Food Research International 73 (2015) 44–51

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Food Research International

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Mediterranean agri-food processing wastes pyrolysis after pre-treatment

and recovery of precursor materials: A TGA-based kinetic modeling study
P. Manara a, D. Vamvuka b, S. Sfakiotakis b, C. Vanderghem c, A. Richel c, A. Zabaniotou a,⁎
a
Dept of Chemical Engineering, Aristotle University of Thessaloniki, Greece
b
Dept of Mineral Resources Eng., Technical University of Crete, Chania, Greece
c
Unit of Biological and Industrial Chemistry, University of Liege-Gembloux Agro-Bio Tech, Passage des Déportés, 2, B-5030 Gembloux, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: Valorization strategies of wastes from agri-food processes are intertwined with clean technological approaches
Received 29 September 2014 and eco-industrial management. By-products from Mediterranean agri-food processes such as olive oil, wine
Received in revised form 13 November 2014 and fruit create a considerable disposal problem for the agro-industry. Their characteristics in combination
Accepted 20 November 2014
with Mediterranean climate enhance microbial development and can be source of health and safety concerns.
Available online 28 November 2014
After pre-treatment and recovery of valuable precursor materials (lignin, pulp), pyrolysis can be used for fuels,
Keywords:
chemicals and carbon bio-based materials production. Since thermal degradation kinetic studies are a key step
Agri-food wastes for the efficient design of thermo-chemical processes, in this study pyrolysis experiments were performed,
Kinetic study using TGA for the estimation of the process kinetic parameters. The independent parallel reaction model validat-
TGA ed against experimental results, showing a good agreement with experimental data, with deviation values rang-
Pyrolysis ing from 1.07 to 3.54%.
Pre-treatment © 2014 Elsevier Ltd. All rights reserved.

1. Introduction high importance. Sustainability, optimization and eco-efficient manage-

Although today there is a wide recognition of the major environ-
mental implications of food production (Foster et al., 2006), studies on
agri-food processing wastes have not yet shown the impacts of
resources wastage from a global environmental perspective (FAO,
2013). According to FAO, each year approximately one-third of all
food produced for human consumption in the world is lost or wasted
(FAO, 2013). In addition to food wastage, food processing by-products
represent a huge amount of wasted resources (although this is largely
the inedible part of produce), that could be valorized for recovery of
compounds with potential application as ingredients in the food, feed,
cosmetics and pharmaceutical industries, and also for fuels and energy
via thermo-chemical, biological and microbial methods (Ieropoulos,
Melhuish, & Greenman, 2005; Ieropoulos, Winfield, & Greenman,
2010; Luque & Clark, 2013).
Despite intense recent research activities on food waste valorization
and in particular the development of environmentally sound and inno-
vative strategies to process such waste/by-products (Budarin et al., in
press; Clark et al., 2013; Lin et al., 2013; Pfaltzgraff, De bruyn, Cooper,
Budarin, & Clark, 2013), economically feasible processes have been
established only for very few by-products (Galanakis, 2012), while the
application and also commercialization of emerging technologies is of
⁎ Corresponding author. Tel.: +30 2310 996274.
E-mail address: azampani@gmail.com (A. Zabaniotou).
ment of waste streams are key issues.
Although, many processing food waste streams are addressed by
technologies for conventional in-plant environmental control (Wang,
Hung, Lo, & Yapijakis, 2005), such as waste-to-energy solutions, global
initiative of resources conservation in the context of circular economy
are not met. Thus, waste management practices with focus on new al-
ternative technological developments, eco-innovative design criteria,
regional and global environmental conservation principals are of high
importance.
Ongoing international research aims to contribute at the develop-
ment of sustainable technological schemes with resource efficiency
and commercialization deployment potential. Research is being con-
ducted on implementing bio-refinery concepts by including a pre-
treatment stage prior to pyrolysis process. The aim of the pretreatment
process is to overcome the recalcitrance of lingo-cellulosic biomass re-
moving and/or modifying the surrounding matrix of lignin and hemicel-
luloses (Alvira, Tomás-Pejó, Ballesteros, & Negro, 2010; Mosier et al.,
2005). As a result of pretreatment deployment, lingo-cellulosic biomass
is converted into a form which renders post processing more efficient
(Zheng, Pan, & Zhang, 2009).
Pyrolysis is a method that could contribute towards by-products val-
orization and resources conservation. Pyrolysis is a fundamental ther-
mochemical process that takes place in an inert atmosphere and high
temperature (400–800 °C). Under pyrolysis conditions, large biopoly-
mers (20,000 to 400,000 a.m.u.) crack into smaller molecules (less
than 200 a.m.u.) with relatively higher energy content (Anex et al.,

http://dx.doi.org/10.1016/j.foodres.2014.11.033
0963-9969/© 2014 Elsevier Ltd. All rights reserved.
 P. Manara et al. / Food Research International 73 (2015) 44–51 45

