BioEnergy Research (2021) 14:175–189

https://doi.org/10.1007/s12155-020-10166-z

Influence of Extractives Content and Lignin Quality of Eucalyptus

Wood in the Mass Balance of Pyrolysis Process
Thiago de Paula Protásio 1 & Michael Douglas Roque Lima 2,3 & Roberthi Alef Costa Teixeira 1 &
Fábio Silva do Rosário 2 & Ana Clara Caxito de Araújo 3 & Maíra Reis de Assis 3 & Paulo Ricardo Gherardi Hein 3 &
Paulo Fernando Trugilho 3

Received: 18 April 2020 / Accepted: 13 July 2020 / Published online: 20 July 2020
# Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
Several studies have highlighted the importance of the chemical composition of Eucalyptus woods in the generation of thermal
energy and charcoal production. However, the influence of wood chemical constituents on the pyrolysis mass balance is still not
sufficiently clear. This paper brings new insights about the influence of extractives and guaiacyl (G) to syringyl (S) ratio of lignin
macromolecule in the carbon, hydrogen, and oxygen balances of the pyrolysis process. Thus, the aim of this research was to
investigate the effect of the wood quality of genotypes of Eucalyptus on the carbonization mass balances. Ultimate analysis,
structural chemical constituents, and lignin composition analyses were carried out in 14 clonal materials of Eucalyptus spp. at 81
months of age. After pyrolysis, the ultimate analysis of charcoal and the carbonization mass balance was also investigated. The
findings show a positive relationship between the percentages of carbon and hydrogen retained in the charcoal with the lignin
content and its composition. E. camaldulensis (clone 1025) and E. grandis hybrids (clone 1039) presented better wood quality for
charcoal production, due to the results of gravimetric yield (35.7%), retained carbon (59.6%), and retained hydrogen (20.2%)
after pyrolysis. In addition, these genetic materials stood out for the high values of lignin (32.0%), extractives soluble in acetone
(2.4%), and mass of guaiacyl per kg of dry wood (27.2 g kg-1) associated with the low S/G ratio (2.5). The extractives content and
lignin composition must be simultaneously analyzed to improve the Eucalyptus clones classification for charcoal production.

Keywords Energy forest . Bioreducing agent . Guaiacyl unit . Ultimate composition . Carbon

Introduction environmental problems, the decentralization, and sustainabil-

ity of the countries’ energy matrix [3, 4]. Forest plantations,
The continuous advance of industrialization demanded a great including in degraded areas, have been encouraged as a solu-
need for energy, mainly from fossil fuels, which resulted in tion to the energy problems of modern society [2].
environmental pollution and higher costs in the energy supply Forest biomass has been used for several energy purposes,
of homes and industries [1]. According to estimates, only 19% directly as firewood and chips, or transformed into solid fuels,
of global energy demand is met by renewable sources, of such as charcoal for domestic use (e.g., barbecue) and to sup-
which biomass contributes 9% of the total, while 10% consists ply the demand of the steel making process [5]. Charcoal
of wind, geothermal, solar, and biofuels [2]. The use of renew- production in Brazil represents 11% of the total world produc-
able energies is an important strategy to increase indepen- tion, and its main application is in the steel industry for the
dence from fossil fuels, providing a reduction in reduction of iron ore and the production of pig iron [6] to
produce the so-called “green steel.” The increase of charcoal
* Thiago de Paula Protásio
production in the industrial plants is a major challenge of a
thiago.protasio@ufra.edu.br sustainable character, in view of the great dependence on coal
and its impacts on the environment [7].
1 The genera Eucalyptus stands out in the energy production
Federal Rural University of Amazonia-UFRA, Campus Parauapebas,
Parauapebas, Pará, Brazil due to its rapid growth, high volumetric productivity, and wood
2 properties suitable for cogeneration and conversion into steel
Federal Rural University of Amazonia-UFRA, Campus Belém,
Belém, Pará, Brazil plant charcoal [7–10]. Currently, the forest plantations in Brazil
3 cover an area of 7.83 million ha, in which 5.67 million (72.4%)
Department of Forest Science, Federal University of Lavras-UFLA,
Lavras, Minas Gerais, Brazil consist of Eucalyptus crops [6]. Therefore, it is required to select
176
and indicate the genetic materials most suitable for the produc-
tion of charcoal with high productivity and adequate quality as
reducing agent in blast furnaces of companies.
For the charcoal production, it is essential to consider some
qualitative criteria of wood, such as high values of basic density
(≥ 500 kg m−3) and content of lignin (≥ 28%), to ensure high
yield and satisfactory quality of the bioreducer [11–13]. The
wood chemical composition, specifically the carbohydrates and
lignin contents, and the anatomical features, such as fibers of
thicker cell walls with a smaller width, are related to the wood
performance during pyrolysis and can directly influence the mass
balance of the thermochemical conversion process of wood into
charcoal [14, 15].
In addition to the productivity of forests destined for charcoal
production and wood quality [11], several studies have highlight-
ed the importance of evaluating the chemical composition of
Eucalyptus wood, especially the lignin macromolecule [16, 17].
Woods with high lignin contents and low syringyl/guaiacyl
(S/G) ratios are prone to increase the charcoal yield [14, 16].
Araújo et al. [18] have investigated this issue on Eucalyptus
wood and charcoal, but reported no correlation between the S/
G ratio and the carbonization process yield for Eucalyptus clones.
On the other hand, Castro et al. [16] reported a significant neg-
ative correlation between S/G ratio and charcoal yield for
Eucalyptus clones. In short, few studies were conducted to better
understand the relationship between wood chemical constituents
and gravimetric yielded of wood/charcoal from fast-growing
Eucalyptus plantations. Thus, the few results reported in the lit-
erature suggest that the S/G ratio is not the key factor to control
carbonization mass balance [18].
Here, we hypothesize that phenols derived from lignin, such
as the guaiacyl (G) and syringyl (S) mass present in the wood
need to be considered for the correct classification of superior
genetic materials for the bioreducer production. Although the S/
G ratio is used to classify Eucalyptus clones for bioenergy [11,
19], research on the lignin quality specifying the G and S content
per wood mass is incipient in the literature. Thus, the aim of this
research was to analyze the effect of Eucalyptus spp. in the
carbonization mass balances and; thus, to understand how the
wood quality can influence the yields of the products and by-
products of pyrolysis. The detailed analysis of the carbonization
mass balances and the wood and charcoal properties will allow a
better understanding of this thermochemical process and may
assist in the choice of the best genetic materials for charcoal
production, a relevant industrial input in Brazil.
Material and Methods
Wood Sampling
In this study, 14 genetic materials of Eucalyptus spp. from a
clonal test installed at 3 m × 3 m spacing by the Plantar group,
Bioenerg. Res. (2021) 14:175–189
located in the Curvelo town, Minas Gerais state (18° 45′
06.44″ S; 44° 33′ 39.16″ O and 690 m altitude) were analyzed
at 81 months of age (Table 1).
Vwb commercial volume of wood, with bark, DBHwb di-
ameter at breast height, with bark, BD wood basic density.
Mean ± standard deviation. Source: Protásio et al. [11, 20]
Three trees of medium diameter were sampled by genetic
material. The diameter at breast height (1.30 m from the soil)
and the commercial height of 42 trees were measured. Disks
with 2.5 cm thick were removed in five longitudinal positions,
at 2, 10, 30, 50, and 75% of the tree commercial height, con-
sidered up to a minimum diameter of 4.0 cm with bark, as
recommended by Downes et al. [21]. The disks removed from
the trees were cut into four wedges passing through the pith.
Two opposite wedges from all the longitudinal positions were
used to determine the chemical composition of the wood,
carbonizations on a laboratory scale, and ultimate analysis of
the charcoal produced.
Chemical composition of the wood
One sample composed of the disks taken from all the longitu-
dinal sampling positions was considered for the wood chem-
ical characterization. Samples ground, sieved, and retained
between 200 mesh (0.074 mm) and 270 mesh (0.053 mm)
sieves were used for ultimate analysis. The fraction that was
retained between the 40 (0.420 mm) and 60 mesh (0.250 mm)
sieves was used in the other wood analyses.
The insoluble lignin content (Klason) was obtained accord-
ing to the methodology of Gomide and Demuner [22], and the
soluble lignin content (Klason) in sulfuric acid was deter-
mined according to the method of Goldschimid [23]. The total
lignin was obtained by the sum of insoluble and soluble lignin.
The lignin degradation was carried out by the alkaline ox-
idation method of the wood with nitrobenzene, followed by
high-performance liquid chromatography (HPLC), for the
quantification of its derivatives, according to the methodology
of Chen [24], with some adaptations described in Araújo et al.
[18] and Protásio et al. [20]. HPLC analyses were carried out
in a chromatograph Shimadzu® model CBM-20A (Kyoto-
Japan), equipped with an LC-18 column and UV-SPD-20A
detector, operating at 280-nm wavelength. The mobile phase
was composed of acetonitrile:water (1:6 v/v), pH adjusted to
2.6 with trifluoroacetic acid, and injected at a flow rate of 1.0
mL min−1. The oven temperature was adjusted to 40 °C. The
injection volume of the lignin samples was 20 μL and the
lignin oxidation products were quantified using the vanillin
and syringaldehyde standards. Subsequently, the mass of
syringyl and guaiacyl units per kilogram of dry wood and
the S/G ratio were determined. It is worth mentioning that
the masses of the syringyl and guaiacyl units were not deter-
mined directly, but by quantifying the mass of syringaldehyde
and vanillin, respectively, which are the main products
Bioenerg. Res. (2021) 14:175–189 177

