Overview of fuel properties of biomass fast pyrolysis oils

Lu Qiang, Li Wen-Zhi, Zhu Xi-Feng

*
Key Laboratory for Biomass Clean Energy of Anhui Province, University of Science and Technology of China, Hefei 230026, China
a r t i c l e i n f o
Article history:
Received 28 May 2008
Accepted 2 January 2009
Available online 14 February 2009
Keywords:
Biomass
Fast pyrolysis
Bio-oil
Fuel property
a b s t r a c t
Fast pyrolysis of biomass is one of the most promising technologies for converting biomass to liquid fuels.
As a result, this technology has gained extensive attention in the last two decades. The pyrolysis liquids,
known as the bio-oils, have been regarded as promising candidates to replace petroleum fuels to be used
in various thermal devices. However, bio-oils are totally different from petroleum fuels. Therefore, the
successful utilization of bio-oils in terms of liquid fuels requires adequate understanding of their fuel
properties. This review concentrates on the detailed fuel properties of bio-oils and discusses how these
properties affect the utilization of bio-oils.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Fossil fuel shortage and severe environmental problems have
attracted great attention on the exploitation of clean renewable
energies. The utilization of lignocellulosic biomass resources will
play an increasingly important role in the future [1]. There are
various conversion technologies to produce liquid fuels, among
which fast pyrolysis of biomass has been experiencing rapid devel-
opment in the recent years, because it can offer an alternative way
to solve liquid fuel shortage problems [2,3].
Fast pyrolysis is a thermal decomposition process that occurs
in the absence of oxygen to convert biomass into liquid products
(bio-oils) together with non-condensable gases and solid chars.
The essential principles to obtain high yields of bio-oils include
moderate pyrolysis temperature (500 C), very high heating
rates (10
3
10
5
C/s), short vapor residence times (<2 s) and rapid
quenching of pyrolysis vapors. A number of pyrolysis reactors
have been developed that include bubbling uid bed, transport
bed, circulating uid bed, rotating cone, vacuum pyrolysis reactor,
ablative reactor, and screw reactor [46]. Since 1990s, several
research organizations have successfully established large-scale
fast pyrolysis plants. Bio-oils are renewable liquid fuels, and are
highly regarded as substitutes of petroleum fuels. However, bio-
oils are totally different from petroleum fuels. It is necessary to
develop new technologies for the successful utilization of bio-oils,
which requires adequate understanding of their overall fuel prop-
erties [79].
2. Bio-oil
Bio-oils, also referred to as biomass pyrolysis liquids, pyrolysis
oils, or bio-crude oils, are dark brown, free owing liquids with
an acrid or smoky odor. They are complex mixtures of compounds
that are derived from the depolymerization of cellulose, hemicellu-
lose and lignin. Chemically, they comprise quite a lot of water,
more or less solid particles and hundreds of organic compounds
that belong to acids, alcohols, ketones, aldehydes, phenols, ethers,
esters, sugars, furans, nitrogen compounds and multifunctional
compounds [10]. The molecular weights of these compounds vary
signicantly, from as low as 18 (water) to as high as 5000 or more
(pyrolytic lignins). The average molecular weight varies in the
range of 3701000 g/mol. Till now, over 300 organic compounds
have been identied in different bio-oils. Most of the compounds
are in low concentrations. Fractionation is widely used to separate
bio-oils into groups of compounds to facilitate analysis and quan-
tication of compounds [11,12]. However, complete chemical
characterization of bio-oils is almost impossible mainly due to
the presence of pyrolytic lignins [13]. The pyrolytic lignins are
derived from the partial cracking of lignin molecules. They cannot
be determined by gas chromatography or high performance liquid
chromatography. Analysis of the pyrolytic lignins shows that they
are constituted by oligomers (mainly tetramers), and their basic
units are very similar to milled wood lignins [1416]. As can be
seen, bio-oils are totally different from petroleum fuels in chemical
compositions, which will result in the vast difference in the fuel
properties between them.
The chemical compositions of bio-oils are determined by many
factors, such as biomass type, feedstock pretreatment (particle
size and shape, moisture and ash contents), pyrolysis conditions
(temperature, heating rate, residence time, pressure, gaseous
0196-8904/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2009.01.001
* Corresponding author. Tel.: +86 551 3600040; fax: +86 551 3606689.
E-mail address: xfzhu@ustc.edu.cn (X.-F. Zhu).
Energy Conversion and Management 50 (2009) 13761383
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j our nal homepage: www. el sevi er . com/ l ocat e/ enconman
environment) as well as vapor ltration and condensation (lter
type, condensing method and medium, cooling rate). Therefore,
bio-oils produced from different materials and by different
pyrolysis reactors may differ greatly from one another. As a re-
sult, the fuel properties of different bio-oils usually vary in wide
ranges.
3. Fuel properties of bio-oils
3.1. Homogeneity
In general, most bio-oils are homogeneous in appearance. How-
ever, some forestry and agricultural materials contain substantial
amounts of extractives whose pyrolysis products are different in
solubility, polarity and density from normal bio-oils. It was
reported that bio-oils produced from extractive-rich feedstocks
would separate into two phases: a top phase rich in extractives
and a bottom phase resembling the normal bio-oils [17,18]. The
proportions of the top phase depend on the feedstocks, and can
reach up to 20 wt% of the whole bio-oils. The major compounds
in the top phase are extractives (2550 wt%), pyrolytic lignins
(2040 wt%) and water soluble compounds (2040 wt%) [19]. It is
to be noted that many raw biomass materials contain a few extrac-
tives. The bio-oils produced from them will not undergo this kind
of phase separation, because the small amounts of extractives can
be dispersed in the bio-oil matrix.
