Article

Cite This: Energy Fuels 2018, 32, 5115−5124 pubs.acs.org/EF

Bio-Oil Viscosity of Sisal Residue: Process and Temperature Influence

Luis G. G. Pereira* and Carlos A. M. Pires
Chemical Reaction Engineering Laboratory, PPEQ, Escola Politécnica, UFBA, Rua Aristides Novis, no. 2, 2° andar, Federaçaõ ,
Salvador, Bahia Brazil, CEP 40210-910
*
S Supporting Information

ABSTRACT: The viscosity of sisal residue bio-oil was evaluated using the variation of the operational conditions of the fast
pyrolysis process in a fluidized bed. The bio-oil was produced in a pilot plant from tests that were designed using the technique of
experimental design. In this work, the effect of the flow rate of the inert gas (N2), the biomass mass flow rate, and the reaction
temperature on the viscosity at the shear rates of 40 and 75 s−1 was investigated. The lowest viscosity was obtained when the N2
flow rate and the temperature were at their lowest values (8 N m3/h and 450 °C) and the biomass flow was at its highest value
(1560 g/h). The low-viscosity bio-oil was used to investigate the influence of the shear rates at its most critical flow condition
(2−26 s−1) at temperatures of 60−110 °C. It was found that at 60 °C, the bio-oil viscosity ranged from 2699 to 353 mPa·s when
the shear rate increased from 2 s−1 to 26 s−1. The lower value of this viscosity (353 mPa·s) is equivalent to the higher value
reported in the literature. An empirical model of viscosity versus temperature was determined and compared with existing
models. This evaluation was performed at three shear rates (2 s−1, 14 s−1, and 26 s−1) and at temperatures ranging from 60 to 110
°C. The model proposed in this study showed deviations much smaller than those obtained with the application of the most used
models.

1. INTRODUCTION
The exploitation of renewable energy sources is considered to
be promising for the global production of fuel. The exploration
of new sources of energy emerges as a strategy to meet the
rapid increase in energy consumption and a decrease in the
current reserves of fossil fuels around the world.1,2 Biomass can
be conveniently converted into bio-oil by thermochemical
processes such as fast pyrolysis and high-pressure liquefaction.3
Comparatively, fast pyrolysis stands out due to the high liquid
yield (up to 75 wt %), which can be easily stored and
transported to biorefineries for more effective conversion into
fuels and various chemicals.4,5
According to Mahinpey et al.,6 the yield and properties of the
products formed in the pyrolysis are strongly influenced by the
configuration of the reactor, by the reaction parameters
(temperature, heating rate, residence time, pressure and
catalyst), and by the characteristics of the biomass, such as
granulometry, shape, and structure. Therefore, the properties of
the bio-oil produced, such as fluidity and viscosity, can vary
significantly with the operating conditions of the process,
interfering with the flow of the fluid and its subsequent
application. The bio-oils commonly found in the literature have
viscosity values ranging from 100 to 400 mPa·s at 40 °C.4
However, the work of Pereira and Pires7 showed that the bio-
oil of sisal residue had very high viscosities, with values reaching
2000 mPa·s. These authors reported that bio-oil from sisal
residue caused incrustations on the inner walls of the pilot plant
heat exchangers, making it difficult to recover.
Most of the works on bio-oil developed by researchers are
related to the production of liquid from various biomasses and
processes. Soria-Verdugo8 studied the effect of inert gas velocity
and bed temperature during pyrolysis. Westerhof et al.9
evaluated the influence of reaction temperature on the yield,
composition, and quality of the bio-oil produced. In addition to
these studies, the work of Heo et al.10 evaluated the distribution
and characteristics of the products of the fast pyrolysis of rice
husks in a fluidized bed under different reaction conditions.
However, no work has quantitatively assessed the influence of
operating conditions and the interactions between them, for
example, on the bio-oil viscosity. The lack of interest in this
topic may have been due to the moderate viscosities attributed
to the bio-oils produced by the more traditional biomasses,
which may not be influenced by the operating conditions of the
process. However, for bio-oils considered to have higher
viscosities, it becomes essential to study the influence of process
operating variables on the decrease of viscosity.
The objective of this work was to study the influence of the
operational variables of the fast pyrolysis process on the
viscosity of the bio-oil produced from sisal residue. In addition,
an empirical model was developed to describe the viscosity
behavior of this bio-oil as a function of temperature. The bio-oil
samples used in this work were produced from tests whose
operational variables were arranged based on the experimental
design methodology. The response surface methodology was
chosen to evaluate the influence of the operational variables and
their interactions on the bio-oil viscosity, and the operational
conditions that produced the bio-oil of lower viscosity were also
defined. A new correlation between viscosity and temperature
was proposed for the bio-oil of sisal residue, and the results
were compared with others from correlations found in the
literature.
Received: November 22, 2017
Revised: March 19, 2018
Published: March 30, 2018

