Review

pubs.acs.org/IECR

Bio-oils Upgrading for Second Generation Biofuels

Inês Graça,† José M. Lopes,†,* Henrique S. Cerqueira,‡ and Maria F. Ribeiro†
†
IBB, Institute for Biotechnology and Bioengineering, Centre for Biological and Chemical Engineering, Instituto Superior
Técnico/Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
‡
OSX, Praça Mahatma Gandhi, 14/11th floor, 20031-100 Rio de Janeiro, RJ, Brazil

ABSTRACT: The envisaged upgrading of lignocellulosic biomass derived feedstocks (bio-oils) in dedicated units or by
coprocessing in existing units of the refinery, to partially replace crude oil in the production of transportation fuels, is a topic that
has been receiving much attention from both industry and academia in recent years. Regardless of lignocellulosic biomass origin,
these feedstocks are complex mixtures of many oxygenated hydrocarbons. Therefore, their upgrading toward liquid fuels must
include oxygen removal. So far, two main routes have been proposed, considering many studies at laboratory scale and others
from industry: catalytic hydrotreatment (HDT), mainly hydrodeoxygenation (HDO), and catalytic cracking, technologies that
are already present in today’s refineries configuration. HDO has been performed at high hydrogen pressure, using catalysts based
on those typically applied in conventional hydrotreating, as well as a new type of supported noble metal and transition metal
catalysts. Catalytic cracking occurs at atmospheric pressure, using acid catalysts, mainly the active phases of fluid catalytic cracking
(FCC) catalysts (HY and HZSM-5 zeolites). The present review is then focused on the upgrading possibilities of renewable
nonedible feedstocks, obtained from biomass fast pyrolysis or liquefaction, in petroleum refineries, toward the production of
second generation biofuels. It includes the recent studies concerning the alternative of bio-oils coprocessing together with crude
oil feedstocks. In fact, although all these feedstocks have the potential to be directly converted into transportation fuels in
dedicated units, it seems more attractive to upgrade them in combination with conventional feedstocks.

1. INTRODUCTION biopolymers, cellulose (glucose polymer), hemicellulose (shorter

The partial replacement of crude oil by renewable sources to
produce high quality transportation fuels is a timely and in-
teresting topic. It helps to reduce the dependence from petroleum
as well as carbon dioxide emissions responsible for the greenhouse
effect, due to its CO2 neutrality.1,2 Contrarily to heavy oil, biomass
presents the advantage of containing negligible amounts of sulfur,
nitrogen, and metals and is easily available in many countries.
Moreover, although several renewable sources, such as biomass,
wind, solar, and hydropower, can be used to generate heat and
power, biomass is currently the only renewable source of carbon
that can be converted into liquid fuels,3−5 which can be used in the
actual infrastructure of the transportation sector.1
Many types of biomass feedstocks are available for the
production of biofuels, namely sugars, vegetable oils (“first
generation” biofuels) and lignocellulosic biomass, as residues
from agriculture and forestry (“second generation” biofuels).3
In recent years, first generation biofuels (bioethanol and bio-
diesel) have been increasing their market share, mainly because
of their blending with conventional fuels. However, it should be
mentioned that lignocellulosic biomass can be grown in com-
bination with food or on nonagricultural lands, therefore not
compromising the sustainable utilization of fertile land, that is,
not competing with food production.1,6 Lignocellulosic biomass
consists of an abundant renewable source of carbon,7 con-
vertible into liquid carburant, which could be introduced in an
existing downstream process, increasing the production of com-
mercial fuels in a sustainable manner.
The key difference between petroleum and renewable raw
materials is the higher oxygen content of the latter: residues
from biomass typically contain between 35 and 50 wt % oxygen.1
Lignocellulosic materials comprise three different types of
polymers of various sugars, principally xylose), and lignin
(propyl-phenol polymer).3,8,9 These three essential compo-
nents form an insoluble three-dimensional network with a very
complex structure, which makes the lignocellulosic biomass
more difficult to convert than sugars or vegetable oils.3
Pyrolysis and liquefaction are the two main processes devel-
oped to directly convert biomass feedstocks into liquid products,
generally called bio-oils.10−14 Whatever the process, this trans-
formation is carried out in one single reactor and a very large
fraction of the biomass energy (50−90%) can be converted into
liquids. Fast pyrolysis technology15 involves short residence
times (typically less than 2 s), fast heating rates, high tem-
peratures, in the range of 400−700 °C, and low pressures (1−5
atm), in an oxygen-free atmosphere. On the other hand, liquefac-
tion occurs at high hydrogen pressure (50−200 bar), in a lower
temperature range of 250−325 °C. Thus, pyrolysis presents a
lower capital cost than liquefaction, favoring its commercialization.1
These biomass derived oils constitute an alternative energy
source, but they cannot be directly used as transportation fuels.
They are complex mixtures of more than 400 different oxygenated
hydrocarbons, as carboxylic acids, aldehydes, alcohols, ketones,
esters, ethers, phenols, furans and carbohydrates. Mainly due to
their oxygen-rich composition, bio-oils have some undesired prop-
erties for fuel applications: low heating value (less than 50% of that
of conventional fuel oils), immiscibility with hydrocarbon fuels,
thermal and chemical instability, high density, corrosiveness, etc.1,9,16,17
Received: June 28, 2012
Revised: November 14, 2012
Accepted: November 20, 2012
Published: November 21, 2012

