Energies 2013, 6, 514-538; doi:10.

3390/en6010514
OPEN ACCESS

energies
ISSN 1996-1073
[Link]/journal/energies
Review

Catalytic Fast Pyrolysis: A Review

Theodore Dickerson 1,2 and Juan Soria 1,2,*
1
Applied Environmental Science and Technology, School of Engineering, University of Alaska
Anchorage, 3211 Providence Drive, ENGR 201, Anchorage, AK 99508, USA
2
Agricultural and Forestry Experiment Station, University of Alaska Fairbanks,
1509 S. Georgeson Drive, Palmer, AK 99645, USA

* Author to whom correspondence should be addressed; E-Mail: jasoria@[Link];

Tel.: +1-907-746-9450; Fax: +1-907-745-6268.

Received: 9 November 2012; in revised form: 7 December 2012 / Accepted: 21 December 2012 /
Published: 21 January 2013

Abstract: Catalytic pyrolysis is a promising thermochemical conversion route for

lignocellulosic biomass that produces chemicals and fuels compatible with current,
petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared
towards the elimination and substitution of oxygen and oxygen-containing functionalities
in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress
has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of
metal catalysts and the production of aromatics from bio-oil using cracking zeolites.
Research is currently focused on developing multi-functional catalysts used in situ that
benefit from the advantages of both hydrodeoxygenation and zeolite cracking.
Development of robust, highly selective catalysts will help achieve the goal of producing
drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass
streams. The current paper will examine these developments by means of a review of
existing literature.

Keywords: pyrolysis; bio-oil; catalytic upgrading; fast pyrolysis; multifunctional catalysts;

hydrodeoxygenation; zeolites
Energies 2013, 6 515

1. Introduction

Growing interest in renewable technologies has led to the development of hydroelectric, solar,
wave, geothermal, and wind power plants that can potentially displace fossil fuel based energy
production [1]. However, existing infrastructures require hydrocarbons for manufacturing goods
ranging from plastics and chemicals to fuel oil, lubricating oil, and hydraulic fluids. This has led many
to look towards biomass as the only sustainable alternative to fossil fuels capable of yielding
petroleum like products [2–6]. As is the case with all potentially disruptive technologies, though,
proper environmental mitigation and lifecycle planning must be included when considering the
production and use of biofuels [7,8]. Hydrocarbons can be produced from biomass via biological,
biochemical, and thermochemical processes as shown in Figure 1 [9].

Figure 1. Schematic of biomass conversion technologies.

Pyrolysis is touted to be one of the most promising thermochemical technologies with the potential
to convert cheap, local, and abundant lignocellulosic biomass such as grasses and trees into a useful
form [10–13], and commercial scale plants, such as Kior in Mississippi, have begun construction and
operations. Thermal technologies include direct combustion, gasification, liquefaction, and pyrolysis,
all of which have the benefit of using lignocellulosic materials. Only pyrolysis and liquefaction produce
a liquid product, and although recent work on liquefaction has shown promising results [14–16], it is
currently a nascent technology with high capital costs due to the high pressures required. Pyrolysis has
the advantage of low capital investment and a liquid final product that can be transported and
converted via catalysis to fuels and valuable products such as food flavorings, fertilizers, resins, and
other specialty chemicals that are fully compatible with existing petroleum infrastructure. This
provides significant economic advantages over ethanol that requires parallel infrastructures.
Furthermore, all pyrolysis products can be utilized in the pyrolysis system. Gas can be burned to help
dry the incoming biomass and operate the reactor [5,17], and char and ash are promising soil
Energies 2013, 6 516

amendments [18] and a potential C sink [19]. Chars can also be used as a fuel [20], and there is potential
to expand the resource base to include non-traditional feedstock such as lignin [21], sewage sludge,
chicken litter [22], and even salmon waste [23]. The current paper will examine the catalytic processing
necessary to transform lignocellulosic biomass into hydrocarbons using pyrolysis platforms.

2. Pyrolysis

Pyrolysis is the thermochemical decomposition of biomass at temperatures between 400 and 650 °C
in the absence of O2. The decomposition process releases volatile species, while the solid,
non-volatiles are collected as bio-char. A portion of the gas-phase volatiles condense into a black,
viscous fluid termed bio-oil [24] that has a variety of synonyms including pyrolysis oil, bio-crude oil,
bio-fuel oil, wood liquid, wood oil, liquid smoke, wood distillates, pyroligneous tar, and pyroligneous
acid [5]. Pyrolysis methods differ in their residence time, temperature, and heating rate, which in turn
greatly affect the percentages of gas, char, and liquid products in a semi-predictable manner, while the
resulting, individual chemical species remain hard to predict and quantify [5,10]. Pyrolysis methods
can be grouped into two large categories, slow and fast (or flash) pyrolysis.
Slow pyrolysis consists of slow heating rates of 0.1–1 °C/s, a residence time anywhere from hours
to minutes, and a temperature range of 400–600 °C. It has been used for centuries to produce methanol
and yields approximately equal quantities of char, gas, and liquid [5,10,25].
Fast pyrolysis is a relatively new, promising technology involving a high liquid yield achieved
through rapid heating rates of 10 to >1000 °C/s, short residence times of <2 s, temperatures of
400–650 °C, and rapid quenching of the vapors [5,6]. For a more extensive review of reactors,
processes, and their corresponding liquid products see Bridgwater et al. [6].
Bio-oil varies according to process conditions and feedstock. Most studies have focused on fast
pyrolysis oil that can be generalized as consisting of hydroxyaldehydes, hydroxyketones, carboxylic
acids, furan/pyran ring containing compounds, anhydrosugars, phenolic compounds and oligomeric
fragments of lignocellulosic polymers with some examples represented in Scheme 1. These products
stem from the original biomass composition consisting of cellulose, hemicelluloses, lignin, extractives,
lipids, proteins, simple sugars, starches, water, hydrocarbons, ash, and other compounds [5].

Scheme 1. Representative compounds of bio-oil.

Reactions under pyrolysis conditions are complex and not fully understood due to the range of
reaction temperatures and the complex biomass composition, but they can be generally classified as a
Energies 2013, 6 517

simultaneous mix of dehydration, depolymerization, re-polymerization, fragmentation, rearrangement,

and condensation, as represented by some examples in Scheme 2. These reactions result in a bio-oil
containing over 300 individual compounds [22,26,27]. For more extensive reviews of the elemental and
chemical composition of biomass and bio-oil see Yanik et al. [28], Branca et al. [29], Lu et al. [13],
Valtiner et al. [30], Ralph et al. [31], Evans et al. [32], Marsman et al. [33], and Sipila et al. [34].

Scheme 2. Representative pyrolysis reactions.

From an applied perspective, bio-oil can be burned directly as a substitute for fuel oil in various
static applications such as boilers and furnaces [6]. However, it is not miscible with fossil fuels, but is
miscible with water up to 35%–40%. The result is that the liquid gradually “ages” as the polyphenols
polymerize, leading to a variable viscosity, ranging from 10 to 10,000 cp. It “ages” faster with
exposure to light, O2, or heat above 80 °C, leading to storage issues. The pH is relatively low due to
the presence of organic acids, further increasing corrosion and storage issues. There are suspended
solids ranging from 0.3% to 3%, which have the potential to negatively affect combustion
characteristics by plugging nozzles, and the presence of oligomeric fragments can lead to solid, tar-like
deposits on pipes and reactors [35]. Bio-oil characteristics are contrasted to petroleum crude oil in
Table 1 [22,36] to highlight areas where bio-oil needs improvements.
To overcome these issues, bio-oil must be modified chemically or ‘upgraded’ by the removal and
modification of unwanted compounds, most of which contain oxygen. Many times, the final product is
evaluated by its O/C ratio and H/C ratio, with low O/C and high H/C ratios indicating a higher quality
liquid product. These ratios are especially important if the bio-oil is to be used as a substitute for
demanding petrochemical applications such as transportation fuels that need a clean, homogenous fuel
stream [37]. To achieve these results, bio-oil can be re-volatilized in a catalytic environment, generally
referred to as catalytic upgrading, or biomass can be pyrolyzed in the presence of catalysts that affect
the desired changes before the initial condensation, generally referred to as catalytic fast pyrolysis.
Ideally, a single reactor would fulfill all process requirements and produce a quality liquid fuel from
the initial, solid biomass [38,39]. Due to its potential in a wide variety of situations, many consider
catalytic fast pyrolysis to be the most promising way to improve the final, liquid composition [5,40].
The challenge is to design catalysts that positively affect all of the over 300 volatilized, organic
compounds through various cracking and reforming reactions. This is important for biorefineries and
will help them become cost competitive with current infrastructure. Improving catalysts’ activity,
selectivity, and stability is essential for progress in the field of biomass utilization.
Energies 2013, 6 518

Table 1. Bio-oil vs. crude oil characteristics.

Composition Bio-oil Crude Oil
Water (wt %) 15–30 0.1
pH 2.8–3.8 -
density (kg/L) 1.05–1.25 0.86
viscosity 50 °C (cP) 40–100 180
HHV (MJ/kg) 16–19 44
C (wt %) 55–65 83-86
O (wt %) 28–40 <1
H (wt %) 5–7 11–14
S (wt %) <0.05 <4
N (wt %) <0.4 <1
Ash (wt %) <0.2 0.1
H/C 0.9–1.5 1.5–2.0
O/C 0.3–0.5 ≈0

3. Catalytic Upgrading

3.1. Introduction

The addition of catalysts to the pyrolysis system enhances reactions that include cracking,
decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation, and hydrogenation as
summarized in Scheme 3 [22].

Scheme 3. Representative catalytic upgrading reactions.