Although most bio-oils are macroscopic single phase liquids, in
fact, they possess microscopic multiphase structures that will be
discussed below.
3.2. Microscopic multiphase structure
Compounds in bio-oils are of different sizes and natures. There
are highly polar compounds (water, acids and alcohols), less polar
compounds (esters, ethers and phenolics) and non-polar com-
pounds (hexane and other hydrocarbons). These compounds are
not completely mutual soluble. According to Radlein [20], bio-oils
can be considered as microemulsions. Water and water soluble
molecules form the continuous phase. Water insoluble materials
are dispersed as micelles in bio-oils. Some multipolar compounds
act as emulsiers to stabilize the structures.
Prez et al. [21] pointed out that the complex structures of
bio-oils could be attributed to the presence of char particles,
waxy materials, aqueous droplets, and heavy compound micelles.
They studied the multiphase structures of two bio-oils produced
from vacuum pyrolysis of SWBR (softwood bard residues) and
HWRF (hardwood rich in bre). The SWBR-derived bio-oil was
observed to have large droplets of 2080 lm containing crystals
and aqueous droplets of 5 and 10 lm at 25 C. This macroemul-
sion could be separated by creaming into two phases after heat-
ing to 60 C. The HWRF-derived bio-oil was observed to have
only a small amount of crystals and char particles dispersed in
the oil matrix. The differential scanning calorimetry analysis of
the extractive-rich top phase exhibited a clear endothermic phe-
nomenon over the range of 060 C. This was believed to be
caused by the melting of the waxy materials. In addition, the
rheological studies conrmed the existence of a network com-
posed of heavy compounds and waxy materials at low tempera-
tures in the bio-oils.
Fratini et al. [22] employed small-angle neutron scattering to
reveal the microstructures of bio-oils. The results showed that
bio-oils were nanostructured uids constituted by a complex con-
tinuous phase and nanoparticles mainly formed by the association
of units of pyrolytic lignins. The aggregation of these units
produced branched structures that were characterized by a fractal
dimension of 1.41.5 and an aggregation number of 5080.
3.3. Oxygen
Bio-oils retain most of the original oxygen in the feedstocks.
Their oxygen contents vary in the range of 3560 wt% (wet basis),
which is determined mainly by the water contents. Oxygen is pres-
ent in almost all organic compounds in bio-oils. It is known to be
the primary reason for the vast differences between bio-oils and
petroleum fuels. These oxygenated compounds make bio-oils po-
lar, and thus non-miscible with non-polar petroleum fuels. This
will be a defect for the utilization of bio-oils. Moreover, the high
oxygen content is responsible for the low heating value, corrosive-
ness and instability of bio-oils, which will be discussed below.
3.4. Water
Water is the most abundant single component in bio-oils. It
results from original moisture in feedstocks and dehydration
reactions during fast pyrolysis process. The water contents of
bio-oils usually vary in the range of 1530 wt%, depending on
the initial moisture in feedstocks and pyrolysis conditions. Some
water in bio-oils is in the form of aldehyde hydrates, while much
of it is probably hydrogen bonded to polar organic compounds.
The content is recommended to be determined by Karl-Fischer
titration [23].
Bio-oils have limited solubility with water. With the increase in
water content, the microemulsion structure will be destroyed and
bio-oils tend to separate into an aqueous phase and a heavier or-
ganic phase. To maintain homogeneity,the upper limit of the water
content is determined by the chemical compositions of bio-oils,
which are usually in the range of 3035 wt% [20]. Once this kind
of phase separation takes place, it will bring great trouble to the
utilization of bio-oils. In order to prevent this, the original moisture
in feedstocks is usually required to be below 10 wt% so as to con-
trol the water of bio-oils in a favorable level.
Water is hard to be removed from bio-oils. The presence of
water has both negative and positive effects on the storage and uti-
lization of bio-oils. On the one hand, it lowers heating values, and
may cause phase separation of bio-oils. Moreover, it increases
ignition delay, and reduces combustion rates and adiabatic ame
temperatures during the combustion process. In addition, it will
lead to premature evaporation and subsequent injection difcul-
ties during the preheating process. On the other hand, it helps to
reduce viscosity and facilitate atomization. Furthermore, it is ben-
ecial for reducing pollutant emissions during combustion [24].
Water lowers and evens the temperature proles in chambers that
are important for suppressing NO
x
formation. It also contributes to
the microexplosion of droplets, which is benecial for sufcient
combustion. In addition, OH radicals from water can inhibit the
formation of soot and can also accelerate its oxidation.
3.5. Heating value
The lower heating value (LHV) of bio-oils is typically 1418
MJ/kg, which is much lower than that of petroleum fuels (41
43 MJ/kg). It is attributable to the high oxygen content. However,
the density of bio-oils is about 1.2 g/ml comparedwiththat of petro-
leum fuels, which is 0.81.0 g/ml. Therefore, the volumetric energy
density of bio-oils can reach 5060% of that of petroleum fuels.