© 2012 American Chemical Society 275 dx.doi.org/10.1021/ie301714x | Ind. Eng. Chem. Res. 2013, 52, 275−287
Industrial & Engineering Chemistry Research
The bio-oils produced are usually dark brown organic liquids
that have a distinctive smoky odor.18,19 Typically, the fast
pyrolysis oils present higher oxygen content, higher acidity, and
lower heating value than liquefaction oils. Independently of the
origin, the bio-oils must undergo upgrading treatments in order
to increase their stability and to become commercially useful.
They require chemical transformations to increase volatility and
thermal stability and reduce viscosity through oxygen removal
and molecular weight reduction.20
In 2007, the review by Huber and Corma21 reported the
increasing interest in biofuels production from biomass-derived
feedstocks in petroleum refineries, thus taking advantage of
economy of scale and experience by using existing infrastructures.
It is also important to remark that many research efforts on the
study of these possibilities have been, as well, carried out by several
oil companies.
Two main routes for partial or total elimination of oxygen
atoms have been proposed: catalytic cracking and catalytic
hydrotreating.21−26 The stoichiometric equations representative
of these processes can be summarized as follows:27
Decarboxylation:
C6H8O4 → C4 H8 + 2CO2
Hydrodeoxygenation:
C6H8O4 + 4H 2 → C6H8 + 4H 2O
Cracking:
C6H8O4 → C4.5H8 + H 2O + 1.5CO2
The catalytic cracking of bio-oils removes oxygen by simu-
ltaneous dehydration−decarboxylation reactions, using cracking
catalysts (zeolites, silica−alumina) at atmospheric pressure.28
The oxygen can be eliminated as water, carbon monoxide, carbon
dioxide, and short-chain acids. The oxygenated feedstock is con-
verted into a lighter hydrocarbons fraction, falling particularly
in the gasoline boiling range and containing high aromatics
contents.21,28
The other method proposed is the catalytic hydrotreatment
(HDT) or hydrodeoxygenation (HDO), performed at high
temperature, under high hydrogen pressure, in the presence of
a heterogeneous catalyst.29,30 The reactions occurring are elim-
ination of oxygen as water, elimination of nitrogen as ammonia,
and hydrogenation-hydrocracking of large molecules, leading to
the production of hydrocarbons in the diesel range. The reaction
conditions and the catalysts first tested (e.g., NiMo, CoMo sulfide-
based catalysts) were similar to those used in the petroleum refining
HDT processes. The degree of deoxygenation can be modulated
from simple stabilization, that is, elimination of more reactive
functions such as carbonyl, olefins, and carboxyls, to complete
refining with a maximal hydrocarbon yield that will be a function
of the extent and how the oxygen atoms are removed.11 The
residual amount of oxygenates is a function of the HDO
severity.31−33
Catalytic cracking has been considered as a cheaper alterna-
tive.28,34 It offers significant processing and economic advantages
over catalytic hydrotreating because hydrogen is not required
and operates under atmospheric pressure, thus reducing operat-
ing costs. However, the poor hydrocarbons yields, the extensive
coking observed during catalytic cracking of bio-oils, and the
quality of the fuels obtained (significant amounts of phenolic
compounds) are drawbacks that need to be overcome. Cracking
of bio-oils with zeolite catalysts is less well developed than
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Review
hydrotreating and there is a wider range of possibilities to be
explored with mono- and multifunctional catalysts.11
Both upgrading technologies present important operating
problems, such as reactor plugging, rapid catalyst deactivation,
and low liquid product yields, due to the bio-oil tendency to poly-
merize even under mild heating. To overcome or minimize these
problems, the possibility of coprocessing the bio-oils with con-
ventional feedstocks in existing refinery units was envisioned.34−36
In these cases, a previous partial hydrotreatment of the bio-oil
would be necessary in order to stabilize the feedstock and increase
its miscibility with petroleum fractions. In fact, because of the
above-mentioned chemical instability, small miscibility with hy-
drocarbons,35 and corrosiveness,37 its direct addition to estab-
lished processes like FCC21,38 or HDT34 is not straightforward,
thus creating the need for at least one previous HDO upgrading
step.
Therefore, the management of hydrogen plays a key role in
eliminating the dependence upon external fossil fuels.39 It will
be desirable to minimize the hydrogen requirements, trying to
couple strategies that consume less hydrogen with those that
produce hydrogen from renewable energy sources, such as solar,
wind or biomass.21
Very recent reviews, from 2011 and 2012, reported the huge
research activity concerning these two refining bio-oils upgrad-
ing methods, HDO and catalytic cracking, in the perspective of
dedicated units development.40−42
The aim of the present paper is to review the upgrading
possibilities of renewable nonedible feedstocks, as lignocellulosic
biomass derived oils, by coprocessing or in dedicated refining
units, toward the production of end-usable liquid fuels (second
generation biofuels).
2. HYDRODEOXYGENATION (HDO)
Bio-oils hydrotreating is based on a modification, or extension,
of conventional HDT process existing in refineries. It differs
from processing petroleum or coal liquids because of the im-
portance of HDO, as opposed to nitrogen (HDN) or sulfur
removal (HDS), and naturally the term deoxygenation is assumed
for upgrading biomass derived oils. In this process, oxygen is
removed through a family of deoxygenation reactions, which
can be represented as follows:11
C6H8O4 + 6H 2 → 6CH 2 + 4H 2O
It should be mentioned that most of the HDO previous reports
focused on model molecules representative of bio-oil fragment
studies, while the majority of recent works focus on catalysts
development, the work being extended from small batch reactor
tests, in universities, to demonstration scale processing, in
petroleum refining laboratories.
Since the first Furimsky review on HDO,43 published in
1983, the growing concern about the upgrading of coal and
biomass-derived liquids led to an expansion of HDO under-
standing studies. Maggi and Delmon24 published a review in
1997, and many studies about the catalytic chemistry, kinetics,
and mechanisms of HDO reactions, using various model oxy-
genated compounds, were collected and reported in another
review by Furimsky in 2000.22 Classical HDT catalysts (sulfided
CoMo and NiMo) have been the first and most extensively
tested ones. Their deactivation problems were identified and
new and promising catalytic systems, based on noble metals
supported on carbon, were announced.
The extensive work that has been undertaken over the past
25−30 years in the field of catalytic hydrotreating of biomass-derived
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Industrial & Engineering Chemistry Research
Table 1. Tested Catalysts, Reactivity, And Main Products Obtained in the HDO Transformations of Model Oxygenate
Compounds
oxygenate catalysts relative reactivity
guaiacol31,32,44−46 CoMo/Al2O3 low
Rh,Pd,Pt/ZrO2
Ni2P,Fe2P,MoP,WP/silica
anisole48,49 CoMo/Al2O3 high
Ni−Cu/supports
phenol50−58 CoMo/Al2O3 most refractory
Ni/Y zeolite or silica
cresols50,59−61 CoMo/Al2O3 high, effective at mild conditions
Pt/carbon
aldehydes and ketones63−65 noble metals/zeolites high
esters66,67 NiMo,CoMo/γ-Al2O3 high
acids68,69 NiMo,CoMo/Al2O3 high
Pd/carbon
furans70−76,79 NiMo,CoMo/Al2O3 or carbon high
Pt/SiO2 or Al2O3 or TiO2
liquids is documented in papers from Elliot et al.,20 Mortensen
et al.,40 Choudhary and Philips,41 and Bridgwater.42
The chemistry of HDO (and catalytic cracking) of bio-oils,
including reactions mechanisms and their relations to active
sites in the catalysts, kinetic models, and deactivation, were
extensively reviewed by Mortensen et al.40
2.1. Model Compounds HDO. The lab-scale studies
involving different oxygenate model compounds have con-
tributed to the understanding of HDO mechanisms. Most of
these studies were performed in fixed-bed reactors, using pure
hydrogen (20−50 bar), at temperatures in the range 250−450 °C
and focused on catalyst development. Table 1 summarizes the
main data concerning the HDO reactivity of most relevant
oxygenates, as well as the tested catalysts and products obtained.
Guaiacol revealed to be more refractory to deoxygenation
than carbonyl and carboxylic groups31,32 and to have a higher
coking tendency. The proposed basic reaction scheme involves
the guaiacol hydrogenation into catechol and then into phenol.
For the new catalyst formulations, monometallic or bimetallic
