SUM 2014, Second Symposium on Urban Mining

ENERGETIC CHARACTERIZATION OF PINE

PELLETS BIOCHAR
L.B. SANTOS*, M.V. STRIEBECK**, M.S. CRESPI***, C.A. RIBEIRO*** AND
M. DE JULIO*
* BUILDING ENGINEERING Department, Aeronautical Institute of Technology,
Marechal Eduardo Gomes Square 50, 12228-900, Sao Jose dos Campos, Brazil
** CHEMICAL ENGINEERING Department, National University of Buenos Aires
Province Center College Engineering , del Valle Avenue 5737, B7400JWI
Olavarria, Argentina
*** ANALYTICAL CHEMISTRY Department, Paulista State University - Chemistry
Institute, Professor Francisco Degni Street 55, 14800-060 Araraquara, Brazil

SUMMARY: The wood pellets are mainly used for heating environments, commercial and
residential, well as fuel for production of thermal and electric energy in industrial plants. Moreover,
the heterogeneity and variable moisture content, combined with the high cost of transport, are
limiting challenges that must be overcome with new technologies and new products. In this context,
roasting and pyrolysis are attractive alternatives for increasing energy density and decrease the
moisture content of the samples, based on thermochemical conversion in non-oxidizing atmosphere.
To perform the energetic characterization of biochar from pine pellet were produced samples using
different heating rates (5 to 30C/min), different residence temperatures (200, 280 and 570C) and
different time residence (one hour and half hour). The high heating value (HHV) of each variant
was measured and was observed that the heating rate did not influence significantly the results, with
a 5% variation between the lowest and highest heating rate. However, the HHV was significant
compared to the pellet in nature, when it has been found an energetic gain over 80%. In general, the
biochar form pine pellets obtained by roasting or pyrolysis have appropriated characteristics
compared to pellets in nature, showing greater amount of energy per unit, high stability, reduced
moisture content and reduced ash content.
1. INTRODUCTION
Burning wood pellets is mainly used for heating environments (commercial and residential
environments), but can also be used as fuel for generating electricity in industrial plants, or even in
power plants. The versatility and availability of biomass, combined with its characteristic of
renewable energy and do not contribute to global warming, are strong arguments to enhance its use
worldwide.
Moreover, the heterogeneity and variable humidity, combined with the high cost of transport, are
limited challenges that must be overcome with new technologies and new products (GARCIA et al.,
2012). In this context, roasting and pyrolysis are attractive alternatives for increasing energy density

Proceedings SUM 2014, Second Symposium on Urban Mining

Bergamo, Italy; 19 21 May 2014
2014 by CISA Publisher, Italy

SUM 2014, Second Symposium on Urban Mining

and decrease the moisture content of the samples, based on thermochemical conversion in nonoxidizing atmosphere (procedure that contributes to the generation of additional products
appreciable
economic
value).
These advantages make interesting the use of pyrolyzed biomass for energy purposes, requiring,
however, a proper characterization. Thus, the aim of this work was to produce and characterize
biochar from pine pellet for further use of it as fuel.
Brito et al. (1978) showed the calorific value, moisture content, density and immediate analysis
as the most important properties of wood for use as fuel. Thus, the present study produced biochar
of the pine pellet and determined the properties of the same following the above recommendation.

2. MATERIALS AND METHODS

The biomass used in the study, constituted of residues from Araucaria angustifolia (pine pellets),
was obtained by the BrBiomassa Company, from Maringa, Parana State, Brazil. The development
process of biochars made in this work consisted of subjecting the sample to a slow pyrolysis (since
it presents the highest yields in solids) in a muffle furnace under inert atmosphere and atmospheric
pressure, following several temperature settings (200, 280 and 570C) and residence time (hour and
a half hours), in addition to varying the heating rate (5 to 30 C/min).
2.1 Particle density
The bulk density is the mass of sample per volume occupied by the particle (solid and internal pore
volume). The particle density of the biochar was determined by determining the mass of the sample
in a calculated volume using a caliper (ASTM D 792).
2.2 Bulk density
The bulk density is the mass of sample in a specific volume (ASTM E873 and NBR 6922). In this
study we used a regular container (prism) with a capacity of around 0.2 m 3. The bulk density was
calculated by Equation 1
Dgran = mbiochar / Vrecip

