molecules

Article
Investigating the Effect of Operational Variables on the Yield,
Characterization, and Properties of End-of-Life Olive Stone
Biomass Pyrolysis Products
Sina Ebrahim Atakoohi 1 , Elena Spennati 1,2, * , Alessandro A. Casazza 1 , Paola Riani 2,3
and Gabriella Garbarino 1,2,4, *

1 Dipartimento di Ingegneria Civile, Chimica e Ambientale (DICCA), Università degli Studi di Genova,
Via Opera Pia 15, 16145 Genova, Italy; [email protected] (S.E.A.);
[email protected] (A.A.C.)
2 INSTM, UdR Genova, Via Dodecaneso 31, 16146 Genova, Italy; [email protected]
3 Dipartimento di Chimica e Chimica Industriale (DCCI), Università degli Studi di Genova, Via Dodecaneso 31,
16146 Genova, Italy
4 CNR SCITEC G. Natta, Via Golgi 19, 20133 Milano, Italy
* Correspondence: [email protected] (E.S.); [email protected] (G.G.)

Abstract: In recent years, biomass has emerged as a promising raw material to produce various
products, including hydrocarbons, platform chemicals, and fuels. However, a more comprehensive
evaluation of the potential production of desirable value-added products and chemical intermediates
is required. For these reasons, this study aimed to investigate the impact of various operating
parameters on the pyrolysis of end-of-life olive stone, an agriculture and food industry waste, using
a tubular quartz reactor operated at 773 K. The results revealed that the product compositions
were comparable under batch or semi-batch nitrogen feeding conditions and with reaction times of
1 or 3 h. The product distribution and composition were significantly influenced by changes in the
heating rate from 5 to 50 K min−1 , while the effect of changing the biomass particle size from 0.3 to
5 mm was negligible in the semi-batch test. This work provides a comprehensive understanding of
Citation: Atakoohi, S.E.; Spennati, E.; the relationship between pyrolysis operational parameters and obtained product distribution and
Casazza, A.A.; Riani, P.; Garbarino, G. composition. Moreover, the results confirmed the possible exploitation of end-of-life olive stone
Investigating the Effect of waste to produce high-added value compounds in the zero-waste strategy and biorefinery concept.
Operational Variables on the Yield,
Characterization, and Properties of Keywords: olive stone; process parameters; waste valorization; biochar; bio-oil; pyrolytic gas
End-of-Life Olive Stone Biomass
Pyrolysis Products. Molecules 2023,
28, 6516. https://doi.org/10.3390/
molecules28186516
1. Introduction
Academic Editor: Dimitrios Kalderis The increasing energy demand, driven by industrialization and population growth,
Received: 11 July 2023
has put a strain on the world’s resources, particularly fossil fuels. The widespread use
Revised: 26 August 2023
of these fuels has contributed significantly to global warming by emitting CO2 into the
Accepted: 30 August 2023
atmosphere. To address this issue, it is crucial to explore alternative energy sources that
Published: 8 September 2023 are sustainable, reliable, and environmentally friendly [1]. The adoption of a zero-waste
strategy, which involves the valorization and reutilization of wastes to produce other useful
products, holds great potential as a solution to several environmental challenges. This
approach can help to improve energy efficiency, reduce air and water pollution, mitigate
Copyright: © 2023 by the authors. greenhouse gas emissions, and preserve natural resources [2–6].
Licensee MDPI, Basel, Switzerland. Biomasses, as a natural resource, have gained considerable attention as a potential
This article is an open access article source of raw materials for various products including hydrocarbons, platform chemicals,
distributed under the terms and and fuels. However, there are still significant challenges to be addressed to fully realize
conditions of the Creative Commons the potential of biomasses in meeting the global energy demand. Therefore, the functional
Attribution (CC BY) license (https://
impact of biomasses on the global energy cycle is contingent upon conducting further
creativecommons.org/licenses/by/
research to assess the practicality of their large-scale implementation and to evaluate the
4.0/).

Molecules 2023, 28, 6516. https://doi.org/10.3390/molecules28186516 https://www.mdpi.com/journal/molecules

Molecules 2023, 28, 6516 2 of 19

potential for generating valuable chemical intermediates and products [7]. The olive sector
is a major contributor to the agricultural biomass waste stream. Olive stones, a byproduct
of olive oil production and table olive consumption, are generated in significant quantities.
Olive groves cover 11.5 million hectares, a small but significant portion of the world’s
arable land. Despite the large amounts of olive stones produced by the olive oil industry,
the table olive industry alone generates approximately 30,000 ton/y [8,9]. Olive stones
make up 20 wt.% of olive and consist of 80 wt.% endocarp and 20 wt.% seed [10]. The
usual olive stone composition is 21.9 wt.% hemicellulose, 31.9 wt.% cellulose, and 26.5 wt.%
lignin. Carbon, followed by oxygen, and hydrogen to a much lower extent are the most
abundant elements of olive stones. The ash content is typically less than 2 wt.% and is
composed of inorganic compounds such as K2 O, CaO, MgO, SiO2 , Fe2 O3 , and Al2 O3 [8,11].
Among the available thermochemical conversion technologies to convert biomass to
biofuels and intermediates, pyrolysis is a promising technique owing to the production of
bio-oil, biochar, and pyrolytic gas [12]. However, due to the wide range of parameters affect-
ing the pyrolysis process and the diversity of biomass sources, significant variability in the
yield and composition of the products can be expected [13]. Therefore, optimizing and ad-
justing process conditions to achieve the most desirable products while considering economic
viability is a major challenge in pyrolysis. Key experimental parameters that influence the
biomass pyrolysis process include peak temperature (highest treatment temperature) [14], gas
residence time [15], type of carrier gas employed to maintain the oxygen-free conditions [16],
the heating rate of the feedstock, size, and shape of biomass [12,17], absolute pressure [13,18],
and biomass moisture and ash contents.
According to previous studies, an increase in peak temperature leads to a decrease in
char yield and a gradual increase in fixed-carbon content in the final char [19–23]. Moreover,
it has been observed that an increased gas residence time throughout the pyrolysis process
results in a slight increase in final char yield due to a higher contact time between volatiles
and solid, leading to a transition from vapor to solid carbonaceous matrix (char) phase [15].
Some researchers have investigated the impact of absolute pressure in pyrolysis, indicating
that this parameter does not significantly affect the char yield, but a higher pressure slightly
increases the gaseous species and decreases the liquid products [13,24,25]. Likewise, it has
been reported that no change in char yield has been observed by changing the type of carrier
gas from an inert one, i.e., N2 to CO2, or a mixture of N2 /CO2 . However, the presence
of CO2 in the carrier gas resulted in a substantial increase in CO concentration among
gaseous products, potentially due to the occurrence of the reverse Boudouard reaction
(CO2 + C → 2CO) and reverse Water Gas Shift (CO2 + H2 CO + H2 O) [25,26]. In the
existing literature, some researchers have utilized an oxygen-free environment through
purging, while others have employed a continuous flow of inert gas, primarily nitrogen.
Particle size and heating rate have been reported to have a significant effect on product
yield, with higher heating rates and smaller particle sizes being more favorable in increasing
bio-oil yield [27,28]. Additionally, the mineral composition of the biomass has been found
to play a crucial role in secondary pyrolysis reactions and affect the reactivity of obtained
pyrolysis char. As an example, trace amounts of inorganics like K, Na, P, Ca, and Mg that
are present in biomass tend to increase char and gas formation while decreasing bio-oil
production [29]. Furthermore, the initial moisture content of the biomass has been found
to impact both product distribution and the physicochemical properties of the bio-oil [30],
with different energy demands.
Together with all the above-mentioned parameters, it is also important to take into
consideration that the type of biomass feedstock employed can significantly impact the
pyrolysis process, and the effects of operational conditions may vary based on the biomass
type [31–33]. The composition of pyrolysis products is deeply dependent on the composi-
tion of the biomass and the relative mass ratios of its organic and inorganic compounds.
Studies have shown that the pyrolysis of cellulose or hemicelluloses leads to a higher
production of oil compared to lignin, which contributes to a greater percentage of char [29].
Molecules 2023, 28, 6516 3 of 19

Consequently, it is important to consider not only the abundance and affordability of

biomass but also its suitability concerning the desired goal of pyrolysis.
This work aims to valorize the end-of-life olive stone, a notably abundant form of
biomass residue of the agriculture and food industry, as raw material for the thermal
pyrolysis process. The primary objective of this study is to comprehensively investigate
the impact of pyrolysis key process parameters—namely biomass particle size, pyrolysis
time, heating rate, and the presence or absence of nitrogen as carrier gas flow (in batch and
semi-batch modes)—with the dual aims of cost minimization and a thorough exploration
of their influence on products distribution, composition, biochar properties, bio-oil and gas
composition, as well as the determination of optimal operational conditions. This research
seeks to cover all these aspects within a single comprehensive work focusing on a real
end-of-life industrial product.

