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Kinetic Study of Pyrolysis of Coniferous Bark Wood and Modified Fir Bark Wood

https://doi.org/10.3390/fire6020059

“We report on the kinetics of pyrolysis of bark wood of four coniferous tree species: fir (Abies sibirica), larch (Larix sibirica), spruce (Picea obovata), and cedar (Pinus sibirica) denoted as FB, LB, SB, and CB, respectively. Thermogravimetry (TG) and differential scanning calorimetry (DSC) methods were used to study the influence of KCl and K3PO4 compounds on the process of thermal decomposition of fir bark and determine the main thermal effects accompanying this process. As a result of the studies carried out, it was found that KCl additives practically do not affect the decomposition of hemicelluloses, but they shift the maximum decomposition of the cellulose peak in the direction of decreasing temperature to 340.9 °C compared to untreated bark (357.5 °C). K3PO4 promotes the simultaneous decomposition of hemicelluloses and cellulose in the temperature range with a maximum of 277.8 °C. In both cases, the additions of KCl and K3PO4 reduce the maximum rate of weight loss, which leads to a higher yield of carbon residues: the yield of char from the original fir bark is 28.2%, in the presence of K3PO4 and KCl it is 52.6 and 65.0%, respectively. Using the thermogravimetric analysis in the inert atmosphere, the reaction mechanism has been established within the Criado model. It is shown that the LB, SB, and CB thermal decomposition can be described by a two-dimensional diffusion reaction (D2) in a wide range (up to 0.5) of conversion values followed by the reactions with orders of three (R3). The thermal decomposition of the FB occurs somewhat differently. The diffusion mechanism (D2) of the FB thermal decomposition continues until a conversion value of 0.6. As the temperature increases, the degradation of the FB sample tends to R3. It has been found by the thermogravimetric analysis that the higher cellulose content prevents the degradation of wood. The bark wood pyrolysis activation energy has been calculated within the Coats–Redfern and Arrhenius models. The activation energies obtained within these models agree well and can be used to understand the complexity of biomass decomposition.”

“The pyrolysis of the initial and modified (with potassium compounds) biomasses was implemented with a NETZSCH STA 449 F1 Jupiter thermal analyzer. A sample of 15–16 mg was loaded into the analyzer and heated from 25 to 900 °C at a rate of 10 °C/min. The high-purity carrier argon gas was supplied at a flow rate of 50 mL/min. The TGA experiments were repeated 3 times; the weight loss curves were found to be similar.”

3.1. Thermogravimetry Analysis

Figure 1 shows the thermogravimetry (TG) (a) and differential thermogravimetry (DTG) (b) profiles of the FB, LB, SB, and CB pyrolysis at a heating rate of 10 °C/min.
Figure 1. TGA analysis of pyrolysis of bark wood: TG (a) and DTG (b) curves.
The curves have the typical appearance of pyrolysis of lignocellulosic materials. The thermal decomposition of bark samples started at about 200 °C, followed by a major loss of weight in the temperature range of 200 and 380 °C, during which the bulk of the volatiles was released, and it was essentially completed by 700 °C, with the evolution of secondary gases, leading to the formation of char. The amount of char obtained for FB, LB, SB, and CB is 28.2, 32.6, 32.1, and 31.7%, respectively. By the end of pyrolysis (700 °C), the fir bark showed a greater weight loss compared to other studied bark samples, which indicates a higher content of the carbohydrate component.
In the faster step of the conversion process, two distinct peaks are clearly observed in all the DTG curves. The first, occurring at lower temperatures, represents the decomposition of hemicellulose present in each material, and the second corresponds to the decomposition of cellulose. For the flat tailing section, lignin is responsible, which is known to decompose slowly over a broader temperature range [30,31].
By comparing the DTG peaks (Figure 1b) between investigated bark woods, it can be noticed that they are similar in position but differ in height. The maximum decomposition rate decreases in a row: FB, LB, CB, and SB (6.5, 6.3, 5.9, and 5.3%/min, respectively). It can be assumed that the rate of decomposition of the main period of pyrolysis of the bark of wood is associated with the content of cellulose, as noted in [32].

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