catalysts prepared by the impregnation of Rh, Pd, and Pt on
ZrO2 support,44 similar or better activities than those of the
classical CoMo/Al2O3 catalyst were obtained and less carbon
deposition was found.44 More recently, transition metal phos-
phides (Ni2P, Fe2P, MoP, and WP supported on silica) also
showed an ability to convert guaiacol into benzene and phenol,45
with higher stability than CoMo/Al2O3 catalyst, due to lower
carbon deposition.46 In the case of the cohydrotreatment of bio-
oils with petroleum cuts, the presence of sulfur on the HDO feed
was thought to have a positive effect on the conversion of
molecules such as guaiacol.47
The anisole HDO, a molecule presenting some similarities
with the compounds resulting from the lignin depolymerization
during fast pyrolysis of wood, can be performed over classical
HDT catalysts.48 The catalyst acidity plays an important role on
anisole conversion into phenol, o-cresol, and benzene. Novel
Ni−Cu catalysts have been prepared with various supports and
showed to be effective in the same transformation.49
Phenol has also been extensively used as a model compound
for bio-oil HDO,50−57 since it is the main final product of other
phenols (alkoxy- and methoxy-phenols) transformation and it
presents the most difficult C−O bond to cleave, being, con-
sequently, particularly resistant to HDO. While typical CoMo/
Al2O3 catalysts mainly promoted the aromatic ring hydrogenation,58
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Review
products
phenol; benzene
phenol; o-cresol; benzene
cyclohexanol; cyclohexanona; cyclohexane; benzene
toluene; cyclohexane
diphenylmethane; toluene
C3−C5 alkanes and alkenes; methanol; carboxylic acids
alkanes
C3−C4 alkanes and alkenes; cyclohexane
it was noticed that, over supported nickel (1.5−20.3 wt %) on
either Y zeolite or silica catalysts, both hydrogenation and
hydrogenolysis reactions of phenol took place.50 Besides cyclo-
hexanone and cyclohexanol, which resulted, respectively, from
partial and full phenol hydrogenation, also cyclohexane was
produced.50 High nickel loadings (∼20 wt %) and temperatures
tended to favor hydrogenolysis reaction, leading to benzene.
Cresols are transformed mainly into toluene and cyclohexane
over sulfided CoMo/Al2O3.50,59,61 Both direct HDO and a
transformation via hydrogenated phenol are possible.22 Noble
metal Pt/carbon catalysts were also recently shown to be active
in the deoxygenating of phenolic hydroxyl groups under mild
conditions, in the presence of diethylamine.62
The most recent studies on aldehydes and ketones HDO re-
ported that benzophenone and several aldehydes can effectively
be deoxygenated over noble metal supported zeolite catalysts.63−65
Benzophenone can be transformed into diphenylmethane over
Pd/zeolites.63 Two mechanisms have been proposed: (i) direct
hydrogenolysis of the CO bond or (ii) hydrogenation to
alcohol followed by hydrogenolytic splitting of the C−OH bond.
The most active catalyst was Pd/beta. The same series of Pd
catalysts was used in the hydrodeoxygenation of aldehydes.64
Benzaldehyde can be converted into toluene. 2-Methyl-2-pentenal
HDO was achieved over Pt, Pd, and Cu catalysts supported on
silica.65 Pt/SiO2 was found to be the most active, whereas Cu/
SiO2 the less active.
Esters can be totally hydrodeoxygenated on sulfided NiMo
and CoMo supported on γ-alumina, at 250−300 °C and 15 bar
of hydrogen,66,67 leading to the formation of C5−C7 alkanes
and alkenes, methanol and carboxylic acids.
The transformation of acid compounds was investigated to a
lower extent. Carbon-supported Pd catalysts were effective in
the stearic acid transformation into heptadecane,68 while sulfided
NiMo/Al2O3 was revealed to be more active than the CoMo/
Al2O3 catalyst in the deoxygenation of heptanoic acid as well as
of methyl heptanoate.69
Furans are present at relatively low contents in the bio-oils.
Nevertheless, they have been tested in many HDO studies
because of their presence in the conventional petroleum feeds,
coal and shale oil. Furans have then to be taken into considera-
tion for HDT coprocessing option. The furan ring hydro-
genation occurs efficiently at typical conditions of hydro-
processing, with the formation of tetrahydrofuran, which suffers
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Industrial & Engineering Chemistry Research
HDO much faster than furan. In fact, classical CoMo and NiMo
supported on Al2O3 or carbon catalysts were extensively used
for furans HDO.70−75 Important products are C3 to C4, both
paraffins and olefins,70 and butadiene.72 The HDO of
benzofuran, which revealed to be a good model molecule for
HDO of a real feedstock, can yield o-ethylphenol and 2,3-
dihydrobenzofuran.74 Dibenzofuran can be transformed into
single-ring hydrocarbons, mainly cyclohexane.75 Detailed mech-
anisms for furan, tetrahydrofuran, benzofuran, and dibenzofuran
transformations are described elsewhere.22,76−78 More recent
studies report the use of Pt-supported catalysts,76,79 butane being
preferentially formed with Pt/TiO2. Other studies on benzofuran
HDO80 pointed out that reduced Mo and NiMO catalysts
are able to activate benzofuran, promoting, in a first step, its
hydrogenation.
2.2. Bio-oil HDO Upgrading. HDT removal of sulfur and
nitrogen from hydrocarbons is a well-established refinery
process, but oxygen removal on the scale needed to upgrade
bio-oils is at development stage. The optimal performance of
current industrial HDT catalysts for petroleum feedstocks cannot
be reproduced over bio-oils HDO, preventing an immediate and
easy coprocessing in the existing HDT processes.
The conditions used for the bio-oils upgrading by HDO
depend on their origin. It is possible to achieve a high HDO
conversion of the high pressure liquefaction oils in a single
step.81 For example, an oxygen removal higher than 95% was
reached from wood liquefaction oil, at 300 °C, over a sulfided
CoMo/Al2O3 catalyst,82 being its deactivation level dependent
on the possible previous desalting treatment.83 The same
catalysts showed, in other examples, to be able to promote
efficiently the pyrolysis oils upgrading.84,85
Nevertheless, in the case of pyrolysis oils, due to the high
tendency of several O-compounds to polymerize, forming coke-
like products, less stable liquids are produced. Therefore, it was
proposed a first stabilization step to remove an important part
of the oxygen content.9,10,31,86−88 After this preliminary treat-
ment, the HDO of the stabilized bio-oils becomes similar to
phenols HDO. This concept of two stage process was introduced
by researchers from Pacific Northwest National Laboratory
(PNNL), in 1989.20 In this improved process, the oil is stabilized
in a first reactor, operating at temperatures lower than 300 °C
and under high pressure of hydrogen; then, it is fed to a second
reactor, where a deeper deoxygenation is achieved at higher
temperatures (350−400 °C).89 Typical petroleum hydrotreating
catalysts (NiMo or CoMo supported on γ-alumina) were used.
Other examples of two stage treatments have been reported,
namely concerning the upgrading of bio-oils from olive oil
industry wastes,90 and from cellulose.91 In the case of cellulose
hydropyrolysis, single and two-stage treatments have been tested,
in a fixed bed reactor. In the single stage tests, a FeS catalyst was
used; for the two-stage tests, the primary oils were passed over a
commercial NiMo/alumina catalyst, at 400 °C, where an
additional reduction of the oxygen content and aromaticity of
the oils were registered, thus producing a lighter oil.91
Recent developments, regarding bio-oils upgrading through
HDO, report also a noble-metal based catalysts promotion of
the hydrotreatment.92 Ru/C, Ru/TiO2, Ru/Al2O3, Pt/C, and
Pd/C catalysts have been tested comparatively to the classical
sulfided NiMo/Al2O3 and CoMo/Al2O3, at 250 and 300 °C,
and pressures of 100 and 200 bar. The Ru/C catalyst was found
to present more interesting properties than the classical ones,
namely concerning the oil yield and deoxygenation level. The
original acidity of the pyrolysis oil was reduced, as well as its
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Review
content in organic acids, aldehydes, ketones and ethers, whereas
phenols, aromatics and alkanes amounts were increased.
Several institutions have been active in catalyst research and
development for the pyrolysis oil upgrading. For instance, Shell
has been evaluating the use of carbon-supported Ru, in order to
upgrade bio-oil from thermal pyrolysis to an extension suitable
for application in FCC,36 as will be further discussed in section
3.2. The oxygen content of the oil phase decreased from 28.0 wt %
(dry basis), at 230 °C, to 15.5 wt %, at 330 °C, operating at