2. Results and Discussion

2.1. Characterization of Biomass
Olive stone particles were first characterized by measuring moisture and ash content,
obtaining values of ~15 wt.% and ~1 wt.%, respectively. Moreover, fresh biomass and its ash
content were separately analyzed by SEM-EDX elemental analysis and reported in Table 1.
The O/C of fresh biomass ratio is 0.79 which agrees with other reports available in the
literature [11], even if neither S nor N were detected in this sample while they were found
in other works, with low percentages [11]. In the ashes, with the exception of oxygen, K
and Ca are the most abundant elements [34]. Moreover, thanks to SEM-EDX point analysis
in the ash sample, few particles containing Al were found. It is worth noting that these
particles could not be identified in the overall elemental analysis of the sample due to their
small amount and the instructional detection limit of 0.1 wt.%. Al-containing particles are
not usually present in the initial biomass, as their content is typically quite low. These
findings are consistent with previous reports, where the percentage of particles containing
Al in the ash sample differs, and is attributed to differences in olive grove conditions, such
as planting and harvesting methods [35–37], as well as the fact that the study used waste
olive stones from an olive oil company, which may have unique properties.

Table 1. SEM-EDX global composition of fresh biomass and ashes. Minimum detection limit ~0.1 wt.%.

O Na K Ca Mg Si P S
Sample C (wt.%)
(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
Fresh Biomass 53 47 n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Ash 5.5 51.5 1.4 24.0 12.8 2.0 1.0 0.8 1.0
n.d. not detectable.

SEM images of fresh olive stone (Figure 1) show a groove and porous surface. More-
over, a vascular system of fibers can be seen in Figure 1a while the parenchyma cells and
plasmodesma of olive stone endocarp are observable in Figure 1b in agreement with other
works [38,39].
Generally, hardness, porous matrix, high carbon, and low sulfur content make olive
stone a proper precursor for further development into carbon-based materials [11,40,41].

2.2. Thermal Pyrolysis Results

Effect of Reaction Time and Nitrogen Flow Condition
The effect of reaction time (1 and 3 h) and N2 flow (batch or semi-batch conditions)
on the pyrolysis products distribution is shown in Figure 2. Biochar (BC) and Liquid (L)
yields were determined by gravimetric analysis and then the amount of Pyrolytic Gas (PG)
was evaluated relying on total mass balances (by difference) [7]. Based on the obtained
results, changing the reaction time from 1 to 3 h and the N2 flow conditions, the product
distribution remained mainly unaffected. Nevertheless, it was noticeable that in both batch
and semi-batch conditions, the amount of char slightly decreases while the amount of
Molecules 2023, 28, 6516 4 of 19

Figure 1. SEM images of “end-of-life” olive stone particles at different magnifications and a
by detecting
liquid different
increases with thesignals:
3 h test backscattered electron
due to the occurrence of signal (a–c),
enhanced and secondary
decomposition, electron si
in line
with available data [42]. However, it is generally recognized that the effect of reaction time
on biomass decomposition
Generally, is most
hardness, prominent
porous matrix,during
highshort time intervals.
carbon, and lowMoreover, the
sulfur content ma
Molecules 2023, 28, x FOR PEER REVIEW 4 of 20
preponderance of the decomposition process takes place within the initial 30 min, according
stone a proper precursor for further development into carbon-based materials [11
to existing literature, when considering the ramp of 50 K min−1 [43].

2.2. Thermal Pyrolysis Results

Effect of Reaction Time and Nitrogen Flow Condition
The effect of reaction time (1 and 3 h) and N2 flow (batch or semi-batch con
on the pyrolysis products distribution is shown in Figure 2. Biochar (BC) and Liq
yields were determined by gravimetric analysis and then the amount of Pyroly
(PG) was evaluated relying on total mass balances (by difference) [7]. Based
obtained results, changing the reaction time from 1 to 3 h and the N2 flow conditi
product distribution remained mainly unaffected. Nevertheless, it was noticeable
both batch and semi-batch conditions, the amount of char slightly decreases w
amount of liquid increases with the 3 h test due to the occurrence of en
decomposition, in line with available data [42]. However, it is generally recogniz
the effect of reaction time on biomass decomposition is most prominent during sh
intervals. Moreover, the preponderance of the decomposition process takes place
the initial 30 min, according to existing literature, when considering the ramp of 50
Figure1.1.SEM
Figure SEMimages
imagesof
of“end-of-life”
“end-of-life”olive
olivestone
stoneparticles
particlesat
atdifferent
differentmagnifications
magnificationsand
andacquired
acquired
[43].
by detecting different signals: backscattered electron signal (a–c), and secondary electron signal (d).
by detecting different signals: backscattered electron signal (a–c), and secondary electron signal (d).

Generally, hardness, porous matrix, high carbon, and low sulfur content make olive
stone a proper precursor for further development into carbon-based materials [11,40,41].

2.2. Thermal Pyrolysis Results

Effect of Reaction Time and Nitrogen Flow Condition
The effect of reaction time (1 and 3 h) and N2 flow (batch or semi-batch conditions)
on the pyrolysis products distribution is shown in Figure 2. Biochar (BC) and Liquid (L)
yields were determined by gravimetric analysis and then the amount of Pyrolytic Gas
(PG) was evaluated relying on total mass balances (by difference) [7]. Based on the
obtained results, changing the reaction time from 1 to 3 h and the N2 flow conditions, the
product distribution remained mainly unaffected. Nevertheless, it was noticeable that in
both batch and semi-batch conditions, the amount of char slightly decreases while the
amount of liquid increases with the 3 h test due to the occurrence of enhanced
decomposition, in line with available data [42]. However, it is generally recognized that
Figure 2. Influence
the effect of reaction
of reaction time ontime and reactor
biomass condition (batch
decomposition or semi-batch)
is most prominent of pyrolysis
during shorttest on
time
Figure 2. Influence of reaction time and reactor condition (batch or semi-batch) of pyrolysi
the distribution
intervals. of BC, L the
Moreover, (HLpreponderance
+ LL), and PG. Theofletter “a” within the same
the decomposition grouptakes
process indicates thatwithin
place there
the
are distribution of BC, L (HL + LL),among
and PG. The letter “a” within the same group indicates th
theno statistically
initial 30 min,significant
according differences
to existing them.
literature, when considering the ramp of 50 K min−1
are no statistically significant differences among them.
[43].
The produced L, which has a Heavy Liquid (HL)/Light Liquid (LL) ratio of 0.53, was
diluted (only HL phase) with chloroform (around 1:10) and characterized by GC-MS. HL
compounds were categorized based on their characteristic functional groups by considering
the reported methodology for other works in the literature [43]. The effect of reaction time
and N2 purging conditions on the distribution of individual HL species is shown in Figure 3.
Phenolics are the main compounds of HL (>65%), at all the operative conditions. Also,
changing the reaction time and N2 feeding condition had no sequential effect on the overall
distribution of HL species. However, it can be mentioned that by the change from batch to
semi-batch condition, ethers percentage was increased; while by increasing the reaction
time, ketones and aldehydes were increased.

