Journal of Thermal Analysis and Calorimetry (2021) 146:881–891

https://doi.org/10.1007/s10973-020-10061-x

Experimental investigation of the delignification process influence

on thermochemical and kinetic properties of biomass
Amanda Alves Domingos Maia1 · Yemall Alexander Maigual Enriquez2 · Leandro Cardoso de Morais3

Received: 16 April 2019 / Accepted: 10 July 2020 / Published online: 22 July 2020
© Akadémiai Kiadó, Budapest, Hungary 2020

Abstract
The study of biomass is extremely important, aiming to discover the potential of alternative source that are capable of promot-
ing the development of new technologies. The thermal behavior and chemical characteristics of the Capsicum waste from the
use for the manufacture of sauces and condiments were investigated using thermogravimetric analysis, higher heating values,
ignition (Ti) and burnout temperatures (Tb) and kinetic study using isoconversional models. Torrefaction and pyrolysis condi-
tions were applied. Characterization based on ultimate and proximate analysis, gravimetric and gravimetric yield factor were
also realized. Thermal analysis showed a biomass conversion between 150 °C and 500 °C. Proximate analysis identified an
average volatile content of 46.5%, and carbon and fixed carbon were 22.3 and 31.1%, respectively. Gravimetric yield varied
between 28 and 58%. Considering the intersection model, ignition and burnout temperature varied between 342–354 °C and
470–503 °C, respectively. The deviation model found an ignition temperature between 210 and 249 °C. Biomass proved to
be a possible source of biofuel with a significant economic potential.

Keywords Thermochemical conversion · Isoconversional methods · Kinetic study · Pyrolysis · Combustion · Torrefaction

Introduction Furthermore, fuel supply has been an extensively dis-

Red pepper of Capsicum gender represents an indispensa-
ble fresh vegetable in Brazil, an important condiment and
spices. Capsicum powder is one of the most important spices
consumed worldwide [1]. In Brazil, Capsicum are integrated
to agribusiness and have an important socioeconomic value,
being a source of jobs, encompassing an annual production
of 30 million tons representing the third higher worldwide
vegetable production and consumption [1–3].
* Amanda Alves Domingos Maia
aadmaia@yahoo.com.br
1
Department of Production Engineering, Federal University
of São Carlos–UFSCar, Campus Sorocaba, Rod. João Leme
dos Santos, km 110 SP–264, Bairro do Itinga, Sorocaba,
São Paulo CEP 18052–780, Brazil
2
Department of Hydrobiological Resources, University
of Nariño, UDENAR, Ciudad Universitaria Torobajo,
San Juan De Pasto, Colombia
3
Institute of Science and Technology, University of São Paulo
State–UNESP, Campus Sorocaba. Av. Três de Março, 511,
Alto da Boa Vista, Sorocaba, São Paulo 18087‑180, Brazil
cussed question and concerns about their future are increas-
ing. There is a growing interest in agricultural wastes used as
biomass especially for those countries having such resources
[4, 5]. Biomass is a source of organic carbon, which can
replace fossil resources by using pyrolysis [6, 7]. Thus, effi-
cient biomass thermal modification technologies worldwide
have been target of so many researches.
The efficiency of the biofuel depends on the chemical
composition of biomass and the operating process charac-
teristics [8]. It is necessary to know the physicochemical
properties of this residue in order to know the thermochemi-
cal conversion process into biomass derived fuels [1, 9] to
understand the structural changes and to determine the reac-
tions during the process [10–12].
The delignification process from biomass waste
has emerged as an attractive along with biofuel production
[13, 14]. This is probably caused by their recalcitrant nature
that prevents the release of monomeric sugars in conversions
into components in a biorefinery [13–15]. Therefore, a fast,
green, low-cost and efficient delignification method can pro-
mote better results to biomass reuse [13, 14, 16].
For these reasons, the aim of the present study was to
investigate the thermochemical conversion of Capsicum,

