2.2.1. Acacia (Acacia dealbata L.)
Acacia-mimosa (family Fabaceae/Leguminosae, order Fabales, and class Magnoliopsida) with the scientific name
Acacia dealbata Link is an allochthonous or introduced woody tree with a large shrub and erect stem
[97].
Acacia-mimosa plays an important commercial role since its wood can be used for the paper production through the kraft process by the amount of cellulose present in the material
[101], allowing the elaboration of several products like cardboard, the paper for writing and printing, which gives it a special shine, considered of high quality, and more advantageous than eucalyptus due to the low amount of alkali it presents
[97], and finally, acacia wood is also used for the production of construction materials and furniture, compounds of interest to the medicinal sector
[123][124], xylooligosaccharides
[125], syringaldehyde, vanillin
[126], and solutions rich in glucose
[127][128]. The bark is used for the production of tannins (substances of plant origin) due to the high amount present in the species (greater than 74%)
[129] and other compounds such as absorbents
[130], those with an antimicrobial and antioxidant capacity
[100][131] and the anti-quorum sensing
[132]. In the perfume industry, flowers are processed to produce fragrances, as well as perfume fixatives
[97], in the production of compounds with anti-inflammatory properties
[133][134] as well as other types of products such as bioherbicides
[135]. In the ecosystem, the pollen in the flowers presents a relevant function for the continuity of sleep
[97]. The extracts from the leaves of
Acacia dealbata are excellent as a raw material in natural products beneficial to health due to their antioxidant activity
[100][136], and the antimicrobials present in the extract
[136] are also used for herbicides production
[135]. Concerning the timber sector, acacia is considered of high quality for the manufacture of furniture and poles and is also used as fuel for heat generation. Two liquid biofuels that can be produced from
Acacia dealbata [97] are bioethanol
[137][138] and bio-oil. Some studies researched the implementation of acacia for bioproducts and biofuels production in a biorefinery-type system, either from the residual material of the species
[139] or from all constituent parts of the species
[140].
Muñoz et al., 2007 studied the pre-treatment with two fungi (
Ceriporiopsis subvermispora and
Ganoderma australe) maintained at a temperature of 27 °C, moisture of 55% for 30 days, and the organosolv delignification was performed at 200 °C, with 60% of ethanol for 1 h. In this first phase, the pulp yield in the case of acacia was between 31% and 51% and obtained 93% of glucan and 2% of lignin. With the objective of producing bioethanol, it was applied to the pulp material with two process types SSF or SHF being utilized for the
Saccharomyces cerevisiae. For the SHF and SSF processes, the best conversion to bioethanol was obtained for acacia in the first process from 40% to 48%, and in the second process, it was 44% to 65%. These results concluded that each stage must be improved to obtain a higher conversion of this species into bioethanol, namely, in the pre-treatment through a decrease in the incubation time and in the stage of saccharification/fermentation to utilize a material with a higher pulp consistency
[141].
Another study that evaluated the possibility of producing bioethanol with
Acacia dealbata through a diluted acid pre-treatment, with this phase the most important because it is where the transformation of the lignocellulosic material in sugars for bioethanol production occurs. It was evaluated for two different systems: SHF and SSF, which included a wash with residual Water Insoluble Fraction (WIF). The
Acacia dealbata presented a high potential to produce bioethanol with 10.31 g ethanol L
−1 obtained during 24 h with the SHF process and with the other process, SSF, it obtained 7.53 g ethanol L
−1 over 48 h, so, under these conditions, SHF obtained the best results. However, it is possible to obtain 12.18 g ethanol L
−1 when the fermentation is made over the soluble fraction of undiluted water in parallel with the SHF process
[142].
To evaluate the potential of
Acacia dealbata in a biorefinery, this species was submitted to an ionic liquid 1-ethyl-3-methylimidazolium acetate pre-treatment for 30 min at a temperature of 150 °C, with 66% of the xylan (20 times higher when compared to untreated raw material) recovered and 88% of cellulose (13 times higher than untreated material). The remaining solid part (substrate) was processed in an enzymatic hydrolysis system (cellulose conversion) for 48 h, which allowed obtaining high yields of fermentable glucose (carbon source) suitable for the biofuels generation like bioethanol and other bioproducts
[128], therefore, the application of acacia in an industrial scale system such as a biorefinery is guaranteed.