© 2018 American Chemical Society 5115 DOI: 10.1021/acs.energyfuels.7b03658

Energy Fuels 2018, 32, 5115−5124
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2. MATERIALS AND METHODS
2.1. Sisal Residue. Sisal (Agave sisalana, Agavaceae family) is a
plant of semiarid regions, and it is cultivated with the aim of producing
natural fibers. Brazil was the leading producer of sisal fibers in 2014,
corresponding to 55% of their world’s production.11
In Brazil, sisal production is concentrated in the state of Bahia, and
its fibers are produced at little scale farms.12 The sisal fibers are
obtained from scraping of sisal leaves, corresponding to 4% of their
weight. Sisal production is notable for generating a substantial amount
of organic residues, which is normally treated as an organic waste, or is
used as a low nutritional value animal feed.12
The sisal residue used in this work was obtained by defibering leaves
of Agave sisalana, which originated from the semiarid region of Bahia.
The sisal residue was transported to the laboratory and stored in a
refrigerator to prevent fermentation from taking place. Prior to the
pyrolysis tests being performed, the biomass was dried in an oven for 4
h at 105 °C. After being cooled to room temperature, the short sisal
fibers were removed from the biomass, leaving dried slices. The
general properties of sisal residue, as well as those of the bio-oil
produced, were reported by Pereira and Pires.7 The sisal residue used
in the reaction was not submitted to any diameter adjustment and
used the same granulometric distribution from the sisal leaf defibration
process. Particle size was determined by sieve openings of 1/4−3/8 in.
and 12 to 31/2 mesh sizes. The average particle length was determined
by the average size of the sieve openings that retained the material and
the size immediately preceding it. The mean size of the residue ranged
from 0.15 to 5.66 mm, and approximately 90 wt% exhibited particle
size between 0.60 and 4.83 mm.
2.2. Fast Pyrolysis Unit. The sisal residue bio-oil was produced in
a pilot-scale fluidized-bed pyrolysis unit. Figure 1 shows a simplified
Figure 1. Pilot bio-oil production unit: (P1) fluidization gas heating
furnace, (P2) biomass storage silo, (P3) pyrolysis reactor, (P4)
cyclones, and (P5) product collection system.
scheme of the production unit, which contains the classical elements: a
biomass feeding and injection system, a bubbling fluidized bed
pyrolysis reactor, a product collection system, data acquisition, and a
control system.
The gas heating furnace (P1) has an electrical resistance with a
power of 13.5 kW/h, and it can heat the fluidized gas up to 760 °C.
The silo (P2) has a storage volume of 10 kg of dry biomass. The
pyrolysis reactor (P3) is made of a stainless-steel pipe with a nominal
diameter of 100 mm and a height of 1000 mm. The reactor has three
1200 W collar resistors, and it is insulated with stone wool. In addition,
the reactor has four thermocouples to indicate the temperature along
the reactor, a bed differential pressure gauge, and a reactor pressure
meter. The system has two cyclones (P4), built-in stainless steel and a
collection system for liquid products (P5), consisting of four shell and
tube heat exchangers that are 800 mm, 25.4 mm in diameter (tube),
and 50.8 mm in diameter (hull). The collection system has a
thermocouple at the input of the first condenser and a thermocouple
at the output of the fourth. The cooling fluid is water, which feeds the
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condensers at 9 °C so that the temperature of the noncondensable
gases at the outlet of the fourth condenser does not exceed 20 °C.
2.3. Experimental Procedure − Bio-Oil Production. The
reactor was charged with 200 mm of silica sand with a diameter of 0.4
mm, and the cooling fluid was fed to the heat exchanger. The air was
drawn into the reactor with sufficient flow to keep the bed fluidized.
The heating resistances of the reactor and the air heating were
actuated so that the reaction temperature was reached. When the
reaction temperature was stabilized, the air was replaced by nitrogen
(inert gas), and a helical bolt led the silo biomass into the reactor with
a flow predefined by the test. After 1 h of reaction, the system was
cooled, and the bio-oil was collected and stored at 1 °C for further
analysis.
2.4. Experimental Procedure − Bio-Oil Viscosity. For
measurements of shear stress and shear rate, a programmable
rheometer, model DV-III + rheometer (Brookfield), was used. Before
the measurements were carried out, the samples were subjected to a
preshear with the objective of homogenizing the bio-oil, thus avoiding
interferences in the measurements due to the presence of bubbles.
Furthermore, the sample was left in contact with the thermostatic bath
for approximately 10 min to establish thermal equilibrium in each test.
A thermostatic bath coupled to the rheometer allowed the
measurements to be carried out at different temperatures with an
accuracy of ±1 °C and within a range from −100 to 150 °C.
The rheometer also has software, Rheocalc v. 2.3, through which it
is possible to program the range of measurements to be performed.
The measurements are reported in table form, which shows the values
of viscosity (mPa·s), torque (%), shear stress (N/m2), shear rate (s−1),
and temperature (°C).
In this work, the measurements were performed at temperatures of
60, 70, 80, 90, and 110 °C with variable shear rates from 2 s−1 to 75 s−1
and increments of 2 s−1. The shear rate range was determined, taking
into account the torque exerted on the spring so as not to exceed the
limit value of 100%.
2.5. Design of Experiments. The study of the influence of the
operational variables of the pyrolysis process on the bio-oil viscosity
was carried out based on statistical predictions. The experiments were
carried out based on the “Statistical Experimental Design” technique,
using the temperature of the reaction medium (°C), the biomass flow
rate that fed the reactor (g/h), and the nitrogen flow rate (Nm3/h).
The other variables were kept constant: the particle size of the sisal
residue, the silica sand mass, and the temperature and flow rate of the
condenser cooling water. The granulometry of the sisal residue was
kept constant because it is intended to evaluate the natural biomass
with the characteristic specification of the defibration process. The
silica sand mass, as well as its specification, was also kept constant
because the heat retention capacity of the sand was enough to keep the
reaction system at constant temperature, even with the injection of
biomass into the reactor. The temperature and flow rate of the cooling
water were kept constant because the capacity of the cooling fluid
exceeds the cooling needs of the reactor effluent gas, maintaining the
temperature of this fluid at the unit outlet at approximately 27 °C over
the entire experimental range.
The tests were defined from the factorial design 23, with three
replicates at the central point, in which the values of the operational
variables were coded as (−1) for lower levels, (+1) for upper levels,
and (0) for the central level (Table 1).
The bio-oil viscosity was defined as the test responses that were
influenced by the operating conditions. However, the viscosity of each
test was defined as the consequence of two different shear rates at 70
Table 1. Lower, Central, and Upper Limits Values for the
Independent Variables
variable −1 0 +1
(N2F) - N2 flow (Nm3/h) 8 11 14
(BioF) - Biomass flow (g/h) 610 1083 1560
(Temp) - Reaction temperature (°C) 450 500 550
DOI: 10.1021/acs.energyfuels.7b03658
Energy Fuels 2018, 32, 5115−5124
Energy & Fuels Article