hydrogen pressures in the range of 200−290 bar. Since a high
hydrogen consumption was observed during the heating up
period, it has been proposed that a first saturation of double
bonds and formation of alcohols from aldehydes and ketones
occur, followed by hydrodeoxygenation/dehydration, at higher
temperatures. Similar observations were made with model com-
pounds (section 2.1).
Honeywell/UOP93 has developed a two-step process for the
conversion of bio-oils into diesel, aviation, and naphtha boiling
point range fuels, or fuel blending components, by two-stage
deoxygenation of the pyrolysis oil and separation of the products.
Taking into account the goals outlined by the United States
for the production of renewable fuels by 2017 (35 billion
gallons per year),94 the work about bio-oils upgrading focused
on catalytic hydroprocessing has continued at PNNL (Pacific
Northwest National Laboratory). Various conversion technol-
ogies for generating gasoline and diesel fuels from bio-oils have
been evaluated, as it was shown in a recent report,94 which studies
a design case to treat 2000 ton/day of hybrid poplar wood chips to
produce 76 million gallons/year of gasoline and diesel. This design
case study involves several processing steps: a fast pyrolysis to
obtain a highly oxygenated liquid product; hydrotreating of the fast
pyrolysis oil into a stable hydrocarbon oil, with less than 2%
oxygen; hydrocracking of the heavy portion of the stable hydro-
carbon oil; distillation of the hydrotreated and hydrocracked oil
into gasoline and diesel fuel blend stocks; and, finally, a steam
reforming of the process off-gas and supplemental natural gas, to
produce hydrogen for the hydrotreating and hydrocracking steps
(Figure 1). The hydrotreating section comprises two catalytic
reaction stages: the first reactor stabilizes the bio-oil by mild hy-
drotreatment (240 °C; 172 bar; LHSV = 1 h−1) and the second
one operates at higher temperature and lower space velocity
(370 °C; 138 bar; LHSV = 0.14 h−1).
Despite promising, several studies about early two stage
processes concluded that the process is too expensive because
of the large amount of hydrogen consumed, the low product
yields, the need to further upgrade the products in a refinery
and the corrosiveness of the raw oil.89 In fact, based on different
scenarios for hydrogen-purchase fast pyrolysis and upgrading,
techno-economic analyses are being performed,95 but the con-
clusions about high costs indicate that some aspects of the bio-
oils upgrading processes require further developments. The
costs are not acceptable for petroleum refiners, and some reports
suggest that lower costs could be achieved by sending partially
deoxygenated materials to a refinery. It means that reducing the
severity of hydrodeoxygenation, leaving about 7 wt % oxygen in
the pyrolysis oil and avoiding aromatics hydrogenation, would
reduce hydrogen consumption and hydrotreating capital costs.
In Europe, a large research Project (BioCoup) has been devel-
oped that has as a major objective to arrive at pyrolysis oil-
derived products with the potential to be cofed in crude oil
refineries. A recent report published by BTG (Biomass Tech-
nology Group)96 summarizes the advantages and problems related
to the several upgrading routes potentially usable in pyrolysis oils
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Industrial & Engineering Chemistry Research
Figure 1. Fast pyrolysis, hydrotreatment, and hydrocracking combined process. Adapted from Jones et al.94
HDT, when the objective is to arrive at transportation fuels.
Indeed, many works have been published, but there are many
discrepancies and the explanations are scarce. For example, in
terms of deoxygenation levels, they vary from 10 to 90%, at
similar operating conditions and same type of catalysts.
Actually, pyrolysis oils obtained from different sources and
processes are completely different, the hydroprocessing itself is
not well understood, and analysis techniques need further de-
velopment. As pointed out in the Choudhary and Phillips
review,41 additional studies should be undertaken in order to
get closer to effective industrial implementation of bio-oils
HDO, namely concerning the effect of bio-oil quality, process
parameters, and catalyst optimization.
3. ACID CATALYSIS UPGRADING OF BIO-OILS
Many studies focusing on bio-oils conversion into liquid trans-
portation fuels were carried out using acid zeolites as catalysts.1,11
Renewable feedstock deoxygenation, with solid acid catalysts, can
be achieved at atmospheric pressure and temperatures in the
range of 350−500 °C.1,11,97 The widely used downstream pro-
cess that can be operated under these conditions is the Fluid
Catalytic Cracking (FCC).98
The FCC process plays a very important role in petroleum
refining, by converting heavy fractions of crude oil into gasoline,
among other valuable products. In this process, there is a con-
tinuous catalyst circulation between the cracking reactor and the
regenerator. The hot catalyst grains promote the endothermic
hydrocarbon feedstock transformation in the cracking unit,
yielding cracked products and a strongly deactivated catalyst, by
rapid coke deposition. In fact, the reactions occurring in the
reactor riser quickly lead, after only a few seconds, to an almost
complete deactivation of the catalyst. The spent catalyst particles,
after separation from the hydrocarbon mixture, are regenerated
by coke combustion, at 650−700 °C. The regenerated hot
catalyst particles are then recycled to the riser, so that an almost
autothermal operation is achieved.
The FCC catalyst contains acidic HY zeolite as the main
active phase dispersed into a matrix. Another zeolite, ZSM-5, in
its acid form, is commonly used as additive in order to increase
the conversion of linear hydrocarbons, leading to the
improvement of the gasoline quality by increasing its octane
number and, mainly, to an enhancement of the production of
valuable light olefins.
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Review
Bio-oils can be blended with conventional FCC feedstock,
but also dedicated modified FCC units can be envisaged, for
renewable feedstocks upgrading.
3.1. Dedicated FCC for Bio-oils Transformation. A
dedicated FCC unit for the bio-oils transformation has not
become a reality yet. The next sections summarize previous studies
concerning the transformation of model compounds and bio-oils
over acid catalysts (catalytic cracking).
3.1.1. Model Compounds Transformation. Depending on
the raw-material used to produce bio-oil, the relative amount of
cellulose, hemicellulose, and lignin can vary, and thus the
corresponding oxygenated building-blocks. This is the reason
why there are many studies dealing with pure oxygenated
model compounds, in order to understand independently the
key reactions involved in bio-oils transformation. In fact, the
transformation of alcohols, aldehydes, ketones, acids, esters,
ethers, phenols, furans, and mixtures, over zeolite catalysts has
been investigated by several research groups.40,99−108
As can be observed in Table 2, alcohols are highly reactive
over HZSM-5 catalysts.101 Dehydration is the major and the
first reaction route of alcohols deoxygenation, which can occur
at relatively low temperatures (around 200 °C), producing
water and the corresponding alkenes. Once formed, the alkenes
oligomerize (250 °C) and, consequently, undergo cyclization
reactions, yielding aromatics (and/or alkylaromatics) through
hydrogen transfer reactions (>350 °C), which lead to coke
formation.101,104 Ethylene, propylene and butenes are also obtained
by the cracking of alkyl aromatics and alkanes.104 A second trans-
formation route should involve the alcohols cracking (decarbon-
ylation), producing hydrocarbon gases (C1 to C5+), CO, and other
alcohols.101,104 It was proposed that the major part of the alcohols
are converted into aromatic hydrocarbons on HZSM-5 zeolites,
representing about 40 wt % of the final products.101
As for alcohols, aldehydes and ketones deoxygenation over
HZSM-5 zeolites proceeds by dehydration and decarbon-
ylation, but they present a lower reactivity (see Table 2).101,105
In addition, a study concerning the transformation of a model
bio-oil ketone, the cyclopentanone, over two HY zeolites pre-
senting different acidities, demonstrated that the ketones reac-
tivity highly depends on the nature of the zeolite acidity. Their
conversion preferentially occurred, at lower temperatures, on
the zeolites with lower acid strength, higher Brönsted acid site
density, and larger concentration of extraframework aluminum
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Industrial & Engineering Chemistry Research Review