Table 1 Eucalyptus clones evaluated in the study

Clone Species/hybrids Vwb DBHwb BD

(m3 tree−1) (cm) (kg m−3)

1004 Eucalyptus urophylla x E. camaldulensis 0.20 ± 0.00 15.1 ± 0.3 563.9 ± 9.0
1005 Eucalyptus urophylla 0.22 ± 0.00 15.8 ± 0.3 542.4 ± 5.4
1006 Eucalyptus urophylla 0.28 ± 0.01 17.2 ± 0.3 495.5 ± 1.5
1008 Eucalyptus urophylla 0.23 ± 0.01 16.6 ± 0.5 455.5 ± 15.3
1009 Eucalyptus urophylla 0.21 ± 0.02 15.5 ± 0.8 569.4 ± 8.5
1015 Eucalyptus urophylla 0.20 ± 0.01 15.0 ± 0.3 518.9 ± 5.7
1023 Eucalyptus urophylla hybrid 0.17 ± 0.02 13.9 ± 0.1 517.4 ± 9.1
1024 Eucalyptus urophylla hybrid 0.18 ± 0.01 14.7 ± 0.4 550.9 ± 6.3
1025 Eucalyptus camaldulensis hybrid 0.16 ± 0.01 14.1 ± 0.3 570.7 ± 7.3
1031 Eucalyptus spp. 0.27 ± 0.00 17.1 ± 0.2 497.8 ± 8.3
1033 Eucalyptus urophylla hybrid 0.23 ± 0.01 15.5 ± 0.2 553.4 ± 0.9
1036 Eucalyptus urophylla 0.18 ± 0.01 14.0 ± 0.2 554.1 ± 7.7
1037 Eucalyptus spp. 0.35 ± 0.04 19.6 ± 0.6 520.8 ± 7.2
1039 Eucalyptus grandis hybrid 0.21 ± 0.01 15.7 ± 0.3 570.0 ± 8.9

derived from the oxidation of these constituent units of the
lignin macromolecule.
The extractives soluble in acetone and ash contents were de-
termined according to the procedures described in the standards
T 280 pm-99 [25] and D1762-84 [26], respectively. The carbon
(C), hydrogen (H), nitrogen (N), and sulfur (S) contents were
obtained by ultimate analysis, performed in an Elementar® ana-
lyzer Vario Micro Cube (Langenselbold-Germany). The oxygen
content was obtained by difference [O (%) = 100 − C (%) − H
(%) − N (%) − S (%) − Ashes (%)]. All elements were quantified
in relation to the dry wood mass. The data regarding the chemical
composition of the analyzed woods are available in the study of
Protásio et al. [20].
Charcoal production and process mass balance
The carbonizations in the laboratory scale were performed for
each tree in an electric oven (muffle) with a metal reactor
connected to a water-cooled condenser, which is coupled to
a condensable gas collecting bottle. Approximately 500 g of
wood of the opposite wedges from the disks removed at dif-
ferent heights in the trees were used in each carbonization.
The wood samples were previously oven dried at 103 ± 2
°C. The initial temperature of carbonization was 100 °C and
the final temperature was 450 °C. The electric oven remained
stabilized at 450 °C for 30 min. The heating rate of the electric
oven was 100 °C h−1 and the total time of carbonization was 4
h.
The gravimetric yield in charcoal (GYC) of each sample
from the different Eucalyptus clones was calculated on a dry
basis after carbonization (Equation 1).
 
DMC
GYC ¼  100 ð1Þ
DMW
where, GYC is the gravimetric yield in charcoal (%, dry basis);
DMC, dry mass of charcoal (g); and DMW, dry mass of wood (g).
The same procedures adopted for wood were followed for
the ultimate analysis and ash determination of the charcoal
(see item “Chemical composition of the wood”). For the de-
termination of C, O, and H balances, the contents of these
elements present in charcoal and wood and the GYC were
considered (Equations 2, 3, and 4). The percentages of C, O,
and H retained in the charcoal structure, based on the dry mass
of each chemical element present in the wood, were consid-
ered in the calculations. Finally, the percentages of C, O, and
H volatilized were obtained by difference, which is,
subtracting from 100% the percentage of each element
retained in charcoal.
 
CCC
RC ¼ GYC  ð2Þ
CCW
where, RC is the retained carbon in charcoal (%); GYC, gravi-
metric yield in charcoal (%, dry basis); CCC, carbon content
in charcoal (%); and CCW, carbon content in wood (%).
 