°C (40 s−1 and 75 s−1). The shear rates used exemplify the viscosity the modified average sum of the squares, and the P-value for each
behavior of the bio-oil in situations in which the fluid is submitted to parameter as the results of the performed analysis of variance.
different shear stresses. The experimental unit of pyrolysis was considered as a pilot due to
The tests performed in this work, as well as the corresponding the dimensions of the equipment and the operational conditions
viscosities, are shown in Table 2. The results seem logical if it is imposed on the process. These characteristics make the operating
considered that the increase in shear rate causes the decrease of conditions of this unit similar to those of an industrial unit. The
viscosity in all tests carried out. similarities are related to the accuracy of the data collected by the
acquisition system and in the instruments, so they are related to the
Table 2. Matrix of Factorial Experiment with Independent operational procedure for the bio-oil collection. For this reason, and
Variable Levels because the tests had a short duration in relation to the size of the
pyrolysis unit, the range of significance of the variables was increased
viscosity (mPa·s) such that the statistical confidence used was 80%.
test N2F BioF temp 40 s−1 75 s−1 A lower P-value is attributed to a higher importance of that factor
and model. P-value amounts lower than 0.2 (confidence level of 80%)
1 −1 −1 −1 150.928 128.493 indicate that the studied parameter is significant in the results of the
2 +1 −1 −1 196.308 136.787 model.
3 −1 +1 −1 57.618 47.454 2.6. Models for Viscosity and Temperature. The theoretical
4 +1 +1 −1 134.101 113.808 determination of viscosity from fluid temperature data usually uses
5 −1 −1 +1 228.686 136.923 empirical models. In the case of liquids, the viscosity decreases with
6 +1 −1 +1 149.908 129.580 increasing temperature under isobaric conditions. The dependence of
7 −1 +1 +1 79.288 66.762 viscosity on temperature can be described by the Guzman−Andrade
8 +1 +1 +1 163.420 136.923 equation (eq 1).16,17
9 0 0 0 131.807 105.921
10 0 0 0 110.136 89.197 ln η = A + (B /T ) (1)
11 0 0 0 148.123 110.408
where η is the dynamic viscosity in mPa·s; T is the temperature of the
fluid in °C; and A and B are the adjustable parameters. This equation
The relationship between the viscosity and the fast pyrolysis is quite simple, and it fits in close approximation to the experimental
condition is complex, and the best way to evaluate this behavior is by data of a wide variety of both organic and inorganic liquids.18
studying the interaction effects using statistical design.13 Therefore, the For associated liquids and mixtures of high viscosity hydrocarbons,
response surface methodology (RSM) was chosen for this study.13−15 the relationship between ln η and 1/T becomes slightly curved, so the
This approach consists of a group of statistical techniques that allows a Guzman−Andrade equation cannot adequately apply. Some authors
reduction in the number of experiments and a prediction of the proposed modifications in this equation in order to improve the
influence of the factors on the chosen response using a mathematical results, generally including a third constant to correct the curvature or
model. The latter can be graphically represented with response functions of the liquid molar volume in parameters A and B.17,19 For
surfaces that show the extent of the influence of the parameters or the this reason, Vogel20 proposed eq 2 and Girifalco21 proposed eq 3:
significance of their interactions and can then be used to provide the
optimal conditions to improve a process. The best approach for ln η = A + [B /(C + T )] (2)
comparing various measures is the analysis of variance
(ANOVA).13−15 ANOVA is the statistical treatment most commonly
applied to the results of experiments to determine the percentage ln η = A + (B /T ) + (C /T 2) (3)
contribution of each parameter. ANOVA helps in formally testing the
significance of all main factors and their interactions by comparing the Poling et al.17 reported the values of the parameters A, B, and C of a
mean square against an estimate of the experimental errors at specific range of liquid hydrocarbons in recommended temperature ranges.
confidence levels. The significance of the RSM model involves the The models of Guzman−Andrade, Vogel and Girifalco were not
degree of freedom, the sum of squares, the contribution of each applied to bio-oil, and there is no reference in the literature to any
parameter in the prediction model, the modified sum of the squares, other type of model for this purpose.

Table 3. ANOVA Results of Viscositya

shear rate (s−1)
40 75
variables SS df MS P SS df MS P
(1) N2F 2023.05 1 2023.05 0.06 2362.14 1 2362.14 0.01
(2) BioF 10614.45 1 10614.45 0.00 3479.30 1 3479.30 0.00
(3) Temp 847.64 1 847.64 0.18 238.13 1 238.13 0.20
(1) by (2) 4705.16 1 4705.16 0.02 2297.17 1 2297.17 0.01
(1) by (3) 1696.83 1 2023.05 0.08
(2) by (3)
(1) (2) (3) 2171.63 1 2171.63 0.06
lack of fit 539.75 2 269.87 0.57 276.93 3 92.31 0.69
pure error 726.29 2 363.14 249.91 2 124.95
total SS 23324.76 10 9132.75 10
R2 0.95 0.94
R2 adj 0.87 0.88

a
Shear rate: 40 s−1, and 75 s−1. (SS) sum of squares; (df) degree of freedom; (MS) mean square; (P) P-value.