In Spain, a study was carried out in which several
Acacia dealbata plantations were evaluated (by the high invasive degree of this species in the south of Galiza and north of Portugal) to characterize the species in relation to the moisture content, volatile percentage, HHV and LHV to determine its energy potential, in several constituent parts of the species such as the trunk and the thin leaves and branches. According to the values obtained, the average moisture content (35.29% for the trunk and 35.22% for the leaves and branches); volatiles (83.58% for trunks and 77.28% for leaves and branches); ashes (0.80% for the trunk and 2.32% for the leaves and branches) and HHV when the material is free of water (without moisture) is 4797.93 kcal kg
−1 for the trunk and 5181.10 kcal kg
−1 for the leaves and branches. In turn, the LHV is 4478.65 kcal kg
−1 for the trunk and 4865 kcal kg
−1 for the leaves and branches. With these results, the viability of acacia-mimosa as fuel in combustion systems for heat production or in cogeneration systems, due to the values obtained of the calorific power
[143] is guaranteed.
In Portugal, the main species for producing wood pellets for burn-in boilers is the
Pinus pinaster and for this cause, it is important to compare this type of material with other species like acacia-mimosa for the quantity of material that can be found in the territory
[96]. It can serve as a carbon reservoir because it is a fast-growing species, it also rapidly removes the carbon present in the atmosphere through CO
2, mitigating climate change, thus confirming its potential for the production of material with high carbon content
[144] such as biochar that can be obtained through the pyrolysis process at 450 °C for 8 h
[145].
An acacia plantation with 2 ha can yield 140 t of biomass for wood pellets production that has a similar quality to those produced with
Pinus Pinaster Aiton and
Eucalyptus globulus L., with the only exception being the amount of Cl which was slightly higher
[89]. In another study, on the contrary, it was found that the chemical composition (ash content, N and Cl) of
Acacia dealbata and
Eucalyptus globulus are the main factors that hinder their use for producing certified pellets. The use of the waste material of these species serves as a solution for the collection and reuse of the material, and it should be used in processes where certified products are not required
[146], creating a system that complies with the criteria governed by the circular economy. In a fluidized bed reactor with a turbulent regime, two different types of pellets were burned: one produced with maritime pine and the other with acacia-mimosa, and the contaminants [CO
2, CO, and nitrogen oxides (NO
x)] formed in each case were verified and compared. The pellets produced by both species presented a lower emission of contaminants and a better combustion behavior due to the type of reactor used (fluidized bed)
[147].
Vicente et al., 2019 analyzed the emissions of pellets produced from Acacia seen as an invasive species in Portugal, specifically located in the coastal areas, to be utilized like fuel at a residential level. Among the properties evaluated were the particulate matter PM
10 (anhydrosugars like levoglucosan 284 µg g
−1 PM
10 and polyaromatic hydrocarbons 8.77 µg g
−1 PM
10), CO (2468 ± 485 mg MJ
−1), sulfur dioxide (SO
2) (222 ± 115 mg MJ
−1), and NO
x (118 ± 14 mg MJ
−1). All these values were considered elevated because the acacias trees were grown in zones with high salt concentrations. For this reason, to obtain a solid fuel from acacia with minor production of emissions, the pre-treatment of the material before the pelleting including the drying step must be optimized, mixing the acacia with other materials to obtain a biofuel with other properties, to incorporate additives that allow major compaction of the particles and to control the air supply during the combustion
[148].
In another study, Amutio et al., 2013 evaluated several types of wastes from
Cytisus multiflorus (50%) and
Spartium junceum (50%) both identified as Bio1,
Acacia dealbata identified as Bio2, and, lastly,
Pterospartum tridentatum identified as Bio3 in the pyrolysis technology. The process occurred in a Conical Spouted Bed Reactor (CSBR), with a temperature of 500 °C, continuous biomass input in the system, and continuous removal of the char. In the liquid phase, the bio-oil (main product) was constituted of water, phenols, ketones, acids, furans, and a lesser quantity of saccharides, aldehydes, and alcohols. The results showed that the yield of bio-oil was 79.5% (Bio1), 72.1% (Bio2), and 75.1% (Bio3) being higher for the Bio1 due to the higher quantity of hemicellulose and cellulose in this species, that favors the bio-oil production. The char yield was 16.6% for Bio1, 23% (Bio2), and about 20% for Bio3. In the relation to the gas phase, the quantity produced was between 4% and 5% for the three species. These results showed the high benefits of these species for the bio-oil generation in a CSBR reactor, being possible to maximize the yield of the liquid phase with high heat and mass transfer rates, a low residence time of the volatile elements, and continuous removal of char, conditions that were maintained in this process
[119].