species than over the zeolites with higher acid strength but

1.1−1.9; coke, 1.6−4.0; gas, 0.3−2.1; aliphatic, 0.2−0.7; aromatics, 0.3−1.1; eugenol isomers, 47.8−40.4;
lower acid site density.107
The carboxylic acids transformation is very dependent on the
reaction temperature. An important rise of the propanoic acid

3.2−17.8; coke, 6.1−26.7; gas (mainly CO2), 5.3−38.3; aliphatic, 0.7−1.4; aromatics, 0.8−8.0
conversion was observed by increasing the temperature, as
shown in Table 2.101 Carboxylic acids deoxygenation pre-
dominantly occurs by decarboxylation, with CO2 and hydrocarbon
gases formation and, to a lesser extent, by dehydration.101,105
Phenolic species (Table 2) are much less reactive than the
4.7−15.0; coke, 2.1−5.0; gas, 4.8−9.1; aliphatic, 3.2−5.0; aromatics, 29.4−48.5
9.5−12.9; coke, 2.9−7.8; gas, 9.1−15; aliphatic, 2.1−0.2; aromatics, 36.3−39.9

other oxygenated molecules over HZSM-5 zeolite.99,101,104

Alkylated phenols and aromatic hydrocarbons are the main
1.7; coke, 8.3; gas, 42.1; aromatics, 17.6; other furans and phenols, 1.7

reaction products. To a much lower extent, also cracking of the

alkyl groups, leading to the formation of hydrocarbon gases, as
trace; coke, 2.9; gas, trace; aromatics, 55.0; other furans, 13.5
trace; coke, 7.5; gas, 2.9; aromatics, 29.9; other phenols, 57.8

well as condensation-type reactions, leading to coke, occur over

this zeolite. This also showed that decarboxylation and de-
main products: % select

carbonylation were not the major routes for phenols conversion.

Deoxygenation of alkyl- and alkoxyphenols compounds occurred
preferentially through hydrolysis and dehydration (through
hydrogen transfer) reactions.99,103
54.7; coke, 2.0; gas, 22.8; aromatics, 9.4

The conversion of furfural and furan over HZSM-5 zeolite

was also studied,100 being that relatively low conversions were
obtained (Table 2). Furfural catalytic conversion involved de-
carbonylation into furan, through the attack of the zeolite acid
sites. Furan is less reactive than furfural, yielding some poly-
meric materials as a result of the ring-opening reactions, in the
presence of an acid and water. Benzofuran was also found as
one of the major products of furan transformation, resulting
from thermal cycloaddition reactions, involving furan and un-
saturated intermediates originating from the coke.
Hence, the O-compound families presented great differences
in their reactivity, as well as in their reaction pathways. How-
fraction,
fraction,
fraction,
fraction,

fraction,
fraction,
fraction,
fraction,
Table 2. Reactivity and Product Distribution of Pure Oxygenates over HZSM-5100−102

ever, the reactivity of the individual components can change

when mixed, which is due to a synergistic effect established
aqueous
aqueous
aqueous
aqueous

aqueous
aqueous
aqueous
aqueous

between the reactants and the products,101,106 as, for example,

the observed phenols conversion increases in a mixture.
3.1.2. Bio-oils Transformation. The performance of differ-
ent acid catalysts (HZSM-5, HY, HMOR, silicalite and silica−
convn (%)
85.0−98.2

62.1−94.8
24.2−99.9

56.8−60.0

alumina) in the catalytic upgrading of bio-oils was tested by

5.1−9.3

several authors, in a temperature range of 290−450 °C.109−116

65.5
58.9
44.0
100

The products obtained were an organic liquid fraction, con-

sisting of aliphatic and aromatic hydrocarbons and O-compounds,
char, coke, tar or residue, water and gas, essentially consisting of
temp (°C)
330−410

330−410
330−410
330−410
330−410

CO, CO2, and the remaining C1−C6 paraffins and olefins (Table 3).
500

500
500
450

Table 3. Product Distribution, Organic Distillate Fraction

Composition and % Deoxygenation Obtained for the
cat. mass (g)

Upgrading of Bio-oils over Different Catalysts,

WHSV = 3.6 h−1 and 370 °C111,112
3.3
2
10
2
2
2
2
10
10

silica−
HZSM-5 HY HMOR silicalite alumina
WHSV (h−1)

Product Yields (wt %)

char 12.0 21.2 26.6 27.0 16.6
3.6

3.6
3.6
3.6
3.6
4

4
4
1

coke 8.5 14.8 14.8 16.5 24.4

gas 14.3 10.4 14.8 15.4 8.8
organic distillate 33.6 24.6 12.3 10.8 16.8
2-methylcyclopentanone