Eq. 1

Where Dgran. is the bulk density of coal (g.cm-3); mbiochar is the weight biochar (kg); Vrecip. is the
container volume (m3).
2.3 Heating values
The heating value is defined as the amount of energy in the form of heat released by the combustion
of a unit mass of wood (JARA, 1989). The Higher Heating Value (HHV) is one in which
combustion takes place at constant volume and in which the water formed during combustion is
condensed and the heat which derived from this condensation is recovered (BRIANE & DOAT,
1985). The Lower Heating Value (LHV) is the energy actually available per unit mass of fuel after
deducting losses from evaporation of water (JARA, 1989). The Higher Heating Value (HHV) of
biochar was determined by bomb calorimetry, model IKA C 2000, according to ASTM E7 and
NBR 8633, using mass of 0.5 g in duplicate. The Lower Heating Value (LHV) was obtained by
Equation 2 (BRITO, 1993):

Proceedings SUM 2014, Second Symposium on Urban Mining

Bergamo, Italy; 19 21 May 2014
2014 by CISA Publisher, Italy

SUM 2014, Second Symposium on Urban Mining

LHV = HHV 600 ( 9H/100)

Eq. 2

Where LHV is the Lower Heating Value (kJ / kg); HHV is the Higher Heating Value (kJ / kg), and
H is the hydrogen content (%).
2.4 Moisture and ash
Moisture and ash content were determined by gravimetric technique, according to ASTM D-3173,
ASTM D-3174, NBR 8289 and NBR 8293. The samples were heated at 105C until constant
weight. After that, the same sample was used for the determination of ash content, raising the
temperature to 775 C maintaining per one hour.
2.5 Thermal stability evaluation
The thermal stability of the biochar and pellet samples was determined by thermal gravimetric
analysis performed in an apparatus SDT-2960 from TA Instruments. For these analyzes, was used
35 mg of sample, in alumina pan, under an atmosphere of nitrogen and air (gas flow of 50 ml min-1)
at a heating rate of 10-30C min-1, from ambient temperature ( 25C) to 850C.

3. RESULTS AND DISCUSSION

3.1 Gravimetric yield of biochar
The temperature is presented as the key process variable. Several experiments were performed in
order to identify the influence of final pyrolysis temperature, for a given plant species on the yields
of charcoal, liquid and gas. Data shows that the behavior of the coal, when the pyrolysis
temperature increases, is losing its volatiles, which will enhance its liquid and gas phases. Although
the charcoal yield decreases with increasing temperature, there is a significant improvement in fixed
carbon content, this indication of quality input (MARCILLA et a.l, 2000).
Another notable impairment is observed when yields are compared in coal and liquids in
different heating. Several studies show that it is possible to significantly increase the recovery of
liquid products by increasing the heating rate (BRIDWATER, 1999a, 1999b; DERMIBAS, 2005).
When the heating is conducted at a low heating rate, the temperature takes to reach a particular
value, where a higher rate of thermal decomposition of biomass components occurs, there is a
reduced speed and output the newly formed components of the system. To remain in the system
under high temperature, the newly formed components suffer further decomposition reactions
(secondary reactions), mainly being converted into compounds of lower molecular mass (in most
gases, such as CO2, CO and H2O) and biochar (Ranzi et al ., 2008; PEREZ-GARCIA et al., 2008).
According to Tables 1 and 2, there was a lower yield of biochar in high temperatures of
residence and high heating rates, corroborating the results found in the literature. Thus, the reactions
of secondary thermal decomposition contribute to increase the yield of biochar in the decrease of
heating rate (Table 1). However, in this work has not been possible to observe a increase in yield
with increasing residence time. This phenomenon can be explained by the fact that the system used
in the pyrolysis not be closed, allowing the removal of volatile as they were being produced.
Cellulose, hemicellulose and lignin are major constituents of the biomass taken into account in
the studies of pyrolysis as a means of biomass energy utilization. Despite the importance of these
three constituents in the process, the difficulty of implementation and the inaccuracy of the methods
of quantification of these components, coupled with the complexity of reactions thermal
decomposition biomass, make it common in many of these works not quantify the biomass studied