13
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882
considering thermal delignification in oxidizing and inert
atmosphere and different heating rates which may cause dif-
ferent characteristics at biomass combustion and pyrolysis
processes. Heating rates varying may also cause different
ignition/burnout temperatures and volatile yield of biomass,
so it is thus essential to choose suitable conditions [17].
The minimum temperature that allows an ignites spon-
taneously of biomass without external source of ignition is
defined as ignition temperature [18–20]. The ignition tem-
perature of biochar is related to its safety in storage and
delivery [21]. The burnout temperature of a biofuel is an
indicator of its reaction degree. The higher the burnout
temperature, the fewer the combustible components in the
biofuel [22].
Different heating rates were used for the kinetic study
to obtain the apparent activation energy and pre-exponen-
tial factor considering Kissinger–Akahira–Sunose (KAS)
and Ozawa–Flynn–Wall (OFW) isoconversional methods.
These methods allow this study without knowing the kinetic
model of the reaction mechanism. An extensive and accu-
rate knowledge of their characteristics is highly important.
However, studies related are scarce. So, it is important to
investigate these processes, which can provide the data for
the better biofuel production.
Materials and methods
Sample preparation
The biomass of this study was Capsicum spp. Samples were
washed and dried by oven drying Solab model SL-100/42
at 105 °C to constant mass [23]. Dried biomass was ground
in a Wiley mill, MA048-Marconi, and sieving in a Solotest
sieve, NBR# 200 (74 µm).
Ultimate and proximate analyses
Ultimate analysis was used to determine the C, H and N con-
tent of the biomass and biochar. This analysis was performed
on a PerkinElmer Mark Model 2400 Series II.
Proximate analysis was based on standard ASTM D
1762–84 [24] and presents mass percent of the moisture,
volatile matter (VM) content and ash content, whereas the
fixed carbon (FC) content was determined by difference. It
is the easiest and most widely used method to characterize
a biomass fuel.
Calorific value
A HHV was calculated using two equations based on the
carbon, hydrogen and nitrogen content [25]. An ordinary
13
A. A. D. Maia et al.
least squares regression and a partial least squares regres-
sion method are given in Eqs. 1 and 2, respectively:
HHV = 1.87C2 − 144C − 2802H + 63.8CH + 129N + 20147
(1)
HHV = 5.22C2 − 319C − 1647H + 38.6CH + 133N + 21028
(2)
where (C) is carbon, (H) is hydrogen and (N) is nitrogen
content. HHV was calculated using an average from two
methods and corrected for ash content, providing a dry ash
free basis (daf).
Gravimetric yield and gravimetric yield factor
The gravimetric yield (GY) was obtained for biomass after
pyrolysis process in a muffle furnace (Quimis-Q318S21).
Dried biomass was put on porcelain pans during the pyrol-
ysis process and was sustained up until temperature peaks
of 250, 350 and 450 °C. The process resulted in biochar
BC250, BC350 and BC450. The gravimetric yield of these
biochar is determined by Eq. 3 [26]:
( )
mf
GY = ∗ 100 (3)
mi
where GY is the gravimetric yield of biochar (%); mf is the
final mass after pyrolysis (g); and mi is the initial mass of
biomass (g).
According to [26], gravimetric yield factor (GYF) is
defined as the ratio between the gravimetric yield percent-
age and the fixed carbon rate and was determined for the
biochar considering Eq. 4:
GYF = (GY∕100) ∗ (FC∕100) (4)
where GYF is the gravimetric yield factor and FC is the
fixed carbon (%).
Thermal analysis
Thermal analysis was carried out at three different heating
­ in−1, using a simultaneous DSC-
rates 7.5, 15 and 20 °C m
TG equipment, TA Instruments, model SDT Q600, from
25 °C to 800 °C. Air and nitrogen analytical degree was
purge gas at a 120 mL min−1 flow rate. In order to elimi-
nate the mass and heat transfer interference, small masses,
about 5.0 mg, were considered and analyzed in alumina
pans. The TA Instruments software provides the mass loss
(TG) and the derivative mass loss (DTG) curves, loaded
as a function of temperature and time at heating process.
Experimental investigation of the delignification process influence on thermochemical and… 883

