Article

pubs.acs.org/EF

Phase Behavior and Fuel Properties of Bio-Oil/Glycerol/Methanol

Blends
Mingming Zhang and Hongwei Wu*

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Publication Date (Web): July 9, 2014 | doi: 10.1021/ef501176z

School of Chemical and Petroleum Engineering, Curtin University, GPO Box U1987, Perth 6845, Western Australia, Australia
ABSTRACT: This study investigates the phase behavior and fuel properties of a series of bio-oil/glycerol/methanol blends. The
results show that even though glycerol has a poor solubility in bio-oil, homogeneous bio-oil/glycerol/methanol fuel blends can be
prepared with appropriate amount of methanol addition. Compared to the bio-oil or glycerol alone as a fuel, the bio-oil/glycerol/
methanol blends have improved fuel properties (higher heating value, lower viscosity, and lower surface tension, etc.). Taking
into safety consideration during storage and transportation of a fuel and the possible ratio of glycerol to methanol that may be
obtained from biodiesel production process, potential feasible compositions of the bio-oil/glycerol/methanol blends (bio-oil
70 wt %; glycerol 20 wt %; methanol 10 wt %) are recommended as burner fuel for combustion applications. Further
accelerated aging experiments of selected fuel blends in the recommended composition range indicate that the fuel blends
experience decreases in the viscosity and total acid number and an increase in water content of the fuel blends upon long-term
storage.

1. INTRODUCTION
Biodiesel is considered to be an alternative liquid transport fuel
and has attracted substantial research and development in
recent years.16 The rapid growth of biodiesel industry has
become the major driver for the supply of glycerol.13 The
annual global biodiesel production is expected to reach 37
billion gallons by 2016, leading to an annual production of 19
million tons of glycerol as a huge accumulated stockpile.4,5
Therefore, the management and utilization of such a large-scale
waste stream is of critical importance to not only the economic
performance of the value chain but also the environmental
sustainability associated with waste disposal.5,7,8
Combustion is considered as a key technology for glycerol
utilization for several advantages including drastic volume
reduction (glycerol converted into ue gas), easy integration
into biodiesel production process (for on-site heat supply,
hence, reducing the dependence on fossil fuel), large-scale
application and exibility to directly accommodate glycerol
product without rening.2,913 Unfortunately, direct combustion of glycerol faces some challenges due to several undesirable
fuel properties. For example, glycerol has high viscosity so that
it is dicult to pump, atomize, ignite, and even maintain a
ame.12,14 Therefore, incomplete combustion often occurs,
leading to the formation of unburned toxic products that are of
safety and pollution concerns.11,14,15 Additionally, without
rening, the crude glycerol from biodiesel production process
may contain high concentrations of certain impurities that must
be taken into consideration. These impurities include high
content of inorganic species (primarily Na (13 700 ppm) and
P (1530 ppm)), which are excessive for direct combustion
due to ash-related issues,1012 and high alcohol content (up to
50%) that may cause major safety concerns during storage and
transportation.16
One possibility to address the challenges with direct
combustion of glycerol and mitigate the associated problems
is to mix glycerol with other fuels to make fuel blends. For
example, a previous study10 blended glycerol with yellow grease
2014 American Chemical Society

for combustion, although the result was not satisfactory mostly

due to the diculties in maintaining a homogeneous mixture.
Therefore, there is a great need to develop fuel blends with
alternative fuels. A good choice is bio-oil, which is a renewable
fuel produced from biomass fast pyrolysis and can nd various
potential applications.1724 Bio-oil contains both polar and
nonpolar compounds25 so that blending glycerol with bio-oil
may produce feasible fuel blends.
Therefore, the motive of this study is to investigate the
possibility of blending glycerol with bio-oil for fuel applications.
Considering the presence of alcohol (typically methanol) in the
crude glycerol from biodiesel production system,9,2629 this
study focuses on the fundamental research into the phase
behavior, rheological properties, fuel properties, and stability of
bio-oil/glycerol/methanol blends. The key objectives are to
work out the feasible range for producing and formulating the
bio-oil/glycerol/methanol blends.