As shown in Scheme 3, catalytic upgrading can enhance the properties of bio-oil by removing
oxygenated compounds via H2O and CO2, reducing molecular weight, and altering chemical structures
to resemble those of petrochemical products. Interestingly, biomass has within its chemical framework
Energies 2013, 6 519

naturally present ions that can have catalytic effects under pyrolysis reaction conditions [41], such as
reducing the bio-oil yield in favor of char and gaseous species [42]. This effect was observed with the
most abundant inorganic components of biomass, including silica, Na, K, Mg, and Ca [43]. Both the
cations and anions present were shown to have an effect on the pyrolysis products [44], while
demineralization was shown to increase the yield of anhydrosugars [45]. To study this, biomass was
stripped of its natural minerals, and these catalytic elements were then reintroduced individually using
ion exchange and sorption. The way in which these ions were reintroduced into the biomass had an
affect on the final yields with ion exchange showing a greater catalytic effect than sorbed ions [46].
Catalytic effects of inorganics found in ash have also been studied. Patwardhan et al. [47] studied
the pyrolysis of pure cellulose in the presence of switchgrass ash, a representative mix of water-soluble
salts of alkali and alkaline earth metals. It was discovered that as little as 0.5% ash resulted in a tripling
of the formic acid and quadrupling of glycoaldehyde, whereas the levoglucosan yield was halved. The
comparative yields of each chemical species were changed, but the individual species themselves were
unaffected. Most of these inorganic salts can be extracted with an acid wash, even though some
alkaline earth metals associated with organic macromolecules are resistant to extraction. It is therefore
important to take into consideration that pyrolysis is inherently a catalytic process unless pretreated,
and when studying the selectivity of additional catalysts, the catalytic effects of various naturally
occurring minerals should be evaluated.
In industrial settings, it is required that additional catalysts not found in natural plant biomass are
added in order to achieve the desired upgrading effects. However, due to the diverse mixture of species
and reactions present, bio-oil cannot currently be upgraded using a single technique. For example,
oligomeric fragments cause coking in a steam reforming process but are desirable for catalytic
cracking or hydrocracking [48,49].
Overcoming issues like these will require further development of catalysts beyond what has been
previously studied [25]. Catalysts should be highly active, selective to particular products, resistant to
deactivation, readily recycled, and cheap. Most catalysts used in the upgrading of bio-oil are
supported, meaning the metal catalyst is dispersed on a different and cheaper material such as carbon,
silica, or alumina. Supported catalysts are cost effective and can generally be used at higher
temperatures due to the dispersed metal particles’ resistance to sintering, or melting together.
Furthermore, the support itself can act as a catalyst. Different catalysts have different mechanisms for
eliminating oxygen and catalyzing other desired reactions as shown in Scheme 2 and 3. Two main
routes for upgrading have dominated the research and development fields, hydrodeoxygenation and
zeolite cracking.

3.2. Hydrodeoxygenation

Hydrodeoxygenation (HDO) is a hydrogenolysis process that removes oxygen from a feedstock.

Carbon-oxygen bonds are cleaved with hydrogen in the presence of a catalyst producing CO2 and H2O
and partially eliminating oxygen from the final product. This type of reaction can be achieved through
sulfide/oxide and transition metal catalysts through a combination of chemisorption, proton donation,
and desorption. The catalyst reactivity relies on the number and strength of both Lewis acid and
Brønsted acid sites on the catalyst/support system. Supports affect both the acidity and reactivity of the
Energies 2013, 6 520

catalyst compound. Ideally, they should be stable and have a low affinity for carbon formation and a
high affinity for activation of oxy-compounds [22].
HDO produces a quality, energy dense, non-corrosive, naphtha-like product, which can be further
upgraded to other chemicals [25]. HDO also has the advantage of easy separation of water and benefits
to turbines from the separation of alkali metals from the hydrocarbon product when oxygen levels are
reduced to less than 2%. However, it has the major disadvantage of consuming large quantities of
high-pressure H2, 600–1000 L/kg bio-oil, thus increasing costs [41]. It is important to note, though,
that consumption is also high for some petroleum feedstocks that are difficult to hydrocrack. Just like
the petroleum industry in the past, the bio-oil industry needs further technological development.
Fortunately, feedstocks for biofuels are not fundamentally more difficult to upgrade than those in the
petroleum industry [50]. Furthermore, if HDO is emphasized as opposed to hydrogenation of the aromatic
rings, hydrogen consumption can be significantly reduced while raising the final octane rating [51].
Using current technology, hydrogen is generally co-fed into the system at a pressure of 75–300 bar.
To a certain extent, high pressure helps increase the solubility of the H2 in the bio-oil and thereby
increase hydrogenation via better accessibility to the catalyst. However, even at a low pressure of
5 bar, positive results have been observed [52]. Typical residence times range from 3 to 4 h for batch
reactors. Using a Ru/C catalyst at 350 °C and 200 bar in an autoclave setup, final liquid yield was
highest for a 4 h reaction time [53]. Temperatures range from 250 to 450 °C. Coke formation generally
increases with time and temperature, as does deoxygenation [22]. From 360 to 390 °C and a 5 min to
1 h reaction time, deoxygenation was shown to increase in the presence of a cobalt molybdate catalyst
in an autoclave setup [54]. However, for HDO of wood based bio-oil over a Pd/C catalyst in a fixed
bed reactor at 140 bar, the degree of deoxygenation plateaued at 340 °C and gave way to cracking.
Furthermore, the gas yield increased three-fold and the final liquid yield decreased from 75% to 56%
when increasing the temperature from 310 to 360 °C [55]. Clearly catalyst choice and operating
conditions impact the final products. A balance must therefore be struck between residence time,
temperature, deoxygenation, gas, and coke formation.
Current research focuses on improving catalyst effectiveness and longevity. The petroleum industry
has been eliminating sulfur from petrochemicals for years using a similar hydrogenolysis process
called hydrodesulfurization (HDS). Therefore, many catalysts have already been extensively studied
by the petroleum industry for HDS. Due to the similarities between the two, much of the knowledge
about HDO has been extrapolated from previous HDS experience with cobalt/molybdenum and Ni,
Co, Mo in oxide forms on silica and alumina supports. It has been noted that the high acidity of Al2O3
supports causes unacceptable coking, and the material has furthermore been shown to sinter at high
temperatures in the presence of water and therefore deactivate [56].
Catalytic work has therefore been undertaken on both catalysts and supports. For example, research has
shown that neutral carriers such as C generally show lower coke formation than alumina supports [57].
Longevity of the catalyst and therefore low coke formation is important because catalyst functionality
including oil yield and resulting H/C ratio is directly affected by the number of recycles, even if O/C
ratios seem to be unaffected [53]. Different supports have also been shown to give different final liquid
yields and degrees of deoxygenation. For example, Ru/TiO2 and Ru/C yielded more final liquid with
lower oxygen content than Ru/Al2O3 in an autoclave setup at 450 °C and 350 bar of H2 [58]. A
Energies 2013, 6 521

possible mechanism for HDO of a lignin-derived compound such as guaiacol on a supported metal
catalyst is given in Scheme 4 [12,22].

Scheme 4. Possible mechanism for HDO of guaiacol.

Several alternative approaches to more traditional catalyst development have also been explored.
Gutierrez et al. [56] found that multiple noble metals used simultaneously interacted with each other
and gave different results than simply the two separate catalyst results combined. HDO of guaiacol
was studied using zirconia-supported mono- and bi-metallic noble metal catalysts in a batch reactor at
80 bar. Rh, Pd, Pt, RhPd, RhPt, and PdPt all performed better in the hydrogenation of guaiacol at
100 °C and at 300 °C than the conventional sulfided CoMo/Al2O3 catalyst which deactivated due to
carbon deposition and contaminated the product with sulfur. Rh and RhPt completely converted the
guaiacol at 100 °C to a variety of products, but deoxygenation only took place at 300 °C. The
bimetallic catalysts containing Rh gave better results than the monometallic Pt and Pd catalysts in
terms of guaiacol hydrogenation. The PdPt catalyst was less reactive than that of the separate
monometallic catalysts. This indicates that catalysts react with each other in a variety of ways when used
simultaneously, in addition to reacting with the biomass. These interactions are not fully understood.
Reduction of H2 consumption has been studied using the donation of H2 by a liquid with an easily
donated, acidic proton that lowers the H2 pressure required. Xiong et al. [59] studied obtaining
hydrogen from formic acid over Ni, Pd, and Ru on various supports in a batch reactor at 40 bar, a
temperature of 150–230 °C, and a reaction time of 5–7 h. The catalyst supports did not make a
significant difference, but Ni and Ru outperformed Pd in final product quality. Oxygen content was
lowered while a reduction in the unsaturated components was observed, along with the conversion of
organic acids into esters. All of these reactions occurred without obvious coke formation. In another
study, Kunkes et al. [60] described a method of reforming polyol over Pt-Re/C, where reforming refers
to C-C cleavage and the corresponding production of H2, CO, and CO2. These products can be used to
de-oxygenate the remainder of the feed thus eliminating the need for co-feeding of hydrogen while
producing gasoline and diesel type hydrocarbons. Similarly, Pt elements can promote the water-gas
shift (WGS) reaction [61]. Pt/Al2O3 has been studied with a model bio-oil in an autoclave at 350 °C
under 10 bar of nitrogen. The catalyst showed selectivity for producing H2 in situ, eliminating the need
for co-feeding of hydrogen [62]. Clearly, further research on catalysts and corresponding reaction
conditions modified to obtain desired products is needed. See Wildschut et al. [58] and Elliott [51] for
more in depth work on HDO including product properties and molecular composition of HDO oils. For
Energies 2013, 6 522

a comparison of several methods for characterizing HDO oils see Oasmaa et al. [63]. Table 2 [22]
provides a summary of the yield, product quality, and operating conditions for several catalysts
investigated for HDO. DOD (%) stands for degree of deoxygenation.

Table 2. Summary of catalysts investigated for HDO.