OCC
RO ¼ GYC  ð3Þ
OCW
where, RO is the retained oxygen in charcoal (%), GYC, gravi-
metric yield in charcoal (%, dry basis); OCC, oxygen content in
charcoal (%); and OCW, oxygen content in wood (%).
178
 
HCC
RH ¼ GYC  ð4Þ
HCW
where, RH is the retained hydrogen in charcoal (%); GYC,
gravimetric yield in charcoal (%, dry basis); HCC, hydrogen
content in charcoal (%); and HCW, hydrogen content in wood
(%).
Statistical analysis
The data were submitted to the Bartlett, Durbin-Watson, and
Shapiro-Wilk tests, at the level of 5% of significance, to verify
the homogeneity of the variances, autocorrelation of the resid-
uals, and normality, respectively. Subsequently, univariate
analyses of variance were performed, in which a completely
randomized design was adopted, aiming to evaluate the effect
of clones on the wood chemical characteristics and the car-
bonization process, considering three repetitions. The follow-
ing variables were analyzed in the wood: total lignin content,
S/G ratio, grams of guaiacyl kg−1 of wood, grams of syringyl
kg−1 of wood, content of extractives soluble in acetone, and
ultimate analysis composition. The following variables were
analyzed in the charcoal: contents of carbon (C), hydrogen
(H), nitrogen (N), and sulfur (S). In the pyrolysis process were
analyzed the gravimetric yield in charcoal, retained C, volatil-
ized C, retained H, volatilized H, retained O, and volatilized
O. The Scott-Knott test was used at levels of 5% and 10% of
significance, for the multiple comparisons of means and uni-
variate grouping of Eucalyptus clones.
Multivariate statistical techniques are more efficient in
grouping and selecting Eucalyptus clones compared to univar-
iate procedures [19]. Thus, the clones were grouped by prin-
cipal component analysis (PCA), specifically by dispersion
analysis of scores. Variables with the greatest contributions
to the principal components (PC) were identified based on
the eigenvectors.
Canonical correlation analysis was applied to verify the
linear correlations between the pyrolysis mass balance and
wood chemical characteristics. Each variable was represented
by 3 replicates and 14 Eucalyptus clones, totaling 42 observa-
tions. This multivariate statistical analysis was performed be-
tween the group formed by the wood characteristics (indepen-
dent variables - X) and the group formed by the variables of
the pyrolysis process (dependent variables - Y). Group X was
represented by the following variables: total lignin, extractives
soluble in acetone, S/G ratio, and mass of guaiacyl and
syringyl units per kilogram of dry wood. On the other hand,
group Y was composed of the following variables: gravimetric
yield in charcoal and the percentages of C, H, and O retained
in the charcoal. Thus, it was possible to determine four canon-
ical functions or four pairs of canonical statistical variables,
interpreted by the canonical charges and the crossed canonical
Bioenerg. Res. (2021) 14:175–189
charges. The level of explained variance, that is, the percent-
age of variance in the dependent canonical statistical variable
that can be explained by the independent canonical statistical
variable, was determined by squaring the canonical correla-
tion (canonical R2). The same procedure was adopted by
Protásio et al. [27] in the canonical correlation analysis be-
tween the characteristics of charcoal.
All statistical analyses were performed in R software, ver-
sion 3.4.3 [28], using the packages car [29], lmtest [30], CCA
[31], CCP [32], and yacca [33].
Results and discussion
Chemical composition of the wood and charcoal
Clone effect was verified by the F (Table 2) and Scott-Knott
tests in the contents of total extractives, total lignin, S/G ratio,
mass of guaiacyl, and syringyl per kg of wood (Table 3). For
the content of extractives soluble in acetone, there was the
formation of four groups of clones, in which clones 1039
(E. grandis hybrid), 1037 (Eucalyptus spp.), and 1036
(E. urophylla) had higher mean values (2.48%). The choice
of these genetic materials can result in an increase in gravi-
metric yield in charcoal (GYC) due to the higher content of
extractives. These chemical constituents may have a direct
correlation with the charcoal production, depending on their
chemical constitution and resistance to thermal degradation
[16, 17]. Extractives are complex macromolecules that can
increase the energy value of biomass [34] and positively in-
fluence the energy yield and the mass balance of pyrolysis
[14]. The extractives present different form and composition,
which may explain the variability (0.7 to 2.6%) and the for-
mation of four groups among the studied clones. The extrac-
tives soluble in acetone represent chemical components as
fatty acids, resin acids, sterols, waxes, and non-volatile hydro-
carbons [25]. These substances can present high molecular
mass and thermal degradation range between 250 and 505
°C [35], consequently, contributing to increase the charcoal
production. Despite the lower proportion of extractives com-
pared to lignin macromolecule, these secondary components
should not be neglected in the classification of the best
Eucalyptus clones for the production of bioreducer.
Regarding the total lignin content, clones 1039, 1025,
1009, 1033, 1006, 1005, and 1008 were statistically similar
and formed the group with the highest mean (31%). This value
is considered suitable, based on studies available in the liter-
ature for the genera Eucalyptus, which reported lignin con-
tents ranging from 28 to 32% [7, 19]. In our study, low vari-
ability of the clones was verified for the total lignin content in
the wood. This is probably related to genetics pre-selections
made by forestry companies in Brazil in which materials with
lower percentages of lignin were disregarded. Lignin is a
Bioenerg. Res. (2021) 14:175–189 179

Table 2 Variance analyses for the wood chemical composition of the Eucalyptus spp. clones

Property Variation source Degrees freedom Sum square Mean square F value

Extractives content Clone 13 17.546 1.350 34.41*

Residuals 28 1.098 0.039
Total lignin Clone 13 85.710 6.593 5.64*
Residuals 28 32.730 1.169
S/G ratio Clone 13 7.231 0.556 9.62*
Residuals 28 1.619 0.058
Mass (g) of guaiacyl per kg of dry wood Clone 13 212.832 16.372 2.34*
Residuals 28 195.702 6.989
Mass (g) of syringyl per kg of dry wood Clone 13 2115.505 162.730 3.88*
Residuals 28 1174.633 41.950

*Significant (p < 0.05)

macromolecule with a complex chemical structure considered
in the literature as the main responsible for the charcoal pro-
duction due to its high thermal stability [15]. Thus, clones
1039 (E. grandis hybrid) and 1025 (E. camaldulensis hybrid)
stood out due to the higher proportion of lignin and extractives
soluble in acetone. Considering the sum of the percentages of
total lignin and extractives soluble in acetone, the clones with
the greatest possibility of presenting better results in the car-
bonization C balance are in order: 1039 (1st), 1025 (2nd), and
1033 (3rd).
Considering the S/G ratio, 3 groups of clones were formed,
in which 64% of the evaluated genetic materials are part of the
group of lowest mean. Clones 1039 and 1025 are in this group
and numerically presented the lowest S/G ratios. Lower S/G
ratio is required for the classification and selection of genetic
materials for charcoal production, as well as for reducing raw
material costs [16, 17]. It is expected that wood with a lower S/
G ratio will provide greater efficiency in the carbonization
process, higher productivity of the charcoal plants, and lower
gas emissions resulting from the thermal decomposition of the
wood. This is related to the chemical structure of guaiacyl (G)
monomeric units being more condensed and, consequently,
more thermally stable [13, 15]. According to Wang et al.
[15], the reactivity of the lignin linkages is influenced by the