Figure 2. Influence of reaction time and reactor condition (batch or semi-batch) of pyrolysis test on
 reaction time and N2 purging conditions on the distribution of individual HL species is
shown in Figure 3. Phenolics are the main compounds of HL (>65%), at all the operative
conditions. Also, changing the reaction time and N2 feeding condition had no sequential
effect on the overall distribution of HL species. However, it can be mentioned that by the
Molecules 2023, 28, 6516 change from batch to semi-batch condition, ethers percentage was increased; while 5 ofby
19
increasing the reaction time, ketones and aldehydes were increased.

a
a,b
Others a
c
a
Nitrogenated a 3h Batch
b
a 3h Semi-batch
a
Ethers a
a,b 1h Batch
b
a
1h Semi-batch
a
Ester b
a
a
a
Alcohol b
a
a,b
Acids a
b
c
b
Aldehyde a

a
Ketone b
c

Phenolic a

0 10 20 30 40 50 60 70
Yield (%)
Figure
Figure 3.3. Influence
Influence of
of the
the reaction
reaction time
time and
and N
N22 feeding
feeding condition
condition (batch
(batch or
or semi-batch)
semi-batch) on
on the
the HL
HL
product distribution evaluated by GC-MS analysis. Different letters (a–c) in the same group indicate
product distribution evaluated by GC-MS analysis. Different letters (a–c) in the same group indicate
statistically significant differences among mean values.
statistically significant differences among mean values.

BC samples were
BC samples werecharacterized
characterizedbyby SEM-EDX
SEM-EDX (Table
(Table 2), FT-IR,
2), FT-IR, and UV-vis-NIR
and UV-vis-NIR spec-
spectroscopy (Figure 4). SEM-EDX results showed the
troscopy (Figure 4). SEM-EDX results showed the presence of K and Ca which presence of K and Ca iswhich
typicalis
typical for olive stone in agreement with literature data (CaO and
for olive stone in agreement with literature data (CaO and K2 O content of 14–33 wt.% and K 2 O content of 14–33
wt.%
2–32 and
wt.%,2–32 wt.%, respectively)
respectively) [41] and[41]theirand their presence
presence could
could also bealso
duebetoduetheto the eventual
eventual final
final treatments
treatments carried carried
out inouttheinindustrial
the industrial
plant.plant.
In BCs,In carbon
BCs, carbon and oxygen
and oxygen contents
contents seem
seem to be independent
to be independent of applied
of applied pyrolysispyrolysis conditions.
conditions. However,However,
a slighta increase
slight increase
in carbon in
carbon content in the absence of N flow (batch condition) could
content in the absence of N2 flow (batch condition) could be due to a further decomposition
2 be due to a further
decomposition
of the tarry vapors of theonto
tarrythevapors
solid onto the solid carbonaceous
carbonaceous matrix through matrix through
secondary secondary
reactions, in
reactions,
agreementinwith agreement with the
the literature literature [15].
[15].
FT-IR and UV-vis spectra of BCs, obtained from the different investigated conditions,
showed similar features.
Table 2. SEM-EDX These spectra
global composition arein
of BC typical of highly
different carbonaceous
pyrolysis solids,in
conditions (change with few
reaction
residual
time and N functional
2 gas). groups. Carbonaceous matrix could strongly absorb the IR radiation
and cover the characteristic features of still incompletely converted biomass. However,
Biomass Reaction N2
Heating Rate FT-IR spectra show characteristic absorptions
C (%) in the OH region (3600–3400
O (%) K(%) and Ca
1700–1500
(%)
Size Time (h) Condition
cm ), due to adsorbed water on KBr, and a weak band of C−C deformation at 1420 cm−1
−1

3
[1,7] and a complex Batchfeature in-between
82.5 15.5 cm−1. The1.5UV-vis-NIR 0.5
1000–800 spectra
− 1
3
demonstrate full Semi-batch
absorption of light 81.5
in both the 15.5 and UV range.
visible 1.9 1.1 the
Nevertheless,
1–5 mm 50 K min 1 Batch 84.0 14.5 1.5 0.0
1 Semi-batch 81.0 16.5 1.5 1.0

FT-IR and UV-vis spectra of BCs, obtained from the different investigated conditions,
showed similar features. These spectra are typical of highly carbonaceous solids, with few
residual functional groups. Carbonaceous matrix could strongly absorb the IR radiation and
cover the characteristic features of still incompletely converted biomass. However, FT-IR
spectra show characteristic absorptions in the OH region (3600–3400 and 1700–1500 cm−1 ),
due to adsorbed water on KBr, and a weak band of C−C deformation at 1420 cm−1 [1,7]
and a complex feature in-between 1000–800 cm−1 . The UV-vis-NIR spectra demonstrate full
absorption of light in both the visible and UV range. Nevertheless, the BCs obtained under
Molecules 2023, 28, 6516 6 of 19
Molecules 2023, 28, x FOR PEER REVIEW 6 of 20

batch conditions display a higher level of light adsorption compared to those obtained
under
BCs semi-batch
obtained under conditions.
batch conditions display a higher level of light adsorption compared
PG obtained
to those have been characterized
under semi-batchby means of GC-MS (Table 3) and FT-IR (Figure 5). It
conditions.
should be mentioned that only the PGs obtained from the pyrolysis test of batch condition
have been
Table collected
2. SEM-EDX andcomposition
global analyzed. The FT-IR
of BC spectrapyrolysis
in different clearly showed the(change
conditions presence
in of carbon
reaction
time and N
dioxide 2 gas).
considering the bands centered at 670 cm−1 (bending), 2335 cm−1 (symmetric
and asymmetric stretching), and corresponding bands at 3613 and 3715 cm−1 (overtones).
Biomass Heating Reaction Time
The bands at 1304 cm−1 and 3015 cm−1Nshowed 2 Condition C (%) of
the presence O methane
(%) K(%) Ca (%)
(bending and
Size Rate (h)
stretching rotovibrational modes, respectively). The weak bands at 2960 and 950 cm−1 are
3 Batch 82.5 15.5 1.5 0.5
representative of C-H stretching of other hydrocarbons and CH2 out of the plane mode
of1–5
ethylene (CK 3 Semi-batch 81.5 − 1 15.5 1.9 1.1
mm 50 2H 4 ), −1
min respectively [44]. The band at 2143 cm is due to the stretching
mode of carbon monoxide. The 1 band at 1744 Batch − 1
cm could 84.0 14.5 to 1.5
be assigned 0.0
C=O stretching
characteristic band [45]. 1 Semi-batch 81.0 16.5 1.5 1.0

3h Batch

15
1h Batch

1h Semi-batch

10
3h Semi-batch

300 400 500 600 700

Wavelength (nm)

Figure
Figure 4.
4. (left)
(left)FT-IR,
FT-IR, and
and (right)
(right)UV-vis-NIR
UV-vis-NIR spectra
spectra of
of BCs.
BCs.

TablePG have
3. The been distribution
product characterized by determined
of PG by GC−MS
means of GC-MS (Table 3) and
in batch FT-IR (Figure 5). It
conditions.
should be mentioned that only the PGs obtained from the pyrolysis test of batch condition
have beenCompound
collected and analyzed. The FT-IR spectra Distribution (%)
clearly showed the presence of
3 h without N
carbon dioxide considering the bands centered 2 at 670 cm (bending), −1 1 h without2335 N2 cm−1
(symmetric
N2 , H2 , CO2and
, CO,asymmetric
CH4 , C2 H4 stretching),77.49
and ±corresponding
0.81 bands at 361374.06and 3715 cm−1
± 0.74
(overtones).
Acetaldehyde The bands at 1304 cm and
& 2-Butene −1 6.793015 cm showed the presence
± 0.25 −1 of methane
8.76 ± 0.76
Formic acid,
(bending andmethyl
stretching 2.04 ± 0.70
esterrotovibrational modes, respectively). The weak2.27 bands ± 0.05
at 2960 and
1-Butane,
950 cm−1 are 2-methyl-
representative of C-H stretching0.03 ±of0.02
other hydrocarbons and 0.06CH ± 0.02
2 out of the
Furanmode
plane & Acetone
of ethylene (C2H4), respectively4.63 ±[44].
0.15 The band at 2143 cm 4.57−1 ±is0.06
due to the
1-Butan, 3-methyl- 0.56 ± 0.05 0.31 ± 0.06
stretching mode of carbon monoxide. The band at 1744 cm could be assigned to C=O
−1
Acetic acid, methyl ester 1.58 ± 0.07 1.55 ± 0.09
stretching characteristic
Cyclopropane, ethynyl- band [45]. 0.67 ± 0.00 0.47 ± 0.04
In agreement
Propanal, 2-methyl-with discussed IR data, 0.34GC-MS
± 0.03 analysis revealed that 0.39 ± the0.01
main PGs
compounds are CO2, CO, CH4, and C2H0.58
2,3-Dihydrofuran 4 as ±
observed
0.04 in literature where 1.40 other
± 0.04types of
2,3-Butanedione
biomasses 0.75 ±wood,
such as Arthrospira platensis [1,3], 0.06 rice husk, and forestry 1.41 ± residue
0.08 [46]
2-Butanone
were used as raw feedstock. Moreover, no S-X±vibration
0.42 0.03 has been detected 0.42by ± 0.01
considering
Furan, 2- or 3-methyl-
the detectability limit and experimental3.42 ± 0.09There were no significant
errors. 3.54 ± 0.02
differences
Methyl propionate 0.12 ± 0.02 0.14 ± 0.01
observed in terms of PG compounds as the
1,4-Cyclohexadiene
pyrolysis reaction time was0.09
0.11 ± 0.01
increased
± 0.02
from 1
to2,4-Hexadiene
3 h. It is worth mentioning that evaluating 0.11 ±the
0.01impact of nitrogen feeding0.13 ± 0.02conditions,
whether
Benzenea continuous flow of N2 (semi-batch) 0.16 ±or a batch N2 condition (00.17
0.04 mL±min −1, batch),
0.02
onFuran,2,5-dimethyl
the pyrolysis process, is crucial for process0.21 ±design
0.01 and further possible 0.24applications
± 0.03 of
biomass.
Molecules 2023,
Molecules 28, x6516
2023, 28, FOR PEER REVIEW 7 7ofof20
19