Temp.
Catalyst Pressure (bar) DOD (%) O/C H/C Oil Yield (wt %) Ref.
(°C)
Co-MoS2/Al2O3 350 200 81 0.8 1.3 26 [58]
Co-MoS2/Al2O4 370 300 100 0 1.8 33 [64]
Ni-MoS2/Al2O3 350 200 74 0.1 1.5 28 [58]
Ni-MoS2/Al2O4 400 85 28 - - 84 [65]
Pd/C 350 200 85 0.7 1.6 65 [58]
Pd/C 340 140 64 0.1 1.5 48 [55]
Pd/ZrO2 300 80 - 0.1 1.3 - [56]
Pt/Al2O3/SiO2 400 85 45 - - 81 [65]
Pt/ZrO2 300 80 - 0.2 1.5 - [56]
Rh/ZrO2 300 80 - 0 1.2 - [56]
Ru/Al2O3 350 200 78 0.4 1.2 36 [58]
Ru/C 350–400 230 73 0.1 1.5 38 [66]
Ru/C 350 200 86 0.8 1.5 53 [58]
Ru/TiO2 350 200 77 1 1.7 67 [58]

3.3. Catalytic Cracking with Zeolites

Zeolites are complex, three-dimensional porous structures with varying elemental compositions that
exhibit catalytic activity in up to 50% of their volume. Cracking and dehydration are the main reactions
seen. Adsorption of the oxy-compound occurs on an acid site. This is followed by either decomposition
or bimolecular monomer dehydration, as determined by pore size [22]. As with sulfide/oxide and
transition metal catalysts, the acidity of the zeolite affects the reactivity and yields, with high acidity
leading to a higher affinity for C and water formation [67]. In HZSM-5, one of the most widely used
zeolites, acidity is linked to the Si/Al ratio, with a low ratio indicating high acidity. Pore blockage from
polymerization and polycondensation reactions causes deactivation of the catalyst. Zeolites should
have correct pore size and acidic sites to promote desired reactions while minimizing carbon
formation [22]. A possible mechanism for dehydration of hydroxyl containing compounds (i.e.,
carbohydrates) on an aluminosilicate zeolite is given in Scheme 5 [22].
Zeolites produce aromatics at atmospheric pressures without H2 requirements. The final product
generally has a low heating value. This is due both to its low H/C ratio and high O/C ratio as compared
to HDO oils [6,22]. Research is generally conducted at temperatures from 350 to 600 °C. For
HZSM-5, yields are in the 15% range with predictions of 23% [41]. Excessive C production and
therefore catalyst coking is a problem. In one study, coke deposition at all temperatures led to a
decrease in the catalytic activity after only 30 min time on stream [38]. Furthermore, coke has been
shown to significantly increase at temperatures above 400 °C [68]. Some coke can be burned off, but
irreversible dealumination and loss of acid sites occurs at temperatures as low as 450 °C in the presence
of water [69]. Research on the reduction of coking is important, with a variety of approaches showing
Energies 2013, 6 523

promise. For example, the recycling of non-condensable gases into a catalytic reactor has the potential
to reduce char/coke yields while increasing oil yields [70].

Scheme 5. Aluminosilicate zeolite dehydration of model compound.

The elemental composition of the fast pyrolysis bio-oil feedstock, as measured by its H/Ceff ratio
has been determined to have a large impact on the production of olefins, aromatics, and coke.
Experiments have shown that pyrolytic bio-oil feedstocks with a ratio of at least 1.2 or higher perform
better in zeolite cracking upgrading [39]. Ten feedstocks were studied over HZSM-5. Yields of olefins
and aromatics increased while coke production decreased with increasing H/Ceff ratios. Catalyst life
increased as coke yield decreased. This suggests that it may be beneficial to increase the H/Ceff ratio to
1.2 through hydrogenation of the bio-oil feedstock before upgrading with a zeolite catalyst.
Another method of effectively increasing the H/Ceff ratio is to co-pyrolyze a hydrogen donor such
as methanol. Horne et al. [71] studied the pyrolysis of wood waste in a dual zone, fluidized bed
reactor. Pyrolysis was carried out at 550 °C. Varying amounts of methanol were also injected, and the
pyrolysis/methanol gases were passed over a fixed bed of HZSM-5 held at 500 °C. There was an
overall increase in hydrocarbon products including alkylated phenols and aromatics. The alkylated
products are thought to compete with the production of polyaromatic hydrocarbons (PAHs are
carcinogenic compounds and therefore not desirable) and therefore explain the corresponding decrease
in 3-, 4-, and 5-ring PAHs. The addition of methanol also increased water formation and decreased CO
and CO2 yields, which is in keeping with findings by Chen et al. [72]. However, these observations do
not agree with a study by Evans et al. [73] that showed an increase in the CO2/H2O ratio. In all cases,
methanol had a synergistic effect on yields, and further research on co-pyrolysis seems justified.
Separation of compounds that don’t react well with the particular catalyst being used could also be
used in place of increasing the H/Ceff ratio. Gayubo et al. [74] has proposed separating aldehydes and
phenols before upgrading over HZSM-5.
Temperature was found to have an impact on product composition with high temperatures
producing more light gases. Cheng [38] studied furan conversion to aromatics and olefins using
HZSM-5. Products included CO, CO2, allene, C2-C6 olefins, benzene, toluene, styrene, benzofuran,
indene, and naphthalene. Varying temperatures favored different final products. At 450 °C, benzofuran
and coke formed. At 500–600 °C, aromatics formed. At 650 °C, olefins were produced along with CO
and aromatics.
H2O also plays a role in chemical conversions. The conversion of anisole was studied in a quartz
tube reactor over HZSM-5 at 400 °C [75]. The presence of controlled quantities of water in the feed
Energies 2013, 6 524

was discovered to have a positive effect on catalytic activity. Interestingly, in this study, the
deactivation rate of the zeolite was unrelated to the addition of water. Furthermore, H2 was shown to
have a positive effect on reducing coke formation, which is affirmed by other studies [76]. This is
especially true when a metal function is present [77].
Other zeolites have been studied in comparison to HZSM-5 with mixed results. In one study using a
fixed bed micro-reactor operating at 1 bar, 3.6 weight hourly space velocity (WHSV), and
330–410 °C, HZSM-5 was found to yield more hydrocarbons than HY, H-mordenite, silicalite, and
other silica-alumina zeolites. HZSM-5 and H-mordenite also showed higher selectivity for aromatics
than aliphatics while the other catalysts produced the opposite effect [78]. However, other zeolites do
have some advantages. In a similar study, silicalite produced the least coke. Silica-alumina best
converted the non-volatile fraction of the bio-oil. HZSM-5 produced the most yield in the gasoline
boiling point range while HY and H-mordenite produced less yield and in the kerosene boiling point
range [79]. In another study, catalytic pyrolysis of pinewood over zeolites HBeta-25, HY-12,
HZSM-5-23, and HMOR-20 was conducted in a fluidized bed reactor at 450 °C [80]. Quartz sand was
used for non-catalytic pyrolysis. Oil from each bed was chemically characterized and compared.
Overall, ketones and phenols were produced. HZSM-5 produced more ketones and less alcohols and
acids than other catalysts. It also produced more liquid, similar in quantity to the quartz bed but
containing more water. Mordenite and quartz produced almost no PAHs. One major advantage noted is
that the catalysts were regenerated successfully.
There is also the potential to use biomass in a traditional petroleum fluid catalytic
cracker (FCC) [81,82]. Corma et al. [83] studied the cracking of glycerol and sorbitol using various
FCC catalysts co-fed with vacuum gasoil (a product corresponding to an Arabian Light petroleum
product). This work suggests that biomass and petroleum derived oil streams can be co-fed in an
industrial, petroleum catalytic reactor producing a desirable final product. Samolada et al. [40] also
studied co-feeding of hydrotreated bio-oil in a traditional FCC reactor with promising results. For
more extensive information on zeolite upgrading see Lappas et al. [84], Williams et al. [85],
Murata et al. [86], and Jae et al. [87]. Table 3 provides a summary of the operating conditions and
products for several catalysts that have been investigated for zeolite cracking.

3.4. Catalyst Development

Synthesis of catalysts from renewable materials is an attractive area of active research due to the
cost of mining and synthesizing catalysts. Lin et al. [92] studied the successful synthesis of ZSM-5 and
ZSM-48 from the ashes of gasified biomass containing 70%–87% amorphous silica. The resulting
zeolites showed high silica contents and high crystallinity (>99%). Muradov et al. [93] studied the
catalytic effects of duckweed derived biochar in the reforming of CH4-CO2 at 800 °C. Untreated
biochar showed low activity and rapidly deactivated. CO2 treated biochar showed higher activity but
also deactivated due to carbon deposits from the decomposition of CH4. However, activated carbon has
been shown previously in this paper to be an effective support for noble metals, and therefore biomass
derived, activated carbon seems promising. Future research in this area is needed, as a self-sustaining
system for energy production that includes catalysts would be ideal.
Energies 2013, 6 525

Table 3. Summary of catalysts investigated for zeolite cracking.