2. EXPERIMENTAL SECTION
2.1. Materials. The bio-oil sample used in this study was supplied
by a commercial supplier who used a pilot-scale pyrolysis reactor for
producing the bio-oil from pine wood under fast pyrolysis conditions
at 500 C. The bio-oil was stored in a refrigerator prior to experiment.
Glycerol (G5516) and methanol (analytical grade) were purchased
from Sigma-Aldrich and Chem-Supply, respectively. Typical properties
of the bio-oil as well as glycerol and methanol used in this study are
listed in Table 1.
2.2. Preparation of Bio-Oil/Glycerol/Methanol Blends.
Solubility of the bio-oil/glycerol/methanol blends was examined by
preparing a set of binary bio-oil/glycerol mixtures with various
proportions, followed by progressively adding small amounts of
methanol into the mixtures until a homogeneous blend is observed
under optical microscope (Olympus SL 60/61). As bio-oil itself is a
micro emulsion30 and the dark color can mask the phase separation
Received: May 23, 2014
Revised: June 28, 2014
Published: June 30, 2014
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3. RESULTS AND DISCUSSION

3.1. Phase Behavior of Bio-Oil/Glycerol/Methanol
Ternary System. Solubility of the bio-oil/glycerol/methanol
systems is determined via experiments and presented in a
ternary phase diagram. As shown in Figure 1, the results lead to

Table 1. Fuel Properties of the Bio-Oil, Glycerol, and

Methanol Used in This Study
bio-oil

glycerol

methanol

ultimate analysis (wt %, dafa)

C
H
N
Ob
water content (wt %, arc)
viscosity (25 C, cSt)
surface tension (25 C, mN/m)
density (25 C, g/cm3)
HHV (MJ/kg)g
TANh (mg NaOH/g bio-oil)

42.64
7.55
0.22
49.59
23.5
178.2
35.70
1.21
18.9
49.1

39.13
8.70

37.50
12.5

52.17
n.d.d
694.4e
62.87
1.26e
18.7
n.d.d

50.00
n.d.d
0.8e
22.35f
0.78f
20.8
n.d.d

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Dry and ash free basis for bio-oil, calculated for glycerol and
methanol. bBy dierence. cAs received basis. gCalculated high heating.
d
Not determined. hTotal acid number. eValue reported in ref 42.
f
Value reported in ref 45.

line, solubility of the bio-oil/glycerol/methanol mixtures is determined

by obtaining a homogeneous microscopic picture similar to that of the
bio-oil. The solubility tests were performed at room temperature (25
C), and a magnetic stirrer was used to ensure immediate and
complete mixing of these components. The relative standard error for
this solubility determination method is within 5% of methanol
composition in the blends (on a weight basis).
2.2. Experiments on Accelerated Aging of Bio-Oil/Glycerol/
Methanol Blends. Accelerated aging test was conducted according to
a method stated elsewhere.31,32 Briey, selected samples were sealed in
clean Pyrex glass containers and placed in an oven at 80 C for 24 h,
which is equivalent to aging at room temperature for one year.33 Upon
the completion of the experimental program, the samples were cooled
rapidly in an ice bath. The mass of these samples before and after
heating were then recorded to check volatile loss, which showed there
was no measurable mass loss for all samples studied. The aged samples
together with the corresponding control samples were then subjected
to subsequent analysis.
2.3. Sample Characterization and Analysis. The ultimate
analysis of the bio-oil sample was conducted using a PerkinElmer
CHN/O analyzer. The higher heating value (HHV) of the bio-oil was
calculated based on the elemental composition according to a method
reported by Sheng et al.34 The surface tension of the fuel samples was
determined following Wilhelmy method on a surface tensiometer
(KSV Sigma 701) tted with a round platinum rod probe.23 The bulk
density was measured by a pycnometer (25 mL) with standard
deviations less than 1%. Both surface tension and density measurements were carried out at room temperature (25 C). Water content
and total acid number (TAN) of the fuel samples were determined
using a Karl Fisher titrator (Mettler V30) and an acidbase titrator
(MEP Oil Titrino plus 848), respectively, following methods detailed
elsewhere.35 Fourier transform infrared (FTIR) spectroscopic analysis
was performed to analyze the functional groups of selected samples
using an attenuated total FTIR spectrometer (PerkinElmer Spectrum
100). Peak height ratios were calculated for quantitative analysis
according to a method used previously.32
The rheological property of selected samples was analyzed based on
a method stated elsewhere.35,36 Briey, steady shear tests were carried
out to investigate the ow behavior of samples using a Haake Mars II
Rheometer tted with a coneplate sensor (C35/4 Ti) and a
thermocontroller (Haake TC501). Proper amount of sample (no less
than 0.8 mL) was loaded for analysis each time, and the measurement
temperature was kept at 25 C to avoid intensive evaporation of light
component in the mixture (i.e., methanol). The viscosity of samples
was averaged from at least 50 data points after Newtonian behavior
was observed.