5117 DOI: 10.1021/acs.energyfuels.7b03658

Energy Fuels 2018, 32, 5115−5124
Energy & Fuels
3. RESULTS AND DISCUSSION
3.1. Influence of Operational Conditions on Bio-Oil
Viscosity. Table 3 shows the ANOVA to aid in formally
testing the significance of all main factors and their interactions.
P-values that are greater than 0.2, as is the case for the first
order interactions (biomass flow by reaction temperature -
shear rate: 40 s−1 and 75 s−1; N2 flow by reaction temperature -
shear rate: 75 s−1), indicate that the null hypotheses were
acceptable and that the effects of those variables were removed
from the calculation. P-values that are much lower than 0.2, as
is the case for the other response variables, indicate that those
parameters were important. The coefficient of determination
(R2) indicates how well the variation in response (viscosity)
was explained by the model. Larger values of predicted R2
suggest models of greater predictive ability. The model will give
a better prediction of the viscosity when the regression
coefficient is close to unity. The viscosity models for higher
shear rates, 40 and 75 s−1, had R2 values of 95% and 94%,
respectively, which implies a good adjustment of the
parameters. Adjusted R2 (R2 adj) accounts for the number of
predictors in the model, and it is useful for comparing models
with different numbers of predictors. Table 3 shows that
adjusted R2 did not stay closer to R2 when nonsignificant
variables were removed from the model (R2 adj = 0.87, to 40
s−1; and R2 adj = 0.88, to 75 s−1). However, the adjusted R2
values were high, with the models becoming suitable to predict
the viscosity. Pure-error and lack-of-fit are parts of the residual
sums of squares that are relevant for testing a hypothesis. The
pure-error is the part that cannot be predicted by any additional
terms, while lack-of-fit can be predicted by including additional
terms for the predictor variables in the model. Table 3 shows an
insignificant P-value (>0.2) for lack-of-fit of the bath shear rate,
ratifying that it is not possible to include additional terms. A
mean square pure error equal to 363.14 (40 s−1) and 124.95
(75 s−1) was found, which means that observed values by the
model had reasonable variability compared to the average.
Figure 2 shows how much the relation between the viscosity
calculated by the model and the experimental viscosity stayed
closer. This result is enough to make qualitative predictions of
the influence of the operational variables on the bio-oil
viscosity.
Figure 3 shows three-dimensional surfaces that were plotted
to study the interaction between three pairs of two variables
(biomass flow and N2 flow; reaction temperature and N2 flow;
and reaction temperature and biomass flow) on the bio-oil
viscosity. The combined effects of the biomass flow and the N2
flow were investigated to obtain the viscosity to shear rate of 40
s−1 and 75 s−1, as shown in Figure 3, panels a and d,
respectively. It was observed that the viscosity decreased by
approximately 58% (Figure 3a) and 53% (Figure 3d) when the
N2 flow decreased from 14 N m3/h to 8 N m3/h and the
biomass flow increased from 610 g/h to 1560 g/h. The
combined effects of the reaction temperature and N2 flow were
investigated to obtain the viscosity to shear rate of 40 s−1 and
75 s−1, as shown in Figure 3, panels b and e, respectively. It was
observed that the viscosity decreased by approximately 55%
(Figure 3b) and 48% (Figure 3e) when the N2 flow decreased
from 14 N m3/h to 8 N m3/h, and the reaction temperature
decreased from 550 to 450 °C. The combined effects of the
reaction temperature and biomass flow were investigated to
obtain the viscosity to shear rate of 40 s−1 and 75 s−1, as shown
in Figure 3, panels c and f, respectively. It was observed that the
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Figure 2. Experimental viscosity as a function of calculated: shear rate
(a) 40 s−1 e (b) 75 s−1.
viscosity decreased by approximately 47% (Figure 3c) and 41%
(Figure 3f) when the reaction temperature decreased from 550
to 450 °C, and the biomass flow increased from 610 g/h to
1560 g/h.
These results can be explained by the residence time of the
vapors in the reactor and the water content produced. When
the nitrogen flow is decreased to the lowest value, the residence
time of the molecules in the reactor increases. The products
generated will remain in the reactor longer, resulting in a
decrease in the bio-oil viscosity due to the reduction of the size
of the molecules. Furthermore, the higher biomass flow rate
also contributed to the reduction of viscosity due to the
increase of residence time. In this case, the increased
production of gases and vapors from the pyrolysis reaction
increased the pressure in the reactor, causing an increase in the
residence time of the molecules due to a decrease in the
volumetric flow rate. This fact can be better explained by the
analysis of Figure 4.
With the course of the reaction, the formed gases are
conveyed to the cyclones from a pipe at the reactor top. This
pipe has a much smaller diameter (3 cm) than the reactor
diameter (10 cm), as can be seen in the scheme of the
production unit (Figure 1). Therefore, the amount of gas
produced is much higher than that which leaves the reactor in
the direction of the cyclones, causing the accumulation of gases
inside the reactor, which results an increase in pressure as well
as an increase in the residence time of the molecules. As can be
seen in Figure 4, as the system pressure increases, the gas flow
decreases, as well as the opposite. So, at higher pressures the
gas flow rate is smaller, causing an increase in the residence
time in the reactor, resulting in a less viscous bio-oil.
The reduction of the reaction temperature from 550 to 450
°C favored a decrease in the bio-oil viscosity. According to
Duanguppama et al.22 and Garcia-Perez et al.,5 the bio-oil
viscosity increases with increasing temperature to a certain
DOI: 10.1021/acs.energyfuels.7b03658
Energy Fuels 2018, 32, 5115−5124
Energy & Fuels
Figure 3. Effect of variables N2 flow, biomass flow, and reaction temperatures on the viscosity of bio-oil. Shear rate of 40 s−1: (a), (b), and (c); shear
rate of 75 s−1: (d), (e), and (f).
value and then decreases. Duanguppama et al.22 found a
viscosity increase from 73 mPa·s to 191 mPa·s when the
temperature increased from 400 to 550 °C. However, the
viscosity decreased to 159 mPa·s when the temperature
increased to 600 °C. These authors related the low viscosity
of the bio-oil with its high water content, having as reference
the work of Oasmaa et al.23 According to Asadullah et al.,24 the
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pyrolysis water yield increases at low temperatures (∼450 °C)
due to the favorable dehydration and condensation reactions of
the organic molecules, which favorable proceeds at lower
temperatures, due to the suppression of secondary condensa-
tion reaction at higher temperatures. So, water content
decreases with increasing temperature, which produces a
more viscous bio-oil.
DOI: 10.1021/acs.energyfuels.7b03658
Energy Fuels 2018, 32, 5115−5124
Energy & Fuels Article