Catalyst Temp. (°C) Feedstock Catalyst Effects Ref.
Decreasing the SiO2/Al2O3 ratio from 200/1 to 25/1 and
increasing the catalyst-to-lignin ratio from 1:1 to 20:1
HZSM-5 with decreased the oxygenates and increased the aromatics.
Kraft
varying Si/Al2O3 500–764 Aromatics yield increased from 500 to 650 °C and then [88]
Lignin
ratios decreased at higher temperatures. Under optimal reaction
conditions, the aromatic yields were 2.0% (EHI 0.08) and
5.2% (EHI 0.35).
HZSM-5,
H-USY had the largest pore size and lowest Si/Al ratio (7)
Na/ZSM5, Alkaline
650 and had the best liquid yield of 75% and aromatic yield of [89]
HBeta, and lignin
40%.
HUSY
ZSM-5, ZSM-5, Al/MCM-41, Al-MSU-F type, Criterion-534,
Al/MCM-41, alumina-stabilized ceria-MI-575, Cu2Cr2O5, and
Al-MSU-F, ZnO, biomass-derived ash were selective to the reduction of most
ZrO2, CeO2, oxygenated lignin derivatives. ZSM-5, Criterion-534, and
Cu2Cr2O5, Al-MSU-F catalysts enhanced the formation of aromatic
Criterion-534, Cassava hydrocarbons and phenols. No single catalyst was found to
500 [90]
alumina- rhizome reduce all carbonyl products but ZSM-5, Criterion-534 and
stabilized ceria- MI-575 could reduce most of the carbonyl products that
MI-575, slate, contained hydroxyl groups. ZSM-5, Criterion-534,
char and ashes Al/MCM-41, Al-MSU-F, copper chromite, char and ashes
derived from increased acetic, formic, and lactic acid. MI-575 did not
char and biomass increase acids.
Waste olive
Dolomite 500–800 Dolomite increased cracking and gas production. [91]
husks
HZSM-5,
Al/MCM-41, HZSM-5 was the most effective catalyst for the production
Al-MSU-F, and of aromatic hydrocarbons, phenols, and acetic acid and the
alumina- reduction of oxygenated lignin-derived compounds and
Cassava
stabilized ceria 500 carbonyls containing side chain hydroxyl groups. Only [81]
rhizome
MI-575, pore MI-575 showed a decrease in acetic acid yields. MI-575
sizes 5.5, 31, 15, also showed the most increase in methanol with HZSM-5 a
and NA close second.
respectively

Catalysts can either be mixed with the biomass prior to pyrolysis or separated as to only interact
with the gaseous reactants. It was discovered that separation of the catalyst and biomass was more
effective for the conversion to desirable products [82]. This study involved a catalyst containing Fe
and Cr in their oxide forms, chromite (FeCr2O4) in the combined active phase. It showed promising
results in terms of limited water production. Chromite produces hydrogen from water and carbon
monoxide in the WGS reaction. The catalyst therefore consumes water produced from deoxygenation
through the WGS reaction while producing large quantities of hydrogen. Chromite also showed
selectivity in converting the heavy phenolic compounds to phenol and light phenolics.
Energies 2013, 6 526

3.4.1. Multistage Catalysis

Some work has been conducted on combining the benefits of HDO and cracking in one process
using multiple stages. Early work by Gagnon et al. [94] showed that a catalytic pretreatment consisting
of mild hydrogenation of wood-derived, vacuum pyrolysis oils at 80–140 °C and 41–103 bar over a
ruthenium catalyst prevented coking and polymerization in the following HDO runs at a standard
temperature of 325 °C and 172 bar. Subsequent studies showed that a non-catalytic, hydrothermal
pretreatment followed by catalytic pyrolysis showed an increase in final liquid yield [4]. In
combination, these studies lead to the conclusion that a pretreatment step can have positive effects on
subsequent HDO runs and should be considered an option in future research.
Vispute et al. [11] combined pretreatment, HDO, and catalytic cracking. The first step involved
hydrogenation at 125 °C over a Ru/C catalyst, with no coking or reactor plugging observed. The
second stage involved further hydrogenation at 325 °C over a Pt/C catalyst. Finally, olefins and
aromatics such as benzene, toluene, xylene, ethylene, propylene, and butylene were produced over a
HZSM-5 zeolite catalyst, the first five of which are important building blocks for the chemical
industry. Coke yield was very low due to the previous hydrogenation steps. As the H/Ceff ratio increases,
the thermal stability of the bio-oil improves, reducing coke formation. Furthermore, an increase in the
hydrogen content promotes H2O production and therefore a higher yield of hydrocarbons in the
products, as less carbon is lost to CO and CO2 during deoxygenation. Finally, using this reactor
configuration allows the catalysts to be regenerated in the fluidized bed reactor of the zeolite
upgrading stage. Optimization of each step is required and will depend on the cost of hydrogen and
therefore the optimal amount of hydrogenation. Wang et al. [95] studied a similar process with the
order of each stage reversed. The final product from HDO of catalytic pyrolysis derived bio-oil and
HDO of untreated bio-oil were compared. The former showed higher degrees of deoxygenation. These
studies all demonstrate that a deoxygenated feedstock significantly improves downstream processing,
regardless of the method of deoxygenation in the initial stage. It is therefore critical to find the optimal
combination of stages and reactions that will lead to the highest quality product at the lowest
possible cost.

3.4.2. Multifunctional Catalysts

Research on the use of cracking and HDO catalysts used simultaneously or combined to form one
multifunctional catalyst has shown promising results. Specifically, zeolites doped with metal catalysts
have drawn attention, both for the potential product streams generated and because this line of research
sheds light on the mechanisms of cracking and reforming which are still not well understood. Ideally,
doped zeolites can be integrated into the pyrolysis equipment, catalyzing the production of the desired
products in situ during the initial quenching, thus creating a one-step solids-to-liquids unit which benefits
both the quality of the liquid yield and the economic potential of commercial applications [96]. Some
research on in situ catalytic upgrading has been undertaken including a study using molecular beam
mass spectrometry, a quartz micro reactor, and a HZSM-5 catalyst [73]. Techniques such as this allow
real time analysis and rapid screening of a variety of catalysts, operating conditions, and biomass
streams at minimal expense.
Energies 2013, 6 527

French et al. [37] studied catalytic pyrolysis of biomass in a tubular quartz micro reactor using a
molecular-beam mass spectrometer. Approximately 10 mg of biomass covered with 50–100 mg of
catalyst was pyrolyzed at 400–600 °C. Aspen wood, Avicel PH-105 cellulose, and straw lignin were
tested in combination with 10 commercial zeolites including HZSM-5, and 22 laboratory-prepared
ZSM-5 catalysts with Co, Fe, Ni, Ce, Ga, Cu, and Na substituted for the aluminum and hydrogen
components. Four laboratory X and Y zeolites and four different silica and alumina materials were also
tested. Ni, Co, Fe, and Ga showed the highest yield of hydrocarbons at 16%. Unfortunately,
semi-continuous operation caused partial deactivation of the ZSM-5 catalyst after only 4 min. A
similar study was conducted on the cracking of naphtha over Fe/HZSM-5 [97]. Yields of light olefins
increased with temperature and a moderate WHSV maximized light olefins as expected. However, the
interaction of zeolite and transition metal caused increased olefins yields only up to 6% Fe loading,
with further loading catalyzing the production of aromatics. Results such as these clearly indicate the
need for further catalyst development. It is also important to note that the way in which a catalyst such
as Fe/HZSM-5 is prepared can also have an effect on its reactivity [98]. For more information on fast
pyrolysis and upgrading see Butler et al. [99].
While catalytic development work continues to occur, there has only been scattered research on
multifunctional and novel catalysts. The research spans a wide range of catalyst combinations,
temperatures, and feedstocks in an effort to develop fundamental knowledge on the catalytic effects,
processes, and conditions. The resulting body of literature, summarized on Table 4, with regards to
multifuncional catalysts is built using information from studies using agronomic, algae and woody
biomass feedstocks, as well as fundamental studies utilizing model compounds, including those
present in biomass, and upgraded bio-oil products. Provided in Table 4 is a summary of the current
research on novel and multifunctional catalysts showing operating conditions and resulting products.

Table 4. Summary of results from current work on HDO, zeolite, multifunctional, and
novel catalysts.
Catalyst Temp. (°C) Feedstock Catalyst Effects Ref.
Pt/HZSM-5 increased isomerization and
Pt/HZSM-5 and hydrogenation, increased gas yields, increased C4
400–500 Canola Oil [100]
HZSM-5 iso/n-hydrocarbon ratio, and lowered organic liquid
product (OLP) yield. Steam decreased the OLP yield.
Na2CO3 lowered the initial degradation temperature.
Pretreatment Chlorella Catalyst also increased gas yield and decreased liquid
300–450 [101]
with Na2CO3 algae yield. Resulting bio-oil had higher heating value, more
aromatics, and lower acidity.
Enhanced charring and dehydration and promoted
Corn cob, fir
ZnCl2 production of furfural (FF) and acetic acid (AA). Corn
wood,
impregnated in 250–500 cob gave most FF (8%) at 340 °C with 15% ZnCl2 and [102]
bagasse, and
biomass a yield of 4% AA compared to a non-catalytic yield of
rice husk
FF 0.49%.
Energies 2013, 6 528