Energy balance The burnout index (Db), used to analyze the thermal behav-
ior of the samples, is described in Eq. 8:
Solid residues of biomass were analyzed considering the ( )
dw
energy yields and dry ash free (daf) mass. These calculations dt max (8)
were based on Eqs. 5 and 6 [27]: Db =
Δt( 1 ) ∗ tp ∗ tb
( ) 2
mbiomass
Ymass (%) = ∗ 100 (5) where (dw/dt)max is the maximum combustion rate, ∆t(1/2)
mbiochar daf
the time zone of (dw/dt)/(dw/dt)max = 1/2, tp the correspond-
( ) ing time of (dw/dt)max and tb the burnout time.
HHVbiomass
Yenergy (%) = Ymass (6)
HHVbiochar daf Deviation methods

Ignition and burnout temperatures methods The deviation method (DM) showed the ignition temperature
identified from the DTG curves [19], in oxidizing and nitrogen
Intersection atmosphere, during combustion and pyrolysis process, respec-
tively. Figure 1b shows the determination of the ignition tem-
The ignition temperature (Ti) is the temperature point with perature based on DM.
a decrease in the DTG curve [28]. The ignition temperature In both methods were considered TG and DTG curves at
considered the TG curve and two methods, ‘‘Intersection oxidative atmosphere and three different heating rates, 7.5, 15
Method (IM)” (Fig. 1a). The ignition index Di is calculated and 20 °C ­min−1.
according to Eq. 7:
( ) Kinetic study
dw

Di =
dt max
tp ∗ ti
where (dw/dt)max is the maximum combustion rate, tp is the
corresponding time of the maximum combustion rate and ti
is the ignition time.
The burnout temperature (Tb) is the oxidation process
complete, and it is observed on DTG [28, 29]. Tb was deter-
mined from the single peak of a DTG curve [30, 31]. In
Fig. 1a can be observed the Tb calculated using IM.
(7) Model-free methods are based on an isoconversional process
considering activation energy as a function of the conversion
degree a chemical process [32–34]. In this work, two model-
free kinetics were considered aiming to understand the kinetic
behavior of Capsicum spp. The one-step global model con-
siders only a single reaction in thermochemical processes as
follows [35, 36]:
k
Biomass → Water + (Volatiles + Gases) + (Biochar)

120 8 8 BM-air
(a) (b) BM-nitrogen
Derivative mass loss/%min–1

100
Derivative mass loss/%min–1

B Ti 6 6

80
4 4
Mass/%

60
2 2
40

A 0 0
20
C
0 Tb –2 –2
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
Temperature/°C Temperature/°C

Fig. 1  Determination of ignition (Ti) and burnout (Tb) temperatures considering the intersection method a and ignition temperature from devia-
tion method b

13
884 A. A. D. Maia et al.

where k is the rate constant of reaction and temperature

60
dependence is described by the Arrhenius equation, 9:

Nitrogen
k = Ae(−Ea ∕RT) (9) 50

Ultimate analysis/%
where Ea is the apparent activation energy/kJ mol−1; T is 40

Hydrogen
the absolute temperature/K; R is the universal gas constant
8.31 J/K mol−1; and A is the pre-exponential factor ­(s−1). 30
A kinetic study considering the Arrhenius equation was
previously described in [1]. The kinetic study in this paper