Figure 5.
Figure FT-IR spectra
5. FT-IR spectra of
of PGs
PGs obtained
obtained from
from pyrolysis
pyrolysis test
test carried
carried out
out in
in batch
batch condition.
condition.

In agreement with discussed IR data, GC-MS analysis revealed that the main PGs
Table 3. The product distribution of PG determined by GC−MS in batch conditions.
compounds are CO2 , CO, CH4 , and C2 H4 as observed in literature where other types of
biomasses such as Arthrospira platensis [1,3], wood, rice Distribution (%) residue [46] were
husk, and forestry
Compound
used as raw feedstock. Moreover, no S-X3vibration h without N2 has been detected
1 hby considering
without N2 the
detectability limit and
N2, H2, CO2, CO, CH4, C2H4 experimental errors. There were
77.49 ± 0.81 no significant differences
74.06 ± 0.74 observed
in terms of PG&compounds
Acetaldehyde 2-Butene as the pyrolysis6.79 reaction
± 0.25time was increased 8.76from
± 0.76 1 to 3 h. It
is worth mentioning
Formic acid, methyl ester that evaluating the impact of
2.04 ± 0.70nitrogen feeding conditions,
2.27 ± 0.05whether a
continuous flow of N2 (semi-batch) or a batch N2 condition (0 mL min−1 , batch), on the
1-Butane, 2-methyl- 0.03 ± 0.02 0.06 ± 0.02
pyrolysis process, is crucial for process design and further possible applications of biomass.
Furan & Acetone 4.63 ± 0.15 4.57 ± 0.06
1-Butan, 3-methyl-
2.3. Effect of Particle Size and Heating Rate 0.56 ± 0.05 0.31 ± 0.06
AceticToacid, methyl ester 1.58 ± 0.07
ensure a more reliable comparison with the existing literature, a constant 1.55 ± 0.09 reaction
Cyclopropane,
time of 1 h under ethynyl-
semi-batch conditions with0.67 ± 0.00nitrogen flow was0.47
constant ± 0.04
upheld as a control
Propanal, 2-methyl- 0.34 ± 0.03
in all experiments in this section, with only other parameters being altered [12–16]. 0.39 ± 0.01 This is
2,3-Dihydrofuran
significant as most of the related works in the 0.58 ± 0.04 utilize continuous
literature 1.40carrier
± 0.04 gas flow.
2,3-Butanedione
The effect of changing the heating rate, by keeping 0.75 ± 0.06a constant particle size1.41 (in
± 0.08
the range of
2-Butanone
1.00–1.60 mm), on the pyrolysis product distribution, 0.42 ± 0.03 is shown in Figure 0.426A.
± 0.01
The BC and
PG yield decreased
Furan, 2- or 3-methyl- while the L yield increased by
3.42 ± 0.09increasing the heating rate,
3.54 ± 0.02 which is in
agreement with
Methyl propionate literature reports [47,48]. In general,
0.12 ± 0.02 increasing the heating
0.14 ± 0.01 during
rate
biomass pyrolysis can result in higher yields
1,4-Cyclohexadiene 0.11of±L0.01
and PG products, but 0.09can also lead to
± 0.02
changes in
2,4-Hexadiene the product composition and quality [14].
0.11 ± 0.01 This behavior could be attributed
0.13 ± 0.02 to a
quick
Benzene biomass fragmentation and a higher tar decomposition
0.16 ± 0.04 increasing the heating
0.17 ± 0.02 rate.
Biomass fragmentation refers to the breaking of a part of the solid biomass material into
Furan,2,5-dimethyl 0.21 ± 0.01 0.24 ± 0.03
smaller pieces, which exposes more surface area to the heat source and allows for faster
heating. Tar decomposition, on the other hand, refers to the breakdown of the tars and
2.3. Effect of Particle Size and Heating Rate
other volatile organic compounds that are released from the biomass during heating. The
To ensure
combined effecta of
more reliable
quick biomasscomparison with the
fragmentation andexisting
higher literature, a constant
tar decomposition canreaction
lead to
time of 1 h under semi-batch conditions with constant nitrogen flow
a significant increase in the heating rate, which can in turn affect the overall behavior was upheld as ofa
control in all experiments in this section, with only other parameters
the system [31,49]. The fast biomass decomposition limits the available time for secondary being altered [12–
16]. This is
reactions significant
like tar crackingas most of the related works
and re-polymerization that in thetoliterature
lead utilize
the increase continuous
in liquids [50].
carrier gas flow. The effect of changing the heating rate, by keeping a constant particle size
(in the range of 1.00–1.60 mm), on the pyrolysis product distribution, is shown in Figure
6A. The BC and PG yield decreased while the L yield increased by increasing the heating
 therefore the results shown here are justified.
When increasing the biomass particle size with a constant heating rate of 5 K min−1
(Figure 6C), the distribution of BC, L, and PG was not affected at all. This can be attributed
to the fact that at a slow heating rate, the temperature gradient between the particle
Molecules 2023, 28, 6516 surface and center is negligible, resulting in similar heat transfer rates for particles 8 ofof
19
different sizes.

Figure 6.
Figure Effectof
6. Effect ofparticle
particlesize
sizeand
and heating
heating rate
rate on
on pyrolysis
pyrolysis products
products distribution,
distribution, (A)
(A) variable
variable
heating
heating rate
rate and constant
constant particle
particlesize
size(1.00–1.60
(1.00–1.60mm),
mm), variable
variable particle
particle sizes
sizes andand constant
constant heating
heating rate
rate of (B) 50 K −
min1 −1 and (C) 5 K min− 1
−1. Different letters (a, b) in the same group indicate statistically
of (B) 50 K min and (C) 5 K min . Different letters the same group indicate statistically
significant
significantdifferences
differencesamong
amongmean
meanvalues.
values.

By maintaining a constant heating rate of 50 K min−1 (Figure 6B) while increasing the
biomass particle size, the yields of L, PG, and BC remained constant based on statistical
analysis (L followed a slight increasing pattern). The constancy of L yield at smaller particle
sizes was surprising because smaller sizes typically result in higher heat transfer and greater
biomass decomposition, leading to a higher liquid yield [51]. However, it was reported by
Akhtar et al. [29] that factors such as biomass type, bulk density, and oxygen content can
influence the trend between liquid yield and biomass particle size and therefore the results
shown here are justified.
When increasing the biomass particle size with a constant heating rate of 5 K min−1
(Figure 6C), the distribution of BC, L, and PG was not affected at all. This can be attributed
to the fact that at a slow heating rate, the temperature gradient between the particle surface
and center is negligible, resulting in similar heat transfer rates for particles of different sizes.
HL obtained from the pyrolysis condition with variable heating rate and constant
particle size in the range of 1.00–1.60 mm have been analyzed with GC-MS and the results
are shown in Figure 7. By increasing the heating rate, the phenolic content was decreased
(maximum 20%). On the other hand, the content of aldehyde, alcohol, acetone, and ether
groups was slightly increased. Additionally, the mass ratio between HL and LL was
influenced by increasing the heating rate. The ratio of HL/LL at different heating rates
of 5, 10, 20, and 50 K min−1 were 0.17, 0.39, 0.49, and 0.53, respectively. Therefore, higher
heating rates produce a bio-oil richer in lipophilic compounds in agreement with [51]. The
variation of biomass particle size with constant heating rate did not significantly influence
the distribution and properties of obtained HL and LL.
 (maximum 20%). On the other hand, the content of aldehyde, alcohol, acetone, and ether
groups was slightly increased. Additionally, the mass ratio between HL and LL was
influenced by increasing the heating rate. The ratio of HL/LL at different heating rates of
5, 10, 20, and 50 K min−1 were 0.17, 0.39, 0.49, and 0.53, respectively. Therefore, higher
heating rates produce a bio-oil richer in lipophilic compounds in agreement with [51]. The
Molecules 2023, 28, 6516 variation of biomass particle size with constant heating rate did not significantly influence 9 of 19
the distribution and properties of obtained HL and LL.