Table 3 Wood chemical composition of the Eucalyptus spp. clones

Clone Extractives (%) Total lignin (%) S/G ratio G/kg* S/kg*

1039 2.6 ± 0.3 a 32.6 ± 0.5 a 2.5 ± 0.3 c 27.0 ± 3.1 a 81.6 ± 3.3 a
1037 2.5 ± 0.4 a 29.2 ± 2.5 b 3.3 ± 0.2 b 22.4 ± 0.7 b 89.6 ± 4.6 a
1036 2.4 ± 0.7 a 29.7 ± 1.0 b 2.8 ± 0.2 c 24.4 ± 2.0 a 81.9 ± 2.7 a
1025 2.1 ± 0.1 b 31.3 ± 0.6 a 2.5 ± 0.1 c 27.4 ± 2.5 a 82.7 ± 5.6 a
1024 1.9 ± 0.2 b 29.5 ± 1.0 b 4.0 ± 0.5 a 19.6 ± 2.4 b 93.7 ± 0.9 a
1009 1.6 ± 0.2 c 30.4 ± 0.3 a 3.1 ± 0.2 c 23.4 ± 0.9 b 87.1 ± 3.0 a
1031 1.5 ± 0.1 c 27.9 ± 0.4 c 2.6 ± 0.2 c 25.6 ± 2.1 a 80.9 ± 1.7 a
1033 1.5 ± 0.1 c 30.7 ± 1.2 a 2.9 ± 0.2 c 25.7 ± 2.1 a 89.1 ± 2.1 a
1006 1.2 ± 0.1 c 30.5 ± 0.7 a 3.0 ± 0.1 c 24.3 ± 1.3 a 86.2 ± 2.7 a
1004 0.9 ± 0.0 d 28.0 ± 1.0 c 2.9 ± 0.2 c 25.0 ± 2.3 a 84.4 ± 2.3 a
1015 0.9 ± 0.1 d 29.3 ± 0.6 b 3.2 ± 0.2 b 23.1 ± 1.1 b 89.4 ± 1.6 a
1023 0.8 ± 0.1 d 27.1 ± 1.2 c 3.7 ± 0.4 a 22.5 ± 3.6 b 98.7 ± 10.1 a
1005 0.8 ± 0.1 d 30.1 ± 1.1 a 3.2 ± 0.2 b 22.3 ± 1.6 b 85.3 ± 1.7 a
1008 0.7 ± 0.0 d 31.1 ± 1.3 a 2.8 ± 0.2 c 19.9 ± 6.3 b 66.6 ± 19.5 b
CVe 13.0 3.6 7.9 11.1 7.6

G/kg, mass (g) of guaiacyl per kg of dry wood; S/kg, mass (g) of syringyl per kg of dry wood; CVe, experimental coefficient of variation (%). Means ±
standard deviation followed by the same letter in the column (a, b, c, and d) do not differ according to the Scott-Knott test (p > 0.05). *Means ± standard
deviation followed by the same letter in the column (a and b) do not differ according to the Scott-Knott test (p > 0.10). Source: Protásio et al. [20]
180
substituted functional groups (phenolic hydroxyl group and
methoxyl group), and, consequently, the content of methoxyl
groups in lignin is correlated with the formation of lignin
pyrolysis charcoal. Thus, wood with lignins with high
methoxyl group contents (higher S/G ratio) results in less
charcoal during the pyrolysis process.
The lowest S/G ratios and the highest percentages of lignin
and extractives in wood were observed for the clones 1039
and 1025. Santos et al. [17] verified that the S/G ratio may be
inversely correlated to the wood lignin content. This inverse
relationship is beneficial for carbonization since wood with
higher lignin content and lower S/G ratio could simultaneous-
ly show greater efficiency in converting wood into charcoal
and better quality of this energy input.
The mass of G and S per kg of dry wood observed in the
evaluated clones varied between 19.6 g (clone 1024) and
27.4 g (clone 1025) and between 66.6 g (clone 1008) and
98.7 g (clone 1023), respectively. These values are consistent
with those found by Araújo et al. [18]. The selection of clones
for charcoal production must prioritize a higher proportion of
G in lignin because it can result in an increase in GYC due to
the higher thermal stability [20]. Araújo et al. [18] observed a
significant and inversely proportional effect of the mass of G
on the thermal decomposition of wood between temperatures
of 315 °C and 390 °C; however, this behavior was not verified
at 450 °C (final carbonization temperature). Therefore, re-
search aimed at investigating the effect of oxidation deriva-
tives of the G and S units of lignin on the carbonization mass
balance of Eucalyptus clonal materials is necessary to clarify
these associations.
Analysis of variance indicates that there is no clonal effect
for the ultimate analysis of wood (Tables 4 and 5). For char-
coal, there was a statistical difference between genetic mate-
rials for the contents of C, H, O, and N (Table 4), with the
result attributed to differences in the structural chemical com-
position (lignin quality) and non-structural (extractives solu-
ble in acetone) from the cell wall (see Table 3). The ultimate
analysis of wood and charcoal is fundamental for the classifi-
cation of the best Eucalyptus clones for energy purposes
(Table 5), since knowing the percentages of C, H, and O, the
energy released in combustion can be estimated. In addition,
the management of the firing equipment can be better per-
formed. The C, H, and O contents in the wood may be corre-
lated with the GYC [13].
The clones showed contents of C in the wood varying from
47.5 to 48.9% and from 79.8 to 82.3% for charcoal. The O
content in wood varied from 44.1 to 45.7% and in charcoal
between 11.9 and 15.0%. Due to the pyrolysis process, the O
content reduced approximately 70.4%. This is a satisfactory
result due to the negative relationship between this chemical
component and the energy performance of charcoal [36, 37].
This phenomenon occurs due to the thermal decomposition
process in the absence or controlled presence of O that
Bioenerg. Res. (2021) 14:175–189
promotes the highest concentration of C and volatilization of
O present, mainly in the carbohydrates of the woody cell wall
[7]. In addition, the variation in the O proportion in charcoal
was higher than that observed for wood. On average, the O
content in charcoal varied by 26%, while in wood, it was
found a considerably lower variation among the Eucalyptus
clones (3.6%).
The charcoals of clones 1006 and 1024 had the lowest and
highest O content, respectively. This result is possibly related
to the differences in the chemical composition of the cell wall
of the fibers, especially the composition of the lignin macro-
molecule [15, 38]. The wood of clone 1006 is part of the group
with the lowest S/G ratios and the highest proportions of G
units in lignin (see Table 3). The opposite was observed for
wood from clone 1024, high S/G ratio, and lower proportion
of G units. The S/G ratio of clone 1024 was 36% higher than
that observed for clone 1006. Soares et al. [38] reported that
the amounts of C and O present in the Eucalyptus charcoal are
more related to the type of chemical structure present in the
cell wall and not necessarily to the proportion of these chem-
ical elements in the wood, corroborating with the results de-
scribed in our research.
Analyzing the percentage formulas of the G
(C66.7%H6.7%O26.7%) and S (C62.9%H6.7%O30.5%) units, it can
be seen that the G unit presents proportionally more C than O
in the molecule [38]. The presence of a greater amount of G
units can improve the resistance to thermal degradation of
wood due to the lower number of methoxyl groups (–O–
CH3) present in the molecule and, consequently, in the
amount of active sites in the phenylpropane unit [20]. Wang
et al. [15] reported that the lignins with high methoxyl group
contents (bigger S/G ratio) produce less charcoal during the
pyrolysis process, that is, less resistant to thermal degradation.
Therefore, the lowest S/G ratio and the highest mass of G units
observed for wood from clone 1006 may be associated with
improved resistance to wood thermal degradation and, conse-
quently, the highest proportion between the C and O levels on
charcoal.
In relation to sulfur, insignificant levels were detected for
wood (0.00–0.07%) and charcoal (0.00–0.06%) of Eucalyptus
clones, that is, only traits that do not compromise the
bioenergy use. The nitrogen content stood out due to the mean
observed for charcoal (1.4%), being 2.8 times higher than that
of wood (0.5%). This means that this element did not volatil-
ize during carbonization, and its percentage in charcoal in-
creased due to the thermal decomposition of wood, corrobo-
rating the study by Leite et al. [39]. The nitrogen and sulfur are
relevant to indicate the polluting potential of biomass and
charcoal, due to the release of sulfur and nitrogen oxides dur-
ing burning [40]. Therefore, the results show the advantage of
using energy from Eucalyptus wood and charcoal, compared
to coal widely used in the steel industry, with sulfur contents
of up to 2.07% [41].
Bioenerg. Res. (2021) 14:175–189 181