Carbon
20
was calculated using dried Capsicum spp. and Kissinger–Aka-
hira–Sunose (KAS) and Ozawa–Flynn–Wall (OFW) models 10

described below.
0
0 1 2 3 4
KAS model Samples
*Samples: 1BM; 2BC250; 3BC350; 4BC450
KAS is an isoconversional model [33, 37] without any assump-
tion concerning the method [32]. It was calculated considering
Fig. 2  Changes in elemental composition as result of pyrolysis treat-
Eq. 10: ment at four different final temperatures
( ) ( )
𝛽 AEa E
ln = ln − a (10)
T2 g(∝)R RT
Table 1  Atomic ratio of biomass and BC250, BC350 and BC450
where Eα is activation energy and A is the pre-exponential
Molar element BM BC250 BC350 BC450
factor at a given conversion degree, α, respectively. The tem-
Ratio
perature T is that the conversion α is reached at a heating rate
β. The plot of ln (β/T2) versus 1/T slope gives −Ea/R [32]. H/C 1.27 0.93 0.81 0.59
N/C 0.04 0.04 0.04 0.03
OFW model O/C 0.71 0.45 0.36 0.39

OFW is one of the most common and widely isoconversional

models [33] to study the thermokinetic parameters [38] and
was applied considering Eq. 11 [39]. Results and discussion
Ea
ln (𝛽) = C∝ − (11) Biomass characterization
RT
where β is heating rate; Eα apparent activation energy; Cα These results show significant differences caused by the
function of the conversion degree α; R universal gas constant highly variable composition of biomass. There were large
8.31 J/K mol−1; and T the absolute temperature (K). variations determined by the proximate and ultimate analy-
ses and can represent the moisture contents and ash yields.
Thermodynamic parameter It was found that the ultimate analysis provides a more
detailed chemical composition and it is the most accurate
Pre-exponential factor (A) is the frequency of collisions comparing with proximate data which has low accuracy
between reactant molecules and was calculated according to because it provides only an empirical composition of the
Arrhenius equation [39, 40], considering an intermediate value biomass and biochar. Figure 2 shows changes in elemental
of β (i.e. 15 °C ­min−1) and Eq. 12. A reaction order was not composition at four different pyrolysis temperatures.
previously considered. The pyrolysis process caused a decrease in the C and H,
which can be attributed to the dehydration and decarboxy-
Ea∕
( )
RTm lation reactions during the process.
A = 𝛽Ea exp (12)
RTm2 In Table 1 it is possible to observe the atomic ratio of
H/C, N/C and O/C molar elements of biomass and bio-
char, and Fig. 3 represents a plot of the molecular ratios
of hydrogen to carbon (H/C) and oxygen to carbon (O/C)
based on the Van Krevelen diagram.

13
Experimental investigation of the delignification process influence on thermochemical and… 885

1,3
A greater variability was observed in the volatile and ash
analysis, with the volatile content decreasing with higher
1,2 temperatures. The variation in ash content was the oppo-
1,1 site, being lowest in biomass and highest in biochar, mainly
H/C Atomic Ratio

BC450. The highest HHV was given in BC350 correspond-

1,0
ing to the highest values of carbon and fixed carbon.
0,9 The decrease in the GY with increasing temperature can
0,8
be explained by a greater initial decomposition of biomass
at higher temperature or to secondary decomposition after
0,7 BM
BC250
biochar formation.
0,6 BC350 The GYF decreased from 1.75 to 0.96 as the pyrolysis
BC450 temperature increased from 250 to 450 °C. This may be
0,5
0,35 0,40 0,45 0,50 0,55 0,60 0,65 0,70 0,75 related to the fast heating, which promotes rapid depolym-
O/C Atomic Ratio erization of the solid material to more volatiles compounds.
This comparison shows that the initial composition of bio-
Fig. 3  Van Krevelen diagram for biomass and biochar mass can vary largely and will be important to determining
the final composition of the biofuel.

Table 2  Ultimate, proximate, calorific and gravimetric analyses of Thermal analysis