system, and it is extremely important for the manufacturer to

obtain this information regarding the fluid flow characteristics.
3.2. Influence of Temperature on the Viscosity of Bio-
Oil. The viscosity is the property that requires greater
consideration in the study of the flow of a fluid, since it
quantifies its resistance to deformation when submitted to a
shear stress. Since this property is related to the internal energy
of the substance or mixture, it is highly influenced by changes in
temperature.25 In this section, therefore, the behavior of the
bio-oil viscosity as a function of temperature will be investigated
in a range that allowed its flow when submitted to a set of shear
rates.
The behavior of the bio-oil viscosity as a function of the shear
rate at temperatures of 60, 70, 80, 90, and 110 °C was defined,
Figure 4. Acquisition data of pressure and flow rate as a function of and the profiles are shown in Figure 5a,b.
time. The viscosity of sisal residue bio-oil at 60 °C (near its
melting point of 55 °C) was extremely high when the shear rate
was the lowest and was very high when the shear rate was the
Some tests were carried out to produce 4 additional bio-oil highest. Table 4 is an adaptation of the work of Gollakota et
samples under different operating conditions. The results
(Appendix A, Supporting Information) showed that the water Table 4. Viscosity of Bio-Oils of Various Biomasses
contents of the bio-oil samples are influenced by the biomass viscosity (mPa·s) reference
operational conditions of production, although the variation Pterocarpus indicus 70−350 Luo et al.27
between the samples is small and the water content is close to Fraxinus mandshurica 10−70 Luo et al.27
the value reported by Pereira and Pires7 (biomass = 6.11 wt %; rice straw 5−10 Luo et al.27
bio-oil = 5.18 wt %). This fact reinforces that smaller flow rates rice husk (at 60 °C) 152.32 Zheng28
of drag gas were responsible for the production of a bio-oil with cotton stalk (at 60 °C) 145 Zheng et al.29
lower viscosity due to the increase in the residence time of the corn stover (at 50 °C) 60 Yu et al.30
molecules in the reactor, causing the reduction of their size. pine wood (at 50 °C) 65.136 Hassan et al.31
Figure 3 shows that the viscosity behavior of sisal residue bio- cashewnut shell (60 °C) 38.493 Das and Ganesh32
oil is similar at both shear rates. However, the maximum soybean oil cake (at 50 °C) 80.125 Sensoz and Kaynar33
viscosity was always lower for the shear rate of 75 s−1. The bagasse (20 °C) 141.082 Mohan et al.34
results presented in Table 2 show that at the shear rate of 40 sugar cane 107.101 Islam et al.35
s−1, the viscosity ranged from 57 mPa·s to 228 mPa·s, while the wood pyrolysis bio-oil (at 40−100 Czernik and
viscosity range corresponding to 75 s−1 was 47 mPa·s−136 50 °C) Bridgwater36
mPa·s. Therefore, the decrease of the viscosity due to the contaminated sawdust (40 °C) 72.7−190.6 Duanguppama et al.22
increase of the shear rate to which the fluid is submitted is
observed, characteristic of the pseudoplastic fluids. These
results confirm the influence of the operating conditions on the al.26 with the work of Luo et al.,27 in addition to new results;
viscosity of the bio-oil produced, with trials 3 and 5 producing the table presents the viscosity of bio-oils produced by biomass
the fluid with lower and higher viscosity, respectively. In of various types. The lower viscosity of sisal residue bio-oil
addition, the results also allow evaluation of the bio-oil behavior found at 60 °C (353 mPa·s) was equivalent to the higher
when submitted to various shear stresses if applied, for example, viscosity recorded in Table 4, the temperature of which was not
as a fuel or lubricating oil for various equipment. Therefore, it is reported. However, when observing results at 60 °C, Table 4
concluded that the forces imposed on the bio-oil can interfere shows viscosities that can reach values below half of that found
in the design of the project, for example, in a pyrolysis unit flow for sisal residue bio-oil (2699 mPa·s). At temperatures above 60

Figure 5. Dynamic viscosity of sisal residue as a function of shear rate: (a) all temperatures and (b) 70−110 °C. The bio-oil used was produced
under the condition of lower viscosity: N2 flow of 8 N m3/h, Biomass flow of 1560 g/h and reaction temperature of 450 °C.

5120 DOI: 10.1021/acs.energyfuels.7b03658

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Table 5. Parameters of the Viscosity Models

model A B C D R2
−1
Shear Rate 2 s
G-Aa 0.21 529.99 0.88
Girifalco 10545.30 −1223.78 68049.27 0.96
Vogel 20.57 45.66 −50.70 0.98
eq 4 3.98 × 10−18 1.09 × 104 −9.06 × 105 2.53 × 107 1.00
Shear Rate 14 s−1
G-Aa 0.52 402.85 0.98
Girifalco 5.85 11.22 15195.84 0.99
Vogel 3.30 159.20 −28.19 0.99
eq 4 1.16 × 10−8 4.95 × 103 −3.80 × 105 1.03 × 107 1.00
Shear Rate 26 s−1
G-Aa 0.83 355.71 0.98
Girifalco 5.43 51.93 11787.29 0.99
Vogel 1.27 159.20 −25.22 0.99
eq 4 1.12 × 10−5 3.28 × 103 −2.47 × 105 6.72 × 106 1.00
a
Guzman−Andrade.