Table 4 Variance analyses summary for ultimate analysis of wood and charcoal from Eucalyptus clones

Property Variation source Degrees freedom Wood Charcoal

SS MS F value SS MS F value

Carbon Clone 13 7.60 0.5845 0.34ns 27.44 2.1106 3.64*

Residuals 28 48.343 1.7265 16.23 0.5795
CVe = 2.7% CVe = 0.9%
Hydrogen Clone 13 0.288 0.0221 0.16ns 0.299 0.0230 4.03*
Residuals 28 3.966 0.1416 0.160 0.0057
CVe = 6.1% CVe = 2.1%
Oxygen Clone 13 9.328 0.7175 0.29ns 33.20 2.5536 4.15*
Residuals 28 70.333 2.5119 17.23 0.6152
CVe = 3.5% CVe = 5.9%
Nitrogen Clone 13 0.1964 0.0151 1.01ns 0.2298 0.0177 8.25*
Residuals 28 0.4183 0.0149 0.0600 0.0021
CVe = 22.3% CVe = 3.4%

SQ, sum square; MS, mean square. *Significant (p < 0.05). ns, no significant (p > 0.05). CVe, experimental coefficient of variation

Table 5 Ultimate analysis of wood and charcoal from Eucalyptus clones

Clone Ultimate analysis (%, dry basis)

Type Carbon Hydrogen Oxygen Nitrogen

1004 Wood 48.14 ± 1.38 6.32 ± 0.44 44.67 ± 1.72 0.61 ± 0.17
Charcoal 82.28 ± 0.38 a 3.64 ± 0.04 a 12.38 ± 0.43 b 1.31 ± 0.05 c
1005 Wood 48.34 ± 0.98 6.33 ± 0.35 44.40 ± 1.31 0.63 ± 0.15
Charcoal 80.30 ± 1.48 b 3.58 ± 0.06 b 14.20 ± 1.55 a 1.33 ± 0.01 c
1006 Wood 47.81 ± 1.28 6.16 ± 0.33 45.12 ± 1.58 0.69 ± 0.16
Charcoal 82.16 ± 0.62 a 3.75 ± 0.02 a 11.92 ± 0.63 b 1.54 ± 0.03 a
1008 Wood 47.69 ± 0.95 6.23 ± 0.35 45.27 ± 1.23 0.61 ± 0.16
Charcoal 81.16 ± 0.96 a 3.65 ± 0.04 a 13.46 ± 1.00 a 1.40 ± 0.02 b
1009 Wood 48.48 ± 1.39 6.17 ± 0.25 44.62 ± 1.51 0.56 ± 0.17
Charcoal 81.81 ± 1.36 a 3.66 ± 0.03 a 12.57 ± 1.36 b 1.43 ± 0.07 b
1015 Wood 48.63 ± 0.89 6.35 ± 0.35 44.19 ± 1.04 0.59 ± 0.16
Charcoal 82.23 ± 0.35 a 3.57 ± 0.05 b 12.36 ± 0.36 b 1.28 ± 0.01 c
1023 Wood 48.41 ± 1.18 6.26 ± 0.44 44.65 ± 1.59 0.50 ± 0.07
Charcoal 80.60 ± 0.10 b 3.48 ± 0.03 b 14.32 ± 0.10 a 1.32 ± 0.02 c
1024 Wood 47.72 ± 2.71 6.05 ± 0.66 45.50 ± 3.33 0.57 ± 0.15
Charcoal 79.94 ± 0.85 b 3.45 ± 0.09 b 14.96 ± 0.92 a 1.35 ± 0.02 c
1025 Wood 48.94 ± 1.23 6.23 ± 0.28 44.12 ± 1.33 0.51 ± 0.11
Charcoal 81.71 ± 0.54 a 3.51 ± 0.06 b 12.98 ± 0.46 b 1.28 ± 0.05 c
1031 Wood 47.76 ± 0.31 6.18 ± 0.29 45.36 ± 0.59 0.47 ± 0.03
Charcoal 81.05 ± 0.54 a 3.59 ± 0.05 b 13.57 ± 0.39 a 1.34 ± 0.02 c
1033 Wood 48.41 ± 1.21 6.19 ± 0.44 44.82 ± 1.62 0.45 ± 0.03
Charcoal 81.80 ± 0.45 a 3.52 ± 0.15 b 12.69 ± 0.62 b 1.42 ± 0.05 b
1036 Wood 48.54 ± 0.85 6.18 ± 0.44 44.62 ± 1.23 0.51 ± 0.03
Charcoal 79.82 ± 0.44 b 3.54 ± 0.15 b 14.40 ± 0.48 a 1.44 ± 0.04 b
1037 Wood 47.48 ± 1.85 6.09 ± 0.16 45.71 ± 1.80 0.48 ± 0.10
Charcoal 81.81 ± 0.55 a 3.48 ± 0.03 b 12.80 ± 0.43 b 1.40 ± 0.04 b
1039 Wood 48.60 ± 0.26 6.14 ± 0.21 44.56 ± 0.02 0.49 ± 0.04
Charcoal 81.32 ± 0.69 a 3.48 ± 0.07 b 13.36 ± 0.73 a 1.31 ± 0.02 c
Mean Wood 48.21 ± 1.17 6.21 ± 0.32 44.83 ± 1.39 0.55 ± 0.12
Charcoal 81.29 ± 1.03 3.56 ± 0.10 13.28 ± 1.10 1.37 ± 0.08