biomass and BC250, BC350 and BC450

Material BM BC250 BC350 BC450 Figure 4 shows TG and DTG curves of Capsicum spp. at
oxidizing (A, B and C) and inert atmosphere (D, E, and F)
Ultimate analysis/ %
at three different heating rates.
Carbon 47.8 57.9 62.8 62.1
Figure 4 also shows that lower heating rate is the tem-
Hydrogen 5.1 4.5 4.2 3.1
perature which occurs main thermochemical processes in
Nitrogen 2.1 2.8 2.8 2.5
both atmospheres. Using three heating rates, it was possible
Proximate analysis/ %
to better understand the difference between biomass thermal
Volatile matter 63.6 57.4 48.8 44.6
conversion process.
Ash 9.65 12.8 17.1 21.9
Different stages of mass loss were observed at the oxi-
Fixed carbon 26.7 29.8 34.1 33.5
dizing atmosphere, and the first stage was due to the mois-
Higher heating value/kJ kg−1 19.0 22.7 24.5 23.1
ture loss and release of some light volatiles at temperature
Gravimetric yield/ % – 58.8 43.1 28.7
below 100 °C. The moisture content in the biomass was
Gravimetric yield factor – 1.75 1.47 0.96
8.92%, 9.58% and 10.10% for the heating rates of 7.5, 15,
and 20 °C m ­ in−1, respectively, at the oxidizing atmosphere.
It is possible to observe under inert atmosphere main steps
The O/C and H/C ratio varied with increasing pyroly- of the water evaporation, devolatilization of thermally labile
sis temperature with changes in the elemental composition and more stable volatiles, and biochar formation (Fig. 4a, b
between biomass and biochar, suggesting the increase in and c).
aromaticity during the pyrolysis process. It is possible to The moisture content in the biomass was 9.09%, 9.74%
observe two separate groups: with higher O/C and H/C ratios and 10.78% for the heating rates of 7.5, 15 and 20 °C m ­ in−1,
due to the presence of hemicellulose and cellulose, repre- respectively, at inert atmosphere (Fig. 4d, e and f). The sec-
senting the biomass and the second group, with lower O/C ond step of thermal conversion is represented by gaseous
and H/C ratios, representing the biochar samples. The lower released, a fraction of the condensed, preceding liquid frac-
values observed in the biochar samples could be explained tion. Thermal decomposition of lignin is observed in a tem-
by a higher degree of aromaticity due to hydration, decar- perature range from 150 to 550 °C, and the mass loss rate is
boxylation and decarbonylation promoting a carbon high not as clear as in hemicellulose and cellulose which decom-
content. Based on that, it is possible to conclude that the position process was estimated in the range 160–320 °C with
higher final pyrolysis temperature, the lower the atomic a maximum mass loss rate of about 250 °C characterizing
ratios, which can be related to higher degree of aromaticity, thermal conversion of biopolymers. At temperature range
its recalcitrance and its stability. 250–400 °C, it is possibly associated with carbonaceous
The results for ultimate and proximate analyses, HHV, GY matter formed earlier.
and GYF, obtained for biomass and all biochars, are shown At inert atmosphere, above 400 °C, begin the carboni-
in Table 2. zation phase and biochar formation. Cellulose and lignin

13
886 A. A. D. Maia et al.

120 1.0 120 0.8 120 0.8

Derivative mass loss/%.°C–1

Derivative mass loss/%.°C–1

Derivative mass loss/%.°C–1
100 (a) 0.8 100 (b) 100 (c)
0.6 0.6
80 80 80

Mass/%
0.6
Mass/%

Mass/%
60 60 0.4 60 0.4
0.4
40 40 40
0.2 0.2
20 0.2
20 20

0 0.0 0 0.0 0 0.0

0 200 400 600 800 0 200 400 600 800 0 200 400 600 800
Temperature/°C Temperature/°C Temperature/°C

120 0.4 120

Derivative mass loss/%.°C–1

0.4 100 0.4

Derivative mass loss/%.°C–1

Derivative mass loss/%.°C–1

100
(d) 100
(e) 0.3 80
(f)
0.3 0.3

0.2 60
Mass/%

80 80

Mass/%
Mass/%
0.2 0.2
60 60 0.1 40

0.1 0.1
40 40 0.0 20

20 0.0 20 – 0.0 0 0.0

0 200 400 600 800 0 200 400 600 800 0 200 400 600 800 1000
Temperature/°C Temperature/°C Temperature/°C

