1. Introduction
According to data from the National Forest Inventory of Spain (4th) [
1,
2], more than 600,000 ha of the northwest forestry surface is occupied by
Eucalyptus globulus and
Pinus pinaster. On the other hand,
Acacia spp. is considered an invasive species in Spain by authorities and although it is not very clear in its extension, some studies suggest an increase in the dominance area of these species, which is more important in the case of
Acacia dealbata and
Acacia melanoxylon [
2,
3]. The proposal for the appropriate utilization of the biomass remains of these invasive acacias, as well as of eucalyptus and pine waste, is highly necessary. This renewable biomass is an energy source that has the potential to replace petroleum-derived fuels. Furthermore, it can support local agricultural and forestry industries, given that these approaches typically use the lignocellulosic materials found in forestry residues or forest by products’ waste. Additionally, using an invasive plant which is highly difficult to manage or eliminate can lead to more sustainable forest management with economic returns [
4,
5]. However, the low adoption of innovative technologies and the limitations for the development of new products continue to represent untapped opportunities that have not been adequately addressed.
One approach to processing this biomass waste is through thermal treatment in order to produce charcoal, syngas, or another derivative. To produce biochar, several processes were used, typically categorized as torrefaction [
6], pyrolysis [
7], hydrothermal carbonization-HTC [
8], and microwave carbonization [
9]. Recently, pyrolytic processes for charcoal production have gained significant attention [
6]. In addition to its typical use as fuel, new applications have emerged in the agricultural sector, where it is currently employed in order to improve the physical and chemical properties of soils [
10]. The utilization of this material, commonly referred to as biochar (charcoal of vegetable biomasses origin), enhances soil organic matter content while modifying acidity levels (pH). Likewise, it alters the cation exchange coefficients, allowing to improve the yield in diverse types of crops. Due to its porous structure, biochar is also used as an additive in low rainfall regions, where it effectively stabilizes soil moisture levels [
11]. Additionally, the incorporation of biochar as a structuring agent and base material for nutrients during the composting process has optimized the degradation of organic matter while reducing emissions of ammonia and greenhouse gases. It is also known for its effectiveness in reducing the absorption of heavy metals in contaminated agricultural soils, and as an additive it is considered a climate change mitigation strategy given its ability to sequester solid carbon in agricultural fields for hundreds and even thousands of years [
12]. Among the currently available technologies, pyrolysis constitutes an important alternative for the recovery of these biomasses, offering the flexibility to produce various products. This process yields solid compounds (carbonaceous materials), gaseous components (syn-gases), liquid fractions (bio-oils), or combinations thereof. There is a growing interest in the use of biochar derived from biomass across diverse disciplines to tackle significant environmental challenges [
13].
Pyrolysis involves the thermal decomposition of the biomass under inert atmospheres (with either absence or low oxygen levels) and temperatures exceeding 300 °C [
14]. It is the most common method for producing biochar and also converting the initial biomass waste into other clean sources, such as oil and gas [
15]. Within the pyrolysis process, distinctions are made between a slow, fast, and very-fast system [
16,
17]. Several authors have successfully employed similar pyrolysis processes with different agricultural rest, yielding positive results [
18,
19,
20], and also from pine chips [
21], obtaining a high-performance biochar.
There are numerous parameters in the process with influence on the physicochemical properties of biochar, including the original raw material, reaction temperature, heating rate, residence time, and reaction atmosphere. However, it is particularly important that the system and reactor used involve simple manufacturing, employ affordable materials, are mobile (to be utilized near the biomass source), and feature straightforward operation without the need for non-renewable energy. The primary focus lies in enabling usage in rural areas of the wide world, especially in third-world regions with limited economic resources.
Following these criteria, this study employed a slow pyrolysis system in a straightforward vertical reactor with two parallel chambers. To achieve the desired temperature, a co-fuel process with biomass waste was utilized. Previously, studies [
22] elaborated biochar from acacia wood using a slow pyrolysis process, achieving satisfactory results with temperatures ranging between 300 and 500 °C, with an optimum temperature of 434.8 °C for 1 h using a laboratory electrical furnace. Similarly, Sriburi and Sohi et al. [
23,
24] used a slow pyrolysis process under a low–moderate temperature (450–500 °C) with an extended residence time (2–3 h) in the absence of oxygen to produce biochar from different waste materials, yielding satisfactory results for soil improvement purposes.
This study aims to develop biochar from three different biomass waste materials and compare the parameters from the original biomass and final charcoal. Through the application of thermochemical conversion processes, specifically slow pyrolysis using a simple double grate reactor, it is possible to transform the initial biomass into biochar with a high content of fixed carbon. This heating process does not rely on energy from electricity or fossil sources. Moreover, the syngas produced is redirected back into the heating process, thereby preventing energy and emission into the atmosphere. Additionally, the integration of consecutive processes allows for the utilization of residual heat, further enhancing efficiency. These principles fit into the research and application of biochar in Europe [
25] and takes into account that the diverse physicochemical traits of biochars profoundly influence their broad spectrum of applications [
26].
This is of high interest as it adds value to residual biomass, including invasive plants, thereby increasing their overall value. Comparing the original lignocellulosic biomass with the final biochar obtained after the thermal process allows to observe the enhancements in the original properties and parameters.