Molecules 2023, 28, x FOR PEER REVIEW 10 of 20

Figure 7. Effect
Figure of different
7. Effect pyrolysis
of different conditions
pyrolysis on the product
conditions on thedistribution by GC-MS analysis,
product distribution (a) analysis,
by GC-MS
variable heating rate and constant particle size of 1.00–1.60 mm, (b) variable particle sizes and
(a) variable heating rate and constant particle size of 1.00–1.60 mm, (b) variable particle sizes and
constant heating rate of 50 K min−1, (c)−variable particle sizes and a constant heating rate of 5 K min−1.
1 , (c) variable particle sizes and a constant heating rate of 5 K min−1 .
constant heating rate of 50 K min
Different letters (a–c) in the same group indicate statistically significant differences among mean
Different letters (a–c) in the same group indicate statistically significant differences among mean values.
values.

Also, the higher heating rate resulted in darker LL and this trend was more obvious
when the rate changed from 5 to 10 K min−1 while from 10 to 50 K min−1, the change in LL
color was not clearly distinguishable. In Figure 8, the FT-IR analysis of LL obtained at
various heating rates is reported, showing similar characteristic bands. The OH region
 Figure 7. Effect of different pyrolysis conditions on the product distribution by GC-MS analysis, (a)
variable heating rate and constant particle size of 1.00–1.60 mm, (b) variable particle sizes and
constant heating rate of 50 K min−1, (c) variable particle sizes and a constant heating rate of 5 K min−1.
Molecules 2023, 28, 6516 Different letters (a–c) in the same group indicate statistically significant differences among10mean of 19
values.

Also, the higher heating rate resulted in darker LL and this trend was more obvious
Also, the higher heating rate resulted in darker LL and this trend was more obvious
when the
when the rate
rate changed
changed from
from 55 to
to 10
10 KK min
min−1while
−1
whilefromfrom 1010toto5050
KK minmin,−the
−1 change
1 , the changein LL
in
color was not clearly distinguishable. In Figure 8, the FT-IR analysis
LL color was not clearly distinguishable. In Figure 8, the FT-IR analysis of LL obtained of LL obtained at
various heating rates is reported, showing similar characteristic bands.
at various heating rates is reported, showing similar characteristic bands. The OH region The OH region
exhibits characteristic
exhibits characteristic absorptions
absorptions at at 3600–3400
3600–3400cm cm−−11 and
and 1680–1500
1680–1500 cm cm−−11,, assigned
assigned to to
moisture on KBr, while the CH stretching region shows absorptions
moisture on KBr, while the CH stretching region shows absorptions at 3054–2959 cm 1.. at 3054–2959 cm−−1

The C=O
The C=O stretching
stretchingof ofcarbonyl,
carbonyl,carboxyl,
carboxyl,and and ester
estergroups
groups exhibit a peak
exhibit a peak at 1716 cm cm
at 1716
−1 and
−1
a shoulder at 1800 cm −1. The−bands
1 at 1509 cm −1, 1466 cm − 1−1, and 1426
and a shoulder at 1800 cm . The bands at 1509 cm , 1466 cm , and 1426 cm can − cm
1 −1 can be attributed
− 1
to the
be C-C stretching
attributed of aromatics,
to the C-C stretchingwhereas the 1384
of aromatics, cm−1 band
whereas is mainly
the 1384 cm−1 associated
band is mainly with
CH deformation. Furthermore, the 1331 cm −1 peak may be attributed
associated with CH2 deformation. Furthermore, the 1331 cm peak may be attributed
2 − 1 to the -OH in-plane
deformation
to of the phenolic
the -OH in-plane deformationgroup.of The peaks in the
the phenolic 1000–1300
group. cm−1in
The peaks range relate to various
the 1000–1300 cm−1
C-O and
range C-Ctocoupling
relate interaction
various C-O and C-C stretching,
coupling while the peaks
interaction belowwhile
stretching, 1000 cm −1 may be
the peaks due
below
to -OH
1000 −1 may
cmand -CHbe out-of-plane
due to -OHdeformation modes [1,7].
and -CH out-of-plane deformation modes [1,7].

Figure 8. FT-IR
Figure 8. FT-IRspectra
spectraofofLLLLsamples
samplesobtained with
obtained with biomass
biomassparticle
particlesizesize
in the range
in the rangeof 1.00–1.65 mm
of 1.00–1.65
and
mm heating rate ofrate
and heating (A)of5 (A) 5 K−1min
K min , (B)−110 K 10
, (B) minK−min
1 , (C)
−1, 20
(C)K20 K −min
min 1 , (D) 50 K50min
−1, (D) −1 . −1
K min .

The results of SEM-EDX analysis for BCs produced by altering particle size and heating
rate are presented in Table 4. The analysis revealed that there was no significant change in
the elemental distribution of the BCs because of varying the particle size or heating rate.
However, a lower carbon content was observed in the case of the smallest particle sizes
(0.30–0.35 mm).

Table 4. SEM-EDX global composition of BCs obtained by changing the particle size and heating rate
of pyrolysis tests.

Biomass Heating Rate

C (%) O (%) K (%) Ca (%)
Size (mm) (K/min)
5 81.4 16.4 1.4 0.8
10 82.0 15.6 1.4 1.0
1.00–1.60
20 82.5 14.0 1.6 1.9
50 79.5 17.5 1.5 1.5
1.60–2.30 83.0 14.4 1.8 0.8
2.30–5.00 50 83.0 14.5 1.7 0.8
0.30–0.35 77.5 17.5 2.2 2.8

As an example, SEM micrographs (with different magnifications) of obtained BC with

a particle size in the range of 1.00–1.65 mm and a heating rate of 50 K min−1 are reported
in Figure 9. The SEM images show that the olive stone particles almost maintained their
porous surface. However, it seems that the vascular fiber system (Figure 1a) is damaged
 2.30–5.00 50 83.0 14.5 1.7 0.8
0.30–0.35 77.5 17.5 2.2 2.8

As an example, SEM micrographs (with different magnifications) of obtained BC

with a particle size in the range of 1.00–1.65 mm and a heating rate of 50 K min−1 are
Molecules 2023, 28, 6516 11 of 19
reported in Figure 9. The SEM images show that the olive stone particles almost
maintained their porous surface. However, it seems that the vascular fiber system (Figure
1a) is damaged and compacted to the external surface during pyrolysis (Figure 9a).
and compacted
Moreover, to the external
in Figure 9d, somesurface during pyrolysis
agglomerated (Figure 9a). Moreover,
and non-homogenously in Figure 9d,
distributed Ca
some agglomerated and non-homogenously distributed Ca particles are observable
particles are observable on the BC surface, as indicated by the brighter particles and on the
BC surface, by
confirmed as indicated
SEM-EDXbypointthe brighter
analysis.particles
However, andthese
confirmed by SEM-EDX
inorganic point particles
agglomerated analysis.
However, these inorganic agglomerated particles were not observed in the SEM
were not observed in the SEM images of the fresh biomass, even though some distributed images of
the fresh biomass, even though some distributed brighter particles were envisaged
brighter particles were envisaged at high magnification. The Ca-rich particles have also at high
magnification.
been observedThe Ca-rich
in the particles
BCs in have also been
other conditions. observed
Therefore, in the BCs
it could in other conditions.
be concluded that both
Therefore,
agglomeration and accretion of Ca-rich particles occurred during the pyrolysisparticles
it could be concluded that both agglomeration and accretion of Ca-rich process
occurred
[52]. during the pyrolysis process [52].