Fig. 4  Distributions of TG and DTG curves of biomass in air a 7.5, b 15 and c 20 °C ­min−1 and nitrogen d 7.5, e 15 and f 20 °C ­min−1

degradation and decomposition are almost overlapping, and between thermochemical conversion temperature (250 °C
the thermal conversion of biomass is characterized by the and 450 °C) and this behavior can be explained by previ-
mass ratio of its main components superposition. The maxi- ous delignification process. The content of lignin present
mum mass loss was observed at around 300–400 °C with in biomass can be changed by the effects of pyrolysis time
58% in inert atmosphere and 23% in oxidizing atmosphere, and temperature. Removing lignin content of biomass dur-
which suggested that biomass and biochar were more stable ing pyrolysis/torrefaction process can promote lower and
under inert conditions. higher values of activation energy and HHV, respectively,
This behavior can be explained by particle thermal and an improvement in the carbon content and reduction in
exchange influenced by the release of other particles under the oxygen content. The kinetic behavior of the biomass is
oxidizing atmosphere. Degradation process presented a related to these parameters and can explain an improvement
pattern of almost samples varying according of atmosphere in the thermochemical conversion of the biomass.
used. These steps do not occur uniformly or sequentially but The overlapping of TG and DTG curves at 7.5 °C m ­ in−1
are related to nonlinear chemical and thermal processes pre- and 15 °C m ­ in−1 indicates that higher heating rates can pro-
sented by this biomass. Differences at thermal decomposi- mote mass and heat transfer effects not measurable and are
tion and degradation for biomass samples have been related not recommended to kinetic parameters determination.
to the variations in the elemental and chemical compositions
of the samples at different atmospheres. Total mass loss was Energy balance
higher at smaller heating rates which allow higher volatile
matter and lower ash content conversion. The mass and energy losses of torrefaction process (250 °C)
Considering a great number of pretreatment methods in nitrogen of Capsicum spp. showed that the fuel contains
available to delignify biomasses, it’s possible to notice that up to 65% of the original energy content in the solids. Ana-
thermochemical conversion can be considered a promising lyzing energy balances for the pyrolyzed biomass, it was
method of removing lignin from natural fibers since removal possible to observe that with increasing reaction tempera-
of lignin is a thermally sensitive process and varies with ture process becomes less endothermic and/or more exother-
thermal conditions processes and with the nature of sample mic. The volatilization of acid and organics has the highest
[41–43]. Generally, the major thermochemical conversion of influence on energy balance. Heat process generates a solid
the biomass occurs about 300 °C and 500 °C. fuel with an increase in HHV converting biomass with low-
Considering the biomass pretreated thermally (BC250, energy into a high-energy feedstock. The thermal treatment
BC350 and BC450), it’s possible to notice the difference not only destructed the fibrous structure and tenacity of

13
Experimental investigation of the delignification process influence on thermochemical and… 887

biomass but also increased the calorific value. During ther-
mal process, the biomass devolatilizes decreasing in mass,
but the initial energy content preserved in the solid product.
Thus, the energy density of biochar becomes higher than
the biomass. As the energy of biochar is higher compared to
biomass, larger transportation distances are possible. Moreo-
ver, thermal treatment causes hydrophobic characteristics,
promoting storage more attractive because of the decomposi-
tion behavior. Figure 5 represents mass and energy variation
to three different pyrolysis temperatures.
Ignition and burnout temperatures
The determination of the ignition and burnout temperatures
of biomass could be influenced by heating rate variation,
biomass characteristics, particle size and volatile matter con-
tent. The samples utilized presented a small particle size
70
Mass and Energy yields/%
(74 µm), and it is estimated that its ignition and burnout
characteristics are directly related to heating rate increasing.
The TG and DTG curves considered for ignition and burnout
temperatures determination can be observed in Fig. 6.
According to IM, the ignition temperature of biomass
is between 342 and 355 °C and tends to ascend when the
heating rate increases. This is possibly due to the cellulose
content in biomass. The ignition temperature based on DM
is in the range of 210–250 °C, which is lower than those
based on IM. Table 3 shows the different temperatures of
the DTG peaks according to various heating rates studied.
All ignition and burnout values can be observed in
Table 4.
The lower ignition temperature shows the high vola-
tile contents of biomass and easy ignition. The burnout
temperature indicates that oxidation of biomass occurred
between 470 °C and 503 °C. These higher temperatures
reveal that biomass needs a higher temperature during
the combustion process, as well as longer residence time.
Proximate values of burnout temperatures can be observed
in the literature [31].