Table 4. Cont.
Catalyst Temp. (°C) Feedstock Catalyst Effects Ref.
Increasing the amount of catalyst decreased the oil
MgO at 5%, yield and increased the gas and char yields. MgO
10%, 15%, and increased the oil quality by reducing oxygen levels
550 Cotton seed [103]
20% of raw from 9.56% to 4.90% and converting almost all of the
material long chain alkanes and alkenes to lower molecular
weight hydrocarbons in the diesel range.
Empty palm
Boric Oxide oil fruit Promoted deoxygenation, eliminated 50%–80% of the
mixed with 400 bunch and hydroxyl and methoxy groups, increased both water [104]
biomass oil palm and char yields, and decreased gas yields.
fronds
Al/MCM-41,
Al/MCM-41, Al/MCM-48, and Meso-MFI produced
Al/MCM-48,
more phenolics and reduced more oxygenates than
HZSM-5, Meso-
HZSM-5. HZSM-5 and Meso-MFI produced aromatics
MFI, Pt/
450 Miscanthus due to their acidic sites. Meso-MFI zeolite, which has [105]
HZSM-5
both mesopores and high acidity, performed the best
(0.5%),
overall. Pt enhanced deoxygenation and aromatization
Pt/Meso-MFI
in both cases.
(0.5%)
Meso-MFI and
Meso-MFI reduced oxygenates by 38%.
Pt/Meso-MFI Waste rice
500 Pt/Meso-MFI reduced oxygenates by 49%. Both [106]
(0.5%, ion husk
converted heavy phenols to light phenols and aromatics.
exchanged)
Pt/Hbeta catalyzed both methyl transfer and
hydrodeoxygenation at significantly higher rates than
the monofunctional catalysts. Formed benzene,
Pt/Hbeta,
400 Anisole toluene, and xylenes with lower hydrogen [107]
Pt/SiO2, Hbeta
consumption and a significant reduction in carbon
losses. The rate of deactivation and coke deposition
were moderately reduced.
Ga/HZSM-5 catalyzed decarbonylation, producing
Benzaldehy benzene and CO in the absence of H2. In the presence
Ga/HZSM-5 400–550 [108]
de of H2, it catalyzed toluene production. Addition of
water increased benzene and reduced toluene.
1.5% Zn/H-ZSM-5 produced slightly more aromatics
Zn/HZSM-5 (~5%) than 0.5% Zn/HZSM-5. Zn/HZSM-5 catalysts
300–500 Furfural [109]
(0.5 and 1.5%) yielded more aromatics and olefins and less furan and
coke than HZSM-5.
Increased oxygenated compounds and CO while
Ce/HZSM-5 600 Glucose [110]
reducing coke.
Hybrid Hybrid Pt/HZSM-5 catalyst showed lower
Pt/HZSM-5 Pyrolysis metal-support interaction but a higher catalytic
350–450 [111]
(mixture) and gasoline activity. Pt/HZSM-5 increased C2+n-alkanes and
Pt/HZSM-5 decreased methane and hydrogen requirements.
Energies 2013, 6 529

Table 4. Cont.
Catalyst Temp. (°C) Feedstock Catalyst Effects Ref.
Ir/HY showed better metal dispersion, acidity,
hydrogen adsorption, and metal surface exposure than
Pd/HY, Pt/HY, Pyrolysis
350–450 Pt/HY or Pd/HY. Ni/HY catalyzed less hydrogenation [112]
Ir/HY, Ni/HY gasoline
than the other three. Hydrogen pressure helped
stabilize the catalysts.
(10%) Pd/C,
(30%) Pd/C, Various phenols such as guaiacol, pyrocatechol, and
Pd(OH)2/C, Various resorcinol were formed from lignin. Model compounds
Pd(OAc)2, Pd- lignin types were hydrodeoxygenated, demethylated, and
PEPPSI-iPr and 300 and lignin demethoxylated. Percentage yields were better than [113]
Pd/Lindlar with model many other HDO techniques. Activity of catalysts was
Nafion SAC-13 compounds in the following order; Pd(OAc)2 < Pd-PEPPSI-IPr <
used in every Pd(OH)2/C < 10% Pd/C < Pd-Lindlar.
run.
Bio-oil from
90% conversion of the bio-oil in the feed with a
Pinus
Ni/HZSM-5 selectivity for aromatics of 0.4 (benzene, toluene,
450 insignis with [114]
(1%) xylenes (BTX) selectivity of 0.25). Rapid coke
60%
deposition was observed.
methanol
Ni/Al2O3,
Ni/CeO2, and Initial degradation at lower temp. All reduced tar. 30%
Ni/Al2O3-CeO2 Ni/CeO2 catalyst yielded least amount of tar and least
800 Cellulose [115]
with varying CO. 30% Ni/Al2O3 produced maximum amount of H2
percentages of (43.5 vol % at 800 °C, 15 min residence time).
nickel.
Depending on preparation, Ga/HZSM-5 increased the
rate of aromatics production. Ga seemed to increase
Furan with
the rate of decarbonylation and olefin aromatization,
Ga/HZSM-5 600 pinewood [116]
whereas HZSM-5 catalyzed other reactions such as
sawdust
oligomerization. 41% of the energy in the wood was
converted into usable products.
HZSM-5 almost completely decomposed the aliphatic
C-O bonds and carbonyl groups and eliminated 80% of
the methoxy groups. It showed more deoxygenation
NiCl2, HZSM-5,
700 Kraft Lignin than Ni/ZSM-5. NiCl2 reduced liquid yield while [117]
Ni/ZSM-5
increasing the molecular weight and increasing the gas
yield. It produced more aromatic carbons and less
aliphatic carbons.
Lignocel yielded more hydrocarbons and Miscanthus
more phenols. All catalysts produced more phenols. A
Al/MCM-41, Lignocel
low Si/Al ratio increased product yields and improved
Cu-Al/MCM-41, from beech
500 final composition. Fe and Cu containing catalysts [118]
Fe-Al/MCM-41, wood and
produced the most phenols. The presence of Al/MCM-41
Zn-Al/MCM-41 Miscanthus
reduced oxygenated compounds. Cu/MCM-41
promoted the largest increase of H2 in the gas yield.
Energies 2013, 6 530

Table 4. Cont.
Catalyst Temp. (°C) Feedstock Catalyst Effects Ref.
A significant decrease in non-volatile fraction and
31 catalysts
slight decrease in bio-oil yield were obtained with ZnO
mixed with
Pine (reduced the proportion of heavy fraction in the bio-oil
biomass. 500 [119]
sawdust with a limited decrease in its yield), CuO (exhibited
Included ZnO,
the highest yields in semi-volatile compounds), Fe2O3,
CuO, Fe2O3.
and mixed oxide catalysts containing Cu and Co.
HFer-20, Iron modified zeolites increased coke and methyl
Fe/HFer-20, substituted phenols, decreased methoxy substituted
HY-12, Fe/HY- 400–450 Pine wood phenols, and didn't affect the CO to CO2 ratio. Beta [120]
12, HBeta-25, zeolite was the most active in deoxygenation. All
Fe/HBeta-25 zeolites increased levoglucosan.
K2CO3 was more active producing no saccharides,
aldehydes, or alcohols and substantially reducing the
K2CO3 or
formation of acids, furans, and guaiacols. The yields of
Ca(OH)2 mixed 700 Pine wood [121]
alkanes and phenols were increased. Ca(OH)2 reduced
with biomass
char, increased liquid, and increased alcohols,
opposing the results from K2CO3.
ZnO showed no activity. CaO reduced heavy products
including phenols and anhydrosugars and increased
MgO, CaO,
Poplar formation of cyclopentanones, hydrocarbons, and light
TiO2, Fe2O3, 600 [13]
Wood products including acetaldehyde, 2-butanone, and
NiO, and ZnO
methanol. CaO also reduced acids. Other catalysts
were not as effective. Fe2O3 produced PAHs.
Ni/C mixed with Produced bio-oil with high content of phenols but low
350 Pubescens [122]
biomass contents of acetic acid, furfural, and water.

4. Conclusions

The world currently consumes large quantities of non-renewable hydrocarbons at an ever-increasing

rate. The reserves of fossil fuels are limited, and there are many other problems associated with their
consumption. Biomass has the potential to be a renewable source of hydrocarbons, which could
replace a significant percentage of the world’s fossil fuels in a variety of applications. Currently,
several biological and chemical routes utilize biomass as a source of chemicals and fuels. However,
thermochemical routes can use a wider variety of feedstock, allowing them to utilize non-food based,
lignocellulosic material. Specifically, pyrolysis is touted to be an affective process to convert solid
biomass to a liquid product in high yields. However, the composition of bio-oil is such that it cannot
currently be used in the existing fossil fuel infrastructure for demanding applications, such as
transportation fuels. Catalytic upgrading is touted to be a promising method for converting bio-oil into
higher quality fuels and chemicals. However, many challenges must still be addressed.
The inherent complexity of bio-oil makes finding a single, comprehensive upgrading method
difficult. This is due both to the lack of understanding in relation to specific compounds and the
difficulty in controlling multiple reactions occurring all at once. The oil is difficult to transport,
combust, store, or upgrade. Better catalysts could help solve these problems, but most catalytic
Energies 2013, 6 531

materials are currently expensive and easily deactivated. Furthermore, HDO requires large quantities
of H2 at high pressures and zeolite cracking leads to rapid catalyst deactivation and low quality fuel.
Finally, scaling any of these technologies up to the size of a biorefinery will prove challenging.
Therefore, future research in several areas is required to move the field forward.
Understanding the reaction mechanisms and complex compounds of pyrolysis and bio-oil will
certainly progress technological development. Elucidation of the effects of both indigenous catalysts
and other added catalysts is also critical for the future of the biofuels and biochemicals industry, along
with the effects of biomass impurities on catalyst activity. Both hydrodeoxygenation and zeolite
cracking have been studied under a variety of different reaction and catalytic conditions. However,
more research on both methods is paramount with a specific focus on combining the best of both into
one catalytic fast pyrolysis unit, either single or multi stage. Efforts to reduce pressure and temperature
should be undertaken. Research should also include novel approaches to both methods such as
co-pyrolyzation with a hydrogen donor. Rapid screening using a micro reactor as described in this
paper could be very effective. Work on multifunctional catalysts such as HZSM-5 doped with noble
metal catalysts is also a promising area for further study, along with multiple catalysts used
simultaneously. Finally, optimization of industrial scale facilities should be undertaken. This review
has summarized the current work in this field in the hopes of providing a base of knowledge for further
multifunctional catalyst work.

Acknowledgements

The authors would like to acknowledge U.S.D.A. NIFA McIntire-Stennis (ARK 10-10) and the
USDA Special Grant, Wood Utilization Research Grant (2010-02721) for financial support.