The bio-oils are usually directly measured for their high heating
values (HHVs). The LHV can then be calculated by the following
equation proposed by Oasmaa et al. [25]:
LHV HHV 218:3 H%wt% KJ=kg
Q. Lu et al. / Energy Conversion and Management 50 (2009) 13761383 1377
3.6. Solid
Bio-oils contain more or less solids, mainly char particles and
other materials such as uidized-bed materials used in the pyroly-
sis process. Cyclone separators are commonly used in pyrolysis
sets to get rid of solids in pyrolysis vapors because of their low
costs, but they are only efcient in separating large particles
(>10 lm). Many small particles that escaped from separation will
be condensed with pyrolysis vapors in bio-oils. The solid content
can reach as high as 3 wt%, and the particle size usually varies in
the range of 1200 lm with most particles being below 10 lm.
Solid content is measured as the amount of solvent insoluble
materials. Ethanol is powerful for extractive-free bio-oils. Whereas
a neutral solvent is required to dissolve bio-oils with extractives,
and a mixture of methanol and dichloromethane is recommended
[23]. The particle size distribution of solids can be determined by
optical instruments [2527].
Solid particles will bring many negative effects to the storage
and combustion of bio-oils [7]. First, the char particles tend to
agglomerate slowly and settle at the bottom of the vessels. Even
if ltration is performed to remove large particles, the left submi-
cron particles will aggregate to formlarge ones during storage. Sec-
ond, the solids increase the apparent viscosity of bio-oils, leading
to difculties in pumping and atomization. Third, the solids will
cause erosion and blockage to the fuel injection systems. Fourth,
the char particles will act as catalysts to accelerate the ageing reac-
tions of bio-oils, resulting in the increase in viscosity and even in
phase separation with solids adsorbed with pyrolytic lignins to
form gummy tars. Fifth, the char particles will contribute to form
slow-burning carbonaceous cenospheres and consequently un-
burned particles in the ue gas.
3.7. Ash
During the pyrolysis process, most inorganic compounds
(ashes) in biomass sequester in char particles. Hence, the ash con-
tents of the char particles are 38 times higher than those of the
feedstocks. For some raw biomass materials with high ash contents
such as rice husks (around 15 wt% ash), the ash contents of char
particles can reach as high as 50 wt%. A study conducted by Agble-
vor and Besler [27] revealed that alkali metals would not leach
from the char particles to bio-oils under storage conditions.
Ash content is determined as the amount of residues when
heating bio-oils to 775 C with oxygen supply. Direct heating of
bio-oils will result in foaming and splashing due to their high
water contents. Thus, the rst controlled evaporation of water at
105 C is needed before rapid heating to 775 C [25].
Metals in ashes are believed to cause signicant high-tempera-
ture corrosion and deposition to thermal devices during the com-
bustion of bio-oils [28]. Alkali metals of potassium and sodium
can form low melting compounds that will stick to the hot compo-
nents such as turbine blades and then corrode these components.
As can be seen, the presence of solids and ashes is highly unde-
sirable. Therefore, it is necessary to reduce the solid content. It is
difcult to solve this problem by ltration of bio-oils. Some solids
of small sizes will slip through lters, and the ltration will gener-
ate bio-oil/char sludge [26,29]. Nevertheless, ltration of pyrolysis
vapors, which has been studied in NREL and VTT, has been vali-
dated to obtain bio-oils with ash contents below 0.01 wt% and
alkali metals below 10 ppm [7,30].
3.8. Viscosity
Viscosity of a uid is a measure of its resistance to shearing
forces or angular deformation during motion. It will play an impor-
tant role in the design and operation of the fuel injection system, as
well as in the atomization quality and subsequent combustion
properties of the fuel.
Viscosities of homogeneous bio-oils can be measured as either
dynamic viscosity (l) or kinematic viscosity (c) by different visc-
ometers such as capillary viscometer, rotaviscotester, or falling ball
viscometer. However, for poor bio-oils with phase separation, it is
recommended to measure dynamic viscosities by closed-cup rota-
viscotester [23]. Viscosity measurement at elevated temperatures
seems to be a problem, since vapor formation caused by the evap-
oration of light volatiles will make the measurement troublesome.
Radovanovic et al. [31] proposed a measuring method to solve this
problem by using a falling ball viscometer. At temperatures above
which the vapor formation started, falling time of the ball uctu-
ated strongly in the repeated experiments. Viscosities of bio-oils
could be determined by the lowest values.
Generally, viscosities of bio-oils vary in a wide range (10100 cP
at 40 C). Moderate preheating of bio-oils is useful to reduce their
viscosities and to facilitate pumping and atomization. However, at
temperatures higher than 80 C, the whole properties of bio-oils
will be totally altered as a result of accelerated ageing reactions
[32].
3.9. Rheological property
The rheological property of a uid can be described by the fol-
lowing equation:
s s
o
lD
n
where s is the shear stress, s
o
is the yield stress, and D is the shear
rate. For Newtonian uids, s
o
= 0, n = 1, which indicates that their
viscosities will remain constant under different shear rates. The cor-
relation between c and l is as l = qc, where q is the density of the
uid. For non-Newtonian uids, their viscosities vary with different
shear rates. There are several kinds of non-Newtonian uids, such
as Bingham uids, Pseudoplastic uids and Dilatant uids.
Most bio-oils behave as Newtonian uids at temperatures lower
than 80 C. However, some bio-oils rich in extractives may exhibit
non-Newtonian uid behaviors. Ba et al. [33,34] investigated the
steady and dynamic rheological properties of the SWBR-derived
bio-oil. The steady rheological study discovered a phase-transition
temperature of the bio-oil at 46 C. The dynamic rheological study
showed that the bio-oil exhibited loss-modulus-dominant behav-
iors. According to these results, it could be concluded that the
waxy materials, pyrolytic lignins and solids in the bio-oil formed
three-dimensional structures (<46 C). This structure would melt
and disappear at higher temperatures. As a result, the bio-oil
behaved in a manner similar to that of a Bingham plastic uid
and a Newtonian liquid before and after 46 C, respectively. These
results were also conrmed by the viscosity measurement study
carried out by Boucher et al. [35] and by the detailed rheological
study performed by Prez et al. [21].