Means for the charcoal followed by the same letter (a, b, and c) in the column do not differ according to the Scott-Knott test (p > 0.05). The data regarding
the wood ultimate composition are available in the study of Protásio et al. [20]
182
Gravimetric Yield and Mass Balance of the
Carbonization Process
There was statistical difference between the clones for the
GYC (Fig. 1 and Table 6). Clones 1025 (E. camaldulensis
hybrid), 1039 (E. grandis hybrid), 1024 (E. urophylla hybrid),
1033 (E. urophylla hybrid), and 1031 (Eucalyptus spp.)
showed the highest GYC. These clones were part of a single
group with mean of 35.2% for GYC, a difference of 3.1% in
relation to the second group. Disregarding clone 1024, the
others were characterized by the highest number of G units
per dry mass of wood and the lowest S/G ratio. Genetic ma-
terials 1025 and 1039 showed high contents of lignin and
extractives soluble in acetone in wood and the highest percent-
ages of C. The literature has shown the influence of low S/G
ratio [13, 14] and higher levels of lignin [15, 42], extractives
soluble in acetone [14], and C [13] in GYC, corroborating the
reported findings. As previously reported, the lignin present in
the cell wall of Eucalyptus fibers is formed by different pro-
portions of syringyl (S) and guaiacyl (G) basic units. The main
difference between G and S units is the amount of methoxyl
groups (–O–CH3) in aromatic rings (see topic “Chemical
composition of the wood and charcoal”). This directly influ-
ences the number of active sites in the phenylpropane unit and
the thermal stability of lignin [13]. The relationship between
lignin chemical structure and pyrolysis behaviors of the bio-
mass is meaningful. As the S unit has only two active sites
associated with carbon atoms, the number of ether linkages
(C–O–C) is greater, for example, β-aryl-ether bonds (β–O–4)
[15, 43]. In most cases, this type of bond is easily cleaved [15],
and; therefore, lignins with a higher proportion of S units are
less resistant to thermal degradation during pyrolysis. On the
other hand, G unit has three active sites associated with carbon
atoms and, consequently, has a lower proportion of ether link-
ages (C–O–C) and a greater amount of carbon-carbon bonds
(e.g., 5-5 and β-5 linkages). Wang et al. [15] reported that
carbon-carbon linkages such as β-5 present relatively low
reactivity and affirmed that the cleavage of linkages
Fig. 1 Gravimetric yield in
charcoal (GYC) and sum of lignin
(Lig) and extractives soluble in
acetone (Ext) of the studied
Eucalyptus clones. Columns
followed by the same letter do not
show difference according to the
Scott-Knott test (p > 0.05). The
error bars for both properties rep-
resent the standard deviation
Bioenerg. Res. (2021) 14:175–189
combining the carbon atoms in different aromatic rings, such
as 5-5, is difficult. Therefore, wood with a greater proportion
of G units present a higher condensation degree and is more
resistant to thermal degradation [15, 44, 45]. These observa-
tions, combined with the results of the wood chemical com-
position (see Table 3), explain the results of gravimetric yield
in charcoal for Eucalyptus clones: 1025, 1039, and 1033 (Fig.
1).
Despite the higher S/G ratio, clone 1024 showed more than
31% of the dry wood mass represented by lignin and extrac-
tives (Lig + Ext), which may justify the higher GYC (35.1%).
Santos et al. [17] stated that high lignin content in wood
should be prioritized when evaluating Eucalyptus clones for
carbonization. The lignin macromolecule has greater thermal
stability and, therefore, is directly related to the production of
charcoal. Due to the complexity of chemical bonds (e.g.,
carbon-carbon linkages such as β-1, β-5, and 5-5), the ther-
mal degradation of lignin shows a broader peak compared to
cellulose and hemicellulose due to the successive cleavage of
linkages as there action temperature increases [15].
On the other hand, Araújo et al. [18] and Castro et al. [16]
have reported no correlation between the S/G ratio with the
GYC for Eucalyptus clones at different ages. Araújo et al. [18]
suggested that this divergence of results shows that the greater
number of G units or low S/G ratio does not necessarily imply
the occurrence of more thermally stable bonds, justifying the
greater GYC obtained for the wood carbonization of clone
1024. Liu et al. [43] analyzed two lignin samples with similar
functional groups and S/G ratio, but with differences in side-
chain linkages. Therefore, the results suggest that it is possible
to obtain higher productivity of charcoal from raw materials
with a high S/G ratio, as long as the wood presents a higher
percentage of lignin and extractives soluble in acetone (≥
31%). In addition, it is important to verify the type of linkages
between the S and G monomers, mainly the frequency of β-
aryl-ether bonds (β-O-4) and carbon-carbon bonds (e.g., 5-5
and β-5 linkages), because this may influence in the propor-
tion of C and O in the charcoal. Guo et al. [45] and Zhang et al.
Bioenerg. Res. (2021) 14:175–189 183

Table 6 Variance analyses for gravimetric yield and mass balance of the carbonization process

Property Variation source Degrees freedom Sum square Mean square F value

Gravimetric yield in charcoal Clone 13 15.797 1.2151 3.65*

Residuals 28 9.331 0.3333
CVe = 1.7%
Retained carbon Clone 13 52.951 4.073 1.18ns
Residuals 28 96.640 3.451
CVe = 3.2%
Volatilized carbon1 Clone 13 52.951 4.073 1.18ns
Residuals 28 96.640 3.451
CVe = 4.5%
Retained hydrogen Clone 13 10.164 0.7819 0.46ns
Residuals 28 47.834 1.7083
CVe = 6.6%
Volatilized hydrogen1 Clone 13 10.164 0.7819 0.46ns
Residuals 28 47.83 1.7083
CVe = 1.6%
Retained oxygen Clone 13 21.849 1.6807 2.79*
Residuals 28 16.873 0.6026
CVe = 7.6%
Volatilized oxygen1 Clone 13 21.849 1.6807 2.79*
Residuals 28 16.873 0.6026
CVe = 0.9%

CVe experimental coefficient of variation. * Significant (p < 0.05). ns no significant (p > 0.05). 1 The percentages of C, O, and H volatilized were obtained
subtracting from 100% the percentage of each element retained in charcoal. Therefore, the sum square, mean square, and F value were similar to the
values obtained for the variance analyses of each element retained in the charcoal