Figure 1. Phase diagram of bio-oil/glycerol/methanol ternary system

(based on wt %).

some important observations. First, either bio-oil or glycerol is

miscible with methanol. This observation is consistent with
reports in open literature;25,37,38 both bio-oil/methanol and
glycerol/methanol binary systems are single-phase solutions.
Second, for the binary system of bio-oil/glycerol, no
measurable amount of glycerol or bio-oil was found dissolvable
in each other. The results are opposite to the initial expectation
that some glycerol may be soluble in bio-oil as the water
present in bio-oil may be miscible with glycerol.38 The results
in Figure 1 show that bio-oil and glycerol blends do not form
homogeneous solution. Third, the phase conversion line, which
represents the minimum methanol required for making the
initial glycerol/bio-oil mixtures in homogeneous solutions,
clearly divides the ternary diagram into two regions. Blends
with compositions below the phase conversion line are not
homogeneous. Addition of more methanol into the system can
greatly improve the solubility of glycerol in bio-oil and vice
vasa.
The mechanism possibly responsible for the insolubility of
glycerol in bio-oil, and the function of methanol addition, is
sketched in Figure 2, in which the presentation of the bio-oil

Figure 2. Schematic diagrams illustrating the possible solubility

mechanism of (a) binary bio-oil/glycerol system without methanol
addition and (b) ternary bio-oil/glycerol/methanol system.
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structure follows the convention used previously (see GarciaPerez et al.30). As shown in Figure 2a, in absence of methanol,
glycerol molecules tend to attract to each other rather than
disperse in bio-oil structure, likely due to the entangled
structure of glycerol and the network structure of bio-oil. The
strong intermolecular force (hydrogen bonding) of glycerol and
its elongated shape make glycerol become entangled,14,39 and
thereby dicult to disperse unless appropriate amount of
compound(s) with comparable intermolecular force could be
engaged.40 Although it is possible for some components of biooil (e.g., water) to be individually soluble with glycerol, such
accessibility might be low due to a network structure formed by
some heavy compounds (e.g., oligomers) in bio-oil.30,41 On the
other hand, methanol as an amphiphilic compound could help
the dispersion of glycerol as illustrated in Figure 2b. Therefore,
with the addition of suitable amounts of methanol, a
homogeneous mixture can be formulated and prepared. This
is also clearly evidenced by the microscopic photographs of
glycerol/bio-oil mixtures before and after methanol addition as
shown in Figure 3.
3.2. Fuel Properties and Feasible Range of Bio-Oil/
Glycerol/Methanol Blends. Fuel properties of selected biooil/glycerol/methanol blends (Blend 1Blend 6) on the phase
conversion line in Figure 4 are shown in Table 2. It can be seen
that the HHV of the mixtures slightly increased compared to
the bio-oil or glycerol alone, which is due to the high HHV of

