. Energy Fuels 2006;20:2155–63.
[37] Qin K, Jensen PA, Lin W, Jensen AD. Biomass gasification behavior in an [57] Mullen CA, Boateng AA. Chemical Composition of bio-oils produced by fast
entrained flow reactor: gas product distribution and soot formation. Energy pyrolysis of two energy crops. Energy Fuels 2008;22:2104–9.
Fuels 2012;26:5992–6002. [58] Aznar MP, Corella J, Delgado J, Lahoz J. Improved steam gasification of
[38] Li C, Suzuki K. Tar property, analysis, reforming mechanism and model for lignocellulosic residues in a fluidized bed with commercial steam reforming
biomass gasification – an overview. Renew Sustain Energy Rev 2009;13: catalysts. Ind Eng Chem Res 1993;32:1–10.
594–604. [59] Srinakruang J, Sato K, Vitidsant T, Fujimoto K. A highly efficient catalyst for tar
[39] Vizcaíno AJ, Arena P, Baronetti G, Carrero A, Calles JA, Laborde MA, et al. gasification with steam. Catal Commun 2005;6:437–40.
Ethanol steam reforming on Ni/Al2O3 catalysts: effect of Mg addition. Int J [60] Kong M, Fei J, Wang S, Lu W, Zheng X. Influence of supports on catalytic behavior of
Hydrog Energy 2008;33:3489–92.
nickel catalysts in carbon dioxide reforming of toluene as a model compound of tar
[40] Kiel JHA Primary measures to reduce tar formation in fluidised-bed biomass
from biomass gasification. Bioresour Technol 2011;102:2004–8.
gasifiers. Final Report SDE Project P1999-012. Netherlands Energy Research
[61] Efika CE, Wu C, Williams PT. Syngas production from pyrolysis – catalytic
Foundation; 2004.
steam reforming of waste biomass in a continuous screw kiln reactor. J Anal
[41] Abu E-RZ, Bramer EA, Brem G. Review of catalysts for tar elimination in
biomass gasification processes. Ind Eng Chem Res 2004;43:6911–9. Appl Pyrolysis. 2012;95:87–94.
[42] Wang TJ, Chang J, Wu CZ, Fu Y, Chen Y. The steam reforming of naphthalene [62] Nishikawa J, Nakamura K, Asadullah M, Miyazawa T, Kunimori K, Tomishige K.
over a nickel–dolomite cracking catalyst. Biomass Bioenergy 2005;28:508–14. Catalytic performance of Ni/CeO2/Al2O3 modified with noble metals in steam
[43] Baker EG, Mudge LK, Brown MD. Steam gasification of biomass with nickel gasification of biomass. Catal Today 2008;131:146–55.
secondary catalysts. Ind Eng Chem Res 1987;26:1335–9. [63] Chaiprasert P, Vitidsant T. Effects of promoters on biomass gasification using
[44] Colby JL, Dauenhauer PJ, Schmidt LD. Millisecond autothermal steam reform- nickel/dolomite catalyst. Korean J Chem Eng 2009;26:1545–9.
ing of cellulose for synthetic biofuels by reactive flash volatilization. Green [64] Wang L, Li D, Koike M, Watanabe H, Xu Y, Nakagawa Y, et al. Catalytic
Chem 2008;10:773–83. performance and characterization of Ni–Co catalysts for the steam reforming
[45] Li XT, Grace JR, Lim CJ, Watkinson AP, Chen HP, Kim JR. Biomass gasification in of biomass tar to synthesis gas. Fuel 2012;112:654–61.
a circulating fluidized bed. Biomass Bioenergy 2004;26:171–93. [65] Bimbela F, Chen D, Ruiz J, García L, Arauzo J. Ni/Al coprecipitated catalysts
[46] Sehested J. Four challenges for nickel steam-reforming catalysts. Catal Today modified with magnesium and copper for the catalytic steam reforming of
2006;111:103–10. model compounds from biomass pyrolysis liquids. Appl Catal B: Environ
[47] Caballero MA, Aznar MP, Gil J, Martin JA, Frances E, Corella J. Commercial 2012;119–120:1–12.
steam reforming catalysts to improve biomass gasification with steam–oxygen [66] Astruc D. Transition-metal nanoparticles in catalysis: from historical back-
mixtures. 1. Hot gas upgrading by the catalytic reactor. Ind Eng Chem Res ground to the state-of-the art. Nanoparticles and catalysis. Weinheim,
1997;36:5227–39. Germany: Wiley-VCH Verlag GmbH & Co. KGaA; 2008; 1–48.
[48] Aznar MP, Caballero MA, Gil J, Martin JA, Corella J. Commercial steam [67] Li J, Yan R, Xiao B, Liang DT, Du L. Development of nano-NiO/Al2O3 catalyst to
reforming catalysts to improve biomass gasification with steam–oxygen be used for tar removal in biomass gasification. Environ Sci Technol
mixtures. 2. Catalytic tar removal. Ind Eng Chem Res 1998;37:2668–80. 2008;42:6224–9.
[49] Caballero MA, Corella J, Aznar M-P, Gil J. Biomass gasification with air in [68] Li J. Development of a nano-Ni–La–Fe/Al2O3 catalyst to be used for syn-gas
fluidized bed. Hot gas cleanup with selected commercial and full-size nickel- production and tar removal after biomass gasification. BioResources
based catalysts. Ind Eng Chem Res 2000;39:1143–54.
2009;4:1520.
[50] Corella J, Orio A, Aznar P. Biomass gasification with air in fluidized bed:
[69] Azadi P, Farnood R, Meier E. Preparation of multiwalled carbon nanotube-
reforming of the gas composition with commercial steam reforming catalysts.
supported nickel catalysts using incipient wetness method. J Phys Chem A
Ind Eng Chem Res 1998;37:4617–24.
2009;114:3962–8.
[51] Corella J, Orio A, Toledo J-M. Biomass gasification with air in a fluidized bed:
[70] Li J, Yan R, Xiao B, Liang DT, Lee DH. Preparation of nano-NiO particles and
exhaustive tar elimination with commercial steam reforming catalysts. Energy
Fuels 1999;13:702–9. evaluation of their catalytic activity in pyrolyzing biomass components.
[52] Kinoshita CM, Wang Y, Zhou J. Effect of reformer conditions on catalytic Energy Fuels 2007;22:16–23.
reforming of biomass-gasification tars. Ind Eng Chem Res 1995;34:2949–54. [71] Liu J, Li J, Liao S. Fuel gas production from catalytic steam gasification of
[53] Garcia L, French R, Czernik S, Chornet E. Catalytic steam reforming of bio-oils municipal solid wastes. 2nd Conference on Environmental Science and
for the production of hydrogen: effects of catalyst composition. Appl Catal A Information Application Technology. Wuhan 2010;3:652–5.
2000;201:225–39. [72] Feng Y. Influence of catalyst and temperature on gasification performance by
[54] Leung DYC, Yin XL, Wu CZ. A review on the development and commercializa- externally heated gasifier. Smart Grid Renew Energy 2011;2:177.
tion of biomass gasification technologies in China. Renew Sustain Energy Rev [73] Salge JR. Renewable hydrogen from nonvolatile fuels by reactive flash
2004;8:565–80. volatilization. Science 2006;314:801–4.
[55] Wang D, Czernik S, Chornet E. Production of hydrogen from biomass by [74] Dauenhauer PJ, Colby J, Schmidt LD. Reactive flash volatilization of nonvolatile
catalytic steam reforming of fast pyrolysis oils. Energy Fuels 1998;12:19–24. carbohydrates for synthesis gas. Salt Lake City, UT; 2007.