References

1. Demirbas, A. Global renewable energy resources. Energy Sources Part A Recovery Util.
Environ. Eff. 2006, 28, 779–792.
2. Huber, G.W.; Iborra, S.; Corma, A. Synthesis of transportation fuels from biomass: Chemistry,
catalysts, and engineering. Chem. Rev. 2006, 106, 4044–4098.
3. Serrano-Ruiz, J.C.; Dumesic, J.A. Catalytic routes for the conversion of biomass into liquid
hydrocarbon transportation fuels. Energy Environ. Sci. 2011, 4, 83–99.
4. Stephanidis, S.; Nitsos, C.; Kalogiannis, K.; Iliopoulou, E.F.; Lappas, A.A.; Triantafyllidis, K.S.
Catalytic upgrading of lignocellulosic biomass pyrolysis vapours: Effect of hydrothermal
pre-treatment of biomass. Catal. Today 2011, 167, 37–45.
5. Balat, M.; Balat, M.; Kirtay, E.; Balat, H. Main routes for the thermo-conversion of biomass into
fuels and chemicals. Part 1: Pyrolysis systems. Energy Convers. Manag. 2009, 50, 3147–3157.
6. Bridgwater, A.; Peacocke, G. Fast pyrolysis processes for biomass. Renew. Sustain. Energy Rev.
2000, 4, 1–73.
7. Trimble, J.L.; Vanhook, R.I.; Folger, A.G. Biomass for energy: The environmental-issues.
Biomass 1984, 6, 3–13.
Energies 2013, 6 532

8. Committee on Economic and Environmental Impacts of Increasing Biofuels Production.

Renewable Fuel Standard: Potential Economic and Environmental Effects of U.S. Biofuel Policy;
National Academies Press: Washington, DC, USA, 2011.
9. Demirbas, F.M. Biorefineries for biofuel upgrading: A critical review. Appl. Energy 2009, 86,
S151–S161.
10. Mohan, D.; Pittman, C.U., Jr.; Steele, P.H. Pyrolysis of wood/biomass for bio-oil: A critical
review. Energy Fuels 2006, 20, 848–889.
11. Vispute, T.P.; Zhang, H.; Sanna, A.; Xiao, R.; Huber, G.W. Renewable chemical commodity
feedstocks from integrated catalytic processing of pyrolysis oils. Science 2010, 330, 1222–1227.
12. Pandey, M.P.; Kim, C.S. Lignin depolymerization and conversion: A review of thermochemical
methods. Chem. Eng. Technol. 2011, 34, 29–41.
13. Lu, Q.; Zhang, Z.-F.; Dong, C.-Q.; Zhu, X.-F. Catalytic upgrading of biomass fast pyrolysis
vapors with nano metal oxides: An analytical Py-GC/MS study. Energies 2010, 3, 1805–1820.
14. Soria, A.J.; McDonald, A.G.; Shook, S.R. Wood solubilization and depolymerization using
supercritical methanol. Part 1: Process optimization and analysis of methanol insoluble
components (bio-char). Holzforschung 2008, 62, 402–408.
15. Soria, J.A. Unlocking hydrocarbons from biomass. Agroborealis 2010, 41, 39–40.
16. Soria, A.J.; McDonald, A.G.; He, B.B. Wood solubilization and depolymerization by
supercritical methanol. Part 2: Analysis of methanol soluble compounds. Holzforschung 2008,
62, 409–416.
17. Speight, J. Synthetic Fuels Handbook: Properties, Process and Performance; McGraw-Hill
Professional: New York, NY, USA, 2008.
18. Lehmann, J.; Rillig, M.C.; Thies, J.; Masiello, C.A.; Hockaday, W.C.; Crowley, D. Biochar
effects on soil biota: A review. Soil Biol. Biochem. 2011, 43, 1812–1836.
19. Roberts, K.G.; Gloy, B.A.; Joseph, S.; Scott, N.R.; Lehmann, J. Life cycle assessment of biochar
systems: Estimating the energetic, economic, and climate change potential. Environ. Sci.
Technol. 2010, 44, 827–833.
20. Ozcimen, D.; Ersoy-Mericboyu, A. Characterization of biochar and bio-oil samples obtained
from carbonization of various biomass materials. Renew. Energy 2010, 35, 1319–1324.
21. Nowakowski, D.J.; Bridgwater, A.V.; Elliott, D.C.; Meier, D.; de Wild, P. Lignin fast pyrolysis:
Results from an international collaboration. J. Anal. Appl. Pyrolysis 2010, 88, 53–72.
22. Mortensen, P.M.; Grunwaldt, J.D.; Jensen, P.A.; Knudsen, K.G.; Jensen, A.D. A review of
catalytic upgrading of bio-oil to engine fuels. Appl. Catal. A Gen. 2011, 407, 1–19.
23. Freitas, S.R.; Soria, J.A. Development of a gasification system for utilizing fish processing waste
and coastal small diameter wood in rural areas. Energy Fuels 2011, 25, 2292–2300.
24. Yaman, S. Pyrolysis of biomass to produce fuels and chemical feedstocks. Energy Conver.
Manag. 2004, 45, 651–671.
25. Bulushev, D.A.; Ross, J.R.H. Catalysis for conversion of biomass to fuels via pyrolysis and
gasification: A review. Catal. Today 2011, 171, 1–13.
26. Faix, O.; Meier, D.; Fortmann, I. Thermal-degradation products of wood: A collection of
electron-impact (EI) mass-spectra of monomeric lignin derived products. Holz als Roh- und
Werkstoff 1990, 48, 351–354.
Energies 2013, 6 533

27. Faix, O.; Fortmann, I.; Bremer, J.; Meier, D. Thermal degradation products of wood. Eur. J.
Wood Wood Prod. 1991, 49, 213–219.
28. Yanik, J.; Kommayer, C.; Saglam, M.; Yueksel, M. Fast pyrolysis of agricultural wastes:
Characterization of pyrolysis products. Fuel Process. Technol. 2007, 88, 942–947.
29. Branca, C.; Giudicianni, P.; Di Blasi, C. GC/MS characterization of liquids generated from
low-temperature pyrolysis of wood. Ind. Eng. Chem. Res. 2003, 42, 3190–3202.
30. Valtiner, S.M.; Bonn, G.K.; Huck, C.W. Characterization of different types of hay by solid-phase
micro-extraction gas chromatography/mass spectrometry and multivariate data analysis.
Phytochem. Anal. 2008, 19, 359–367.
31. Ralph, J.; Hatfield, R.D. Pyrolysis-GC-MS characterization of forage materials. J. Agric. Food
Chem. 1991, 39, 1426–1437.
32. Evans, R.J.; Milne, T.A. Molecular characterization of the pyrolysis of biomass. Energy Fuels
1987, 1, 123–137.
33. Marsman, J.H.; Wildschut, J.; Mahfud, F.; Heeres, H.J. Identification of components in fast
pyrolysis oil and upgraded products by comprehensive two-dimensional gas chromatography and
flame ionization detection. J. Chromatogr. A 2007, 1150, 21–27.
34. Sipila, K.; Kuoppala, E.; Fagernas, L.; Oasmaa, A. Characterization of biomass-based flash
pyrolysis oils. Biomass Bioenergy 1998, 14, 103–113.
35. Oasmaa, A.; Czernik, S. Fuel oil quality of biomass pyrolysis oils—State of the art for the end
user. Energy Fuels 1999, 13, 914–921.
36. Zhang, Q.; Chang, J.; Wang, T.; Xu, Y. Review of biomass pyrolysis oil properties and
upgrading research. Energy Conver. Manag. 2007, 48, 87–92.
37. French, R.; Czernik, S. Catalytic pyrolysis of biomass for biofuels production. Fuel Process.
Technol. 2010, 91, 25–32.
38. Cheng, Y.T.; Huber, G.W. Chemistry of furan conversion into aromatics and olefins over
HZSM-5: A model biomass conversion reaction. ACS Catal. 2011, 1, 611–628.
39. Zhang, H.; Cheng, Y.T.; Vispute, T.P.; Xiao, R.; Huber, G.W. Catalytic conversion of
biomass-derived feedstocks into olefins and aromatics with ZSM-5: The hydrogen to carbon
effective ratio. Energy Environ. Sci. 2011, 4, 2297–2307.
40. Samolada, M.C.; Baldauf, W.; Vasalos, I.A. Production of a bio-gasoline by upgrading biomass
flash pyrolysis liquids via hydrogen processing and catalytic cracking. Fuel 1998, 77, 1667–1675.
41. Bridgwater, A.V. Production of high grade fuels and chemicals from catalytic pyrolysis of
biomass. Catal. Today 1996, 29, 285–295.
42. Sekiguchi, Y.; Shafizadeh, F. The effect of inorganic additives on the formation, composition,
and combustion of cellulosic char. J. Appl. Polym. Sci. 1984, 29, 1267–1286.
43. Raveendran, K.; Ganesh, A.; Khilar, K.C. Influence of mineral matter on biomass pyrolysis
characteristics. Fuel 1995, 74, 1812–1822.
44. Muller-Hagedorn, M.; Bockhorn, H.; Krebs, L.; Muller, U. A comparative kinetic study on the
pyrolysis of three different wood species. J. Anal. Appl. Pyrolysis 2003, 68–69, 231–249.
45. Scott, D.S.; Piskorz, J.; Radlein, D. Liquid products from the continuous flash pyrolysis of
biomass. Ind. Eng. Chem. Process Des. Dev. 1985, 24, 581–588.
Energies 2013, 6 534