2010; Dauenhauer, Colby, Balonek, Suszynski, & Schmidt, 2009). Aside
from energy applications, pyrolysis can also be used to produce
advanced materials including carbon materials, with a wide range of
applications, illustrating the potential to convert waste materials into
valuable chemicals (Arancon, Lin, Chan, Kwan, & Luque, 2013).
Several groups of researchers have investigated the perspective of
combining pre-treatment with pyrolysis (Girisuta et al., 2012; Huang,
Wei, Yin, & Wu, 2012; Jae et al., 2010; Melligan et al., 2012). Kinetic
studies of pyrolysis are essential for feasibility assessments, efficient
process design and also scaling up to industrial applications (Conesa,
Font, Marcilla, & Caballero, 1997; Jakab, Faix, Till, & Székely, 1995;
White, Catallo, & Legendre, 2011).
The present study aims to deepen in the understanding of pyrolysis
mechanism and kinetics, elucidate reaction pathways, and quantify the
effect of the pre-treatment process on the thermal degradation behavior.
In this work, the proposed technological scheme involves pre-treatment
and post-pyrolysis of Mediterranean agro–industrial waste by-products
(olive, wine, fruit). Specifically, the agri-food processing residues, being
subjected to two different pre-treatment/fractionation processes (micro-
wave and organosolv), delivered lignin and pulp which are valuable pre-
cursor materials for further applications. Pyrolysis was further applied to
the fractionated materials for biofuels and carbon bio-based materials
production.
2. Materials and methods
2.1. Materials preparation and characterization
Samples of olive kernel, grape pomace/seeds and peach kernels
were selected from agro-industries established in Western Macedonia,
Greece. All food wastes were milled to a particle size b1 mm by a cutting
mill, according to the standard procedures, that were followed in the
study regarding pre-treatment protocols. Samples of raw materials
were naturally dried in the atmosphere (25 °C). Then, TGA experiments
were performed.
A chemical (organosolv) and a physicochemical (microwave) pre-
treatment process were applied to the three selected Mediterranean
agri-food processing by-products. The methods have been described
in a previously published work by the authors (Manara, Zabaniotou,
Vanderghem, & Richel, 2014). The organosolv process consisted in
wastes treatment with formic acid/acetic acid/water (30/50/20 v/v%),
for 3 h at 107 °C, while the physicochemical method was conducted
by immersing the waste in a water/ethanol (8/92 v/v%), H2SO4 0.32 M,
solvent and further exposing the slurry to microwave irradiation (max-
imum 250 watts) for 1/2 h at 150 °C.
Raw materials, as well as the post pre-treatment products (pulp and
lignin) were characterized for their composition (lignin, carbohydrate
content). In particular, acid insoluble lignin (Klason lignin) and acid
soluble lignin were determined according to the procedure described
in Sluiter et al. (Sluiter et al., 2008). Additionally, monosaccharides
were determined as alditol acetates using gas chromatography, accord-
ing to the procedure described by Blakeney et al. (Blakeney, Harris,
Henry, & Stone, 1983). The analyses were carried out with a Hewlett
Packard (HP6890) gas chromatograph, equipped with a flame ioniza-
tion detector. The components were identified using a high perfor-
mance capillary column, HP1-methylsiloxane (30 m × 0.32 mm i.d,
0.25 μm film thickness, Scientific Glass Engineering, S.G.E. Pty. Ltd.,
Melbourne, Australia). Data were analyzed using ChemHP software.
Glucose, xylose, arabinose, mannose and galactose, 2-Deoxyglucose
(internal standard), were obtained from Sigma-Aldrich (St. Louis, MO,
USA), while solutions of known concentrations were used as standards.
Analyses were performed in duplicate. The anhydro corrections were
used to obtain the concentration of the polymeric sugars from the con-
centration of the corresponding monomeric sugars (conversion factor
for monosaccharide to polysaccharide (0.88 for pentoses and 0.90 for
hexoses)).
Furthermore, in order to estimate the crude protein content in
the solid lingo-cellulosic materials, the nitrogen content of the mate-
rial was measured by Kjeldahl methods (1015 TECAROR) and multi-
plied by a commonly used conversion factor, equal to 6.25, which is
used for animal feeds and other materials (Tkachuk, 1997). The
method was also applied to determine the protein content in the iso-
lated lignin.
2.2. Thermogravimetric analysis (TGA)
Thermogravimetric analyses were performed using a TGA analyzer
unit (Perkin Elmer), under a flowing nitrogen atmosphere at atmo-
spheric pressure. Approximately 10 mg of sample was heated in a por-
celain crucible up to 850 °C, at a rate of 10 °C /min. The sample weight
loss and rate of weight loss were recorded continuously as functions
of time or temperature.
Preliminary tests with different sample masses and sizes and gas
flow rates were carried out, in order to check the influence of heat and
mass transfer. Small masses (10-15 mg) of each material, thinly distrib-
uted in the crucible and particle sizes of −250 μm were found proper to
be used in the experiments, in order to eliminate the effects of eventual
side reactions and mass and heat transfer limitations. Analyses were
performed in duplicate.
The following samples were subjected to TGA analyses:
a) Olive kernel (OK).
b) Grape pomace/seeds (GK).
c) Peach kernel (PK).
d) Lignins derived by using the organosolv pre-treatment, named
OK-FAL, GK-FAL, PK-FAL.
e) Lignins derived by microwave pre-treatment, named OK-MTL,
GK-MTL, PK-MT.
f) Solid fraction derived by using organosolv pre-treatment, named
OK-FASP, GK-FASP, PK-FASP.
e) Solid fraction derived by using microwave pre-treatment, named
OK-MTSP, GK-MTSP, PK-MTSP.
2.3. Kinetic modeling
In this work, the independent parallel first-order reactions model
was used.
2.3.1. Independent Parallel Reactions (IPR) model
According to the independent parallel first-order reactions model,
the decomposition of biomass is described by three or more indepen-
dent parallel first order reactions, each corresponding to the decompo-
sition of the biomass constituent components. The overall rate of
conversion for N reactions and the thermal decomposition of the indi-
vidual components can be expressed as:
dðm=moÞ da
¼ −Σci  i i ¼ 1; 2; 3; …:N ð1Þ
dt dt