3.10. Flash point, pour point and cloud point
Flash point of a liquid fuel is dened as the lowest temperature
for the vapor above the liquid to be ignited when exposed to a
ame. It is an important parameter for fuel handling to prevent re
hazard. The ash points of bio-oils are usually measured with
closed-cup testers and vary in the range of 4070 C or above
100 C, depending on the contents of light organic volatiles. It is
usually difcult to measure the ash points at 70100 C, due to
the strong evaporation of water which will inhibit the ignition of
the fuel vapor [25].
Pour point of a liquid fuel is dened as the lowest temperature
at which a liquid can ow without disturbance. It is a parameter to
1378 Q. Lu et al. / Energy Conversion and Management 50 (2009) 13761383
describe the uidity of fuels at low temperatures. The loss of uid-
ity of liquid fuels is usually caused by the increase in viscosity or
crystallization of waxy materials. Generally, the pour points of
bio-oils derived from wood are between 12 and 33 C [25].
Bio-oils derived from other materials may go beyond this range.
For example, Sipil et al. [36] reported that a bio-oil sample from
straw had a pour point of 36 C.
Another parameter used to describe the low temperature prop-
erties of liquid fuels is the cloud point. It is dened as the highest
temperature at which a cloud of waxy crystals rst become visible.
As mentioned above, Prez et al. [21] and Ba et al. [33,34] all con-
rmed that the SWBR-derived bio-oil contained three-dimensional
structures at temperatures below 4050 C. But direct measure-
ment of the cloud point was not performed by them according to
the standard methods. Oasmaa et al. [25] followed the ASTM D
2500 method to test the cloud point of a bio-oil sample with no
waxy materials, in order to check if other components in the bio-
oil could cause a similar phenomenon. The bio-oil was cooled to
21 C and lost uidity, but no clouding phenomenon was ob-
served. However, it was difcult to conclude from the test that
the bio-oil had no cloud point because the dark color of the bio-
oil might make observation difcult.
3.11. Thermal conductivity, specic heat capacity and surface tension
Thermal conductivity is a parameter to express the ability of a
material to conduct heat. Specic heat capacity is dened as the
amount of heat required to increase the temperature of one gram
of a substance by one degree. Thermal conductivity and specic
heat capacity are essential parameters in the designing of equip-
ments concerning heat transfer, such as heat exchangers and atom-
izers. Only limited reports are available on the two parameters at
present. According to these results, the thermal conductivity and
specic heat capacity of bio-oils may be 0.350.4 W/mK and 2.5
3.5 KJ/kg K, respectively, in the temperature range of 2060 C.
Both values are higher than those of diesel fuels.
Surface tension is a measurement to attract of molecules to one
another on a liquids surface. It is an essential parameter for the
atomization of liquid fuels. The surface tension of bio-oils varies
in the range of 2840 mN/m at room temperature, which is higher
than that of petroleum fuels. The high surface tension can be partly
attributed to the water whose surface tension value is as high as
72 mN/m (at 25 C). Like other liquids, surface tension of most
bio-oils decreases slightly with the increase in temperature. While
Prez et al. [21] found that the SWBR-derived bio-oil exhibited a
distinct reduction of surface tension at around 45 C, due to the
melting of the three-dimensional structure.
3.12. Stability
Bio-oils are not products of thermodynamic equilibrium. Many
components in them will take part in diverse reactions during stor-
age. Oasmaa and Kuoppala [37] concluded that the instability of
bio-oils can be described as (1) a slow increase in viscosity during
storage; (2) a fast increase in viscosity by heating and (3) evapora-
tion of volatile components and oxidation in air.
3.12.1. Chemical and physical changes of bio-oils during storage
Diebold [38] concluded that the chemical reactions may take
place during ageing of bio-oils. Aldehydes seem to be the most
unstable fraction. They can react with water to form hydrates; with
alcohols to form hemiacetals, acetals and water; with phenolics to
form resins and water; with proteins to form dimers; and with one
another to form oligomers and resins. Moreover, acids can react
with alcohols to form esters and water; mercaptans will react to
form dimers; and olens will polymerize to form oligomers and
polymers. In addition, oxygen in air will oxidize the bio-oil to form
more acids and reactive peroxides that catalyze the polymerization
of unsaturated compounds. Furthermore, the char particles will act
as catalysts to accelerate the ageing reactions.
The properties of bio-oils will be changed as a result of these
ageing reactions. First, chemical reactions change the polarity of
bio-oils. For example, esterication reactions convert highly polar
organic acid and alcohol molecules into esters with relatively
low polarity and extremely polar water. Second, polymerization
reactions generate large molecules that have poor mutual solu-
bility with other compounds in bio-oils. These changes are the
primary reason for the increase in water content and viscosity
as well as for the phase separation observed during the storage
of bio-oils.