methanol (see Table 1) present in the system. The viscosity of

the blends is ranged from 22.5 to 130.1 cSt (at 25 C), which is
signicantly lower than that of the bio-oil (178.2 cSt, 25 C) or
especially glycerol (694.4 cSt, 25 C)42 alone. This viscosity
range is well within the specication of viscosity for No. 4 to
No. 6 fuel oil (26.4194.0 cSt, 38 C).43 The density and
surface tension of the fuel blend 16 are ranged from 1.20
1.07 g/cm3 and 35.0233.21 mN/m, respectively; they are
close to or slightly lower than those of the bio-oil (1.21 g/cm3
and 35.70 mN/m, respectively) but signicantly lower than
those of glycerol especially with regard to the surface tension
(62.87 mN/m). Viscosity, density, and surface tension are three
properties most related to the atomization or spray behavior of
fuel. Ohnesorge number calculated from the value of these
three properties is an important parameter for predicting the
Sauter mean diameter (SMD) of a spray droplet, thereby
estimating spray or atomization quality.44 The Ohnesorge
numbers of the mixtures, calculated following a method
detailed elsewhere,23 are also listed in Table 2. The low
Ohnesorge numbers of the blends (0.52.9) compared to the
bio-oil (4.0) and glycerol (11.1) alone implies improved
atomization quality of the blend. Overall, the fuel properties of
the bio-oil/glycerol/methanol blends even along the phase
conversion line are better than those of the bio-oil or glycerol
alone, suggesting that these fuel blends are suitable for burner
use. The improvement of fuel properties is most likely due to
the addition of methanol (with a viscosity of 0.8 cSt and surface
tension of 22.35 mN/m at 25 C42,45). Therefore, for the
mixtures above the phase conversion line with higher methanol
percentage, the fuel properties are expected to be better.
However, the high proportion of methanol in the fuel mixture
may raise other concerns as discussed below.
First, ash point needs to be considered for safe storage and
handling of fuels. Flash point of a mixture system is largely
inuenced by the component with lowest ash point.46 In the
case of the bio-oil/glycerol/methanol system, the ash point of
methanol (11 C) is much lower than that of glycerol (160 C)
and bio-oil (40110 C);47 therefore, the ash point of the
mixture will be signicantly aected by the percentage of
methanol. It is well-accepted that addition of up to 10%
methanol can improve bio-oil properties without causing
signicant decline in fuel ash point.27,47,48 Therefore, likewise,

Figure 3. Representative microscopic photographs of a bio-oil/

glycerol mixture before and after methanol addition. Panel (a) is for a
bio-oil/glycerol blend with composition (based on wt %) of 78.8%
bio-oil and 21.2% glycerol. Panel (b) is for a bio-oil/glycerol/methanol
blend with composition (based on wt %) of 70.7% of bio-oil, 19.0% of
glycerol, and 10.3% of methanol.

Figure 4. Potential feasible range (based on wt %) of bio-oil/glycerol/methanol blend. Lines 1, 2, and 3 represent blends with xed glycerol-tomethanol ratios of 0.5:1, 1.25:1, and 2:1, respectively. Line 4 represents blends with xed methanol percentage of 10%. The numbers 16 represent
the fuel blends (Blend 16) on the phase conversion line selected for analysis in Section 3.2. The numbers 7 and 8 represent Blend 7 and Blend 8
selected from the feasible range for accelerated aging tests in Section 3.3.
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Table 2. Fuel Properties of Selected Fuel Blends with Compositions Located on Phase Conversion Line (wt %, Bio-Oil/
Glycerol/Methanol)
elemental analysis (wt %)a
fuel blends
blend
blend
blend
blend
blend
blend