dai −Ei
¼ Ai  exp  ð1−ai Þ ð2Þ
dt RT
where: dm/dt is the total mass loss rate, m is the observed mass at time
t, mo is the initial dry mass, mchar is the final mass at the end of the
pyrolysis, Ai is the pre-exponential factor, i is the component index, Ei
is the activation energy, ai is the conversion (0 b ai b 1), T is the temper-
ature, R is the universal gas constant and ci is the fraction of volatiles
i i
produced by the i-th component: ci ¼ mo −m
m
char
.
o
46 P. Manara et al. / Food Research International 73 (2015) 44–51

An algorithm in Matlab® code, developed at the Technical University 3.2. Thermal decomposition characteristics
of Crete, was used to obtain the optimal parameters (Ei,Ai,,ci) that mini-
mize, under constraints, the objective function: Table 2 shows thermal degradation onset temperature, major degra-
dation temperatures, weight loss at 200–600 °C and percentage of
" charred residue at 800 °C. The TG and DTG curves obtained from the
j¼Z

X 
calc #2
dm exp dm pyrolysis of the three raw materials, as well as their pre-treatment
O:F: ¼ j− j ð3Þ
j¼1
dt dt products (lignin and pulp), at a heating rate of 10 °C/min, for both
pre-treatment techniques, are depicted in Figs. 1, 2, 3.
Depolymerization of material (such as olive kernel, grape pomace/
where (dm/dt)exp is the experimentally observed DTG (differential seeds, peach kernels, as well as the derived materials (lignins and
thermogravimetric) curve (¼ dðm=mo
dt
Þ
) and (dm/dt)calc is the calculated pulp), is a complex mechanism and proceeds by several competing
and concurrent reactions. During these reactions, cleavage of various
DTG curve (¼ −Σci  da dt
i
), obtained by the analytical solution of the
bonds takes place in a wide range of temperatures, based upon the
kinetic differential Eqs. (2) with the given set of parameters.
bond energy. The obtained DTG curves showed that the different sam-
The deviation between the observed and the calculated curves at the
ples of agri-food processing wastes, as well as their pre-treatment prod-
optimal set of parameters was calculated as follows:
ucts (lignins and pulp) underwent decomposition at several different
temperatures. The DTG peaks among the samples differed in position
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi and height, implying a direct impact on thermal decomposition charac-
O:F:  ðZ−NÞ
Devð%Þ ¼ 100  ð4Þ teristics by the specific distribution of organic and inorganic constituent.
maxð−dm=dtÞexp