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(Ranzi et al., 2008). For this reason, in this study the content of cellulose, hemicellulose and lignin
were not quantified in the pellet used in the study of Pine. The lack of this information does not
result in major problems in interpreting the results since the thermal decomposition these
components tends to occur in characteristic temperatures, independent of biomass studied.
Hemicellulose is the least stable of the three components of the biomass, and its thermal
decomposition takes place in the range of 150-350C and a maximum rate of about 270C.
Cellulose has a similar chemical composition to the hemicellulose, but due to its crystalline
arrangement, is more resistant to thermal decomposition, which occurs in the range of 275-400C,
with maximum around 350C. The lignin thermal decomposition occurs of 250-500C, but without
any temperature range in which the decomposition rate is more intense (YANG et al., 2007).
With such information, it can be inferred that the income which occurred on heating to 280C
(yield above 25%) is close to the average lignin content (25.18%) plus a bit of holocellulose (72%)
found in samples of Pinus oocarpa by Morais et al. (2005), while the yield of coal pyrolysis at
570C (yield below 25%) is close to the same lignin content found by the author, but already in a
reduced percentage. This comparison is consistent with the knowledge that the lignin component
whose content is at best correlates with the biomass yield of biochar, while cellulose and
hemicellulose are the main responsible for the production of bio-oil and non-condensable gases
(ANTAL & GRNLI, 2003).
3.2 Thermal gravimetric analysis
The thermal decomposition resistance of the samples was also tested, and all samples exhibited high
thermal stability compared with the pellet in nature, especially biochars produced at 570C of
temperature residence (Figures 1 and 2) and low heating rate (Figure 3).
In the initial stage of heating the samples was noted an event, commonly associated with loss of
water or volatiles present in the samples. Patterns of decomposition of biochars were not similar to
the pellet. Due to biochar had undergone a previous heat treatment thermal analysis; they have a
lower mass loss in the first event thermal decomposition (Figures 1 and 2), characteristic region of
the hemicellulose decomposition. It was observed that, under nitrogen atmosphere, the biochars
only had a small decomposition above temperatures which were produced.
The mass loss in the first event of decomposition, under an atmosphere of air, calculated on the
mass of the sample without the moisture content, was 71% for the pellet. Although this value be
included also the mass loss from the decomposition of other wood components, it is similar to the
sum of hemicellulose and cellulose in Pine (Morais et al., 2005). For biochars this mass loss varied
from 35 to 44%, suggesting that this reduction in mass loss is linked to the loss of hemicellulose
that biochar suffered from the preliminary heat treatment in its production.
The second thermal event has had its peak at 470C in the pellet and at 475, 580 and 630C in
the biochar 200C, 280C and 570C respectively, and resulted in reduction of 13, 45, 55, and 41%
of dry weight, respectively. The highest temperature to biochar is due to the partial transformation
undergone by cellulose with thermal pretreatment, increasing its temperature resistance (Wooten, et
al., 2004) occurred. The highest mass loss of these biochars associated with this second event must
have occurred because of its enrichment in cellulose, caused by the previous decomposition of
hemicellulose.
The third event of mass loss reinforces this hypothesis, with identical pattern thermal
decomposition among biochars, which culminated in the loss of additional mass of 13, 4 and 11%
for biochar 200C, 280C and 570 C respectively, with heating up to 850C.