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1
2
3
4
5
6

(93.8/4.3/1.9)
(84.2/10.8/5.0)
(63.8/22.8/13.4)
(46.8/30.1/23.1)
(24.7/42.7/32.6)
(10.8/51.1/38.1)

heating value

viscosity

density

surface tension

Ohnesorge
numbera

Ob

HHV
(MJ/kg)a

(cSt, at 25 C)

(g/cm3, at 25 C)

(mN/m, at 25 C)

(dimensionless)

42.39
42.00
41.15
40.40
39.47
38.89

7.69
7.92
8.47
9.03
9.65
10.02

49.72
49.90
50.24
50.47
50.83
51.07

0.20
0.18
0.14
0.10
0.05
0.02

18.90
18.95
19.08
19.24
19.40
19.48

130.1
90.3
40.3
31.0
36.2
22.5

1.20
1.19
1.15
1.11
1.05
1.07

35.02
34.96
33.33
33.90
32.99
33.21

2.9
2.0
0.9
0.7
0.8
0.5

Calculated value. bBy dierence.

homogeneous bio-oil/glycerol/methanol blends. Such a feasible

range has the boundaries of three criteria lines (lines 1, 3, and 4
in Figure 4), that is, the lowest theoretically possible glycerolto-methanol ratio of 0.5:1, the highest glycerol-to-methanol
ratio of 2:1, and the recommended highest 10% methanol in
the blends.
3.3. Accelerated Aging of Bio-Oil/Glycerol/Methanol
Blends. In this section, two fuel blends (Blend 7, with
composition of 87.7% bio-oil, 7.5% glycerol, and 4.8%
methanol and Blend 8, with composition of 75.5% bio-oil,
14.6% glycerol, and 9.9% methanol) were selected from the
blend composition in the potentially feasible range in Figure 4
for studying the changes in fuel properties of the fuel blends
under accelerated aging correlating to one year storage at room
temperature. The composition of these two blends is listed in
Table 3. Figure 5 presents the ow behavior of the fuel blends
as well as the bio-oil before and after aging. Both of the blends
exhibit Newtonian behavior like the bio-oil does when shear
rate is greater than 30 s1. This observation is consistent with
previous studies on ow behavior of bio-oil;55 the presence of
glycerol and methanol in the blend did not change such ow
behavior. The changes in viscosity, water content, and TAN of
the fuel blends due to aging are illustrated in Figure 6, the
calculated water content and TAN of fuel Blend 7 and Blend 8
are obtained via direct addition, considering each value of
individual fuel compound and the percentage of each individual
compound in the fuel blend mixture.
The data in Figure 6 show that before aging, the viscosity,
water content and TAN of the bio-oil/glycerol/bio-oil blends
are all lower than those of the bio-oil blank. When comparing
the calculated value with the measured value before aging, it can
be seen that the decreases of water content and TAN in the
mixtures are due to the dilution of bio-oil by glycerol and
methanol. The decrease in the viscosity of the bio-oil/glycerol/
methanol blends compared to that of the bio-oil before aging is
due to the inuence of methanol. It is well-known that
methanol addition can signicantly decrease the viscosity of
bio-oil.18,27,47,56 Substantial viscosity reduction of glycerol upon
methanol addition was also reported.42
Additionally, Figure 6 shows that after aging, the viscosity,
water content, and TAN of the bio-oil blank did not experience
signicant change due to the long-term storage (over 12
months) prior to experiment, which is consistent with our
previous ndings.35 However, noticeable changes were found
for the bio-oil/glycerol/methanol blends (Blend 7 and Blend
8). The decrease of viscosity after accelerated aging (see Figure
6a) is likely due to the increase of water content (see Figure
6b). Both the increase in water content and the decrease in