3.2.1. DTG analysis

where Z is the number of data points and N is the number of parameters
employed in the model.
3. Results and discussion
3.1. Characterization of agri-food wastes
The compositional characteristics of the agri-food processing waste
materials before and after the pre-treatment protocols, are presented
in Table 1 (measured according to the protocols described in the previ-
ous Section 2.1). Concerning lignin content, olive kernels contained
~ 29 wt% (dry basis), while grape pomace/seeds and peach kernels
contained ~41 wt.% and ~ 40.5 wt.% (dry basis), respectively. Regarding
the content in polysaccharides, olive kernels contained ~ 60.5 wt.%
(dry basis), while grape pomace/seeds and peach kernels contained
~ 25.2 wt.% and ~ 44.2 wt.% (dry basis), respectively. The pulp-solid
residual part (SP) after pre-treatment process had almost in all cases,
higher lignin content compared to the original waste. The obtained
lignins that derived from both pre-treatment processes applied on the
three agro-wastes, were of high purity (N 82 wt. %).
Furthermore, analyses of the protein content showed that olive
kernel consisted of almost 4.5 wt.% (dry basis), while grape pomace/
seeds and peach kernels contained N23 and ~1.5 wt.% protein on dry
basis, respectively. The lignins, which have derived from grape pomace/
seeds, were contaminated with proteins.
The different thermal degradation behaviour that the various sam-
ples presented (Figs. 1–3) is attributed to the differences in the inherent
structural and chemical characteristics of the samples that are related to
the specific cellulose, hemicellulose and lignin content (Mc Kendry,
2002). Among the three bio-polymers (hemicellulose, cellulose and
lignin), hemicellulose was the most reactive compound degrading
between the range of 200 and 350 °C (Wu, Zhao, Li, & He, 2009). In gen-
eral, the first regime represented the decomposition of hemicellulose
present in each material while the second corresponded to the decom-
position of cellulose. For the flat tailing section lignin was responsible,
which is known to decompose slowly over a broader temperature
range.
The depolymerization of polysaccharides involved the following
processes; dehydration, decarboxylation, decarbonylation and cleavage
of glucoside bonds, C-H, C-O and C-C bonds (Hoareau, Trindade,
Siegmund, Castellan, & Frollini, 2004). Hemicellulose consisted of vari-
ous saccharides (xylose, mannose, glucose, galactose, etc.), and present-
ed an amorphous structure, rich in branches, which easily volatilized
evolving out CO, CO2, and some hydrocarbon, etc., at low temperatures
(Yang, Yan, Chen, Lee, & Zheng, 2007). Anhydridization (dehydration
and caramelization) and polymerization of xylose took place during
the initial stage of heating. Above the temperature of 200 °C, xylose
underwent depolymerization and evolution of breakdown products
(Lappalainen, Pitkanen, Heikkila, & Nurmi, 2006; Sahoo, Seydibeyoglu,
Mohanty, & Misra, 2011).

Table 1
Chemical composition of raw materials and the products (pulp, lignins) after the pre-treatment protocols (wt% dry basis).

Olive derived pulp derived Grape Derived derived Peach Derived derived-Lignins
kernel Lignins pomace/seeds pulp Lignins kernel pulp

Components (wt% dry basis) FA⁎ MW⁎⁎ FA⁎ MW⁎⁎ FA⁎ MW⁎⁎ FA⁎ MW⁎⁎ FA⁎ MW⁎⁎ FA⁎ MW⁎⁎

Lignin 29.1 35.2 28.8 97.8 100 41.3 63.7 78.1 n.d⁎⁎⁎ 82.5 40.5 50.8 57.4 100 100
Klason lignin 26.0 39.3 37.9
Acid soluble lignin 3.1 2.9 2.6
Polysaccharides 60.5 51.1 68 2.2 - 25.2 9.6 6.3 n.d⁎⁎⁎ 4.1 44.3 38.9 45.6 - -
Glucan 37.7 44.7 67.7 9.0 6.2 5.8 21.2 29.9 45.2
Xylan 19.4 5.6 0.2 12.5 2.8 0.1 20.2 8 0.2
Mannan 0.3 0.3 0.1 0.5 0.3 0.1 0.0 0.2 0.1
Galactan 1.8 0.3 0.1 1.9 0.3 0,2 2.3 0.6 0.1
Arabinan 0.9 0.1 0.0 1.2 0 0.1 0.4 0.1 0.1
Rhamnan 0.4 0.1 0.0 0.1 0 0.1 0.2 0.1 0
Protein 4.4 - - 23.5 n.d⁎⁎⁎ 13.53 1.6 - -
Ash 2.7 9.5 2.9
⁎ FA: Formic/acetic acid pre-treatment.
⁎⁎ MW: Microwave pre-treatment.
⁎⁎⁎ n.d, not defined.
 P. Manara et al. / Food Research International 73 (2015) 44–51 47

Table 2
Thermogravimetric analysis of the agri-food processing waste.

