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Energy Evaluation of Biochar Obtained from the Pyrolysis of Pine Pellets

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Energy Evaluation of Biochar Obtained from the Pyrolysis of Pine Pellets J Therm Anal Calorim (2016) 126:1879–1887 DOI 10.1007/s10973-016-5683-4 Energy evaluation of biochar obtained from the pyrolysis of pine pellets 1 2 3 3 Lidya B. Santos • Maria V. Striebeck • Marisa S. Crespi • Jorge M. V. Capela • 3 1 Clovis A. Ribeiro • Marcelo De Julio Received: 1 June 2015 / Accepted: 3 July 2016 / Published online: 22 July 2016 Ó Akade´miai Kiado´, Budapest, Hungary 2016 Abstract The wood pellets are mainly used in heating compared to pellets in nature, showing a greater amount of environments, commercial and residential, as well as fuel energy per unit, high stability, reduced moisture content for production of thermal and electric energy in industrial and reduced ash content. The kinetic of combustion to plants. Furthermore, the heterogeneity and variable mois- biochar in oxygen-rich atmosphere showed the dependence ture content, combined with the high cost of transport, are between the activation energy and conversion degree, with limiting challenges that must be overcome with new a continuous decrease in the activation energy, character- technologies and new products. In this context, torrefaction istic of complex processes comprised by initial reversible and pyrolysis are attractive alternatives for increasing reaction followed by an irreversible one. energy density and decreasing the moisture content of the samples, based on thermochemical conversion in a non- Keywords Energetic characterization Á Torrefaction Á oxidizing atmosphere. Samples were produced to perform Pyrolysis Á Pine pellets Á Biochar Á Non-isothermal kinetic the energetic characterization of biochar from pine pellet using different heating rates 5–30 °C min-1, different residence temperatures 200, 280 and 570 °C and different Introduction residence time (1 and 0.5 h). The high heating value (HHV) of each variable was measured and allowed to Burning wood pellets is mainly used for warm-up environ- observe that the heating rate did not influence of a signif- ments (commercial and residential environments), but it can icant way the results, in other words, a 5 % variation also be used as fuel for generating electricity in industrial between the lowest and highest heating rate. Notwith- plants, or even in power plants. The versatility and avail- standing, the HHV was expressive compared to the pellet ability of biomass, combined with its characteristic of in nature, when it has been found an energetic gain over renewable energy and do not contribute to global warming, 80 %. In general, the biochar from pine pellets obtained by and in addition its cost is an average 25–50 % less than fossil torrefaction or pyrolysis has appropriated characteristics heating fuels, are strong arguments to enhance its use worldwide [1–5]. Moreover, the heterogeneity, low energy density, and variable humidity, combined with the high cost & Clovis A. Ribeiro [email protected] of transport, are limited challenges that must be overcome with new technologies and new products [6–9]. In this con- 1 Building Engineering Department, Aeronautical Institute of text, torrefaction and pyrolysis are attractive alternatives for Technology, Marechal Eduardo Gomes Square 50, increasing energy density and decreasing the moisture con- Sa˜o Jose´ dos Campos 12228-900, Brazil 2 tent of the samples, based on thermochemical conversion in a Chemical Engineering Department, National University of non-oxidizing atmosphere (a procedure that contributes to Buenos Aires Province Center College Engineering, del Valle Avenue 5737, B7400JWI Olavarria, Argentina the generation of an additional product of appreciable eco- nomic value). These advantages make interesting the use of 3 Analytical Chemistry Department, Sa˜o Paulo State University IQ/UNESP, Professor Francisco Degni Street 55, pyrolyzed biomass for energy purposes, requiring, however, Araraquara 14800-060, Brazil a proper characterization. Thus, the aim of this work was to 123 1880 L. B. Santos et al. produce and characterize biochar from pine pellet for further combustion takes place at constant volume and in which the use of it as fuel. It has shown the caloric value, moisture water formed during combustion is condensed, and the heat content, density and immediate analysis of the most impor- which derived from this condensation recovered [18]. The tant properties of wood for use as fuel. Thus, the present lower heating value (LHV) is the energy available per unit study produced biochar of the pine pellet and determined the mass of fuel after deducting losses from evaporation of water. properties of the same following the above recommendation The HHV of biochar was determined by bomb calorimeter, [10–12]. model IKAC2000, according to ASTM E7 [19], using the mass of 0.5 g in triplicate. The LHV was obtained by Eq. 2 [20]: LHV ¼ HHV À 51:14 Â H ð2Þ Materials and methods T where