2.2.2. Maritime Pine (Pinus pinaster Aiton)
Pinus pinaster Aiton is a woody fast-growing species
[149] belonging to the family Pinaceae, order Pinales, and class Pinopsida, which requires a lot of insolation and is able to resist shade only in the first months after germination
[150].
This species presents a fundamental function in the economics and rural development in the commercialization of wood, namely for carpentry in exterior and interior areas (floors and parquet), as well as in the real estate sector for the high quality of the material, wood treated for the production of poles, scaffolding shipyards, packaging and pallets for the storage and transport of goods, bodyworks
[149], fiber and particle agglomerates in the phosphorus industry, in the manufacture of fence fencing, toys, blinds
[151], in the pulp production through the amount of cellulose present in the trunk, of resin for the generation of a great range of chemical products by the presence of terpenic oils of good quality
[152] and firewood, in their simple form for the production of heat at the domestic level. Other uses applied to this species are in the manufacture of poles, furniture, and building materials like particle boards
[153] and they serve as shading for recreation and picnic areas. The resin is utilized to make rosin and turpentine, the main components in the production of soaps, glues, oils, waxes, medicines, and varnishes. The bark is used to produce tar
[154], polyphenols, tannin, antioxidants, adhesives, bio-oil, and particle boards (from the bark partially liquefied)
[155].
Maritime pine can be used for several biofuels production using the biochemical process like biogas and bioethanol and in thermochemical conversion
[156] through solid fuels production of pellets
[157][158] and briquettes in heating, gasification, and pyrolysis systems.
Pinus pinaster is the principal material in the pellets production in Portugal as it is made of soft wood, an aspect that facilitates grinding, due to its low ash content and greater amount of extractives when compared to other species such as Eucalyptus
[157], and because of the availability of the species in the territory.
Pinus pinaster wood was studied for its viability for biofuel production in a biorefinery. The pre-treatment for the material was carried out for aqueous fractionation to obtain the hemicellulose saccharides solution (liquid) and another phase, the solid-state composed of cellulose and lignin. The liquid solution (constituted for polymeric or oligomeric hemicellulose saccharides) was treated with H
2SO
4 (up to 4 wt%) and heated (up to 130 °C) to transform substrates into sugars. The saccharification was achieved almost totally under certain conditions for possible fermentation. After the solid phase (conversion of cellulose) is mixed in the acid medium under microwave irradiation, levulinic acid is obtained to produce valeric biofuels and formic acid for further use in the fuel cell. In the case of the lignin, it was recovered like solid residue using a method with acid
[159].
The main species causing fires in Portugal are
Genista tridentata,
Cistus ladanifer,
Cytisus spp., and
Acacia dealbata (species that make up the first mixture), coming from marginal lands, and
Pinus pinaster and
Eucalyptus globulus (constituting the second mixture) integrated into the forest system, therefore, it was proposed to study the fractionation of each mixture as feedstock in a biorefinery for a year, to assess their potential to produce biofuels and other bioproducts. Each mixture was subjected to an autohydrolysis between 190 °C and 240 °C (non-isothermal conditions) to compare the two: the effects of fractionation of each mixture (solubilization of hemicellulose in oligosaccharides and the achieved recovery of lignin and cellulose), the heating values obtained to evaluate their potential as biofuel, and the behavior of enzymatic cellulose hydrolysis for the glucose formation. Excellent results were obtained for both mixtures, such as high oligosaccharide recovery, HHV (the solid part can be used as fuel), and improved glucose obtention (from 45% to 90%)
[99]. This type of mixture represents a suitable material for biofuel production (including bioethanol) and products of high commercial value in a biorefinery-type installation, being seen as an alternative to reduce the material load causing fires.
A study about the heating values from different species, allowed researchers to know what species are most significant to solids biofuel production, namely, wood pellets. It was evaluated that several species like
Castanea sativa,
Eucalyptus globulus,
Quercus robur,
Salix babylonica,
Populus ×
canadensis,
Pseudotsuga menziesii, maritime pine, among other types, were classified as softwoods and hardwoods. The results show that hardwoods had an HHV between 17,631.66 and 20,809.47 kJ kg
−1 and the softwoods had values ranging from 19,660.02 to 20,360.45 kJ kg
−1 (the value for the maritime pine is 20,237.89 kJ kg
−1 i.e., below the species with the highest HHV). In relation to the LHV, the hardwoods had a value between 14,411.54 and 17,907.85 kJ kg
−1 and the softwood values were between 15,629.71 and 16,935.72 kJ kg
−1, with the last value corresponding to the maritime pine, namely, the highest LHV. The study considers the
Pinus pinaster to be one of several species having the best conditions for application in the thermochemical processes, mainly, combustion
[160].