SUM 2014, Second Symposium on Urban Mining

3.3 Particle density

The particle density is one of parameters used to explain the resistance of a given carbonized
material, in addition to the degradation of wood components and morphological structure thereof. It
is a property that depends on the nature of the raw material (precursor material) and also in the
manufacturing process of coal.
The particle density values are shown in Table 3. The biochars prepared in this work show great
variation in particle density for temperature residence. It was hoped to increase the particle density
with an increase in temperature of residence due to loss of volatile compounds from wood and
mainly as a concomitant increase in structural organization of biochar in relation to the pellet.
However, it was observed that the particle density decreased to 280C residence temperature. The
reason for this phenomenon may be linked to the large formation of small pores in the structure of
biochar at this temperature. As for biochar at 570C there is formation of large pores and cracks,
with great loss of the initial compounds pyrolyzed sample, which provides a higher particle density.
Regarding the length of residence was not possible to clearly distinguish any pattern of behavior
with increasing residence time.
3.4 Heating value
It was measured the heating value of the biochars produced at 570C and 200C temperature
residence at different heating rates (Table 4), and it was observed that the heating rate did not
influence significantly the results, with variation of 5 % between the lowest and highest heating
rate. However the temperature of residence had a greater influence on the heating value, it was
observed a 10% variation between the variants (Table 4). The data of the heating value of biochars
(higher and lower) are contained in Table 5.
The heating value increased significantly as there was an increase in residence temperature of
280C, won approximately 10% in energy when compared with other variants of biochar and 80%
more when comparing with the pellet. This energy gain might be due to secondary reactions
occurring in the sample during the pyrolysis, for example as a result of structural changes (or steric)
or exposure of aromatic compounds. After this temperature residence, the heating value back to
decrease, as observed for biochar produced at 570C. This decrease in heating value is associated
with total decomposition of hemicellulose and cellulose and partial decomposition of lignin, which
are materials with high energy capacity.
However, the calorific value has an asymptotic behavior with respect to residence time, thus
prolonging the residence time indiscriminately in order to improve the characteristics of the final
product does not provide favorable results.
3.5 Moisture and ash
The moisture content, expressed as a percentage relative to the original weight, affects adsorptive
capacity of biochar. For the adsorption of organic molecules, the efficiency decreases as the
moisture content increases, this is because certain pores that would be available for adsorption are
filled with water molecules.
The moisture of biochar occurs by absorbing water from the atmosphere in samples, due to the
hygroscopicity of biochars. By comparing the residence times, it was observed an increase of water
in biochars with increasing residence time (Table 6).
This result may be associated with an increased pore size of the biochar, mainly in one produced
at 570C, as a result of additional loss of mass suffered in relation to other biochars. The highest
moisture in pellet is associated with hydrophilic character of cellulose and hemicellulose, which had
already suffered some degradation in thermal biochars produced at 200C.

SUM 2014, Second Symposium on Urban Mining

Furthermore, tests were conducted to demonstrate the moisture resistance of biochars and can be
observed that they were unchanged when immersed in water for several hours, shows that the
hydrophobic character of the samples.
Low ash content was observed, this feature is important due to the low residue generated after
power generation (Table 6).
It is observed that both results were consistent with the thermal gravimetric method, which
showed low moisture content and ash.
3.6 Bulk density
The bulk density is very important to quantify volumes of products with irregular shapes because it
provides information that may be useful for logistics and transportation, since it considers the voids
between a particle and supply of real volume data for transport. Furthermore, it is used to calculate
the energy density. It has been shown that the density increases with decreasing particle size due to
the fact that the voids between the particles are smaller, in this way the greater the bulk density, the
greater the weight that can be transported or stored in a container fixed volume thereby minimizing
transport and storage costs (MANI et al., 2006; OBERNBERGER & THEK, 2004).
The bulk density provides the degree of compaction of one material relative to another (Table 7).
For example, the pellet is 1.397 times more compressed than biochar produced at 570C (540.9 /
387.1 = 1.397). Therefore, in an immediate analysis suggest that the pellet would be advantageous
as compressed fuel; however these two materials do not carry the same heating value per unit
volume. So, it is necessary to analyze the heating value of each of them for comparison of
proportion.
3.7 Energy density
The energy density was obtained by multiplying the bulk density and LHV (Table 8).
The energy density increased when the residence temperature was increased (minimum increase of
around 4% and maximum around 25%), but was little changed in relation to the variation of
residence time. From this test, it can be concluded that there is a greater amount of energy per unit
volume, in biochar in particular biochar produced at 570C.

4. CONCLUSION
In general, the heating treatment of pellets confers superior characteristics to biochar compared to
pellet in nature, showing greater amount of energy per unit volume, reduced moisture content and
reduced ash. This represents a greater generation of energy per volume of product per unit mass, a
reduction in the space required for storage and transportation of this fuel, and an improvement in
the storage and transport of biochar. The optimum conditions were observed in biochars produced
at 570C temperature residence, with an increase of 25% in energy density, 30% reduction in bulk
density and a 67% reduction in moisture content, all in relation to pellet in nature. This fact
indicates that this treatment can be a vehicle to enable the use of biomass residues, mainly in the
form of pellets heat-treated.