(ODF)
model compounds
4-methylcyclohexanol

water 28.9 26.2 27.3 24.4 26.8

ODF Composition (wt %)
propanoic acid

aromatic 79.5 16.3 39.4 9.2 5.5

hydrocarbons
methanol

eugenol

furfural
phenol

anisole

aliphatic 3.5 45.0 13.1 36.6 47.8

furan

hydrocarbons
% deoxygenation 90.1 73.3 59.1 73.0 73.3

280 dx.doi.org/10.1021/ie301714x | Ind. Eng. Chem. Res. 2013, 52, 275−287

Industrial & Engineering Chemistry Research
It was then observed that bio-oils can be upgraded over these
catalysts, with the production of an organic liquid fraction presenting
high hydrocarbon content. The HZSM-5 zeolite was found to be the
best catalyst tested, with the highest production of liquid products
and the smaller coke deposition. In fact, a higher deoxygenation rate
was achieved with the HZSM-5 zeolite (Table 3).
These studies demonstrated that HZSM-5 and HMOR cata-
lysts produced more aromatic hydrocarbons (toluene, xylenes,
and trimethylbenzenes) than HY, silicalite, and silica−alumina,
which were more selective for the production of aliphatic hy-
drocarbons (alkylated cyclopentene, cyclopropane, pentane and
hexane, see Table 3). HY and HMOR could be used to provide
hydrocarbons within kerosene boiling point range, whereas
HZSM-5 is useful to produce hydrocarbons in the gasoline
range. Hence, by changing the type of catalyst, it is possible to
adjust the composition of the organic distillate fraction resulting
from bio-oils deoxygenation. The operating conditions of the
process can also be adjusted to regulate the organic liquid
fraction and gasoline yields.117
The bio-oils conversion results from thermal and thermo-
catalytic transformations (Figure 2).113 Thermal effects induce
Figure 2. Scheme of thermal and catalytic transformations of bio-oils
over acidic zeolites. Figure adapted with permission from ref 113.
Copyright 1995 Elsevier.
the bio-oils separation into two fractions: light and heavy
organics. The thermocatalytic effects are dependent on the
porosity and acidity of the catalyst. Over acid zeolites (i.e.,
HZSM-5, HY and HMOR, Figure 2), the heavy organic fraction
can be cracked into light organics or polymerize to form coke
(deposits on the catalyst surface) and char (solid particles not
deposited on the catalyst). The light organics consist of various
acids and esters, ketones, alcohols, ethers and phenols. First,
they are deoxygenated with water and carbon oxides formation.
Then, the hydrocarbons formed undergo cracking and oligo-
merization reactions, producing a C2−C6 olefins mixture. These
species can suffer several aromatization reactions (cyclization,
alkylation, hydrogen transfer, isomerization), leading to aromatic
and consequently to coke formation. The results also reveal that
gasification of char is a reaction occurring during bio-oil thermo-
catalytic conversion. The gasification produces carbon oxides and
hydrocarbon gases (mainly olefins). Over silica−alumina cata-
lysts, the olefins produced are reoxygenated to light organics.
Moreover, cyclization reactions do not take place with this type
281
Review
of catalyst, the final product being predominantly constituted by
noncyclic aliphatic hydrocarbons. For silicalite, the reaction
pathways are similar to those of acidic zeolites. However, deoxy-
genation by dehydration seems to be lower over silicalite than
over acidic zeolites (see Table 3).111,112 It should be noted as
well that in the absence of hydrogen, that is, under catalytic crack-
ing conditions, the reduction in the oxygen content is coupled
with a loss in carbon, because part of the oxygen is removed as
carbon oxides (CO and CO2). Thus, at constant coke + char, a
catalyst that favors CO2 formation instead of CO will result in a
higher hydrocarbon yield. Hence, thermally induced separation
and polymerization, as well as thermocatalytic deoxygenation,
cracking, and aromatization, were the main reactions involved in
bio-oils conversion. During the bio-oils upgrading, between 30 and
40 wt % of the bio-oil was converted into coke.112,113
Sharma and Bakhshi118 developed a dual reactor system,
where two catalytic reactors, at different temperatures, were
used in series. It was possible to increase nearly 2-fold the organic
distillate products and the aromatic hydrocarbons yield, as well as
to reduce the coke plus char formation (10 wt % lower than in the
single reactor). Another studied possibility to reduce coke
deposition was to cofeed steam during bio-oils upgrading over
HZSM-5 zeolites.110 Still, the residue content increased from
negligible values to 8−10 wt %, resulting in a decrease of the
catalyst activity. The presence of steam also induced a change in
the catalyst selectivity: less aromatic and more aliphatic hydro-
carbons were obtained.
As the FCC unit operates in continuous reaction−regeneration
cycles, the behavior of the HZSM-5 zeolite in the upgrading of
bio-oil was tested doing repeated upgrading−regeneration
cycles.119−121 It was observed that the continued regeneration
of the zeolite provokes an irreversible deactivation of the
catalyst, due to a loss of acidity through dealumination, induced
by the presence of steam at high temperatures. To improve the
hydrothermal stability, modified HZSM-5 zeolites have been
tested with higher Si/Al ratios and impregnated with Ni,122
which was revealed to maintain their kinetic behavior for up to
10 reaction−regeneration cycles.
A hydroprocessed oil derived from biomass was also tested in
the catalytic conversion, in a comparative study with hydro-
processed vacuum gasoil.38 It was observed that the catalytic
cracking of hydroprocessed bio-oils gives less gasoline and
gasoil yields, which are compensated by higher coke amounts
when compared to the hydroprocessed vacuum gasoil. Further-
more, more light products were obtained for the transformation of
hydrotreated bio-oils. However, the butane and butene yields,
which are more valuable products, were higher for the catalytic
cracking of the conventional hydrotreated vacuum gasoil.
Despite some catalyst stability improvements, a common
concern reported in the literature relative to both HDO and cata-
lytic conversion processes is still the catalyst deactivation, either by
coke deposition and/or chemical changes. In addition, further im-
provements would be important, namely concerning the fuel yields
and composition (significant amounts of aromatic compounds).
3.2. Coprocessing of Bio-oils in FCC. Biofuels could
more quickly relieve the increasing demand for petroleum if
economical opportunities for coprocessing them in traditional
petroleum refineries are identified and developed. Thus, a
sound option consists of blending the bio-oils with the con-
ventional FCC refining streams to further processing in the
existing refinery units. This approach would minimize the
investment cost by using an already existent infrastructure.
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Industrial & Engineering Chemistry Research
3.2.1. Coprocessing Studies with Model Compounds. To
evaluate the possibility to partially replace the classical FCC
feedstocks by bio-oils, some recent works analyzed the in-
fluence of the presence of controlled amounts of model oxygenated
compounds on the cracking properties of the catalysts over
hydrocarbon transformations. Methylcyclohexane and n-heptane
cracking were performed in the presence of phenol or guaiacol
(oxygenated compounds representative of partially hydrotreated
bio-oil) over HY and HZSM-5 zeolites (the most active phases in
the FCC catalyst) in a fixed-bed reactor, at 350 and 450 °C.123−127
Phenolic molecules lead to a further deactivation of the zeolites,
along with time-on-stream (TOS), due to their adsorption on
the Brönsted and Lewis acid sites, simultaneously to the coke
molecules deposition from the reactants transformation. This
effect is of increasing relevance along with TOS, and can be
controlled to avoid important deactivation levels at the first
reaction times, by regulating the O-compound incorporation in
the feed. Since FCC operates at very short residence times (a few
seconds), the mentioned cofeeding possibility deserves to be con-
sidered. Nevertheless, the resistance to the poisons was revealed to
be lower for the HZSM-5 zeolite, because of the narrowness of its
channels.
For the large pores HY zeolite,123,125,127 phenol adsorption is
partially reversible, being thermodynamically controlled: the
higher the temperature, the lower the amount of poison ad-
sorbed on the catalyst. The observed detrimental impact of
phenol on HY activity is significantly dependent on the type of
hydrocarbon to be transformed by cracking. An important de-
activating effect was noticed since the beginning of the reaction
for the n-heptane transformation (representative of alkane
compounds in conventional FCC charges) with 4% of phenol
incorporation in the feed. Contrarily, for methylcyclohexane
(representative of naphthenes in conventional FCC charges),
the additional deactivation induced by phenolic molecules, at
the same feed composition, was noticed only after a few
minutes of TOS. Furthermore, while for n-heptane the same
deactivation level was observed in the presence of phenol at
both studied temperatures, for methylcyclohexane the increase
of the temperature reduced the deactivating effect of phenol.
The impact of the oxygenated molecules is, in fact, related to
the type of acid sites required for the hydrocarbon cracking:
n-heptane needs stronger acid sites than methylcyclohexane.
Phenols tend to first adsorb on the stronger acid sites, being then
retained on the weaker ones, where the adsorption is less favored
with the increase of the temperature. Hence, the transformation of
the different compound families constituting conventional FCC
feedstocks could be influenced at different levels when copro-
cessed with hydrotreated bio-oils containing phenolic compounds.
The cracking of n-alkanes over HY zeolite seems to be more
affected than naphthenes by the presence of this type of oxygenated
molecules, mainly for the first values of TOS.
On the other hand, n-heptane transformation over HZSM-5
zeolite is less affected by the presence of phenolic molecules
than methylcyclohexane.124,126,127 The n-heptane diffusion
through the narrow and tortuous HZSM-5 channels is more
favored than methylcyclohexane, particularly when the amount
of carbonaceous materials deposited on the zeolite increases.
So, the effect of phenol adsorption inside the ZSM-5 pores
would be stronger over the reduction of methylcyclohexane
accessibility to active sites. Considering that linear alkanes
are the main hydrocarbons converted into the ZSM-5 pore