Figure 9.
Figure 9. SEM
SEM Images
Images of
of obtained
obtained BC
BC obtained
obtained with
with particle
particle size
size in
in the
the range
range of
of 1–1.65
1–1.65 mm
mm and
and
heating rate of 50 K min−−11. Images are acquired by detecting different signals: secondary electron
heating rate of 50 K min . Images are acquired by detecting different signals: secondary electron
signal (a–c), and backscattered electron signal (d).
signal (a–c), and backscattered electron signal (d).

The thermogravimetric analyses of BC samples are shown in Figure 10. The first
weight loss in all the samples occurred in the temperature range of 323–423 K due to free
water evaporation. This could be confirmed by the endothermic peak at 373 K detectable
in the DTA curves. For raw biomass (Figure 10A), a rapid weight loss is evident in the
range of 473–823 K due to the decomposition of hemicellulose (493–588 K), cellulose (573–
673 K), and lignin (423–1173 K) [53]. This could also be confirmed by the DTA exothermic
peak centered at 623 K. Nassar et al. reported that in the case of using a heating rate
of 10 K min−1 , lignin decomposes very slowly, losing only 40% of its initial mass below
973 K [54]. Therefore, it could be concluded that the following decrease in biomass weight
(~5%), in the range of 823–1173 K, is mostly due to the further decomposition of lignin.
This could be confirmed by DTA peaks centered at 873, 1023, and 1123 K.
In the TGA and DTA analyses of BC samples (Figure 10B–E), and in the temperature
range of 423 to 1073 K, two weight loss sections with different slopes are observable.
The first one (range of 423–773 K) could be due to the desorption of surface-adsorbed
compounds (~4%). In fact, considering that BCs are the solid product of pyrolysis, the
weight loss could not be attributed to the degradation and decomposition of hemicellulose,
cellulose, or lignin. The second part (range of 773–1173 K) is due to the decomposition
of remaining lignin in the BCs. The weight loss behavior in the mentioned ranges is also
confirmed by a broad exothermic peak in the DTA curves.
 peak centered at 623 K. Nassar et al. reported that in the case of using a heating rate of 10
K min−1, lignin decomposes very slowly, losing only 40% of its initial mass below 973 K
[54]. Therefore, it could be concluded that the following decrease in biomass weight (~5%),
in the range of 823–1173 K, is mostly due to the further decomposition of lignin. This could
Molecules 2023, 28, 6516 be confirmed by DTA peaks centered at 873, 1023, and 1123 K. 12 of 19

Figure 10. TG and DTA curves of (A) raw biomass, BC obtained with: (B) heating rate 50 K min−1 and
Figure 10. TG and DTA curves of (A) raw biomass, BC obtained with: (B) heating rate 50 K min−1
particle size 1.00–1.65 mm, (C) heating rate 5 K min−1 and−1particle size 1.00–1.65 mm, (D) heating rate
and particle−size 1.00–1.65 mm, (C) heating rate 5 K min and particle size 1.00–1.65 mm, (D) heating
50 K min 1 and particle size 2.30–5.00 mm, (E) heating rate 5 K min−1 and particle size 2.30–5.00 mm.
rate 50 K min−1 and particle size 2.30–5.00 mm, (E) heating rate 5 K min−1 and particle size 2.30–5.00
mm. In this section, FT-IR spectra of fresh olive stone (Figure 11A) are reported to make
a comparison with BCs. Spectra show several bands that are representative of various
functional groups contained in the starting biomass. Also, it is comparable to the spectra
of LL (Figure 8) which shows the presence of phenolic, alcoholic, carbonyl, and carboxyl
groups together with water. In particular, the broad band centered at 3448 cm−1 is due to
O-H stretching of water, phenolic and alcoholic groups. The band at 2918 cm−1 represents
-CH stretching of aliphatics and aromatics while the band at 1736 cm−1 and its shoulder
at 1800 cm−1 correspond to C=O bond stretching of carbonyl, carboxyl, and ester groups.
The bands at 1600, 1509, 1466, and 1426 cm−1 can be related to C-C stretching of aromatics
while the band at 1380 cm−1 is mainly related to CH2 deformation (scissoring). The -OH
 deformation modes of cellulosic units are also present in this region whereas the band at
1331 cm−1 could be due to -OH in-plane deformation of the phenolic group. The peaks in
the range of 1000–1300 cm−1 are related to different C-O and C-C coupling interaction
stretching while the peaks below 1000 cm−1 are likely due to -OH and -CH out-of-plane
Molecules 2023, 28, 6516 deformation modes [1,7]. 13 of 19
FT-IR spectra of BC samples obtained with biomass particle size in the range of 1.00–
1.65 mm at different heating rates (considering that the change in heating rate was the
most effectivemodes
deformation parameter on the yield
of cellulosic units of
areBC)
alsoare shown
present in in Figure
this region11. The obtained
whereas the bandBCs at
present almost
− 1 the same characteristic bands, like the one previously discussed
1331 cm could be due to -OH in-plane deformation of the phenolic group. The peaks (Figure 4).
As expected,
in the the1000–1300
range of characteristic
cm−bands observed
1 are related in the spectra
to different C-O andof fresh
C-Cbiomass
couplinghave mostly
interaction
disappeared which is due to the decomposition
− 1 and carbonization of biomass
stretching while the peaks below 1000 cm are likely due to -OH and -CH out-of-plane by pyrolysis
reaction.
deformation modes [1,7].

Figure 11.
Figure FT-IR spectra
11. FT-IR spectraof of(A)
(A)fresh
fresholive
olivestone,
stone,andandBCBCobtained with
obtained withbiomass particle
biomass sizesize
particle 1–1.65 mm
1–1.65
and and
mm heating rate of
heating (B)of5 (B)
rate 5 K−min
K min 1 , (C)
−1,10 K 10
(C) minK−min
1 , (D)
−1, 20
(D)K20 K−
min 1 , and
min (E) 50
−1, and (E)K50min−1 . −1
K min .

FT-IR spectra of BC samples obtained with biomass particle size in the range of
1.00–1.65 mm at different heating rates (considering that the change in heating rate was
the most effective parameter on the yield of BC) are shown in Figure 11. The obtained
BCs present almost the same characteristic bands, like the one previously discussed
(Figure 4). As expected, the characteristic bands observed in the spectra of fresh biomass
have mostly disappeared which is due to the decomposition and carbonization of biomass
by pyrolysis reaction.
Table 5 presents an overview of outcomes from some of the prior studies that focused
on pyrolysis parameters and their impacts. However, given the diverse range of parameters,
characterizations, operational setups, and conditions employed in these studies, making a
direct comparison is unfeasible.

Table 5. Presents an overview of outcomes from some of the prior studies that focused on pyrolysis
parameters and their impacts.

Main PG
Pyrolysis Products Yield Composition Main L BC
Biomass Ref.
Condition (wt. %) (Order Based on Composition Analysis
Abundance)
PG ∼
= 78
Fast, at 1123 K, with
L∼
= 12 CO, H2 , CO2 , CH4
300–500 K s−1 , static N2 ∼
BC = 10
Wood n.a. n.a. [55]
PG ∼
= 23
Slow, at 1123 K, with 10 K m−1 ,
L∼
= 61 CO, CO2 , H2 , CH4
for 30 min, static N2 ∼
BC = 16
Molecules 2023, 28, 6516 14 of 19

Table 5. Cont.