Sample⁎ Onset temperature (°C) Major degradation temperatures (°C) % Degradation at 120–600 °C Charred residue at 800 °C, (wt%)

1st 2nd 3rd

1 OK 171 281 324 360–600 68.8 23.7

2 GK 180 320 380–500 500–600 51.2 37
3 PK 232 293 351 400–600 66.3 25
4 OK-FAL 106 170 400 450–800 ⁎⁎ 61.2 27.5
5 GK-FAL 105 180 400 500–800⁎⁎ 56.8 12
6 PK-FAL 102 180 380 500–600 50.3 34,5
7 OK-FASP 180 295 370 290–500 75.7 16.6
8 GK-FASP 195 297 350 392–548 55.3 35.8
9 PK-FASP 245 305 358 380–575 74.1 20.5
10 OK-MTL 133.5 256 365 480–800⁎⁎ 55.3 38.5
11 GK- MTL 106 250 372 437 68.9 24.5
12 PK-MTL 111 200 370 480–600 49.2 43.5
17 OK-MTSP 105 187.5 364 460–600 58.6 34.5
14 GK-MTSP 157 348 500–700 40.4 47
15 PK-MTSP 117 200 370 480–600 57.3 33.2
⁎ a) olive kernel (OK), b) grape pomace/seeds (GK), c) peach kernel (PK), d) the corresponding lignins derived by organosolv pre-treatment, named OK-FAL, GK-FAL, PK-FAL, e) the
corresponding lignins derived by microwave pre-treatment, named OK-MTL, GK-MTL, PK-MT, f) the corresponding solid part derived by organosolv pre-treatment, named
OK-FASP, GK-FASP, PK-FASP, e) the corresponding solid part derived by microwave pre-treatment, named OK-MTSP, GK-MTSP, PK-MTSP.
⁎⁎ Broad peak.

It has been reported that DTG peaks for hemicelluloses and celluloses
appear approximately at 268 °C and 355 °C, respectively (Yang et al.,
2007). Cellulose is comprised of a long polymer of glucose, branch-free,