60
These temperature variations suggest that cellulose con-
50
tent changes the ignition characteristics and decomposi-
40 tion of lignin since the cellulose has compounds that are

30
Table 3  Temperature and intensity of DTG peaks at three heating
20
rates of Capsicum spp.
10
Material Heating rate/°C ­min−1
0 7.5 15 20
BC250 BC350 BC450
Mass yield (daf) Energy yield (daf) BM Temperature/°C
1st peak 453.95 473.34 487.08
Fig. 5  Mass and energy yields (dry ash free) for biochar at treated at Intensity/% ­min−1–% °C−1
temperatures of 250, 350 and 450 °C. *Samples: 1BC250; 2BC350;
3 1st peak 6.2–0.80 10.9–0.69 12.6–0.60
BC450

120 1.0
7.5 °C/min 7.5 °C/min
15 °C/min 15 °C/min
20 °C/min 20 °C/min
Derivative mass loss/% °C–1

100 0.8

80 0.6
Mass/%

60 0.4

40 0.2

20 0.0

0 – 0.2
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
Temperature/°C Temperature/°C

Fig. 6  Distributions of TG and DTG in terms of (% and %/ °C) of biomass three heating rates

13
888 A. A. D. Maia et al.

Table 4  Ignition and burnout temperatures of Capsicum spp. biomass lower is the carbonaceous material of the biochar shorter
Material Heating rate/°C ­min−1 is the burnout time.
Figure 7 represents the ignition and burnout temperatures
7.5 15 20
variation and are directly related to heating rate. A higher
BM Ignition temperature (Ti)/°C heating rate presented higher Ti and Tb.
IMa 342.50 354.57 354.84 Ignition index agrees with the results of ignition tem-
DMb 210.39 221.14 249.74 perature, and his higher value is indicative of better
Burnout temperature(Tf)/°C ignition performance. The influence of heating rates
IM 470.04 488.41 503.93 on the burnout time must be considered, so the burnout
a
time represents burnout performance of biomass. The
Intersection method (air as purge gas)
b
larger value of indexes represents better combustibil-
Deviation method (air and nitrogen as purge gases)
ity. The ignition and burnout index can be observed in
Table 5.

490 Kinetic study

420
Biomass kinetic study showed complicated and unknown
350 processes during thermochemical conversion, characterizing
Temperature/°C

multi-step biomass degradation.

280
Figure 8 presents biomass degradation as a function of
210 absolute temperature (Kelvin) at heating rates of 7.5, 15 and
20 °C ­min−1 and oxidizing atmosphere.
140
The activation energy value can be observed in
Ti/DM
70 Ti/IM Table 6, and the highest values of Eα represent a greater
Tb/DM difficulty for thermal conversion of biomass into bio-
0 char. This can be explained by the presence of mineral
0 4 8 12 16 20
Heating rate/ ºC min–1
elements in biomass. This mineral composition can
be a barrier, preventing the diffusion of heat and the
release of volatiles during the carbonization process.
Fig. 7  Ignition and burnout temperatures considering the intersection
and deviation methods varying according to heating rates The activation energy variation also suggests biomass
complexity.
At the temperature range of 460–720 K, the acti-
easily volatilized. At lower heating rates, it is possible to vation energy was between 61–193 kJ mol −1 and
observe the lowest burnout temperature because of that 72–201 kJ mol−1 for KAS and OFW, respectively. Acti-
the volatile matter presents some complex characteristics, vation energy variation can also show a difficult capa-
being harder to decompose and lower ash content compar- bility of ash formation indicating a thermal conversion
ing other heating rates. The results also showed that the efficiently. OFW model showed higher values than KAS