Oasmaa and Kuoppala [37] found that the major physicochem-
ical changes of bio-oils during storage took place in the rst 6
months. The main chemical change was the increase in high-
molecular-mass lignin materials, while the decrease in aldehydes,
ketones and lignin monomers. The physical changes included the
increase in viscosity, density, ash point and pour point, while
the decrease in heating value. Meier et al. [39] analyzed the chem-
ical changes of 70 calibrated compounds over 32 weeks under
three different storage conditions: room temperature with day-
light, room temperature in the dark, cool and dark in the refriger-
ator. Most compounds were observed to undergo only minor
changes during the testing period. While some compounds chan-
ged signicantly, such as vinyl-guaiacol, vinyl-syringol, and 3-hy-
droxy-5,6-dihydro-(4H)-pyran-4-one and so on. Cooling bio-oils
could delay but could not prevent polymerization reactions. Fratini
et al. [22] illustrated that the fundamental process in the ageing of
bio-oils was the aggregation of pyrolytic lignins. The process con-
tinued until the heaviest lignin-rich fraction separated out of the
oil matrix as a viscous sludge.
3.12.2. Thermal stability of bio-oils
At elevated temperatures, ageing reactions will be accelerated.
Four stages can be observed during heating of bio-oils: thickening,
phase separation, gummy formation from the pyrolytic lignins (at
around 140 C), and char/coke formation from the gummy phase at
higher temperatures [25]. Boucher et al. [32] treated a bio-oil sam-
ple at 50 and 80 C, respectively, to nd out that the whole proper-
ties of the bio-oil were signicantly altered at 80 C, while no
signicant variations were observed for the bio-oil kept at 50 C
for a week. Chaala et al. [40] investigated the thermal stability of
the bio-oil rich in extractives, and found that the ageing rate of
the top phase was less pronounced than that of the bottom phase.
Moreover, they pointed out that the increase in molecular weight
for maintaining the bio-oil for a week at 80 C was equivalent to
maintain the sample for 1 year at room temperature. Thus, deter-
mining the ageing properties of bio-oils very quickly was possible
by maintaining them at elevated temperatures. Prez et al. [41]
studied the thermal stability of a bio-oil sample in the presence
of stainless steel and copper at 80 C. They found that contacting
of metal strips with the bio-oil did not affect much of the bio-oil
ageing process during the test period of 264 h.
The stability of bio-oils can be determined in terms of the
increasing rates of viscosity and/or water content. The proposed
method is to measure the viscosity (20 and 40 C, respectively)
and water content of bio-oils before and after storage at (1) 80 C
for 6 h, (2) 80 C for 24 h and (3) 50 C for 7 days [23].
3.13. Distillation and thermogravimetric property
The pyrolysis vapors are not true vapors, but are mixtures of
true vapors and many micron-sized droplets (aerosols). Many
non-volatiles will be formed during the condensation process.
Q. Lu et al. / Energy Conversion and Management 50 (2009) 13761383 1379
Therefore, once pyrolysis vapors are condensed as bio-oils these
cannot be totally distilled to be vapors.
In view of atmospheric distillation, bio-oils start boiling below
100 C and stop at 250280 C leaving 3550 wt% of residues.
The non-volatile residue obtained in vacuum distillation will be
less than that obtained in atmospheric distillation for the same
bio-oil. This is because heating bio-oils during atmospheric distil-
lation will cause signicant polymerization reactions to form
non-volatile large molecules [29].
Thermogravimetric analysis (TGA) is a type of testing that is
performed on samples to determine the changes in weight in rela-
tion to changes in temperature. It is widely used to characterize the
evaporation, thermal decomposition and combustion properties of
bio-oils. The weight loss process of bio-oils in inert atmospheres
can be divided into two stages: the evaporation of light volatiles
(<150200 C) and the subsequent thermal decomposition of
unstable heavier components (<350400 C). In the case of the
TGA tests performed in air, the weight loss of bio-oils will undergo
three stages. The rst two stages are similar to those in inert atmo-
spheres and the third stage is the combustion of chars formed in
the rst two stages (>400 C). The oxygen will participate in the
second and third stages. It has been validated that oxygen can react
with bio-oils in the second stage to form lms outside the liquids.
These lms would prevent the vapor from evolving [33,34].
Branca et al. [42,43] studied the relationship between the
chemical compositions of four bio-oils (provided by BTG, Dynamo-
tive, Ensyn and Pyrovac) and their thermogravimetric behaviors in
air. The results indicated that the total amounts of volatiles
released from different bio-oils agreed well with the contents of
chemical compounds presenting boiling points in the correspond-
ing range. Based on the measured curves, they proposed a devola-
tilization mechanism based on the introduction of eight lumped
classes of volatile products and a corresponding number of parallel
reactions.
It is essential to note that TGA tests are usually conducted at
low heating rates (130 C/min). They differ greatly fromthe actual
combustion process. Therefore, TGA tests can only be treated as the
rst step to know a fuels evaporation, decomposition and combus-
tion kinetics.
3.14. Atomization property
Atomization is the process of breaking a liquid into small
droplets for spray combustion. Various ways have been developed
to generate sprays with the basic principle of a high relative
velocity between the liquid and the surrounding air. The spray
quality is characterized by the parameters of droplet size, droplet
velocity and spray angle. It is determined by atomization condi-
tions, fuel properties and atomizer conguration. The spray prop-
erties will strongly inuence the operation performance of the
thermal devices. In regard to the liquid properties, viscosity and
surface tension are the most important parameters. The droplet
size of the spray increases with the viscosity and surface tension
of the liquid.
The viscosity and surface tension of bio-oils are higher than
those of light petroleum fuels. Thus, favorable atomization of
bio-oils requires strict conditions, i.e. bio-oil preheating to reduce
viscosity and/or high atomization pressures. Chiaramonti et al.