Main PG
Pyrolysis Products Yield (wt. Composition Main L BC
Biomass Ref.
Condition %) (Order Based on Composition Analysis
Abundance)
H:C ∼= 0.37
Slow, at 823 K, with 5 K m−1 , for PG ∼
= 33 yorg :ywater = 0.27
O:C ∼= 0.08
60 min, atm of N2 with residence L∼
= 39 CO2 , CO, H2 , CH4 Detailed analysis
∼ SBET = 229 m2 g−1
time of 100 s, pressure of 0.2 MPa BC = 28 n.a.
Wheat straw Vultra = 0.08 cm3 g−1 [13]
Slow, at 748 K, with 5 K m−1 , for H:C ∼= 0.46
PG ∼
= 36 yorg :ywater = 0.43
60 min, atm of CO2 /N2 = 0.3 with O:C ∼= 0.11
L∼
= 35 CO2 , CO, CH4 , H2 Detailed analysis
residence time of 150 s, pressure ∼ SBET = 203 m2 g−1
BC = 29 n.a.
of 0.55 MPa Vultra = 0.05 cm3 g−1
For N2 of 100 For N2 of 100
At 823 K, with 300 K min−1 , for cm3 min−1 C∼= 70%
10 min, N2 of 50, 100, 200, PG ∼= 30 O∼= 16%
Molecules 2023, 28, x FOR PEER
400 cmREVIEW
3
min−1 L∼= 44 N∼ = 6% 15 of 20
Cotton seed BC ∼= 26 n.a. H∼ = 9% n.a. [47]
cake For rate of 5 K For rate of 300 K
At 823 K, with 5, 100, 300, min−1 min−1 C ∼= 70%
700 K min−1 , for 10 min, N2 of PG ∼= 21 O∼= 16%
Slow, at 773 100K, 3
cmwith min−1 L∼= 47 N∼ = 6% Phenolics ≅
For 60 BC ∼
min and = 32 H∼ = 9% C ≅ 84.0%
50 K min −1, biomass
At 873 K, with 5 K min−1 , for static N2PG ∼
68% H:C ∼
= 23 =O ≅ 15.5%
0.40
size of 60 1–5 mm,N2for
min, static , pressure of L∼= 44 CO2 , CO, CH4 , H2 Ketones ≅ O:C ∼
5% = 0.07
0.1 MPa
Vine shoots 60 or 180 min, static −1
PG ≅ 27 ∼ 33
BC = CO 2, CO, H2, CH4, C2H4 SBET = 109 K
n.a. Ethers ≅ 10% ∼
m2≅g−11.5%
[25]
At 873 K, with 5, K min , for PG ∼
= 27 H:C = 0.38
60 min, static CO2 , pressure of L ≅ 47 L ∼ O:C ∼ 0.05 ≅ 0.5%
=Ca
N2 or a flow 0.1 ofMPa
100 = 43 CO2 , CO, CH4 , H2
Alcohols ≅ 8% 2 g−1
BC ≅ 26 BC ∼ = 30 SBET = 57 mH = n.a.
mL min −1
0.5 mm BC ∼ = 18
Ester ≅ 6%
Olive At 950 K, with 10 K s−1 , biomass 1.0 mm BC ∼
husk Slow, at 773 K, with
Olive
= 24 n.a. n.a. n.a. This
[21]
size of <0.5, 1.0, 1.5, 2.0 mm 1.5 mm BC ∼ = 29
stone 5, 10, 20, 50 K ∼
2.0 mm BC = 36 Phenolics ≅ work
For 5 K min−1 and C ≅ 81.4%
min−1 , biomass size − For 60 min and Phenolics ∼= 68% 84% C ∼ = 84.0%
O ≅ 16.4%
1
Slow, at 773 K, with 50 K min1.0–1.6 , mm static N2 Ketones ∼= 5% O∼ = 15.5%
of biomass
0.30–0.35, size of1.0–
1–5 mm, for 60 or
PG ∼
= 27
CO2 , CO, H2 , CH4 ,
Ethers ∼ Ketones ≅ 6%
10% K∼= 1.5%
180 min, static N2 or a flow of PG ≅ 30 ∼ K ≅ 1.4%
C2 Hn.a.
=
4 ∼ ∼
1.6, 1.6–2.4, 100 mLandmin−1
L = 47
Ethers ≅ 4%
Alcohols = 8% Ca = 0.5%
Olive stone L ≅ 35 BC ∼
= 26 Ester ∼
= 6% H = n.a.
Ca ≅ 0.8%This work
2.4–5.0 mm,
Slow, at 773for 60 5, 10, 20,
K, with For 5 K min−1 and Phenolics ∼ Acids ≅ 2%
= 84% C∼ = 81.4%
50 K min , biomass size of BC ≅ 35
− 1
1.0–1.6 mm ∼
Ketones = 6% ∼
O = 16.4%H = n.a.
min, 0.30–0.35,
N2 flow1.0–1.6,of 100 1.6–2.4, and PG ∼
= 30 n.a. = 4%Ester ≅ 5%
Ethers ∼ K∼= 1.4%
2.4–5.0 mm, for −1 60 min, N2 flow of ∼
L = 35 ∼
Acids = 2% ∼
Ca = 0.8%
mL min 100 mL min−1 BC ∼
= 35 Ester ∼
= 5% H = n.a.
n.a. not available.
n.a. not available.

3.3.Materials
Materialsand
andMethods
Methods
3.1.Materials
3.1. Materials
In this
In this work,
work, end-of-life
end-of-life olive
olive stones
stones were
were used
used as
as the
theraw
rawmaterial,
material, which
whichwas
was
providedby
provided byaacompany
companylocated
locatedininPuglia,
Puglia,Italy.
Italy.The
Theolive
olivestones
stonesdisplayed
displayedananoverall
overall
particle
particlesize
sizeof
of1–5
1–5mm,
mm,and
andthey
theywere
wereused
usedwithout
withoutany
anychemical
chemicalpretreatment
pretreatmentbut
butonly
only
by
bycrashing
crashingandandsieving
sievingoperation
operation(Figure
(Figure12).
12).All
Allthe
thechemicals
chemicalsused
usedininthis
thiswork
workwere
were
provided
providedby byCarlo
CarloErba
Erbareagents
reagents(Milan,
(Milan,Italy)
Italy)with
withaapurity
purityabove
above99%.
99%.

Figure12.
Figure 12.Industrial
Industrial“end-of-life”
“end-of-life”olive
olivestone
stonewaste
wastebiomass
biomass(endocarps).
(endocarps).

3.2. Characterization of Biomass

Received biomass was characterized in terms of moisture and ash content,
morphological and elemental composition, thermogravimetric analysis (TGA-DTA), and
FT-IR (Nexus Thermo Fisher instrument, Madison, WA, USA) spectrophotometer.
Molecules 2023, 28, 6516 15 of 19

3.2. Characterization of Biomass

Received biomass was characterized in terms of moisture and ash content, morpholog-
ical and elemental composition, thermogravimetric analysis (TGA-DTA), and FT-IR (Nexus
Thermo Fisher instrument, Madison, WA, USA) spectrophotometer. Moisture and ash con-
tent were measured in agreement with AOAC methods [7]. Morphological and elemental
composition was investigated by a Zeiss Evo 40 equipped with a Pentafet Link Energy
Dispersive X-ray Spectroscopy system managed by the INCA Energie 450 × 3 (Oxford
Instruments, Analytical Ltd., Bucks, UK). Thermogravimetric analysis (TGA and DTA) was
conducted using a TG-DSC Netzsch Geratebau STA 409 (Selb, Germany), equipped with a
Molecules 2023, 28, x FOR PEER REVIEW 16 of 20
Netztch410 furnace temperature controller. In brief, about 60 mg of biomass was placed
3
in a 0.1 cm alumina crucible and located inside the instrument in which the sample was
flushed with nitrogen at a flow rate of 40 mL min−1 , and then the temperature was raised
from room temperature
3.3. Pyrolysis a rate of 10 K min−1 .
to 1173 K at Set-Up
Plant and Experimental
The thermal pyrolysis of olive stone endocarp particles was performed using a
3.3. Pyrolysis Plant and Experimental Set-Up
tubular quartz reactor within a vertical oven (Carbolite, MTF 10/25/130, Pocklington, UK).
The The
olivethermal pyrolysis were
stone particles of olive stone endocarp
pre-dried particles
in an oven for 24was performed
h at using aoftubular
a temperature 378 K,
quartz
following Ref. [56]. Afterward, the quartz reactor was charged with 10.00 gUK).
reactor within a vertical oven (Carbolite, MTF 10/25/130, Pocklington, The
of dried
olive stone particles were pre-dried in an oven for 24 h at a temperature of 378 K,
biomass. The pyrolysis peak temperature (highest treatment temperature) for all the testsfollowing
Ref. [56]. Afterward, the quartz reactor was charged with 10.00 g of dried biomass. The
was 773 K, considered the optimal temperature for pyrolysis based on various reports
pyrolysis peak temperature (highest treatment temperature) for all the tests was 773 K,
(generally pyrolysis can be conducted in a range of 623–923 K) [50,53,57–60]. The reaction
considered the optimal temperature for pyrolysis based on various reports (generally
system was connected to a nitrogen line (N2, Alphagaz 1, Air Liquide, Milan, Italy)
pyrolysis can be conducted in a range of 623–923 K) [50,53,57–60]. The reaction system
providing an oxygen-free atmosphere. The reactor was connected to a Liebig condenser
was connected to a nitrogen line (N2 , Alphagaz 1, Air Liquide, Milan, Italy) providing an
to separate the condensable vapors as a liquid from the gaseous products. A flask was
oxygen-free atmosphere. The reactor was connected to a Liebig condenser to separate the
used to collect the L products. Collected L was made up of two phases: a water-soluble
condensable vapors as a liquid from the gaseous products. A flask was used to collect the L
portion at the top layer, named LL, and a viscous mostly oligomeric lignin-derived
products. Collected L was made up of two phases: a water-soluble portion at the top layer,
fraction settled at the bottom, labeled as HL. Non-condensable gases, named PG, were
named LL, and a viscous mostly oligomeric lignin-derived fraction settled at the bottom,
collected in a latex balloon (in batch condition) or vented (in semi-batch condition). The
labeled as HL. Non-condensable gases, named PG, were collected in a latex balloon (in
solid condition)
batch residue, BC,or was collected
vented inside the
(in semi-batch reactor. AThe
condition). schematic of the BC,
solid residue, reaction system is
was collected
shown in Figure 13.
inside the reactor. A schematic of the reaction system is shown in Figure 13.