Table 5  Biomass ignition and BM Combustion parameters Ignition characteristic Burnout character-
burnout characteristics istic
Heating rate DTGmax tp /min ti /min tb /min Ti /°C Di Tb /°C Df
/% ­min−1

7.5 °C ­min−1 6.2 55 40 58 432.5 2.32E − 03 470.04 2.31E − 05

15 °C ­min−1 10.9 29 21 31 354.57 1.16E − 02 488.41 2.48E − 04
20 °C ­min−1 12.6 22 16 24 354.84 2.82E − 02 503.93 6.46E − 04

13
Experimental investigation of the delignification process influence on thermochemical and… 889

220
90 7.5 ºC min–1
OFW
15 ºC min–1 200 KAS
80

Activation Energy/kJ.mol–1
20 ºC min–1
70 180
Conversion degree/α

60 160

50 140

40 120

30 100

20 80
10 60
0
0 20 40 60 80 100
400 450 500 550 600 650 700 750 800
Conversion degree/%
Temperature/K

Fig. 9  A comparison of E(α) for KAS and OFW

Fig. 8  Biomass thermal behavior at different heating rates in air
atmosphere

Conclusions
Table 6  Kissinger–Akahira–Sunose and Ozawa–Flynn–Wall biomass
activation energy and pre-exponential factor The biomass is an interesting biofuel source, not requiring
Conversion KAS OFW the exacerbated expenditure of energy and time with the
degree /α pyrolysis process. The values obtained for biomass suggest
Eα /kJ mol−1 A /s −1
Eα /kJ mol−1 A /s−1
that it can be used in the biofuel production process, sup-
10 104.05 5.02E + 02 98.65 4.76E + 02 plying small agribusiness. The ultimate analysis provides
15 142.62 6.88E + 02 134.99 6.51E + 02 a more detailed chemical composition, and proximate data
20 193.41 9.34E + 02 201.73 9.74E + 02 presented a low accuracy and provided an empirical com-
25 173.23 8.36E + 02 181.91 8.78E + 02 position of the biomass and biochar. The pyrolysis process
30 131.71 6.34E + 02 140.69 6.78E + 02 promoted a lower C and H and can be attributed to the dehy-
35 172.16 8.30E + 02 181.39 8.75E + 02 dration and decarboxylation reactions during the process.
40 156.01 7.52E + 02 165.46 7.98E + 02 The lower ignition temperature shows the high volatile con-
45 126.06 6.07E + 02 135.75 6.54E + 02 tents of biomass, and the burnout temperature reveals that
50 115.15 5.54E + 02 125.10 6.02E + 02 biomass probably requires longer residence time or higher
55 76.08 3.66E + 02 86.46 4.16E + 02 temperature to complete the combustion process. Biomass
60 61.64 3.23E + 02 72.61 3.49E + 02 kinetic study showed the complexity of the biomass and
65 88.04 4.23E + 02 99.55 4.79E + 02 unknown processes during thermochemical conversion,
70 114.58 5.51E + 02 126.40 6.08E + 02 characterizing the multi-step biomass degradation.
75 123.38 5.94E + 02 135.38 6.52E + 02
80 115.58 5.56E + 02 127.75 6.15E + 02 Acknowledgements This study was financed in part by the Coorde-
85 126.70 6.10E + 02 126.70 6.10E + 02 nação de Aperfeiçoamento de Pessoal de Nível Superior-Brasil
(CAPES)-Finance Code 001 and FAPESP.
90 123.14 5.93E + 02 123.15 5.93E + 02

method. Therefore, it is important to use more than one
kinetic model, allowing a greater range of values and
helping to understand the thermal behavior of biomass.
Both models were considered in the agreement since they
presented a coefficient of determination (­ R 2) between
0.97 and 0.99. Figure 9 shows a comparison of activation
energy for KAS and OFW.
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