[46] extracted lignin from woody biomass and non-woody
biomass and then characterized the chemical structures and
the interunitary linkages of the lignin using nuclear magnetic
resonance spectrometry (NMR). These authors observed var-
ious interunitary linkages in lignin assigned in the side-chain
region of NMR spectra, for example, β-O-4, β-5, β-β, 5-5,
and β-1. The results obtained by Guo et al. [45] suggest that
the percentage of β-O-4 linkages in the lignin of the biomass
is an indicative of the condensation degree. Overall, lignins
with a lower percentage of β-O-4 linkages are more resistant
to pyrolysis due to the higher content of condensed linkages.
Therefore, future studies should consider this technique for
analyzing the interunitary linkages of the lignin in
Eucalyptus wood, simultaneously with the S/G ratio and total
lignin content.
By the F test of the variance analyses (Table 6), there was
no clonal effect for the C and H balances, only for the O
balance (Fig. 2). The percentages of retained C and volatilized
C ranged from 55.5 to 59.8% and 40.2 to 44.5%, respectively.
The percentages of retained H and volatilized H ranged from
19.2 to 20.7% and 79.3 to 80.8%, respectively. The low var-
iation found for the C and H balance of the carbonization may
be related to the lignin content of Eucalyptus woods. There
was low variability in the lignin content (28.03 to 32.64%),
and, consequently, the products derived from the pyrolysis of
this macromolecule can be very similar between the clones.
The different lignin content, S/G ratio, and demethoxylation
degree under determine the distributions of p-hydroxyphenyl
phenols, guaiacyl phenols, and syringyl phenols [43].
For the content of retained and volatilized O, the results
showed amplitude of 9.0 to 11.6% and 88.4 to 91.0%, re-
spectively. The carbonization of wood from clones 1006 and
1024 resulted in the smallest and largest amount of retained
O in the charcoal. As previously reported, this result may be
associated with the S/G ratio of wood lignin in these
Eucalyptus clones. The wood from clone 1006 showed S/
G ratio of 3.0 whereas the wood from clone 1024 showed S/
G ratio of 4.0 (see Table 3). The lower S/G ratio and the
higher proportion of G units of the clone 1006 wood may
explain the lower amount of retained O in charcoal since the
G units have a higher C/O ratio (2.50) in their chemical
composition comparatively the S units that presented a C/
O ratio of 2.06 [38]. In addition, the wood of these clones
had lignin content close to 30%, indicating that the O bal-
ance is more related to the composition than to the lignin
macromolecule content.
184
Fig. 2 Mean values of carbon,
hydrogen, and oxygen balance of
carbonization of wood from
Eucalyptus clones. Means
followed by the same letter do not
differ according to the Scott-
Knott test (p > 0.05)
Grouping of Eucalyptus Clones by Principal
Component Analysis
The first three principal components had the highest ei-
genvalues and explained 73.79% of the total variance of
the data (Table 7). Therefore, these three latent variables
must be considered for the classification and grouping of
Eucalyptus clones for charcoal production. Considering
the eigenvectors, it is noted that the first three principal
components bring together the wood and process charac-
teristics more relevant for the Eucalyptus species selection
for charcoal production.
Researchers have used the principal component analysis
for the classification and grouping of biomasses considering
Bioenerg. Res. (2021) 14:175–189
their energy characteristics, especially in situations where
many variables are measured [47], as in this research with
Eucalyptus clones. The study of eigenvectors can contribute
by highlighting the most important variables in the formation
of the principal components, allowing the Eucalyptus clones
grouping and the dispersion of the properties evaluated in the
wood and in the pyrolysis process of charcoal in the Cartesian
plane [48].
Analyzing the first principal component (PC1), it is ob-
served that the largest positive eigenvectors are related to the
total lignin content, GYC, C, and H retained in charcoal. The
most significant negative eigenvectors refer to the S/G ratio,
C, and H volatilized during pyrolysis. The signs (+ or −) of the
eigenvectors indicate the correlations between the original
Bioenerg. Res. (2021) 14:175–189 185

Table 7 Eigenvectors (ê) and contribution of the original variables (cont) in the first three principal components (PC)

Property PC1 PC2 PC3

ê1 Cont (%) ê2 Cont (%) ê3 Cont (%)

Total lignin 0.293 8.6 − 0.055 0.3 − 0.283 8.0

S/G ratio − 0.290 8.4 − 0.217 4.7 0.472 22.3
G/kg 0.238 5.7 0.057 0.3 − 0.394 15.5
S/kg − 0.210 4.4 − 0.170 2.9 0.294 8.6
Extractives* 0.115 1.3 − 0.213 4.5 − 0.405 16.4
GYC 0.299 9.0 − 0.442 19.6 0.011 0.0
Retained carbon 0.379 14.4 − 0.159 2.5 0.287 8.2
Volatilized carbon − 0.379 14.4 0.159 2.5 − 0.287 8.2
Retained oxygen − 0.158 2.5 − 0.560 31.3 − 0.149 2.2
Volatilized oxygen 0.158 2.5 0.560 31.3 0.149 2.2
Retained hydrogen 0.380 14.4 0.005 0.0 0.204 4.2
Volatilized hydrogen − 0.380 14.4 − 0.005 0.0 − 0.204 4.2
Eigenvalues 4.67 2.43 1.76
Accumulated variance (%) 38.90 20.26 14.63

*Extractives soluble in acetone; G/kg, mass (g) of guaiacyl per kg of dry wood; S/kg, mass (g) of syringyl per kg of dry wood; and GYC, gravimetric yield
in charcoal

variables; thus, the highest contents of lignin and the lowest S/
G ratio are directly related to the highest GYC and the best C
and H balance during thermal decomposition of Eucalyptus
wood, reinforcing the trends previously detected (see items
“Chemical composition of the wood and charcoal” and
“Gravimetric yield and mass balance of the carbonization
process”).
Principal component 1 (PC1) can be interpreted as a gen-
eral index for the classification of Eucalyptus clones for char-
coal production because it presents the most relevant wood
characteristics and the pyrolysis process. Therefore, the higher
the values of this component (scores), the more propitious the
clone for charcoal production will be. Based on the PC1
scores (Fig. 3), the order of the most suitable clones for char-
coal production is: 1025 (E. camaldulensis hybrid), 1039
(E. grandis hybrid), 1006 (E. urophylla), and 1033
(E. urophylla hybrid). The least suitable clonal materials for
the production of bioreducer were 1023 (E. urophylla hybrid)
and 1005 (E. urophylla).
Principal component 2 (PC2) is basically related to the O
balance retained in charcoal and volatilized during pyrolysis.
The eigenvector associated with the percentage of retained
oxygen in charcoal presented a negative contribution in the
second principal component. Therefore, the lower scores of
this principal component indicate a higher proportion of
retained oxygen in charcoal and a lower amount of volatilized
oxygen during pyrolysis. Among the 14 clones evaluated,
1024 was the one with the lowest score for PC2, a result
attributed to the higher O content retained and, consequently,
the lower proportion of volatilized O during the thermal
decomposition of the wood. We attribute this result to the high
proportion of S units, compared to G units, in the wood lignin
of this clone.
Principal component 3 (PC3) showed positive and signifi-
cant eigenvectors for the S/G ratio and mass of S units per kg
of dry wood. The most relevant negative eigenvectors are
associated with the mass of G units per kg of wood and the
content of extractives soluble in acetone. The higher the scores
of this principal component, the less propitious the clone will
be for charcoal production. The high scores in the third prin-
cipal component indicate a high S/G ratio, a higher number of
S units, and a lower proportion of G units and extractives
soluble in acetone in the Eucalyptus wood.
The highest PC3 scores were observed for clones 1023 and
1024, indicating that they are less recommended for charcoal
production. These clones are considered the most dissimilar in
relation to the others. The results found for PC3 corroborate
the previous discussions and reinforce the potential of clonal
materials 1025 and 1039 for the composition of specific ener-
gy forests for the production of charcoal. These two
Eucalyptus clones formed a single group and are considered
similar because they have more suitable wood quality and
characteristics of the pyrolysis process.
Clones 1006, 1008, 1009, 1031, and 1033 formed the
group with the highest number of similar genetic mate-
rials, in which the most relevant characteristics in this
grouping were GYC, retained C, retained H, total lignin,
and grams of G per kg of dry wood. These genetic
materials were ranked as intermediates for the produc-
tion of steel bioreducer.
186
Fig. 3 Scores scattering of the
principal components (PC1, PC2,
and PC3) and grouping of
Eucalyptus clones according to
the chemical characteristics of the
wood and the pyrolysis process
Clones 1004, 1015, and 1037 formed a single group due to
the similarity of GYC (Fig. 1) and are the most similar genetic
materials (Fig. 3). Clones 1005 and 1036 showed similarities
for scores of PC1, PC2, and PC3; therefore, they formed a
single group. These materials had the highest percentages of
C and H volatilized during pyrolysis. For PC1, negative scores
attributed to these clones were found, simultaneously indicat-
ing unfavorable characteristics of the wood and the pyrolysis
process.
The genetic materials 1023 (E. urophylla hybrid) and 1039
(E. grandis hybrid) are the most dissimilar or divergent, due to
the wide variability or inverse relationship between the char-
acteristics of the wood and the pyrolysis process. Thus, clones
with these characteristics are indicated for crossing when the
objective is to increase the variability and expression of the
heterotic effect [11]. The PCA scores reinforce the relevance
of simultaneously considering the characteristics of the wood
and the process for the classification of genetic materials for
charcoal production. The applied technique, combined with
the researcher’s experience, allows minimizing the chances
of failure in the management of the Eucalyptus energy forests
and allows greater control of the productivity of charcoal from
the wood pyrolysis with similar chemical properties.
Canonical Correlations Between the Characteristics of
Wood and Charcoal
Based on the canonical correlation analysis, it is observed that
the first canonical function was statistically significant by the
Hotelling multivariate test (p value = 0.0017), with an approx-
imation of the F distribution. The canonical correlation coef-
ficient can be considered moderate (0.68) and indicates that
Bioenerg. Res. (2021) 14:175–189
approximately 46% of the variance between the groups of
characteristics of wood and charcoal was explained by the first
pair of canonical variables. Through canonical correlation
analysis, the interdependence of the characteristics of groups
X and Y were evidenced, that is, the pyrolysis mass balance
depends on the wood chemical characteristics (Fig. 4). This
result contributes to the more precise identification of the ef-
fect of the wood chemical composition in the bioreducer pro-
duction and, consequently, genetic improvement of the
Eucalyptus clones currently used in Brazil.
According to Hair Junior et al. [49], canonical loads mea-
sure linear correlations between the original variables and
their respective canonical statistical variables, while the
crossed canonical loads represent the correlation between an
original variable in a certain group and the canonical statistical
variable in the other group. The analysis of these correlations
involves examining the signal and its magnitude (Table 8). In
the dependent group (Y), the largest canonical charge, in mod-
ule, is related to the GYC. In the independent canonical sta-
tistical variable (X), the content and composition of the lignin
macromolecule were more important. The same trend was
observed for crossed canonical charges.
Analyzing the sign of canonical charges, it is noticed that
there is a tendency to increase GYC, and the percentages of C
and H retained in charcoal with the increase of lignin, extrac-
tives, and the mass of G units in wood. On the other hand, the
increase in the S/G ratio and the proportion of S units in lignin
results in a decrease in GYC and the percentages of C and H
retained in charcoal. The high S/G ratio of the lignin macro-
molecule is directly related to the higher percentage of O
retained in charcoal due to a higher proportion of O in the S
unit [38].
Bioenerg. Res. (2021) 14:175–189 187