[44] atomized a bio-oil sample with a standard nozzle and mea-
sured the droplet size distribution of the bio-oil spray. They found
that with the preheating of bio-oil to 80 C, the Sauter mean diam-
eter (SMD) of the droplets could be controlled below 50 lm at
pressures higher than 0.6 MPa. A correlation was then concluded
for the prediction of the SMD of bio-oil sprays:
SMD 599:2 FN
0:393
DP
0:418
c
0:251
r
0:277
where FN is the ow number, P is the pressure, and r is the surface
tension. SMD data calculated by this empirical formula agreed well
with the experimental results.
3.15. Ignition property and cetane number
Bio-oils are hard to be ignited. It is inherent to their chemical
compositions. The water in bio-oils is partly responsible for the
difculty in ignition due to its high latent heat of vaporization.
As a result, more energy is required to ignite bio-oils than petro-
leum fuels. At present, bio-oils are usually ignited with the help
of pilot ames, or after the addition of ignition improvers, or with
the preheating of combustion chambers or combustion air.
Cetane number is a parameter that expresses the ignition qual-
ity of a liquid fuel. It is a measure of the readiness of a fuel to auto-
ignite when injected into a diesel engine. A high cetane number
means a low ignition delay period before combustion. The typical
cetane number of diesel oils is around 48. Petroleum fuels with
low cetane number are known to cause rude operation and pis-
ton-knocking problems. However, cetane number of bio-oils is
hard to be measured because pure bio-oils are hard to be ignited
in conventional engines. Ikura et al. [45] proposed a method to cal-
culate the cetane number of bio-oils. They prepared bio-oil/diesel
emulsions with different bio-oil concentrations and measured
their cetane number values. The cetane number of the bio-oil em-
ployed in the tests was then calculated by linear interpolation as
5.6.
Shihadeh and Hochgreb [46] investigated the ignition delay of
two bio-oils (from Ensyn and NREL) in a high-speed diesel engine.
The two bio-oils demonstrated much greater apparent ignition
activation energies than No. 2 diesel oil. Hence, they could not be
auto-ignited without the preheating of combustion air. Further-
more, Shihadeh and Hochgreb [47] examined the relationship
between the pyrolysis conditions and the combustion characteris-
tics of the bio-oils. The bio-oil from NREL exhibited better ignition
performance than the bio-oil from Ensyn. It could be attributed to
the fact that the bio-oil from NREL had lower water content and
smaller average molecular weight.
3.16. Combustion property
3.16.1. Combustion fundamentals
The fundamental combustion properties of bio-oils can be re-
vealed by the combustion tests performed on single bio-oil drop-
lets. In situ video imaging systems are equipped with the test
facilities to allow direct observation of the combustion behaviors
of bio-oil droplets. The tests can be performed in two ways by
employing a bre-suspended single droplet or a stream of free-
falling monodispersed droplets. The main advantage of the rst
way is that it allows simultaneous measuring of the droplet tem-
perature when recording the changes of the droplet. It also allows
studying the combustion behaviors of liquid fuels at high pres-
sures. The main disadvantages are that the minimum droplet size
is limited by the bre diameter, and the presence of bre will inu-
ence the combustion of the liquid. The merits and demerits of the
second way are just opposite to those of the rst way.
The earliest combustion tests of bio-oil droplets were con-
ducted in Sandia National Laboratory [4850]. Streams of monodi-
spersed droplets were injected into a laminar ow reactor. The
experimental conditions were as follows: droplet diameter of
about 300 lm, reactor temperature of 1600 K and O
2
concentra-
tions of 1433%. The results showed that the combustion of bio-
oil droplets underwent several stages followed by droplet ignition,
quiescent burning, microexplosion, disruptive sooty burning of
droplet fragments, formation and burnout of cenosphere particles.
While combustion of the petroleum distillate oil droplets exhibited
1380 Q. Lu et al. / Energy Conversion and Management 50 (2009) 13761383
only quiescent, sooty burning from ignition through burnout under
the same conditions. The combustion of bio-oils could be charac-
terized by two unique features: the microexplosion and the incli-
nation of forming carbonaceous particles. The microexplosion of
bio-oils had great impacts on the heat release rate, droplet burning
time and the extent of cenosphere formation.
Calabria and Alessio [24,51,52] in Istituto Motori of Italy carried
out lots of studies on the combustion behaviors of bre-suspended
single bio-oil droplets. The droplet size varied between 300 and
1100 lm and the furnace temperature changed in the range of
4001200 C. The droplets were observed to undergo initial heat-
ing, swelling and microexplosion before ignition. During this stage,
the temperaturetime curves showed two zones with constant
temperatures (100 and 450 C), which corresponded to the evapo-
ration of light volatiles and the thermal cracking of unstable com-
ponents, respectively. The droplets were ignited at around 600 C.
The combustion of the droplets started with an enveloping blue
ame. Then, the ame developed a yellow tail with its size increas-
ing, which indicated the formation of soot. After that, the ame
shrank and extinguished, and the remaining solid carbonaceous
residues burned leading to the formation of ashes.
Prez et al. [53] also studied the combustion behaviors of bio-oil
droplets. Streams of monodispersed droplets (5862 lm) were in-
jected into a laminar entrained ow reactor in both inert Ar and
ArO
2
mixtures atmospheres (O
2
concentrations of 2050%). The
furnace wall temperature was maintained at 700 and 800 C. The
results indicated that the formation of bubbles inside the droplets
was inuenced by the heat transfer rate. In addition, no microex-
plosion was observed under the test conditions.