Fig. 1. DTG pyrolysis profiles of OK and their pretreatment products 10 °C/min; (A) using Fig. 2. DTG pyrolysis profiles of GK and their pretreatment products 10 °C/min; (A) using
formic/acetic acid treatment, (B) using microwave irradiation. formic/acetic acid treatment, (B) using microwave irradiation.
48 P. Manara et al. / Food Research International 73 (2015) 44–51
Fig. 3. DTG pyrolysis profiles of PK and their pretreatment products 10 °C/min; (A) using
formic/acetic acid treatment, (B) using microwave irradiation.
having a defined and strong structure and thus a high thermal stability.
In our study, the thermal decomposition of raw materials started at
about 200 °C, followed by a major loss of weight in the temperature
range of 200 and 500 °C, during which the major release of the vola-
tiles took place, leading to the formation of char (Vamvuka, Kakaras,
Kastanaki, & Grammelis, 2003).
The first step of the conversion process represented the decom-
position of hemicellulose present in each material and the second
corresponded to the decomposition of cellulose. The DTG curve ended
with the decomposition of lignins.
Lignin is full of aromatic rings and branched. The chemical bond
energy in lignin covers an extremely wide range, which leads to the
degradation of lignin in a wide temperature range (100–900 °C,). Lignin
depolymerization is a complex mechanism consisting of several compet-
ing reactions that result in bond cleavage. Lignin is more thermally stable
than hemicelluloses and cellulose and decomposes at 100–900 °C
(Manara et al., 2014). However, the major degradation occurs in the
range of 200–700 °C (Jakab, Faix, & Tiii, 1997; Sahoo et al., 2011).
The DTG curves showed that the lignins undeent decomposition at
several different temperatures. The differences in DTG peaks among
the lignin could be also attributed to the various lignin structures,
among different samples. The high purity lignins showed different
structures. Specifically, the specific DTG profile of OK-FAL indicated
that the lignins contained at least three different structures that
decomposed at significantly different temperatures. OK-MTL showed
three temperature regimes for pyrolysis. GK- FAL appeared to have
two major DTG peaks. GK- MTL DTG curve was shifted to the right, com-
pared to GK-FAL DTG curve. PK-FAL showed three DTG peaks. PK-FAL
lignins were of high purity, suggesting that in that temperature regime
lignins of different structure degrade. PK-MTL DTG curve had similar
decomposition profile as that of PK-FAL -lignin.
One of the lignin degradation mechanisms is dehydration leading to
the formation of lateral unsaturated chains, carbon monoxide, carbon
dioxide and methane (Jakab et al., 1997). Specifically, lignin degradation
at low temperature (b 400 °C) mostly concerns bond cleavage of low
activation energy, whereas at higher temperature than 400 °C, lignin
degradation was due to stable bonds’ cleavage. Below 400 °C, lignin deg-
radation occured mainly due to the fission of methyl-aryl ether bond
that releases water and formaldehyde (Hoareau et al., 2004; Jakab
et al., 1997; Sahoo et al., 2011).
Water is the most abundant product, due to high hydroxyl and
methoxyl groups in lignin, followed by methane that originates from
the methoxyl groups. Various -OH groups in lignins have different
thermal stabilities. As water is a major degradation product that
originates from various types of hydroxyl groups, DTG curve of lignins
appeared to be different (Jakab et al., 1997; Sahoo et al., 2011).
Above the temperature of 400 °C, decomposition of lignin aromatic
ring occured and whith further increase of the temperature, saturation
of the aromatic rings, C-C bond cleavage of lignin as well as release of
H2O, CO2 and CO (Lappalainen et al., 2006; Sahoo et al., 2011) around
400–600 °C occured, while cracking of the methoxy (−O-CH3) groups
released methane (Sahoo et al., 2011). Lignin released CO2 at 340 °C
and 700 °C, and also CO at above 600 °C, due to the cracking of C-O-C
and C = O bonds.
Concerning proteins that either the raw agri-food processing wastes
(olive kernel, grape pomace/seeds, peach kernel) or some of the pre-
cipitated delivered fractions (lignins during grape pomace/seeds
pre-treatment) contained, the major DTG peaks appeared between
200–570 °C (Kebelmann, Hornung, Karsten, & Griffiths, 2013).
3.2.2. Charred residue
The total mass loss obtained for each sample at 800 °C, (wt%), is pre-
sented in Table 2. In all the cases, the depolymerization of materials that
derived from microwave treatment resulted in a higher percentage of
residual carbon in comparison with the yields that corresponded to
the derived materials from the organosolv pre-treatment. This indicates
that the physicochemical characteristics of materials that resulted from
microwave pre-treatment (lower O/C ratio), favoured rather carboniza-
tion than gasification reactions.
Lignins derived from olive kernel and peach kernel resulted in
higher percentage of charred residue, compared to the originalones,
regardless the pre-treatment process, (Table 2). Specifically, residual
carbon yields of lignins derived from the organosolv procedure with
precoursors materials the olive kernel, grape pomace/seeds and peach
kernels, reached the values of 27.5 wt.%, 12 wt.% and 34.5 wt.%, respec-
tively. The values of residual carbon yields after the depolymerization
by microwave treatment derived lignins were equal to 38.5 wt.%,
24.5 wt.% and 43.5 wt.% (for lignins originating from olive kernel,
grape pomace/seeds and peach kernels, respectively). It was considered
that the resulted char yield was inversely proportional to the amount of
the functional groups of methoxyl, hydroxyl and carboxyl (Jakab et al.,
1997).
3.3. Kinetic modeling
Internal and external heat and mass transport phenomena might in-
fluenced wastes pyrolysis kinetics and yields. Numerous researchers
have developed kinetic models accounting for heat and mass transfer
 P. Manara et al. / Food Research International 73 (2015) 44–51 49

GK experimental GK calculated
limitations (White et al., 2011). However, in general, these complicated
GK-FAP experimental GK-FAP calculated
models were applied to a single biomass particle, taking in account
GK-MTL experimental GK-MTL calculated
several assumptions, unlikely to be used into industrial applications 0.45
(Sadhukhan, Gupta, & Saha, 2008). In addition, particle size effect and
the negligence of the non-uniformity of the bulk (Galwey & Brown, 0.4
1998; White et al., 2011), introduce errors to the developed models
and are considered unreliable, unless they are validated with real exper- 0.35
imental data (Garn, 1990).

Weight loss rate (%/ o C)

Non-isothermal thermogravimetric analysis (TGA) is a well- 0.3
established technique that provides pyrolysis kinetic data that provide
insight in the thermal degradation profile and classify the material’s 0.25
main components, while obtaining sets of kinetic parameters useful
to optimize reactors design for lingo-cellulosic biomass pyrolysis and 0.2
gasification processes (Conesa et al., 1997; Damartzis, Vamvuka,
Sfakiotakis, & Zabaniotou, 2011; Font, Marcilla, Garcia, Caballero, & 0.15
Conessa, 1995).
Compared to flash pyrolysis (heating rates N1000 °C/s), TGA applies 0.1
low heating rates, in the range of 1–200 °C/min and it has been exten-
sively used at temperature up to 900 °C (Saddawi, Jones, Williams, & 0.05
Wojtowicz, 2010), while permits the monitoring of evolution profiles
of products as a function of temperature (Jakab et al., 1995). Therefore, 0
100 200 300 400 500 600 700 800
thermogravimetry, widely used to study the thermal decomposition of
Temperature ( oC)