°C, the viscosity of sisal residue bio-oil ranges from 186 to 22
mPa·s over the entire range of shear rates. Unfortunately, no
viscosity values were found in the literature at temperatures
above 60 °C. For this reason, it can only be stated that the
viscosity of sisal residue bio-oil is very high, reaching values
close to those of other bio-oils only if submitted to
temperatures equal to or above 70 °C.
The results showed the peculiar viscous characteristic of the
bio-oil under study in relation to the various bio-oils found in
the literature, which present similar viscosity values among
them, as shown in Table 4. Fast pyrolysis of eucalyptus was
carried out in the same pilot plant, under similar operating
conditions as the sisal residue tests (N2F = 11 N m3/h; BioF =
1083 g/h and temp = 500 °C), and the results showed that the
viscosity values of the eucalyptus bio-oil are about 10 times
smaller than those coming from the sisal residue (Appendix A,
Supporting Information), being close to those found by other
authors. Figure 5 shows that the viscosity of sisal residue bio-oil
decreases with increasing shear rate, which confirms the yield-
pseudoplastic rheological behavior of this fluid, as reported in
the work of Pereira and Pires.7 It has also been observed that
viscosity is influenced by temperature, and, as discussed above,
the values obtained are comparable to those of other bio-oils at
temperatures above 70 °C. In studies aimed at the application
of bio-oil in various situations, such as the lubrication of
machines or its use as a fuel, it is necessary to know the
behavior of the fluid when submitted to various temperature
conditions and shear stresses. Thus, it is important to qualify
and quantify the influence of these variables on the bio-oil
viscosity so that it behaves conveniently in each condition.
3.3. Model of Viscosity and Temperature. According to
Pereira and Pires,7 the bio-oil produced from sisal residue had
an incredibly waxy and viscous appearance at room temper-
ature, which was very different from the reports in the literature
regarding the bio-oil produced from other biomass sources.
While some authors have reported that bio-oil behaves as a
Newtonian fluid above 46 °C and as a Bingham plastic below
this temperature, sisal residue bio-oil simply does not flow at
temperatures lower than 55 °C. For this reason, it is important
to obtain a viscosity variation model with the temperature, in
order to know the range of values of these variables that allows
fluid flow and, consequently, its application.
5121
The models described by eqs 1, 2, and 3 were applied to sisal
residue bio-oil, and because of this, the specific parameters of
each model were determined from the fit data of viscosity as a
function of temperature (Figure 5) using a nonlinear regression
method based on the Levenberg−Marquardt algorithm. To
improve this analysis, a new model (eq 4) was also proposed,
and then the four models were compared by means of the
deviations obtained between the experimental and calculated
values.
ln η = A + (B /T ) + (C /T 2) + (D/T 3) (4)
The viscosity measurements were obtained at temperatures
of 60, 70, 80, 90, and 110 °C. The parameter adjustments were
performed for the shear rates of 2 s−1, 14 s−1, and 26 s−1, as
they were considered to be representative of the higher
viscosity range. The parameter values of the models are shown
in Table 5.
The models were adequate to represent the influence of
temperature on the dynamic viscosity, based on the high
magnitude values of R2. Equation 4 stood out in relation to the
others with R2 equal to 1.
Figure 6 shows the viscosity behavior as a function of
temperature for the models under study at each shear rate. In
all the graphs, it is visually observed that the four models
present good results at temperatures equal to and above 80 °C
for the three shear rates studied. However, below 80 °C, the
models improve their estimates as the shear rate increases.
Apparently, eq 4 provides more adequate estimates for all shear
rates studied.
To quantitatively evaluate the quality of the adjustment in
each case, Figure 7 shows the behavior of the models’
deviations from the experimental viscosities with respect to
the temperature.
The Guzman−Andrade model was not suitable to describe
the fluid at the shear rate of 2 s−1, providing very high
deviations at all temperatures, especially 60 and 70 °C.
According to Velzen et al.,19 the Guzman−Andrade model
presented inaccuracies when used to describe associated liquids
or blends of high viscosity hydrocarbons, which explains the
poor fit at temperatures close to the bio-oil pour point (55 °C).
The progressive drop in viscosity caused by the increased shear
rate contributed to a better fit of the model, reaching deviations
below 10% at temperatures of 80, 90, and 110 °C. At the rate of
DOI: 10.1021/acs.energyfuels.7b03658
Energy Fuels 2018, 32, 5115−5124
Energy & Fuels
Figure 6. Viscosity versus temperature: Shear rate of 2 s−1 (a), 14 s−1
(b) e 26 s−1 (c).
26 s−1, the relative deviations at 60 and 70 °C still remained
high, making the model inappropriate to predict the viscosity
behavior of sisal residue bio-oil in the temperature range of 60−
110 °C.
The application of the Girifalco model caused a reduction in
the values of the deviations at the temperatures of 60 and 70 °C
in relation to the Guzman−Andrade model for all the shear
rates. However, at 90 °C, the calculated deviations were higher
at the three shear rates. At 80 and 110 °C, the model showed
deviations similar to those of Guzman−Andrade at the shear
rates of 14 s−1 and 26 s−1. Even so, the Girifalco model is
suitable for calculating the viscosity as a function of the bio-oil
temperature at the shear rate of 14 s−1, with the greatest
deviation of 7.06%.
The Vogel model showed behavior similar to the Girifalco
model at the shear rates of 14 s−1 and 26 s−1. The lowest mean
deviation was obtained at 26 s−1, whose result was 6.81%. At
temperatures of 60 and 70 °C, this model showed more
5122
Article
Figure 7. Relative deviations between the experimental data and the
values predicted by the models: Shear rate of 2 s−1 (a), 14 s−1 (b), and
26 s−1 (c).
satisfactory predictions than the first two, although it still
showed relatively high deviations, such as those obtained at 70
°C. At 90 °C, the Vogel model showed poor performance in
relation to the Guzman−Andrade model for the three shear
rates.
Equation 4 was the model that provided the smallest
deviations among the models used at the temperatures and
shear rates evaluated. The exception occurred at the shear rate
of 26 s−1 and a temperature of 80 °C, for which the best result
was the Guzman−Andrade model. A decrease in the shear rate
of 26 s−1 at temperatures of 70−90 °C, with deviations below
5%, is also observed. Equation 4 presented better viscosity