2. Materials and Methods
Biochar was produced from three types of waste biomass: 12-year-old
Pinus pinaster from a failure plantation (due to unsuitable silviculture conditions), 5-year-old
Eucalyptus globulus affected by a fire and weevil infestation, and biomass from a mass of invasive
A. dealbata.
Figure 1,
Figure 2 and
Figure 3 show the original biomass material in forestry (a), processed waste material (b), and final biochar (c). The study thus involves two hardwoods and one softwood, comprising lignocellulosic biomass from widely distributed trees. The three primary components of these lignocellulosic biomasses are cellulose, hemicellulose, and lignin [
27], together with inorganic chemicals and organic extractives, as well as a significant amount of free and bound water.
Biomass and biochars exhibit a multitude of physical, chemical, and mechanical characteristics, which vary depending on the raw material and pyrolysis conditions, making their characterization essential [
28]. For the characterization of the biomass and biochar, different standards of solid biofuels were used to prepare the material [
29] and determinate the following: moisture content (%) [
30,
31], density (kg/m
3) [
32,
33,
34], calorific value (kJ/kg) [
35], volatile matter (%) [
36], ash content (%) [
37], fixed carbon content (%), total carbon, hydrogen, and nitrogen content (%) [
38], and principal major and minor elements of composition (%) [
39,
40,
41]. The biochar yield was determined as the ratio of the prepared biochar weight in relation to the weight of the initial biomass subjected to pyrolysis, according to Equation (1).
where w1 is the weight of the biomass at the moisture content on a wet base before pyrolysis and w2 is the biochar weight at the end of the thermal transformation process.
Fixed carbon is the solid carbon in the biomass and biochar that remains in the pyrolysis process after devolatilization. It is determined from the following Equation (2).
where Vd and Ad were the volatile matter content and the percentage of ashes on a dry basis.
In relation to the thermal process employed for biomass transformation and biochar production,
Figure 4 shows the conditions of the slow pyrolysis process, divided into three phases. The first phase involves water content evaporation and biomass heating, with an increase in the temperature at a rate close to 4.5 °C/min for the first 40 min, reaching a maximum temperature of 540 °C over the next 90 min. In the second phase, pyrolysis occurs with the emission of syngas, with the temperature ranging between 540 and 480 °C for the subsequent 255 min inside the pyrolysis chamber, considering a long residence time [
13]. Finally, there is a third phase of cooling, during which the high residual temperature decreases to room temperature (15 °C) over a span of 15 h.
The reactor employed operates at a semi-industrial scale conducted by the research group.
Figure 5 shows the exterior (a) and interior view (b) of the reactor, along with a real image of the installed unit (c).
Figure 5b shows the double chamber: “chamber 1” where high temperatures are generated using biomass, with a volume of 0.17 m
3 and outlet chimney for gas and smoke; and “chamber 2”, contained inside chamber 1, where the biomass is transformed into biochar, with a capacity of 0.10 m
3, and is sealed from the outside with a 5 mm gas outlet hole. To simplify construction and avoid the need for complex welding, machining, or casting methods, locally available materials and supplies were utilized, allowing for quick and agile assembly while facilitating potential subsequent recycling.
In chamber 1, two types of fuel-biomasses are employed: low-density materials in the upper part of the chamber, comprising residual remains of pine solid wood from pallets with high flammability, and higher-density materials, consisting of pelletized biomass, which provide sustained temperatures over time. The combination of these two types of biomasses, along with the regulation of the combustion air entry through controlled holes in chamber 1, enables the control of the system temperature.
During the process inside chamber 1, combustion occurs as the biomass is heated in the presence of oxygen. Chemically, this exothermic oxidation of material generates high temperatures in the presence of oxygen, producing CO
2 and H
2O along with the hot flue gas that is transmitted to chamber 2. The combustion in chamber 1 produces the temperature for the reactor but is not optimal for producing biochar since it converts most carbon in the biomass to CO
2. However, in chamber 2, a rise in the temperature occurs with a deficiency in oxygen as a consequence of a gas-pressure increment inside. This pressure is expelled outside through a hole dimensioned accordingly. The gas pressure generated inside by the syngas is so high that it prevents the entry of oxygen from the outside. As a result, a thermal process and material flows within the reactor are achieved, comprising three phases, as depicted in
Figure 4. The external flame in chamber 1 never comes into contact with the material undergoing conversion to biochar in chamber 2. The syngas of chamber 2 has been reintroduced into the heating process, contributing to the increase in temperature and preventing the emission of gases into the atmosphere. Temperature profiles were measured with a set of 4 type K thermocouples and a data logger RS in the positions indicated in
Figure 5b.
5. Conclusions
This study demonstrates the feasibility of producing biochar with favorable properties using renewable and sustainable biomass, employing a simple double-chamber reactor and utilizing biomass as a source of thermal energy. The results indicate that all three types of lignocellulosic biomass provide suitable parameters for energy utilization and the production of high-quality biochar, with the biomass of acacia particularly standing out among the three.
The results of biochar produced via slow pyrolysis at temperatures between 400 and 500 °C demonstrate improvements over the values obtained from the original biomass. Biochar yields ranged between 30% and 40%, with a high fixed carbon content, showing the highest value at 77 ± [2.51]% with acacia biomass. The H/C ratio of 0.03 in all three biochars, compared to 0.13 in the biomass, indicates suitable aromaticity and maturation. The main inorganic elements in the three biochars show an increase compared to the original biomass. The high presence of calcium (Ca) and potassium (K) evidence an advantage for use in soil.
The high fixed carbon values enable the biochar utilization for soil remediation and enrichment, carbon sequestration, as filtering elements or another versatile application, as composting organic solid waste, decontaminating water and wastewater, serving as catalysts and activators, as well as in electrode materials and modifiers. The studied lignocellulosic biomass material, along with the selected working conditions and technologies, facilitated the production of high-quality biochar.