network, the impact of the phenolic compounds on this zeolite
action should not be as important as it could be.
282
Review
The greater the size is of the phenolic molecules present in
the hydrotreated bio-oils, the lower is their effect on the
hydrocarbons transformation over the HZSM-5 zeolite, mainly
at higher temperatures.127 In fact, bulky oxygenated molecules
(guaiacol) are preferentially adsorbed on the crystals outer
surface, from which they are more easily removed at higher
temperatures. Contrarily, smaller size phenolic compounds
(phenol) are able to enter on the zeolite pores, but their diffu-
sion is limited due to the polar nature. In this case, the increase
of the temperature does not limit the deactivating effect, the
molecules desorption being kinetically controlled.
The cofeeding of hydrocarbons and oxygenated compounds
was also tested by Domine et al.128 using a catalytic fixed-bed
reactor at 530 °C. Acetic acid, acetone, and isopropyl alcohol
were separately co-injected (2 wt % of the feed) with isooctane,
and the mixtures were transformed over an industrial equi-
librium FCC catalyst. As expected, the addition of the oxygenated
compounds causes a decrease of the isooctane conversion. Acetic
acid and isopropyl alcohol led to a stronger initial deactivation of
the catalyst than acetone. Nevertheless, after successive reaction−
regeneration cycles, the deactivation induced by acetone was more
severe than for acetic acid and isopropyl alcohol, for which the
deactivation was demonstrated to be somewhat reversible. More-
over, in the presence of the oxygenated compounds, high levels
of coke were found and coke was not completely removed by
combustion. The O-compounds addition also provoked changes in
the products distribution. The formation of CO was observed,
resulting from the oxygenated compounds transformation; acetone
apparently suppressed the isooctane secondary cracking reactions,
increasing the amounts of isobutane on the effluent.
Few recent works were performed at conditions close to
those of the FCC process.127,129 The same key bio-oil model O-
compounds previously used in HDO studies, representative of
the major oxygenated groups (acetic acid, hydroxyacetone,
phenol or guaiacol) were mixed with a standard gasoil and
tested in a fixed-fluidized bed reactor, using an industrial FCC
equilibrium catalyst (E-CAT) and a mixture of E-CAT and
ZSM-5 additive, at 535 °C.127,129 These oxygenated molecules
increased the overall conversion (Figure 3), defined as the fraction
Figure 3. Effect of adding different model compounds during cracking
of pure gasoil (■), acetic acid (◊), hydroxyacetone (x), phenol (Δ),
and guaiacol (○). Figure adapted with permission from refs 127 and
129. Copyright 2009/2011 Elsevier.
of the feed converted into gases, gasoline and coke, since they
were considered as products (boiling point in the gasoline
range). In spite of this, the gasoil conversion over pure E-CAT
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Industrial & Engineering Chemistry Research
was not altered by the presence of the O-compounds, while
when the ZSM-5 additive was present, a slight decrease of the
gasoil conversion was noticed. Under FCC conditions, acetic
acid and hydroxyacetone mainly increased the fuel gas and
liquefied petroleum gas (LPG) fractions. Acetic acid was
converted into methane, light olefins (ethylene, propylene and
butylenes), CO, and CO2. With hydroxyacetone, an improve-
ment of the ethylene and propylene production was observed.
On the other hand, phenol (and guaiacol at high conversions)
enhanced the gasoline yield (Figure 3). A detailed analysis of
the gasoline fractions obtained for the phenol and guaiacol
mixtures revealed the presence of methyl- and ethyl-phenols
and an increase of the water and benzene on the effluent, as com-
pared to the pure gasoil transformation. This was also accom-
panied by an improvement of the LPG yield, in the case of
phenol, and by an increase of the fuel gas, mainly methane, for
guaiacol. Under these operating conditions, phenol can suffer de-
hydration into benzene and alkylation, and guaiacol can undergo
disproportionation and be converted into phenol, with methane
and water formation. Furthermore, it was also observed that the
ZSM-5 additive effect toward the increase of light compounds
formation is attenuated by these oxygenated molecules, probably
because of a preferential interaction of such compounds with the
ZSM-5. It was concluded that feed incorporation ratios up to
12.8 wt % of oxygenated compounds could be processed without
major problems to the FCC unit. It should be mentioned that
FCC uses short-contact-time risers, so that the relevant additional
catalyst deactivation induced by the oxygenates, observed in the
model reactions studies, shall be the one observed at short TOS.
Nevertheless, the amount of bio-oil incorporated needs to be
controlled to keep the ZSM-5 additive effect at an acceptable level,
as well as the benzene content in the gasoline range.
3.2.2. FCC Coprocessing Studies with Bio-oils. As
previously discussed, the direct introduction of bio-oils in the
FCC process is limited because of their small miscibility with
hydrocarbons, chemical instability, and high tendency to form
coke. Therefore, a previous stabilization HDO step of the bio-oils
should be envisaged before the cofeeding, as it was proposed by
several authors.34−36,38,130 This step does not need to aim toward
a complete deoxygenation, but only to the reduction of the
highly reactive components that lead to coke formation.36
Mixtures up to 20 wt % of hydrotreated bio-oils and con-
ventional FCC streams were coprocessed over equilibrium FCC
catalysts, in order to analyze the effects of partially replacing the
FCC feedstocks by bio-oils on the conversion, products
distribution, and coke formation.
A coprocessing of 15 wt % of hydrotreated bio-oil and LCO
(light cycle oil) was performed in a MAT fixed bed reactor,
using two commercially available catalysts (RE-USY), with
different rare-earth contents.34 The catalyst with an RE2O3 amount
closer to that generally used for a maximum gasoline yield (0.5 wt %)
was found to be the more suitable for this application. This catalyst
preserved the conversion of heavy compounds within a limited level,
producing acceptable levels of coke (<1 wt %) and gasoline yields
(23−25 wt %). Moreover, it produced a higher RON (research
octane number) gasoline due to the greater aromatic content.
Nevertheless, a lower amount of branched paraffin and saturated
naphthenes were obtained when compared to catalysts with larger
pores. Comparing the biogasoline produced with a common FCC
gasoline, it was verified that olefin and naphthene yields are lower,
whereas the amount of aromatic compounds increases. However, the
obtained biogasoline still met the environmental gasoline specifica-
tions.
283
Review
In another study, a heavy hydrotreated bio-oil fraction was
diluted in LCO and blended with a conventional VGO (vacuum
gas oil), in a proportion of 15/75 wt %.35 This mixture was
introduced in a FCC small-scale pilot plant and converted under
the FCC operating conditions (520 °C, E-CAT). The results
showed that the presence of bio-oil favors the gasoline and diesel
production, but increases the coke yield (about 0.5 wt %). The
gasoline produced contained more aromatics and less olefins and
paraffins. Furthermore, the bio-oils reduced the crackability of
the feedstock; that is, for the same catalyst-to-oil ratio, the
conversion was diminished.
It was also reported that a 20% incorporation level of an
hydrotreated bio-oil (oxygen content up to 28 wt %), fed
together with 80 wt % crude oil to a MAT FCC unit, produced
interesting gasoline fractions, equivalent to the one obtained
from pure crude oil.36
A similar bio-oil coprocessing level, namely a mixture of
80 wt % VGO and 20 wt % hydrodeoxygenated bio-oil (oxygen
content of 21 wt %), was tested in a fixed-bed reactor
simulating FCC conditions.130 The results revealed that the
bio-oil addition induced an increase of the conversion because
the bio-oil already contained molecules in the product range.
Furthermore, it was noticed that the coke formation tendency
was higher in the case of the coprocessing: at 80% conversion,
the coke yield was 2 wt % higher than with pure VGO cracking.
The bio-oils incorporation also affected the products distribu-
tion. An increase of the dry gas yield was also registered, because
of the improvement of the ethane and methane formation
through bio-oils thermal cracking. Furthermore, an enhancement
of the ethylene yield was observed from 35 wt %, for the pure
VGO cracking, to 45 wt % in the case of the coprocessing. On
the other hand, the LPG production decreased for the mixed
feed. The gasoline, LCO, and bottom yields were not signifi-
cantly altered by the bio-oils addition to VGO. A detailed
analysis of the products indicated that the gasoline produced was
richer in branched paraffin and short alkyl-chain benzene deriva-
tives, but also contained amounts of phenol and alkylphenols,
which revealed the low reactivity of these oxygenated structures
under FCC conditions.130,131 Appreciable amounts of CO2 and
water were also found in the effluent, resulting from deoxygenation
reactions, decarboxylation, and dehydration, respectively.130,131 A
final product composition poor in H2 and containing more coke,
aromatics, and olefins was obtained through the coprocessing,
because the oxygen removal from hydrotreated bio-oils occurred
preferentially by dehydration.130,131
Thus, available data, as shown in Table 4, suggest that
controlled cofeeding of bio-oils toward incorporation levels of
about 20%, together with a conventional FCC feedstock, is not
that critical, seeming to be a technically viable option. Despite
some changes in products selectivities reported, the quality of
the produced gasoline was generally preserved (Table 5).
4. FINAL REMARKS
The introduction of renewable materials, namely nonedible
biomass derived oils (bio-oils), into downstream operations is a
timely topic. Two main refining processes have been envisaged
to upgrade these bio-oils toward the production of useful liquid
fuels (second generation biofuels): HDO and catalytic cracking
conversion. Many nonedible feedstocks can be used, but they
all have in common the presence of oxygenated compounds,
which have to be (at least partially) transformed, by oxygen
removal, in order to allow blending with hydrocarbon feedstocks.
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Industrial & Engineering Chemistry Research Review