Fig. 4 Scores of significant

canonical functions by
Hotelling’s test

In addition, lower scores attributed to the canonical statis- materials 1039, 1025, 1006, and 1033 were better classified.
tical variables X and Y indicate the best clones for the charcoal These results confirm the observations previously made about
production, as they present the best wood chemical character- the effect of the wood chemical composition on the pyrolysis
istics, associated with the highest GYC. In this sense, clonal mass balance and reinforce the trends obtained in the principal
component analysis.
Previous research has reported that the lower S/G ratio, or
Table 8 Canonical loads (CL) and crossed canonical loads (CCL) of the higher proportion of G units, contributes to a higher GYC [13,
first canonical function 14, 17], similar to what was observed in our study in the
results of multivariate statistical analyses. Unit G has one
Variable CL CCL
Pyrolysis mass balance (Y)
methoxyl group less in carbon five (C5) of phenylpropane,
and this allows for more stable chemical bonds between aro-
Gravimetric yield in charcoal − 0.54 − 0.37 matic rings and side chains of the lignin macromolecule.
Retained carbon − 0.29 − 0.20 Consequently, it is expected to improve the resistance to ther-
Retained hydrogen − 0.40 − 0.27 mal degradation of wood, which presents higher levels of
Retained oxygen 0.22 0.15 lignin and higher proportions of G units [13, 15, 38].
Wood quality (X) Therefore, lignins with fewer methoxyl groups, or with a
Total lignin − 0.88 − 0.60 higher proportion of G units, provide an improvement in the
Extractives soluble in acetone − 0.18 − 0.12 C and H balance of pyrolysis and minimization of the produc-
Mass of guaiacyl (g) per kg of dry wood − 0.44 − 0.30 tion of by-products during the thermal decomposition of
Mass of syringyl (g) per kg of dry wood 0.41 0.28 wood.
Syringyl/guaiacyl ratio (S/G ratio) 0.71 0.48 The findings of this research provide subsidies for further
studies for understanding better the drivers of the wood
188
pyrolysis process in order to maximize the sustainable produc-
tion of charcoal. These studies will be important for the ratio-
nal expansion of Eucalyptus forests dedicated to the produc-
tion of bioreducers, an important raw material for the steel
industry in Brazil.
Conclusions
Woods with high lignin and extractives soluble in acetone
contents, low S/G ratio, and a higher proportion of guaiacyl
units are prone to promote high gravimetric yield in charcoal,
and better carbon and hydrogen balance during the pyrolysis.
Eucalyptus woods with low S/G ratio, high mass of guaiacyl
units, and a higher amount of extractives soluble in acetone
produced charcoal with higher proportion of carbon and hy-
drogen retained. These characteristics can be considered the
main quality indexes for young Eucalyptus wood intended for
charcoal production and must be simultaneously analyzed.
The results observed indicate that the O balance is more relat-
ed to the composition than to the lignin macromolecule
content.
Eucalyptus camaldulensis (represented by clone 1025) and
Eucalyptus grandis (represented by clone 1039) hybrids are
the most suitable vegetal materials for charcoal production
because they presented most adequate wood quality and better
performance in the pyrolysis mass balance.
Acknowledgment The authors appreciate the National Council for
Scientific and Technological Development (CNPq/Brazil – processes
no. 141439/2014-9 and no. 306793/2019-9), the Coordination for the
Improvement of Higher Education Personnel (CAPES/Brazil–financing
code 001), the Research Support Foundation of Minas Gerais state
(FAPEMIG), and the Plantar Group for the financial support of the pro-
ject. We would also like to thank the anonymous reviewers whose com-
ments and suggestions have made this study scientifically fit.
Authors’ Contributions Thiago de Paula Protásio and Michael Douglas
Roque Lima: conceptualization, methodology, investigation, roles/writ-
ing—original draft; Roberthi Alef Costa Teixeira, Fábio Silva do Rosário,
Ana Clara Caxito de Araújo, and Maíra Reis de Assis: writing—review
and editing; Paulo Ricardo Gherardi Hein: validation, supervision, and
writing—review and editing; Paulo Fernando Trugilho: writing—review
and editing, funding acquisition and project administration.
Compliance with ethical standards
Conflict of Interest The authors declare that they have no conflict of
interest.
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