Figure 13.Scheme
Figure13. Schemeof
ofthe
theexperimental
experimentalsetup
setupused
usedfor
forthe
thepyrolysis
pyrolysistests.
tests.

For
For aasystematic
systematiccomparison,
comparison,two twodifferent
different experimental conditions
experimental have
conditions beenbeen
have in-
vestigated, as described in the following sections. A repeatability test for pyrolysis
investigated, as described in the following sections. A repeatability test for pyrolysis was was
conducted
conducted toto evaluate the percentage
evaluate the percentageerror
errorininthe
theproduct
product yield.
yield. TheThe GC-MS
GC-MS analysis
analysis was
was performed
performed in duplicate,
in duplicate, andand
thethe values
values areareexpressed
expressedasasaverage,
average, while
while the
the error
error isis
expressed
expressedasasthe
thestandard
standarddeviation.
deviation.

3.3.1. Investigation of the Effect of Reaction Time and Nitrogen Purging Conditions
Thermal pyrolysis on olive stone particles (sized 1–5 mm) using a heating rate of 50
K min−1 for 1 or 3 h was performed. Tests have been performed in an O2-free environment
in the presence of a continuous N2 flow (100 mL min−1, semi-batch) or in batch N2 (static
Molecules 2023, 28, 6516 16 of 19

3.3.1. Investigation of the Effect of Reaction Time and Nitrogen Purging Conditions
Thermal pyrolysis on olive stone particles (sized 1–5 mm) using a heating rate of
50 K min−1 for 1 or 3 h was performed. Tests have been performed in an O2 -free environ-
ment in the presence of a continuous N2 flow (100 mL min−1 , semi-batch) or in batch N2
(static atmosphere). Therefore, the effect of reaction time and nitrogen purging conditions
on the distribution and composition of the products have been investigated.

3.3.2. Investigation of the Effect of Biomass Particle Size and Heating Rate
Thermal pyrolysis with a reaction time of 1 h in the presence of 100 mL min−1 of N2
flow with different biomass particle sizes in the ranges of 0.30–0.35, 1.0–1.6, 1.6–2.4, and
2.4–5.0 mm and different heating rates, i.e., 5, 10, 20, and 50 K min−1 were investigated.

3.4. Characterizations of Pyrolysis Products

All the reaction products (BC, L, PG) were analyzed by Fourier Transform Infrared
Spectroscopy (FTIR) using a Nicolet 380 FT-IR Spectrometer (Thermo Scientific, Madison,
WA, USA). All the spectra were elaborated using Omnic Lite Software version 5.12 (Thermo
Electron Corporation, Madison, WA, USA). To analyze the solid product (BC), samples and
KBr were mixed (1 wt.% BC) and pressed, while L samples were dispersed on a KBr-pressed
disk. PG samples were injected into an IR glass cell with KBr windows and analyzed by the
same spectrometer. HL and PG samples were also analyzed by a gas chromatograph-mass
spectrometer (GC-MS) Focus-ISQ supplied with a single quadrupole detector (Thermo
Scientific, Milan, Italy) using a TG-SQC column (30 m × 0.25 mm × 0.25 µm) using He
(>99.99) as carrier gas. To analyze L, the HL phase was diluted with CHCl3 with a ratio
of 1:10 (v/v) and then 1 µL of the diluted L was injected into the GC-MS by using a 10 µL
syringe. To analyze PG, 100 µL of the sample was injected into the GC-MS using the column
mentioned above. The areas of the resulting peaks related to the individual species were
normalized with the area of the total peaks to calculate the relative amount of the various
species in the sample. Moreover, the yield of the products and distribution of HL were
analyzed by Statistica software® version 12 by ANOVA method.
Additionally, BC samples were analyzed by UV-vis-NIR spectroscopy by means of
a V570 instrument (JASCO Corp., Tokyo, Japan) and Thermogravimetry (TGA and DTA)
in the same conditions as those reported in Section 3.2. For the evaluation of BC morphol-
ogy and composition, Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray
spectroscopy (EDX) have been used.

4. Conclusions
In this study, industrial end-of-life olive stone waste was chosen as the feedstock for
pyrolysis to examine the impact of key operational parameters on the pyrolysis products
and provide a comprehensive comparison. Results showed that changing the reaction
time from 1 to 3 h and using N2 feeding conditions, either batch or semi-batch, did not
significantly affect the product distribution and composition. The obtained L, accounting
for approximately 45 wt.%, comprised two phases with a heavy-to-light liquid ratio of
0.53. Phenolic compounds made up over 65% of the HL products. The PG, accounting
for approximately 28 wt.%, was primarily composed of H2 , CO2 , CO, CH4 , and C2 H4 .
BC, accounting for approximately 28 wt.%, was also produced. Increasing the heating
rate while keeping the olive stone particle size constant, affected both distribution and
composition of the obtained products. A decrease in BC yield of about 20% and an increase
in L yield of about 22% were observed with higher heating rates. Additionally, the HL
to LL ratio increased from 0.17 to 0.53, while the phenolic group in the heavy fraction
decreased. However, no significant changes in BC properties were detected. On the other
side, changing the olive stone particle size while keeping the heating rate constant had a
negligible impact.
In conclusion, olive stone has the potential as a precursor for developing carbon-
based materials. The gas produced from olive stone pyrolysis can be used for further
Molecules 2023, 28, 6516 17 of 19

processing to produce syngas and chemicals like methanol. However, the L produced
from the pyrolysis is dominated by oxygenated functional groups, leading to low energy
density and instability. Therefore, further upgrading is necessary to convert the L into
useful chemicals or combustion fuel. This study provides a deeper understanding of the
relationship between pyrolysis parameters and the resulting products.

Author Contributions: Conceptualization, G.G. and E.S.; methodology, E.S., P.R. and A.A.C.; valida-
tion, S.E.A. and A.A.C.; formal analysis, S.E.A. and E.S.; investigation, S.E.A. and E.S.; resources, P.R.
and G.G.; data curation, E.S.; writing—original draft preparation, S.E.A. and E.S.; writing—review
and editing, E.S., G.G. and P.R.; visualization, E.S.; supervision, G.G.; project administration, G.G.;
funding acquisition, G.G. and P.R. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by [INSTM] grant number [INSTM22GE1].
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data will be available on request.
Acknowledgments: G.G. acknowledges the University of Genova for funding in the frame of Fondo
Ricerca di Ateneo 2020 to conduct research. P.R. acknowledges INSTM for funding in the frame
of the project INSTM22GE1. All authors acknowledge Alberto Lagazzo for experimental data for
investigated materials by means of TG-DTA.
Conflicts of Interest: The authors declare no conflict of interest.
Sample Availability: Not applicable.

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