ACKNOWLEDGEMENT
The authors acknowledge CAPES for financial support and BrBiomassa Company for pellet
samples.

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REFERENCES
ANTAL, M.J; GRONLI,M. 2003. The art, science and technology of charcoal production. Eng.
Chem. Res. 42, 1619-1640.
ASTM D3173 -03. 2003. Standard Test Method for Moisture in the Analysis Sample of Coal and
Coke. Easton, MD: American Society for Testing and Materials.
ASTM D3174 -11. 2011. Test Method for Ash in the Analysis Sample of Coal and Coke from Coal.
Easton, MD: American Society for Testing and Materials.
ASTM D792 -13. 2013. Standard Test Methods for Density and Specific Gravity (Relative Density)
of Plastics by Displacement. Easton, MD: American Society for Testing and Materials.
ASTM E7 - 03. 2003. Standard Terminology Relating to Metallography. Easton, MD: American
Society for Testing and Materials.
ASTM E873 - 82. 2013 . Standard Test Method for Bulk Density of Densified Particulate Biomass
Fuels. Easton, MD: American Society for Testing and Materials.
BRIANE, D.; DOAT, J. 1985. Guide technique de la carbonisation: la fabrication du charbon de
bois. Aix-en-Provence, disud.
BRIDGWATER, A. V. 1999a. Principles and practice of biomass fast purolysis process for liquidis.
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BRITO, J. O. 1993. Expression of forestry production in energy units. In: Pan American Forestry
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BRITO, O.J.; FERREIRA, M.; BARRICHELO, L.E.G. 1978. Correlations between physical and
chemical characteristics of wood and charcoal production. II. Basic wood density x Apparent
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DERMIBAS, A. 2005. Pyrolysis of gound beech wood in irregular heating rate conditions. Journal
of Analytical and Applied Pyrolysis. 73, 39-43.
GARCIA, D. P.; CARASCHI, J. C.; VENTORIM, G. 2012. Energetic Caracterization of wood
pellets. 7th International Conference of Bioenergy. 1, 1-6.
GRACIA-PEREZ, M.; WANG, S.; SHEN, J.; RHODES, M.J.; LEE, W.J.; LI, C.Z. 2008. Effects of
temperature on the formation of lignin-derived oligomers during the fast pyrolysis of Mallee
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JARA, E.R.P. 1989. The calorific value of some woods that occur in Brazil. Sao Paulo: Institute for
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MANI S, TABIL LG, SOKHANSANJ S. 2006. Effects of compressive force, particle size and
moisture content on mechanical properties of biomass pellets from grasses. Biomass and
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MARCILLA, A.; GARCIA-GARCIA, S. ASENSIO, A.; CONESA, J. A. 2000. Influence of
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MORAIS, S. A. L.; NASCIMENTO , E. A.; MELO, D. C. 2005. Anlise da madeira de Pinus
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Association of Technical Standards - ABNT.

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CAPTIONS

Figure 1A. TG curves (biochar and pine pellet) under nitrogen atmosphere and heating rate of
30C/min.

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Figure 1B. DTG curves (biochar and pine pellet) under nitrogen atmosphere and heating rate of
30C/min.

Figure 2A. TG curves (biochar and pine pellet), in air atmosphere and a heating rate of 30C/min.

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Figure 2B. DTG curves (biochar and pine pellet), in air atmosphere and a heating rate of 30C/min.

Figure 3. TG curves in air atmosphere and heating rate of 30C/min for samples of biochar
produced at 570C of temperature residence, different heating rates and 1 hour of
residence time.

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Table 1. Gravimetric yield of biochar as function of heating rate for a pyrolysis temperature of
570C.

Table 2. Gravimetric yield of biochar as function of temperature and residence time for a heating
rate of 10C/min.

Table 3. Particle density of biochars and pellet.

Table 4 Table 4. Higher Heating Value of biochars produced at 570C and 200C of temperature
residence at different heating rate.

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Table 5. Higher and Lower Heating Values of the pellet and biochars.

Table 6. Moisture and ash of biochars.

Table 7. Bulk density of pellet and biochars.

Table 8. Energy density of the pellet and biochars.