OK experimental OK calculated
Fig. 5. Comparison between experimental and calculated DTG curves using the IPR model,
OK-FAL experimental OK-FAL calculated
OK-FASP experimental OK-FASP calculated at a heating rate of 10 °C/min (the case of grape pomace/seeds).
1.4

1.2 polymers and other materials, is one of the techniques used to study
the primary reactions of the thermal decomposition of solids. The inter-
Weight loss rate (%/ oC)

1 pretation of the experimental data provides information on the compo-

sition of the material, order of reaction, number of different processes
0.8 that take place in the reaction, and the corresponding kinetic constants
(Conesa, Marcilla, Moral, Moreno-Caselles, & Perez-Espinosa, 1998).
0.6
From a thermal point of view, it is important to classify biomass
components according to temperature response. Towards that direc-
0.4
tion, many models assume a low number of components that degrade
0.2 following parallel reactions (Orfao, Antunes, & Figueiredo, 1999). Since
pyrolysis behaviour is the combination of the thermochemical response
0
100 200 300 400 500 600 700 800
Temperature (oC) PK experimental PK calculated
PK-FAL experimental PK-FAL calculated
(A) PK-FAP experimental
PK-MTL experimental
PK-FAP calculated
PK-MTL calculated
1.2
OK experimental OK calculated
OK-MTL experimental OK-MTL calculated
OK-MTSP experimental OK-MTSP calculated
0.8 1

0.7
Weight loss rate (%/ C)
o

0.8
Weight loss rate (%/ C)

0.6
o

0.5
0.6
0.4

0.3
0.4
0.2

0.1 0.2

0
100 200 300 400 500 600 700 800
o 0
Temperature ( C)
100 200 300 400 500 600 700 800
(B) Temperature ( oC)

Fig. 4. Comparison between experimental and calculated DTG curves using the IPR model, Fig. 6. Comparison between experimental and calculated DTG curves using the IPR model,
at a heating rate of 10 °C/min (the case of olive kernel). at a heating rate of 10 °C/min (the case of peach kernel).
50 P. Manara et al. / Food Research International 73 (2015) 44–51

Table 3
Calculated kinetic parameters (activation energies (E) and pre-exponential factors (A)) for TGA pyrolysis of agri-waste material and the pre-treatment products (pulp and lignins) using
the IPR model.

Sample⁎ A1 E1 C1 A2 E2 C2 A3 E3 C3 A4 E4 C4 Dev
(min−1) (kJ/mol) (min−1) (kJ/mol) (min−1) (kJ/mol) (min−1) (kJ/mol) (%)

Raw agri-foodagri-food processing wastes

1 OK 5.97E + 10 116.5 0.23 1.53E + 12 143.4 0.43 23.4 29.4 0.21 - - - 1.07
2 GK 5.2E + 07 92.2 0.16 5.33 22.6 0.41 - - - - - - 3.36
3 PK 3.13E + 10 117.2 0.25 2.64E + 14 174.9 0.30 66.0 36.8 0.19 - - - 2.67

Chemical pre-treatment (organosolv) derived fractions

Lignins
4 OK-FAL 7.57E + 03 36.7 0.05 1.38E + 08 108.8 0.27 2.75 20.0 0.38 - - - 2.40
6 PK-FAL 2E + 02 25.2 0.1 5.19E + 06 91.3 0.19 0.69 16.2 0.35 - - - 3.13
Pulp
7 OK- FASP 4.9E + 07 92.1 0.23 3.2E + 21 264.6 0.43 2.04 20.5 0.21 - - - 1.07
8 GK-FASP 9.8E + 08 101.7 0.11 1.59E + 13 161.7 0.17 1.5E + 09 126.3 0.06 0.6 15.9 0.32 2.02
9 PK-FASP 2.2E + 11 129.0 0.23 1.1E + 21 254.9 0.35 11.4 28.1 0.24 - - - 1.53

Physicochemical pre-treatment (microwave) derived fractions

Lignins
10 OK-MTL 2.8E + 06 67.5 0.05 2.05E + 06 84.5 0.24 1.27 17.6 0.32 - - - 3.04
11 GK-MTL 1.35E + 09 91.9 0.14 1.25E + 02 37.4 0.42 0.118 6.4 0.21 - - - 2.07
12 PK-MTL 1.99E + 05 49.8 0.03 1.59E + 11 143.5 0.13 1.03E + 09 126.4 0.06 1.154 18.2 0.34 1.72
Pulp
14 GK-MTSP 53.8 31.1 0.25 2.07 23.4 0.22 2.59Ε + 10 102.4 0.01 9.7Ε + 14 305.5 0.04 3.15
15 PK-MTSP 3.18 38.9 0.20 0.434 42.7 0.27 1.28E-03 20.7 0.20 - - - 3.54
17 OK-MTSP 1.02Ε + 11 120.2 0.25 7.07Ε + 02 41.9 0.36 2.26 21.7 0.15 - - - 1.17
⁎ a) olive kernel (OK), b) grape pomace/seeds (GK), c) peach kernel (PK), d) the corresponding lignins derived by organosolv pre-treatment, named OK-FAL, GK-FAL, PK-FAL, e) the
corresponding lignins derived by microwave pre-treatment, named OK-MTL, GK-MTL, PK-MT, f) the corresponding solid part derived by organosolv pre-treatment, named
OK-FASP, GK-FASP, PK-FASP, e) the corresponding solid part derived by microwave pre-treatment, named OK-MTSP, GK-MTSP, PK-MTSP.