no greater than 10% methanol in the glycerol/methanol/bio-oil

system is recommended for safety concerns. Unfortunately, it is
known that the available ash point test methods are not
suitable for bio-oil samples;49 the ash point tests were not
performed in this study.
Second, the ratio of glycerol to methanol can be considered
as such binary blend might be obtained from a biodiesel
production system, reducing the costs associated with glycerol
rening. Figure 4 shows that glycerol/methanol blends with a
ratio between 2:1 and 1.25:1 can be blended with bio-oil in
limited proportion (e.g., less than 20% for a ratio of 2:1) to
produce homogeneous bio-oil/glycerol/methanol blends. However, glycerol/methanol blends with a ratio higher than 2:1
cannot be mixed into the bio-oil for producing homogeneous
fuel blends, and those with a ratio lower than 1.25:1 can be
blended with the bio-oil in any proportion. In most of
commercial biodiesel production systems, molar ratios between
6:1 and 10:1 for methanol to triglycerides (i.e., oil or fat) are
commonly used,50 leading to a theoretical mass ratio of glycerol
to methanol being 1:10.4:1 after transesterication, which
means glycerol/methanol blend with such ratios can be mixed
with bio-oil in any proportion. However, this ratio may increase
in practice due to recovery of methanol and distribution of
methanol in biodiesel and glycerol after phase separation. Up to
80% of excess methanol may end up in glycerol phase,51,52
leading to a theoretically possible glycerol-to-methanol ratio of
1.25:10.5:1, and methanol recovery rate can vary. The higher
the methanol recovery, the higher the cost put into distillation
operation.53,54 Low recovery of methanol on the other hand
can lower the distillation cost and may enhance the purity of
the methanol recovered due to the low distillation temperature
that can be used. Suitable methanol recovery is a trade-o
between the economic benets of producing a bio-oil/glycerol/
methanol blend as a burner fuel and the costs associated with
methanol recycling and glycerol rening in the biodiesel
production system. Nevertheless, based on the assumptions
that the low bound of the methanol-to-triglyceride molar ratio
is 6:1, and 80% of excess methanol is left in glycerol layer after
separation, it is estimated that a maximum of 37.5% methanol
recovery can enable a glycerol/methanol blend with a ratio of
2:1 to be mixed with bio-oil in lower proportion (less than
20%) for producing homogeneous bio-oil/glycerol/methanol
blends. Similarly, at the upper bound of methanol-totriglyceride molar ratio of 10:1, the methanol recovery can be
up to 72.8%. Therefore, depending on the process conditions
and considering the aforementioned safety reason, a potential
feasible blend range (bio-oil 70%; glycerol 20; methanol
10%) can be obtained (see Figure 4) for producing
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Figure 5. Shear stress and viscosity of two bio-oil/glycerol/methanol

blends as a function of shear rate (at 25 C). Blend 7 is a bio-oil/
glycerol/methanol blend with composition (based on wt %) of 87.7%
bio-oil, 7.5% glycerol, and 4.8% methanol. Blend 8 is a bio-oil/
glycerol/methanol blend with composition (based on wt %) of 75.5%
bio-oil, 14.6% glycerol, and 9.9% methanol. Aging test was conducted
at 80 C for 24 h.

TAN (see Figure 6c) imply that there were chemical reactions
taking place during accelerated aging. Esterication between
acidic compounds in bio-oil and glycerol or methanol is most
likely responsible for the decrease of TAN and the increase of
water content. However, on the basis of the data in Figure 6, a
simple calculation as reported previously35 shows that the water
formed by esterication might only account for part of water
increase of the mixtures (25%). To further investigate the
possible reactions that occurred during aging, the changes in
functional groups of the fuel blends before and after aging were
studied via the comparison of FTIR peak height ratios
(according to a previous study32). Figure 7 presents the
FTIR spectra and peak height ratios for the fuel blends before
and after aging benchmarking against the blank bio-oil. Figure
7a shows that the locations of peaks in the FTIR spectra of all
fuel samples are similar to those of bio-oil reported
previously.32 Additionally, Figure 7b shows that after aging,
there is a decrease of peak at 1034 cm1 (representing primary
alcohol CH2OH) and also an increase at 3382 cm 1
(representing OH stretch) of Blend 7 and Blend 8, as results
of reactions consuming methanol and glycerol together with
water formation. Another noticeable change is in the CC
stretch represented by peak at 1646 cm1, suggesting the
formation of alkene or conjugate ketone.32 This is likely due to
glycerol dehydration (known to occur under acidic conditions
and high temperature57,58) that may also contribute to the
increase in water content of the fuel blends after aging.

