Escolar Documentos
Profissional Documentos
Cultura Documentos
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
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.
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):
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.
(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.
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.
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.
Journal of Analytical and Applied Pyrolysis. 51, 3-22.
BRIDGWATER, A. V. 1999b. Pyne Guide 1. A Guide to Fast Pyrolisys of Biomass for Fuels and
Chemicals. United Kingdom: Aston University.
BRITO, J. O. 1993. Expression of forestry production in energy units. In: Pan American Forestry
Congress, I Brazilian Forestry Congress, E-Publishing Inc., Curitiba, pp. 280-82.
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
Density of coal - Prospects for improvement. Newsletter, ESALQ/USP, 6, 1-9.
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
woody biomass. Energy Fuels. 22, 2022-2032.
JARA, E.R.P. 1989. The calorific value of some woods that occur in Brazil. Sao Paulo: Institute for
Technological Research IPT, Technical Communication 1797.
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
Bioenergy. 30, 64854.
MARCILLA, A.; GARCIA-GARCIA, S. ASENSIO, A.; CONESA, J. A. 2000. Influence of
thermal treatment regime on the density and reactivity of activeted carbons from almond shells.
Carbon. 38, 429-440.
MORAIS, S. A. L.; NASCIMENTO , E. A.; MELO, D. C. 2005. Anlise da madeira de Pinus
oocarpa Parte I estudo dos constituintes macromoleculares e extrativos volteis. R. rvore. 29,
3, 461-470.
NORMA ABNT NBR 6922. 1981. Charcoal - physical tests - determination of density - bulk
density - test method. Brazilian Association of Technical Standards - ABNT.
NORMA ABNT NBR 8289. 1983. Coal - Determination of ash - Test method. Brazilian
CAPTIONS
Figure 1A. TG curves (biochar and pine pellet) under nitrogen atmosphere and heating rate of
30C/min.
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.
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.
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 4 Table 4. Higher Heating Value of biochars produced at 570C and 200C of temperature
residence at different heating rate.
Table 5. Higher and Lower Heating Values of the pellet and biochars.