Table 4. Comparison of Products Yields Obtained for catalysts. Supported Ru, Rh, and Pt appeared to be potential
Classical and Bio-oil Blended Feedstocks under FCC catalysts for HDO, but it should be also taken into con-
Conditions.35,36,130 sideration that the possible processing costs rise when noble
convn dry gas LPG gasoline LCO coke
metals are used in a large scale process. Less expensive metal
(%) feed (wt %) (wt %) (wt %) (wt %) (wt %) catalysts, such as Ni and Cu, are potential alternatives, but
65 VGO + 15%LCO 42 19 3.5 further work on these systems is necessary.
VGO + 15% 43 20 4 HDO of bio-oils has been also reported to be accomplished
(LCO+bio-oil) over classical hydrotreatment catalysts, as well as over noble
60 VGO 1.5 8.5 44 25 5.9 metals. In fact, noble metal catalysts are known to be active in
VGO + 20% bio- 2.5 11 44 23 7.8 hydrogenation and hydrodeoxygenation. The particular case of
oil (28% O)
80 VGO 2 26 47 19 3.8
Ru presents high activity toward the reduction of a wide range
VGO + 20% bio- 2.5 24 46 19 5.8 of different oxygenates. The development of bio-oils HDO
oil (21% O) studies and its integration in the refineries are, as well, being
carried out by several companies and researchers, but the costs
related with capital and hydrogen consumption are still very
Table 5. Effect of Bio-oil Incorporation on FCC Gasoline
high. High costs and the need for further catalysts optimization,
Composition and RON.34
among other factors, are thus preventing implementation of
compounds contents (wt %) LCO LCO + 15% bio-oil dedicated HDO units. The immediate and easy coprocessing of
n-paraffins 2.5 2.3 bio-oils with classical crude fractions, in the existing HDT
iso-paraffins 16.7 16.5 processes, does not seem to be feasible. The optimal perfor-
naphthenes 5.2 5.4 mance of current industrial HDT catalysts for petroleum
n-olefins 6.2 5.4 feedstocks cannot be reproduced over bio-oils HDO.
iso-olefins 10.3 8.8 The cracking of bio-oils with solid acid catalysts is less well
diolefins 0.7 0.5 developed than hydrotreating, but a wide range of possibilities
aromatics 58.4 61.1 have been recently explored, with mono- and multifunctional
RON 94.7 95.8
zeolite catalysts, revealing that this is an interesting alternative
for bio-oils transformation into liquid fuels. Compared to
The comparison of both technologies, concerning the main HDO, it is a cheaper alternative, offering significant processing
interesting features and drawbacks of each one on the bio-oils and economic advantages, because hydrogen is not required
upgrading, is presented in Table 6. and operation is under atmospheric pressure.
However, the existence of a dedicated FCC unit for the
Table 6. Comparison of HDO and FCC Technologies for biomass renewable feedstocks transformation needs further
Bio-oils Upgrading development. The poor hydrocarbons yields, the extensive
technology interesting features drawbacks coking observed during catalytic cracking of bio-oils, and the
HDO quality of the fuels obtained (significant amounts of phenolic
dedicated recent improvements on hydrogen consumption compounds) are important reported drawbacks that need to be
HDO catalyst performances overcome.
no need of catalyst H2S catalysts costs Taking into account the actual FCC process features, as in
pretreatments
HDT co- lower capital costs HDN and HDS efficiency
the Resid FCC Process, where the extensive coke deposition is
processing significantly affected by the a solved technological problem, and considering some recent
oxygenates studies, it seems that the coprocessing of bio-oils, in com-
FCC bination with conventional feedstocks, in existing FCC units, is
dedicated cheaper than HDO extensive coking
FCC the most promising bio-oils upgrading alternative in a short-
quality of the fuels term. In addition, relative small investment costs are involved.
FCC co- irrelevant investment need to control of bio-oils Nevertheless, the extent of bio-oil incorporation in the FCC
processing costs incorporation in the FCC feed feed should be controlled to remain at previously studied levels,
good quality gasoline HDO previous stabilization step so that the FCC outcoming products can maintain the desired
specifications
quality, not exceeding the aromatics content specification in
gasoline and keeping at acceptable levels the octane number of
For HDO option, the choice of a catalyst plays a crucial role, gasoline and the light olefins in LPG. This will be a function of
not only in the extent of oxygen removal, but also on the
the bio-oil properties, which depend on the severity of the
predominant pathway, that is, through dehydrogenation,
decarbonylation, or decarboxylation. In a nutshell, the pathway previous partial (and less expensive) HDO upgrading step.
of choice relays on the feedstock availability and logistics, Other aspects needing further research developments, con-
catalyst cost and hydrogen consumption. A great amount of cerning the coprocessing option, are related to the regener-
research work has been devoted to the model O-compounds ability of the catalysts, which will be submitted to numerous
transformations through HDO. Conventional hydrotreating reaction−regeneration cycles in the FCC process, and that was
catalysts were extensively tested in these studies. Nevertheless, proven to be excellent in the pure crude oil FCC. At least, such
catalytic systems based on noble metals supported on ZrO2, as results are expected to be more promising than those obtained
well as transition metal phosphides on silica, showed, in some with a full and nontreated bio-oil feedstock transformation
recent studies, to be more stable than classical CoMo/Al2O3 reported in the literature.
284 dx.doi.org/10.1021/ie301714x | Ind. Eng. Chem. Res. 2013, 52, 275−287
Industrial & Engineering Chemistry Research
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: +351218419073. Fax: +351218419198. E-mail: jmlopes@
ist.utl.pt.
Notes
The authors declare no competing financial interest.
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