Figure 6. Changes in viscosity (a), water content (b), and TAN (c) of
two bio-oil/glycerol/methanol blends before and after aging. Blend 7
is a bio-oil/glycerol/methanol blend with composition (based on wt
%) of 87.7% bio-oil, 7.5% glycerol, and 4.8% methanol. Blend 8 is a
bio-oil/glycerol/methanol blend with composition (based on wt %) of
75.5% bio-oil, 14.6% glycerol, and 9.9% methanol. Aging test was
conducted at 80 C for 24 h.

On the basis of the experiments carried out in this study, the

results suggest that it is possible to prepare homogeneous biooil/glycerol/methanol fuel blends. Compared with bio-oil or
glycerol alone as a fuel, the blend has improved fuel properties
in terms of heating value, viscosity, surface tension, and density
(see Section 3.2). The water content and acidity (i.e., TAN) of
the fuel blend can be improved compared to that of the bio-oil
due to dilution eect. Although fuel properties of the blends
may change during aging, the overall changes are positive (e.g.,
reduced viscosity and TAN). While the increase in water
content may result in reduction in heating value,18 the
increased water content of the fuel blend is still lower than
that of the bio-oil after accelerated aging (see Section 3.3).
Therefore, formulation and preparation of bio-oil/glycerol/
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Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS

REFERENCES

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M.Z. acknowledges the Chinese Scholarship Council (CSC)

and Curtin University for providing scholarships to partially
support her Ph.D. study, and a provider (who has chosen to
remain anonymous) for supplying the fast pyrolysis bio-oil
sample.

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Figure 7. FTIR spectra (a) and peak height ratio (b) of two bio-oil/
glycerol/methanol blends before and after aging, benchmarking against
those of the blank bio-oil. (a) FTIR spectra of (A) blank bio-oil, (B)
Blend 7 before aging, (C) Blend 7 after aging, (D) Blend 8 before
aging, and (E) Blend 8 after aging. Blend 7 is a bio-oil/glycerol/
methanol blend with composition (based on wt %) of 87.7% bio-oil,
7.5% glycerol, and 4.8% methanol. Blend 8 is a bio-oil/glycerol/
methanol blend with composition (based on wt %) of 75.5% bio-oil,
14.6% glycerol, and 9.9% methanol. Aging test was conducted at 80 C
for 24 h.

methanol blends may provide a potential strategy for utilizing

the surplus glycerol from biodiesel production process.

CONCLUSIONS
Although the solubility of glycerol in the bio-oil is poor,
homogeneous ternary bio-oil/glycerol/methanol blends can be
prepared with the aid of methanol addition. The fuel properties
of such blends, including heating value, viscosity, surface
tension etc., are improved compared to the bio-oil or glycerol
as an individual fuel. Considering safe storage and handling of a
fuel and the possible glycerol-to-methanol ratio that might be
obtained from biodiesel production system, blends with a
composition range (bio-oil 70 wt %; glycerol 20 wt %;
methanol 10 wt %) are recommended as potential burner
fuels. The accelerated aging tests of the fuel blends show that
the properties of the fuel blends can change upon long-term
storage, that is, noticeable decreases in viscosity and TAN
accompanied by an increase in the water content.

AUTHOR INFORMATION

Corresponding Author

*E-mail: h.wu@curtin.edu.au. Phone: +61-8-92667592. Fax:

+61-8-92662681.
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Energy & Fuels

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