predictions at all shear rates studied, and it is considered the
most appropriate model to determine the viscosity of sisal
residue bio-oil at the temperatures evaluated.
DOI: 10.1021/acs.energyfuels.7b03658
Energy Fuels 2018, 32, 5115−5124
Energy & Fuels
4. CONCLUSIONS
The bio-oil of sisal residue differs from bio-oils produced from
other biomass, mainly because of its much higher pour point.
This fact is associated with viscosity, whose value ranged from
2699 to 353 mPa·s at 60 °C and shear rates ranging from 2
s−1to 26 s−1. The high viscosity value directly affects the bio-oil
recovery system of the fast pyrolysis unit, which makes essential
the production of bio-oil with the lowest possible viscosity. This
bio-oil condition was found when the pyrolysis unit was
operated with the N2 flow rate and the reaction temperature at
their lowest levels (8 N m3/h and 450 °C, respectively) and
with the sisal residue flow rate at its highest level (1560 g/h).
The lower N2 flow rate and the higher biomass flow rate are
related to the longer residence time of the pyrolysis vapors and
gases, which allows the molecules to breakdown from
secondary reactions. The lower reaction temperature supported
the production of bio-oil of lower viscosity because it also
favored the reactions of dehydration and condensation of the
organic molecules, which are responsible for the greater
production of water.
The models of Guzman−Andrade, Girifalco, and Vogel have
been reported in the literature as equations capable of
predicting the viscosity of an organic fluid as a function of
temperature. However, there are no studies of these equations
applying to bio-oil of any source. For this reason, these
equations were applied to sisal residue bio-oil for three shear
rates (2 s−1, 14 s−1, and 26 s−1), and the deviations were
determined to be high. This result motivated the launch of a
new model, which added a cubic term to the Girifalco equation.
The new equation adequately reproduced the influence of
temperature on the bio-oil viscosity at all the shear rates
considered. This equation will bring more safety to sisal residue
bio-oil flow system projects, which are usually high in viscosity.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.energy-
fuels.7b03658.
Appendix A. Supplementary Data (Table A1: Viscosity of
bio-oils of eucalyptus; Figure A1: Dynamic viscosity of
sisal residue and eucalyptus bio-oil as a function of shear
rate) (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: l.ggomes@outlook.com. Tel: +55 71-3283 9862. Fax:
+55 71-3283 9809.
ORCID
Luis G. G. Pereira: 0000-0002-1055-0300
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the Bahia State Foundation for
Research Support−FAPESB (Project DTE: 0061/2011) and
the BNB−Northeast Bank of Brazil (Covenante no. 945).
5123
Article
■ REFERENCES
(1) Zhang, L.; Liu, R.; Yin, R.; Mei, Y. Upgrading of bio-oil from
biomass fast pyrolysis in China: A review. Renewable Sustainable Energy
Rev. 2013, 24, 66−72.
(2) Morali, U.; Yavuzel, N.; Sensoz, S. Pyrolysis of hornbeam
(Carpinus betulus L.) sawdust: Characterization of bio-oil and bio-
char. Bioresour. Technol. 2016, 221, 682−685.
(3) Xu, Y.; Zheng, X.; Hu, X.; Dearn, K. D.; Xu, H. Effect of catalytic
esterification on the friction and wear performance of bio-oil. Wear
2014, 311, 93−100.
(4) Bridgwater, A. V. Review of fast pyrolysis of biomass and product
upgrading. Biomass Bioenergy 2012, 38, 68−94.
(5) Garcia-Perez, M.; Wang, X. S.; Shen, J.; Rhodes, M. J.; Tian, F.;
Lee, W.; Wu, H.; Li, C. Fast pyrolysis of oil mallee woody biomass:
effect of temperature on the yield and quality of pyrolysis products.
Ind. Eng. Chem. Res. 2008, 47, 1846−1854.
(6) Mahinpey, N.; Murugan, P.; Mani, T.; Raina, R. Analysis of Bio-
Oil, Biogas, and Biochar from Pressurized Pyrolysis of Wheat Straw
Using a Tubular reactor. Energy Fuels 2009, 23, 2736−2742.
(7) Pereira, L. G. G.; Pires, C. A. M. Efect of Temperature on the
Flow Profile of the Bio-oil Produced from the Fast Pyrolysis of Sisal
Residue. Energy Fuels 2017, 31, 2871−2878.
(8) Soria-Verdugo, A.; Morato-Godino, A.; Garcia-Gutierrez, L. M.;
Garcia-Hernando, N. Pyrolysis of sewage sludge in a fixed and a
bubbling fluidized bed − Estimation and experimental validation of the
pyrolysis time. Energy Convers. Manage. 2017, 144, 235−242.
(9) Westerhof, R. J. M.; Brilman, D. W. F.; van Swaaij, W. P. M.;
Kersten, S. R. A. Effect of Temperature in Fluidized Bed Fast Pyrolysis
of Biomass: Oil Quality Assessment in Test Units. Ind. Eng. Chem. Res.
2010, 49, 1160−1168.
(10) Heo, H. S.; Park, H. J.; Dong, J.; Park, S. H.; Kim, S.; Park, Y.;
Suh, D.-J.; Suh, Y.-W.; Kim, S.-S. Fast pyrolysis of rice husk under
different reaction conditions. J. Ind. Eng. Chem. 2010, 16, 27−31.
(11) FAOSTAT. Food and Agricultural commodities production/
Countries by commodity. http://www.fao.org/faostat/en/#home.
Retrieved 09 July 09, 2017.
(12) Broeren, M. L. M.; Dellaert, S. N. C.; Cok, B.; Patel, M. K.;
Worrell, E.; Shen, L. Life cycle assessment of sisal fibre e Exploring
how local practices can influence environmental performance. J.
Cleaner Prod. 2017, 149, 818−827.
(13) Palkar, R. R.; Shilapuram, V. Detailed parametric design
methodology for hydrodynamics of liquid−solid circulating fluidized
bed using design of experiments. Particuology 2017, 31, 59−68.
(14) Behainne, J. J. R.; Martinez, J. D. Performance analysis of an air-
blown pilot fluidized bed gasifier for rice husk. Energy Sustainable Dev.
2014, 18, 75−82.
(15) Yusup, S.; Khan, Z.; Ahmad, M. M.; Rashidi, N. A. Optimization
of hydrogen production in in-situ catalytic adsorption (ICA) steam
gasification based on Response Surface Methodology. Biomass
Bioenergy 2014, 60, 98−107.
(16) Andrade, E.N. da C. The Viscosity of Liquids. Nature 1930, 125,
309−310.
(17) Poling, B. E.; Prausnitz, J. M.; O’connell, J. P. The Properties of
Gases and Liquids, 5th ed.; McGraw-Hill Company, Inc: New York,
2004.
(18) Converti, A.; Zilli, M.; Arni, S.; Di Felice, R.; del Borghi, M.
Estimation of viscosity of highly viscous fermentation media
containing one more solutes. Biochem. Eng. J. 1999, 4, 81−85.
(19) Velzen, D. V.; Cardozo, R. L.; Langenkamp, H. Liquid Viscosity
and Chemical Constitution of Organic Compounds: A New Correlation
and a Compilation of Literature Data; Euratom: Ispra, 1972.
(20) Vogel, H. The law of the relation between the viscosity of
liquids and the temperature. Physik Z. 1921, 22, 645.
(21) Girifalco, L. A. Temperature dependence of viscosity and its
relation to vapor pressure for associated liquids. J. Chem. Phys. 1955,
23 (12), 2446−2447.
(22) Duanguppama, K.; Suwapaet, N.; Pattiya, A. Fast pyrolysis of
contaminated sawdust in a circulating fluidised bed reactor. J. Anal.
Appl. Pyrolysis 2016, 118, 63−74.
DOI: 10.1021/acs.energyfuels.7b03658
Energy Fuels 2018, 32, 5115−5124
Energy & Fuels Article