3.16.2. Evaporation fundamentals
During the spray combustion of liquid fuels, most droplets
evaporate in a vapor cloud rather than burning individually with
sufcient oxygen supply. Therefore, it is necessary to study the
evaporation properties of bio-oil droplets.
Hallett and Clark [54] investigated the evaporation behaviors of
bre-suspended bio-oil droplets (1.41.8 mm) in the nitrogen
atmosphere. Phenomena similar to those observed in the tests
were observed in the combustion tests before ignition of the drop-
lets. The droplets started with initial evaporation, bubbling and
disruption, swelling and collapsing. As time passed by, the droplets
became more and more viscous and the bubbling became less in-
tense. Then, the droplets went into erratic motions, which sug-
gested the happening of polymerization reactions. Finally, the
droplets became irregular and highly porous solid chars.
Allessio et al. [51] carried out the evaporation tests of monodi-
spersed droplets (50100 lm) in a furnace (ranging between 300
and 850 C). Nitrogen was used as the carrier gas. The solid resi-
dues collected at the exit of the furnace were observed to have
two different morphologies: compact, mechanically resistant
spheres with a typical diameter of 1040 lm, and fragile, glasslike
cenospheres with thin walls and menisci with a diameter of 100
200 lm. Similar phenomena were also observed by Prez et al. [53]
who pointed out that the morphologies of solid residues were
inuenced by the frequency of the droplet generation.
3.16.3. Spray combustion of bio-oils in thermal devices
As can be predicted, the spray combustion behaviors of bio-oils
will differ considerably from those of petroleum fuels due to the
vast differences between their combustion fundamentals. It is dif-
cult to ignite bio-oils, but once ignited, they can burn steadily.
The adiabatic ame temperature of bio-oils is 17002000 K com-
pared with that of standard fuels, which is 22002300 K [52]. In
comparison with diesel oils, the combustion of bio-oils exhibits
shorter but wider ames under the same mass ow rates of the
fuels. Moreover, bio-oil ames were very luminous, suggesting
the presence of large amounts of particles that radiated strongly.
This was believed to be benecial for radiant heat transfer for
bio-oils to be used in kilns and boilers [55].
Presently, spray combustion of bio-oils has been studied in boil-
ers, kilns, diesel engines, gas turbines and Stirling engines. Bio-oils
can be used singly, in a duel fuel mode with petroleum fuels, or in
mixtures with methanol, ethanol, diesel (with surfactants) or other
fuels. The current progress in the application of bio-oils in thermal
devices has been reviewed by Czernik and Bridgwater [56] and
Chiaramonti et al. [57].
3.17. Lubricity
Lubricity of a liquid fuel is the ability to reduce wear and fric-
tion. During the combustion process of a liquid fuel, the fuel injec-
tion system should be lubricated primarily by the fuel itself. Fuels
of poor lubricity will cause signicant wear problems. Lubricity of
fuels is determined by their chemical compositions. For most
petroleum fuels, viscosity can be used as an indicator of a fuels
ability to provide wear protection. However, bio-oils are totally dif-
ferent from petroleum fuels. Therefore, it is difcult to predict the
lubricating properties of bio-oil based fuels just by comparison of
their viscosities with those of petroleum fuels.
Oasmaa et al. [25] measured the tribological properties of a bio-
oil sample with two test machines: a high frequency friction tester
and a four-ball wear tester. The rst tester was a totally open sys-
tem. Heat generated during friction would cause evaporation of
the bio-oil and then disturb the measurement. Hence, the tester
was unable to determine the tribological properties of the bio-oil.
The second tester appeared to be suitable. The wear scar diameter
(WSD) of the bio-oil was determined as 0.50.7 mmcompared with
that of the diesel fuel under the same conditions (load 392 N, speed
1430 rpm and test duration 1 h), which was 1.7 mm. The results
indicated that the bio-oil possessed some lubricity.
Lu et al. [58] determined the tribological properties of a bio-oil
sample pyrolyzed from rice husk with a four-ball tester. The maxi-
mum non-seizure load (P
B
value) was measured as 470 N. The WSD
and average friction coefcient values were determined as 0.57 mm
and 0.082 (load 196 N, speed 1450 rpm and test duration 30 min).
3.18. Acidity and corrosion property
Bio-oils usually contain about 712 wt% acids, and have a pH of
24 and an acid number of 50100 mg KOH/g. It has been reported
that bio-oils are very corrosive to aluminum, mild steel and nickel-
based materials. The corrosion rates would be enhanced at
elevated temperatures or with the increase in water contents of
bio-oils [59]. The corrosion-resistant materials include stainless
steel, cobalt materials and various polymers such as polyethylene,
polypropylene and polyester resins.
Fuleki [60] tested the corrosion of a bio-oil sample produced
from Ensyn to aluminum, brass, mild steel and austenitic steel.
The results indicated that brass and austenitic steel would not be
affected by bio-oil. Darmstadt et al. [61] tested the corrosion of
the SWBR-derived bio-oil to aluminum, copper and austenitic steel
at 80 C, and analyzed the chemical changes of metal surface. The
results revealed that oxide and/or hydroxide were covered on all
the three metals after corrosion, but the layers on aluminum and
copper did not stop the underlying metals from further oxidation.
Whereas the stainless steel could be well protected by the compact
passive lm (Cr
2
O
3
) formed on the surface.