46. Richards, G.N.; Zheng, G.C. Influence of metal-ions and of salts on products from pyrolysis of
wood: Applications to thermochemical processing of newsprint and biomass. J. Anal. Appl.
Pyrolysis 1991, 21, 133–146.
47. Patwardhan, P.R.; Satrio, J.A.; Brown, R.C.; Shanks, B.H. Influence of inorganic salts on the
primary pyrolysis products of cellulose. Bioresour. Technol. 2010, 101, 4646–4655.
48. Jones, S.B.; Valkenburg, C.; Walton, C.W.; Elliott, D.C.; Holladay, J.E.; Stevens, D.J.; Kinchin, C.;
Czernik, S. Production of Gasoline and Diesel From Biomass via Fast Pyrolysis, Hydrotreating
and Hydrocracking: A Design Case; Pacific Northwest National Laboratory: Richland, WA,
USA, 2009.
49. Marquevich, M.; Czernik, S.; Chornet, E.; Montane, D. Hydrogen from biomass: Steam
reforming of model compounds of fast-pyrolysis oil. Energy Fuels 1999, 13, 1160–1166.
50. Grange, P.; Laurent, E.; Maggi, R.; Centeno, A.; Delmon, B. Hydrotreatment of pyrolysis oils
from biomass: Reactivity of the various categories of oxygenated compounds and preliminary
techno-economical study. Catal. Today 1996, 29, 297–301.
51. Elliott, D.C. Historical developments in hydroprocessing bio-oils. Energy Fuels 2007, 21.
52. Thangalazhy-Gopakumar, S.; Adhikari, S.; Gupta, R.B.; Tu, M.; Taylor, S. Production of
hydrocarbon fuels from biomass using catalytic pyrolysis under helium and hydrogen
environments. Bioresour. Technol. 2011, 102, 6742–6749.
53. Wildschut, J.; Melian-Cabrera, I.; Heeres, H.J. Catalyst studies on the hydrotreatment of fast
pyrolysis oil. Appl. Catal. B Environ. 2010, 99, 298–306.
54. Su-Ping, Z.; Yong-Jie, Y.; Zhengwei, R.; Tingchen, L. Study of hydrodeoxygenation of bio-oil
from the fast pyrolysis of biomass. Energy Sources 2003, 25, 57–65.
55. Elliott, D.C.; Hart, T.R.; Neuenschwander, G.G.; Rotness, L.J.; Zacher, A.H. Catalytic
hydroprocessing of biomass fast pyrolysis bio-oil to produce hydrocarbon products. Environ.
Prog. Sustain. Energy 2009, 28, 441–449.
56. Gutierrez, A.; Kaila, R.K.; Honkela, M.L.; Slioor, R.; Krause, A.O.I. Hydrodeoxygenation of
guaiacol on noble metal catalysts. Catal. Today 2009, 147, 239–246.
57. Damartzis, T.; Zabaniotou, A. Thermochemical conversion of biomass to second generation
biofuels through integrated process design- a review. Renew. Sustain. Energy Rev. 2011, 15,
366–378.
58. Wildschut, J.; Mahfud, F.H.; Venderbosch, R.H.; Heeres, H.J. Hydrotreatment of fast pyrolysis
oil using heterogeneous noble-metal catalysts. Ind. Eng. Chem. Res. 2009, 48, 10324–10334.
59. Xiong, W.-M.; Fu, Y.; Zeng, F.-X.; Guo, Q.-X. An in situ reduction approach for bio-oil
hydroprocessing. Fuel Process. Technol. 2011, 92, 1599–1605.
60. Kunkes, E.L.; Simonetti, D.A.; West, R.M.; Serrano-Ruiz, J.C.; Gartner, C.A.; Dumesic, J.A.
Catalytic conversion of biomass to monofunctional hydrocarbons and targeted liquid-fuel
classes. Science 2008, 322, 417–421.
61. Panagiotopoulou, P.; Kondarides, D.I. A comparative study of the water-gas shift activity of Pt
catalysts supported on single (MOx) and composite (MOx/Al2O3, MOx/TiO2) metal oxide
carriers. Catal. Today 2007, 127, 319–329.
62. Fisk, C.A.; Morgan, T.; Ji, Y.; Crocker, M.; Crofcheck, C.; Lewis, S.A. Bio-oil upgrading over
platinum catalysts using in situ generated hydrogen. Appl. Catal. A Gen. 2009, 358, 150–156.
Energies 2013, 6 535

63. Oasmaa, A.; Kuoppala, E.; Ardiyanti, A.; Venderbosch, R.H.; Heeres, H.J. Characterization of
hydrotreated fast pyrolysis liquids. Energy Fuels 2010, 24, 5264–5272.
64. Baldauf, W.; Balfanz, U.; Rupp, M. Upgrading of flash pyrolysis oil and utilization in refineries.
Biomass Bioenergy 1994, 7, 237–244.
65. Sheu, Y.H.E.; Anthony, R.G.; Soltes, E.J. Kinetic-studies of upgrading pine pyrolytic oil by
hydrotreatment. Fuel Process. Technol. 1988, 19, 31–50.
66. Venderbosch, R.H.; Ardiyanti, A.R.; Wildschut, J.; Oasmaa, A.; Heeresb, H.J. Stabilization of
biomass-derived pyrolysis oils. J. Chem. Technol. Biotechnol. 2010, 85, 674–686.
67. Aho, A.; Kumar, N.; Eranen, K.; Salmi, T.; Hupa, M.; Murzin, D.Y. Catalytic pyrolysis of
biomass in a fluidized bed reactor: Influence of the acidity of H-beta zeolite. Process Saf.
Environ. Prot. 2007, 85, 473–480.
68. Gayubo, A.G.; Aguayo, A.T.; Atutxa, A.; Aguado, R.; Bilbao, J. Transformation of oxygenate
components of biomass pyrolysis oil on a HZSM-5 zeolite. I. Alcohols and phenols. Ind. Eng.
[Link]. 2004, 43, 2610–2618.
69. Gayubo, A.G.; Aguayo, A.T.; Atutxa, A.; Prieto, R.; Bilbao, J. Deactivation of a HZSM-5 zeolite
catalyst in the transformation of the aqueous fraction of biomass pyrolysis oil into hydrocarbons.
Energy Fuels 2004, 18, 1640–1647.
70. Mante, O.D.; Agblevor, F.A.; Oyama, S.T.; McClung, R. The influence of recycling
non-condensable gases in the fractional catalytic pyrolysis of biomass. Bioresour. Technol. 2012,
111, 482–490.
71. Horne, P.A.; Nugranad, N.; Williams, P.T. Catalytic coprocessing of biomass-derived pyrolysis
vapors and methanol. J. Anal. Appl. Pyrolysis 1995, 34, 87–108.
72. Chen, N.Y.; Walsh, D.E.; Koenig, L.R. Fluidized-bed upgrading of wood pyrolysis liquids and
related-compounds. In Pyrolysis Oils from Biomass; Soltes, J., Milne, T.A., Eds.; American
Chemical Society: Washington, DC, USA, 1988; pp. 277–289.
73. Evans, R.J.; Milne, T. Molecular-beam, mass-spectrometric studies of wood vapor and model
compounds over an HZSM-5 catalyst. In Pyrolysis Oils from Biomass; Soltes, J., Milne, T.A.,
Eds.; American Chemical Society: Washington, DC, USA, 1988; pp. 311–327.
74. Gayubo, A.G.; Aguayo, A.T.; Atutxa, A.; Aguado, R.; Olazar, M.; Bilbao, J. Transformation of
oxygenate components of biomass pyrolysis oil on a HZSM-5 zeolite. II. Aldehydes, ketones,
and acids. Ind. Eng. Chem. Res. 2004, 43, 2619–2626.
75. Zhu, X.; Mallinson, R.G.; Resasco, D.E. Role of transalkylation reactions in the conversion of
anisole over HZSM-5. Appl. Catal. A Gen. 2010, 379, 172–181.
76. Peralta, M.A.; Sooknoi, T.; Danuthai, T.; Resasco, D.E. Deoxygenation of benzaldehyde over
CsNax zeolites. [Link]. Catal. A Chem.2009, 312, 78–86.
77. Santikunaporn, M.; Herrera, J.E.; Jongpatiwut, S.; Resasco, D.E.; Alvarez, W.E.; Sughrue, E.L.
Ring opening of decalin and tetralin on HY and Pt/HY zeolite catalysts. J. Catal. 2004, 228,
100–113.
78. Adjaye, J.D.; Bakhshi, N.N. Production of hydrocarbons by catalytic upgrading of a fast
pyrolysis bio-oil. Part 1. Conversion over various catalysts. Fuel Process. Technol. 1995, 45,
161–183.
Energies 2013, 6 536