LHV is the lower heating value in MJ kgÀ1; HHV is À1 The biomass used in the study is constituted by residues the higher heating value in MJ kg , and HT is the from furniture industry composed solely of Araucaria hydrogen content in %. angustifolia [13], also known as Parana´ pine, Brazilian pine or candelabra tree, shaped like pellets (pine pellets). Moisture and ash The pellets of the wood of Araucaria angustifolia contain 58.3 % cellulose and 28.5 % lignin with long fibers [14] Moisture and ash contents were determined by gravimetric and were obtained by the BrBiomassa Company, Parana´ technique, according to ASTM D-3173 [21], ASTM State, Brazil. The development process of biochar made in D-3174 [22]. The samples were heated at 105 °C until this work consisted of subjecting the sample to a slow constant mass. In a subsequent experiment, the same pyrolysis (since it presents the highest yields in solids) in a sample was used for the determination of ash content, muffle furnace under a nitrogen atmosphere (flow of raising the temperature to 775 °C maintaining per one hour. 1 L minÀ1). Following several temperature settings of 200, 280 and 570 °C and residence time of one hour and a half Thermal stability and kinetic evaluation hours, in addition to varying the heating rate from 5 to 30 °C minÀ1 [15]. The thermal stability of the biochar and pellet samples was determined by a thermal gravimetric analysis performed in Particle density an apparatus SDT À 2960 from TA Instruments. For these analyses, it was used around 3.5 mg of sample, in alumina The bulk density is the mass of the sample per volume pan, under an atmosphere of nitrogen and air (gas flow of occupied by the particle (solid and internal pore volume). 100 mL minÀ1). The heating rate was of 10–30 °CminÀ1, The particle density of the biochar was found by deter- from ambient temperature (±25 °C) to 850 C. mining the mass of the sample in a calculated volume using For kinetics study, the conditions applied for biochars a caliper [16]. were 5, 10, 20, 25 and 30 C minÀ1 heating rates under dynamic air atmosphere to simulate the combustion con- Bulk density dition. Previously to kinetic experiments, several flow rates of air were tested, and the flow of 100 mL minÀ1 was The bulk density is the mass of sample in a specific volume chosen as the most suitable for not providing oscillations in [17]. In this study, it was used a regular container (prism) the signals of TG curves. Preliminary tests indicated that with a capacity of around 0.2 m3. The bulk density was the sample mass of 3.5 mg was suitable for kinetic study, as calculated by Eq. 1: it did not provide any dependence of mass for the profiles observed in thermogravimetric curves [23, 24]. All assays Dgran ¼ mbiochar=Vrecip ð1Þ were performed in inert a-alumina sample holder and À3 where Dgran is the bulk density of coal in kg m ; mbiochar is previously to the experiments, the equipment was cali- 3 the biochar mass in kg; Vrecip is the container volume in m . brated for baseline, mass, and temperature in the proper experimental conditions. Heating values Activation energy: local linear integral The heating value or calorific value of a wood sample is isoconversional method defined as the amount of energy in the form of heat released by the combustion of a unit mass or volume, hence MJ kgÀ1 for The activation energy for combustion of biochars samples solids [18]. The higher heating value (HHV) is one in which was obtained employing the isoconversional integral 123 Energy evaluation of biochar obtained from the pyrolysis of pine pellets 1881 method based on interactive theorem for integral average of final pyrolysis temperature, for a given plant species on the value, analogous to the method of Wanjun and Donghua yields of charcoal, liquid and gas. Data show that the behavior [25], where the kinetics of the reactions of decomposition of the coal, when the pyrolysis temperature increases, is of organic matter can be initially described by the differ- losing its volatiles, which will enhance its liquid and gas ential, Eq. 3, given by: phases. Although the charcoal yield decreases with increas- da A ing temperature, there is a significant improvement in fixed ¼ eÀE=RTf ðaÞ ð3Þ dT b carbon content, this indication of quality input [26]. Another notable impairment is observed when yields are compared to Assuming that the parameters Ea, Aa and the local heating coal and liquids in different heating. Several studies show that rate ba are constants in ½a À Da; a þ Da, from Eq. 3,we it is possible to increase the recovery of liquid products sig- can obtain that: nificantly by increasing the heating rate [27–29].When the Z Z aþDa TaþDa heating is conducted at a low heating rate, the temperature 1 Aa ÀEa DgðaÞ¼ da ¼ e RTdT ð4Þ takes to reach a particular value, where a higher rate of f ðaÞ b aÀDa a TaÀDa thermal decomposition of biomass components occurs, there where DgðaÞ¼gða þ DaÞÀgða À DaÞ and g0ðaÞ¼ are a reduced speed and output and the newly formed com- 1=f ðaÞ.
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