3.19. Toxicity
The establishment of large-scale fast pyrolysis plants and
the handling of bio-oils will expose a large number of people to
Q. Lu et al. / Energy Conversion and Management 50 (2009) 13761383 1381
potential health hazards. Gratson [62] initiated toxicological test-
ing of two wood bio-oils produced from the vortex pyrolysis reac-
tor in NREL. The tests consisted of eye irritation, dermal and
inhalation acute toxicity as well as Ames mutagenicity. The results
showed that the two bio-oils could cause serious eye damage by
direct liquid contact or contact with airborne droplets. The ten-
dency of the bio-oils to penetrate intact skin and cause internal or-
gan damage was not observed. Inhalation of high concentrations of
bio-oils would result in lung damage. In addition, the bio-oils
showed mutagenic abilities in the Ames bacterial mutation assay.
Diebold [63] pointed out that greatest acute toxic threat of bio-
oils came from aldehydes and unsaturated oxygenates, followed by
furans. However, this toxicity might decrease with time due to the
instability of these compounds. According to the known com-
pounds and their concentrations in bio-oils, the projected acute
oral toxicity of bio-oils would be around 700 mg/kg of body
weight. Toxicity of bio-oils to skin was low, but eyes were sensitive
to bio-oils with probable severe corneal damage. The chronic tox-
icity of bio-oils was unclear with one result indicating no tumor
promoting ability and the other result showing the mutagenicity
or chromosome damage.
The presence of polycyclic aromatic hydrocarbons (PAHs) in
bio-oils deserves enough attention due to their potential role in
the incidence of cancer. It has been conrmed that the formation
of PAHs during the pyrolysis of biomass is closely related to the
pyrolysis temperatures. Fortunately, bio-oils produced at the pyro-
lysis temperature of around 500 C usually contain small amounts
of PAHs [63,64]. For instance, Tsai et al. [65] analyzed the PAHs in
bio-oils derived from agricultural wastes by using induction-heat-
ing at 500 C. The results indicated that PAHs in bio-oils were pri-
marily dominant in the low molecular weight PAHs, such as
naphthalene (1.102.45 mg/L) and acenaphthene (0.727.61 mg/
L). However, it is evidenced that a lot of PAHs will be formed dur-
ing the upgrading of bio-oils via catalytic cracking with zeolite cat-
alysts [66,67]. This seems to be a serious problem.
Girard and Blin [68,69] accomplished the Biotox project to com-
pletely assess the toxicity and biodegradability of representative
bio-oils from different processes and temperatures. The aim of
the project was to establish a denitive Material Safety Data Sheet
(MSDS) and a guide of bio-oil production conditions to avoid or
minimize the formation of toxic products. A total of 21 bio-oils
from a wide variety of technologies, feedstocks and production
conditions were measured for their impacts on the environment
and humans. Detailed results are available at the PyNe website.
For a general overview of the results, bio-oils appeared to offer
no eco-toxicological effects, while they exhibited slight mutagenic
effects, but overall these appeared to be less harmful than conven-
tional diesel fuels.
3.20. Biodegradability
During the production, storage, transport and application of
bio-oils, there are risks of accidental leaks of bio-oils. Biodegrad-
ability is the dominant way for the environmental transformation
of most chemicals. Piskorz and Radlein [70] initiated the respiro-
metric biodegradation tests of bio-oils in both aquatic and soil
environments. The bio-oils were inoculated with Returned Acti-
vated Sludge. The biochemical oxygen demand was measured over
5 days. The results indicated that bio-oils were biodegradable. The
biodegradation rates and patterns were similar to, but substan-
tially higher than those of diesel fuels. In addition, the biodegrad-
ability of bio-oils could be enhanced by neutralization with bases
such as lime.
The assessment of the biodegradability properties of bio-oils
was one of the tasks of the Biotox project mentioned above. Blin
et al. [71] examined the aerobic biodegradability properties of
various bio-oils in fresh water by using the Modied Strum (OECD
301B) test method. The bio-oils were inoculated with activated
sludge freshly collected from the aeration tank of the sewage
treatment plant. The results indicated that bio-oils degraded very
fast in the rst 8 days. They exhibited similar shaped curves with
4150 wt% biodegradation after 28 days, compared with only
24 wt% biodegradation of a EN 590 diesel fuel.
4. Conclusions
Fast pyrolysis of biomass to produce bio-oils is still in its early
stage of development. This technology has strong adaptability to
biomass resources, and it offers a convenient way to produce liquid
fuels with high bio-oil yields and low production costs.
Bio-oils are low-grade liquid fuels when compared with petro-
leum fuels. The poor fuel properties include the complex multi-
phase structures, high contents of oxygen, water, solids and ash,
low heating values, high viscosity and surface tension, chemical
and thermal instability, low pH values, and poor ignition and com-
bustion properties. In spite of these poor fuel properties, bio-oils
also have some promising properties. They usually possess some
lubricity and they are less toxic and more biodegradable than
petroleum fuels.
For the commercialization of bio-oils as liquid fuels, fuel speci-
cations need to be established as in the case of petroleum fuels.
Currently, there are no nationally or internationally recognized fuel
specications for bio-oils, but preliminary specications have been
proposed [8]. These specications cover a range of applications in
different thermal devices which have different requirements on
the fuel properties of bio-oils. At present, many bio-oils cannot
meet the fuel specications, and therefore, they cannot be accepted
commercially. Further work is required to be done in the future to
improve the properties of bio-oils.
Acknowledgements
The supports from the National Basic Research Program of
China (No. 2007CB210203) and the National Key Technologies
R&D Program (No. 2007BAD34B02) are greatly appreciated.
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