(23) Oasmaa, A.; Kuoppala, E.; Solantausta, Y. Fast Pyrolysis of

Forestry Residue. 2. Physicochemical Composition of Product Liquid.
Energy Fuels 2003, 17 (2), 433−443.
(24) Asadullah, M.; Ab Rasid, N. S.; KAdir, S. A. S. A.; Azdarpour, A.
Production and detailed characterization of bio-oil from fast pyrolysis
of palm kernel shell. Biomass Bioenergy 2013, 59, 316−324.
(25) Oliveira, R. C.; Barros, S. T. D.; Rossi, R. M. Aplicaçaõ da
metodologia Bayesiana para o estudo reológico da polpa de uva. Rer.
Bras. de Prod. Agro. 2009, 11 (1), 73−80.
(26) Gollakota, A. R. K.; Reddy, M.; Subramanyam, M. D.; Kishore,
N. A review on the upgradation techniques of pyrolysis oil. Renewable
Sustainable Energy Rev. 2016, 58, 1543−1568.
(27) Luo, Z.; Wang, S.; Liao, Y.; Zhou, J.; Gu, Y.; Cen, K. Research
on biomass fast pyrolysis for liquid fuel. Biomass Bioenergy 2004, 26,
455−462.
(28) Zheng, J. Bio-oil from fast pyrolysis of rice husk: Yields and
related properties and improvement of the pyrolysis system. J. Anal.
Appl. Pyrolysis 2007, 80, 30−35.
(29) Zheng, J.; Yi, W.; Wang, N. Bio-oil production from cotton
stalk. Energy Convers. Manage. 2008, 49, 1724−1730.
(30) Yu, F.; et al. Physical and Chemical Properties of Bio-Oils From
Microwave Pyrolysis of Corn Stover. Appl. Biochem. Biotechnol. 2007,
137 (1), 957−970.
(31) Hassan, E.-B. M.; Steele, P. H.; Ingram, L. Characterization of
Fast Pyrolysis Bio-oils Produced from Pretreated Pine Wood. Appl.
Biochem. Biotechnol. 2009, 154, 3−13.
(32) Das, P.; Ganesh, A. Bio-oil from pyrolysis of cashew nut shell
a near fuel. Biomass Bioenergy 2003, 25, 113−117.
(33) Sensöz, S.; Kaynar, I. Bio-oil production from soybean (Glycine
max L.); fuel properties of Bio-oil. Ind. Crops Prod. 2006, 23, 99−105.
(34) Mohan, D.; Pittman, C. U.; Steele, P. H. Pyrolysis of Wood/
Biomass for Bio-oil: A Critical Review. Energy Fuels 2006, 20, 848−
889.
(35) Islam, M. R.; Nabi, M. N.; Islam, M. N. Characterization of
biomass solid waste for liquid fuel production, 4th ICME, Dhaka, 2001;
pp 77−82.
(36) Czernik, S.; Bridgwater, A. V. Overview of Applications of
Biomass Fast Pyrolysis Oil. Energy Fuels 2004, 18, 590−598.

5124 DOI: 10.1021/acs.energyfuels.7b03658

Energy Fuels 2018, 32, 5115−5124