In the District of Bragança in Portugal, a study was conducted on the energy generation (electricity and heat) from the maritime pine because it is a forest species most common in this region. The destination of the energy produced includes several sectors (residential, service, and industrial). The total forest area in Bragança of the
Pinus pinaster is 89,024 ha with an energy content of 4170.5 TJ. However, consider the data of a power factory, 22% of efficiency, a heating value of 18 GJ t
−1, and an operation time of 7200 h year
−1 which can obtain electricity power of 254.9 GWh. Consider the annual yield of this species, and it can be concluded that it is possible to supply the Bragança District with almost 49% of energy and 60% of its electricity demands for each sector, and 84% of the total energy demands of the several sectors mentioned before
[161].
In Spain, the study by Álvarez-Álvarez et al., 2018 was made with the purpose of investigating the potential of different species including maritime pine. the maritime pine obtained the values as follows: the highest HHV of 19,366.277 kJ kg
−1 (mean); the lowest value of ash of 0.602%, and in the ultimate analysis; the percent of C, sulfur (S), and N were 47.775% C, 0.650% S, and 0.494% N. Once again, it can be concluded the importance of
Pinus pinaster in the energy production for the HHV and ash values, although the high concentration of N and S are elements that generate atmospheric pollutants
[98].
Viana, Rodrigues, Godina, Matias, and Nunes, 2018 performed the analysis and evaluation of several characteristics such as density, moisture, proximate and ultimate analysis, HHV, energy density (E
d), Fuelwood Value Index (FVI), and a dimensional value, among others. The most important results obtained for the different parts analyzed of the maritime pine (wood stem, pine needles, and top of the specie) were: 0.22% to 1.92% of ashes, 19.57 to 21.61 MJ kg
−1 of HHV, 2.06 to 8.9 GJ m
−3 of E
d, and the values of the FVI were superior in the case of the wood stem (4658) and top of the species (2861.8). Based on these results, it is guaranteed that the maritime pine represents a biomass with a very high potential to create energy in the form of woodchips, briquettes, and pellets
[118].
Following the previous study, one of the co-authors, Leonel Nunes, published another work where the woodchips produced from maritime pine were analyzed but it also incorporated the bark. It is important to highlight that in almost all species, the bark contains a very high amount of inorganic material that contributes to the superior values of the ashes. Later on, some problems can arise in the industrial boilers and during the combustion as the bark can cause, the incrustation of the scobs in the bottom of the equipment, a factor that increases the number of times that it is necessary to undertake maintenance requiring the boiler to stop
[162].
Several types of materials were studied in Spain, like maritime pine pruning (forestry), grapevine and olive tree pruning (agriculture), and sawdust and marc of grape (industry residues), for its use in the circulating flow gasifier, to evaluate different typologies of biomass, independent of the provenance in the same equipment and conditions, with the objective of determining which materials can be used in gasification systems, whether combined or not. The results show that agricultural pruning wastes (olive and grapevine) presented higher gasification efficiency and yield than forestry (
Pinus pinaster pruning) and industrial (marc of grape and sawdust) wastes, therefore, in the case of gasification, the agricultural wastes are more capable to produce a gas with high potential to be used for heat production or in the alternative, as power using the gas as working fluid through internal engines or gas turbines
[163].
In Montpellier, two-stage gasifiers with a fixed bed were installed (the equipment can be used in pyrolysis and gasification) with the
Pinus pinaster species as raw material. The pyrolysis was studied concerning different operational parameters. In relation to the biomass flow rate, when increased, a low quality of char was obtained. The best efficiency of the process (involving cracking, the heating value, and quality of the solid phase or charcoal and the gaseous phase) was obtained between 650 °C and 750 °C of temperature, 30 min residence time, and 10 and 15 kg h
−1 of biomass flow rate, as the best conditions to optimize the pyrolysis process and obtain some products with high added value as charcoal production with an HHV of 33 MJ kg
−1 and gases with an HHV of 15 MJ Nm
−3 [121].