79. Adjaye, J.D.; Bakhshi, N.N. Upgrading of a wood-derived oil over various catalysts. Biomass
Bioenergy 1994, 7, 201–211.
80. Aho, A.; Kumar, N.; Eranen, K.; Salmi, T.; Hupa, M.; Murzin, D.Y. Catalytic pyrolysis of woody
biomass in a fluidized bed reactor: Influence of the zeolite structure. Fuel 2008, 87, 2493–2501.
81. Pattiya, A.; Titiloye, J.O.; Bridgwater, A.V. Fast pyrolysis of cassava rhizome in the presence of
catalysts. J. Anal. Appl. Pyrolysis 2008, 81, 72–79.
82. Samolada, M.C.; Papafotica, A.; Vasalos, I.A. Catalyst evaluation for catalytic biomass
pyrolysis. Energy Fuels 2000, 14, 1161–1167.
83. Corma, A.; Huber, G.W.; Sauvanaud, L.; O’Connor, P. Processing biomass-derived oxygenates
in the oil refinery: Catalytic cracking (FCC) reaction pathways and role of catalyst. J. Catal.
2007, 247, 307–327.
84. Lappas, A.A.; Samolada, M.C.; Iatridis, D.K.; Voutetakis, S.S.; Vasalos, I.A. Biomass pyrolysis in a
circulating fluid bed reactor for the production of fuels and chemicals. Fuel 2002, 81, 2087–2095.
85. Williams, P.T.; Nugranad, N. Comparison of products from the pyrolysis and catalytic pyrolysis
of rice husks. Energy 2000, 25, 493–513.
86. Murata, K.; Liu, Y.; Inaba, M.; Takahara, I. Catalytic fast pyrolysis of jatropha wastes. J. Anal.
Appl. Pyrolysis 2012, 94, 75–82.
87. Jae, J.; Tompsett, G.A.; Lin, Y.-C.; Carlson, T.R.; Shen, J.; Zhang, T.; Yang, B.; Wyman, C.E.;
Conner, W.C.; Huber, G.W. Depolymerization of lignocellulosic biomass to fuel precursors:
Maximizing carbon efficiency by combining hydrolysis with pyrolysis. Energy Environ. Sci.
2010, 3, 295–303.
88. Li, X.; Su, L.; Wang, Y.; Yu, Y.; Wang, C.; Li, X.; Wang, Z. Catalytic fast pyrolysis of Kraft
lignin with HZSM-5 zeolite for producing aromatic hydrocarbons. Front. Environ. Sci. Eng.
2012, 6, 295–303.
89. Ma, Z.; Troussard, E.; van Bokhoven, J.A. Controlling the selectivity to chemicals from lignin
via catalytic fast pyrolysis. Appl. Catal. A Gen. 2012, 423–424, 130–136.
90. Pattiya, A.; Titiloye, J.O.; Bridgwater, A.V. Evaluation of catalytic pyrolysis of cassava rhizome
by principal component analysis. Fuel 2010, 89, 244–253.
91. Encinar, J.M.; Gonzalez, J.F.; Martinez, G.; Roman, S. Catalytic pyrolysis of exhausted olive oil
waste. J. Anal. Appl. Pyrolysis 2009, 85, 197–203.
92. Kuen-Song, L.; Wang, H.P.; Chang, N.B.; Jou, C.; Hsiao, M. Synthesis of ZSM-type zeolites
from biowaste gasification ashes. Energy Sources 2003, 25, 565–576.
93. Muradov, N.; Fidalgo, B.; Gujar, A.C.; Garceau, N.; T-Raissi, A. Production and characterization
of lemna minor bio-char and its catalytic application for biogas reforming. Biomass Bioenergy
2012, 42, 123–131.
94. Gagnon, J.; Kaliaguine, S. Catalytic hydrotreatment of vacuum pyrolysis oils from wood. Ind.
Eng. Chem. Res. 1988, 27, 1783–1788.
95. Wang, Y.; He, T.; Liu, K.; Wu, J.; Fang, Y. From biomass to advanced bio-fuel by catalytic
pyrolysis/hydro-processing: Hydrodeoxygenation of bio-oil derived from biomass catalytic
pyrolysis. Bioresour. Technol. 2012, 108, 280–284.
96. Li, H.Y.; Yan, Y.J.; Ren, Z.W. Online upgrading of organic vapors from the fast pyrolysis of
biomass. J. Fuel Chem. Technol. 2008, 36, 666–671.
Energies 2013, 6 537

97. Alyani, M.; Towfighi, J.; Sadrameli, S.M. Effect of process variables on product yield
distribution in thermal catalytic cracking of naphtha to light olefins over Fe/HZSM-5. Korean J.
Chem. Eng. 2011, 28, 1351–1358.
98. Song, H.; Tan, B.; Ozkan, U.S. Novel synthesis techniques for preparation of Co/CeO2 as ethanol
steam reforming catalysts. Catal. Lett. 2009, 132, 422–429.
99. Butler, E.; Devlin, G.; Meier, D.; McDonnell, K. A review of recent laboratory research and
commercial developments in fast pyrolysis and upgrading. Renew. Sustain. Energy Rev. 2011,
15, 4171–4186.
100. Katikaneni, S.P.R.; Adjaye, J.D.; Bakhshi, N.N. Conversion of canola oil to various
hydrocarbons over Pt/HZSM-5 bifunctional catalyst. Can. J. Chem. Eng. 1997, 75, 391–401.
101. Babich, I.V.; van der Hulst, M.; Lefferts, L.; Moulijn, J.A.; O'Connor, P.; Seshan, K. Catalytic
pyrolysis of microalgae to high-quality liquid bio-fuels. Biomass Bioenergy 2011, 35, 3199–3207.
102. Lu, Q.; Wang, Z.; Dong, C.-Q.; Zhang, Z.-F.; Zhang, Y.; Yang, Y.-P.; Zhu, X.-F. Selective fast
pyrolysis of biomass impregnated with ZnCl2: Furfural production together with acetic acid and
activated carbon as by-products. J. Anal. Appl. Pyrolysis 2011, 91, 273–279.
103. Putun, E. Catalytic pyrolysis of biomass: Effects of pyrolysis temperature, sweeping gas flow
rate and MgO catalyst. Energy 2010, 35, 2761–2766.
104. Lim, X.Y.; Andresen, J.M. Pyro-catalytic deoxgenated bio-oil from palm oil empty fruit bunch
and fronds with boric oxide in a fixed-bed reactor. Fuel Process. Technol. 2011, 92, 1796–1804.
105. Park, H.J.; Park, K.-H.; Jeon, J.-K.; Kim, J.; Ryoo, R.; Jeong, K.-E.; Park, S.H.; Park, Y.-K.
Production of phenolics and aromatics by pyrolysis of miscanthus. Fuel 2012, 97, 379–384.
106. Jeon, M.-J.; Kim, S.-S.; Jeon, J.-K.; Park, S.H.; Kim, J.M.; Sohn, J.M.; Lee, S.-H.; Park, Y.-K.
Catalytic pyrolysis of waste rice husk over mesoporous materials. Nanoscale Res. Lett. 2012, 7,
18:1–18:5.
107. Zhu, X.; Lobban, L.L.; Mallinson, R.G.; Resasco, D.E. Bifunctional transalkylation and
hydrodeoxygenation of anisole over a Pt/Hbeta catalyst. J. Catal. 2011, 281, 21–29.
108. Ausavasukhi, A.; Sooknoi, T.; Resasco, D.E. Catalytic deoxygenation of benzaldehyde over
gallium-modified ZSM-5 zeolite. J. Catal. 2009, 268, 68–78.
109. Fanchiang, W.-L.; Lin, Y.-C. Catalytic fast pyrolysis of furfural over HZSM-5 and Zn/HZSM-5
catalysts. Appl. Catal. A Gen. 2012, 419–420, 102–110.
110. Neumann, G.T.; Hicks, J.C. Effects of cerium and aluminum in cerium-containing hierarchical
HZSM-5 catalysts for biomass upgrading. Top. Catal. 2012, 55, 196–208.
111. Castano, P.; Gutierrez, A.; Villanueva, I.; Pawelec, B.; Bilbao, J.; Arandes, J.M. Effect of the
support acidity on the aromatic ring-opening of pyrolysis gasoline over Pt/HZSM-5 catalysts.
Catal. Today 2009, 143, 115–119.
112. Castano, P.; Pawelec, B.; Fierro, J.L.G.; Arandes, J.M.; Bilbao, J. Aromatics reduction of
pyrolysis gasoline (pygas) over HY-supported transition metal catalysts. Appl. Catal. A Gen.
2006, 315, 101–113.
113. Liguori, L.; Barth, T. Palladium-nafion sac-13 catalysed depolymerisation of lignin to phenols in
formic acid and water. J. Anal. Appl. Pyrolysis 2011, 92, 477–484.
Energies 2013, 6 538

114. Valle, B.; Gayubo, A.G.; Aguayo, A.T.; Olazar, M.; Bilbao, J. Selective production of aromatics
by crude bio-oil valorization with a nickel-modified HZSM-5 zeolite catalyst. Energy Fuels
2010, 24, 2060–2070.
115. Chattopadhyay, J.; Son, J.E.; Pak, D. Preparation and characterizations of Ni-alumina, Ni-ceria
and Ni-alumina/ceria catalysts and their performance in biomass pyrolysis. Korean J. Chem.
Eng. 2011, 28, 1677–1683.
116. Cheng, Y.-T.; Jae, J.; Shi, J.; Fan, W.; Huber, G.W. Production of renewable aromatic
compounds by catalytic fast pyrolysis of lignocellulosic biomass with bifunctional Ga/ZSM-5
catalysts. Angew. Chem. Int. Ed. 2012, 124, 1416–1419.
117. Ben, H.; Ragauskas, A.J. Pyrolysis of Kraft lignin with additives. Energy Fuels 2011, 25, 4662–4668.
118. Antonakou, E.; Lappas, A.; Nilsen, M.H.; Bouzga, A.; Stocker, M. Evaluation of various types of
Al-MCM-41 materials as catalysts in biomass pyrolysis for the production of bio-fuels and
chemicals. Fuel 2006, 85, 2202–2212.
119. Torri, C.; Reinikainen, M.; Lindfors, C.; Fabbri, D.; Oasmaa, A.; Kuoppala, E. Investigation on
catalytic pyrolysis of pine sawdust: Catalyst screening by Py-GC-MIP-AED. J. Anal. Appl.
Pyrolysis 2010, 88, 7–13.
120. Aho, A.; Kumar, N.; Lashkul, A.V.; Eranen, K.; Ziolek, M.; Decyk, P.; Salmi, T.; Holmbom, B.;
Hupa, M.; Murzin, D.Y. Catalytic upgrading of woody biomass derived pyrolysis vapours over
iron modified zeolites in a dual-fluidized bed reactor. Fuel 2010, 89, 1992–2000.
121. Wang, Z.; Wang, F.; Cao, J.; Wang, J. Pyrolysis of pine wood in a slowly heating fixed-bed
reactor: Potassium carbonate versus calcium hydroxide as a catalyst. Fuel Process. Technol.
2010, 91, 942–950.
122. Luo, J.; Li, J.; Shen, D.; He, L.; Tong, D.; Hu, C. Catalytic pyrolysis of pubescens to phenols
over Ni/C catalyst. Sci. China Chem. 2010, 53, 1487–1491.

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