of the individual biomass components, the differential thermogravi-
metric (DTG) curve can be represented by a sum of the individual com-
ponents’ behaviour. The number of partial reactions can be varied
depending upon the typical number of components proposed. Mass
loss rate curves frequently contain partially overlapping peaks and
mathematical models are typically used for their deconvolution.
Various models have been developed to describe the pyrolysis
process using a number of successive and parallel reactions. Specifically,
models that deal only with the chemical transformation from one phase
to another (Babu & Chaurasia, 2004; Di Blasi, 2008; Janse, Westerhout, &
Prins, 2000) and models that consider biomass as a mixture of its main
constituents, employing reactions for the chemical conversion of these
(Li et al., 2009; Vamvuka, Topouzi, & Sfakiotakis, 2010) are developed.
Iso-conversional models (Flynn, 1983; Kissinger, 1957; Simon, 2004),
according to which only a single step process is considered (Liu &
Yuan, 2008; Wilson, Yang, Blasiak, John, & Mhilu, 2011), are also
developed.
In this study, kinetic parameters were based on the Independent
Parallel Reaction Model. Transport phenomena limitations were ex-
cluded. Specifically, based on the TGA experiments (and the resulting
DTG figures), pyrolysis of agro-waste materials (raw materials, pulp,
lignins) was modelled by a kinetic scheme consisted of three or four in-
dependent first-order parallel reactions. The first pseudo-component
corresponded to hemicellulose, which was reactive at low temperatures
(200–350 °C), the second pseudo-component corresponded to the cel-
lulose fraction, which decomposed over a narrower temperature range
(250–380 °C) and the third, as well as in some cases fourth pseudo-
component corresponded to lignin, the thermal degradation of which
took place over a wide temperature range (200–800 °C).
In the corresponding figures (Figs. 4, 5, 6), the model’s results were
compared with the experimental data. Good fitting was obtained for
all samples, with deviation values, calculated by Eq. (4), varying from
1.07 to 3.54%. Table 3 shows the kinetic data regarding the IPR model.
As it can be observed, cellulose decomposition had the highest
activation energy (143–175 kJ/mol), representing the largest contribu-
tion to the devolatilization process, while lignin decomposition had
the lowest one (29–37 kJ/mol). The lower activation energy of grape
residue corresponding to the first temperature regime may most prob-
ably be explained by the overlaping of hemicellulose and cellulose
decomposition.
Concerning reactivities of the pre-treatment products (lignin and
pulp), both the pre-exponential factor and the activation energy values
of the lignin produced from the chemical pre-treatment process
(organosolv), were lower than those of the raw materials, whereas
kinetic parameters of the pulp produced from the chemical pre-
treatment process were significantly higher (Table 3).
On the other hand, the physicochemical pre-treatment (microwave)
process resulted in decreased thermal degradation of the samples, as
compared to the chemical pre-treatment process, so that the kinetic
parameters were generally decreased. An exception to this behaviour
showed the peach kernel.
4. Conclusions
A non-isothermal thermogravimetric analysis (TGA) was performed
to obtain pyrolysis kinetic data from 3 agri-food processing wastes
(olive kernel, peach kernel and grape pomace). The independent parallel
reaction (IPR) model was used in this study.
Prior to pyrolysis, samples were submitted into 2 different pre-
treatment (microwave and organosolv). The materials that were
delivered from microwave pre-treatment were prone to carbonization
rather than gasification reactions and have resulted in a higher percent-
age of residual carbon, comparing with the derived materials from the
organosolv pre-treatment. Furthermore, lignins derived from olive and
peach kernel, regardless the pre-treatment process, resulted in higher
percentage of charred residue, comparing with the non-pre-treated bio-
mass and the corresponding pulp.
Among the two pre-treatment used methods, the physicochemical
pre-treatment (microwave) process resulted in decreased thermal deg-
radation of the samples, as compared to the chemical pre-treatment
process, so that the kinetic parameters were generally decreased.
 P. Manara et al. / Food Research International 73 (2015) 44–51 51

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