Biomass Conversion and Biorefinery (2022) 12:4847–4861

https://doi.org/10.1007/s13399-020-01104-2

ORIGINAL ARTICLE

Thermal degradation characteristics, kinetics,

thermodynamic, and reaction mechanism analysis of pistachio shell
pyrolysis for its bioenergy potential
Supriya Gupta 1 & Goutam Kishore Gupta 1 & Monoj Kumar Mondal 1

Received: 22 May 2020 / Revised: 15 October 2020 / Accepted: 22 October 2020 / Published online: 25 October 2020
# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
The research work aims to estimate the bioenergy potential of pistachio shell and study its degradation kinetics which is necessary
for the efficient design and optimization of thermochemical processes for bioenergy generation. Initial characterizations (prox-
imate, ultimate, higher heating value, and compositional analysis), kinetic study, and thermodynamic analysis accompanied by
reaction mechanism are investigated. Physicochemical characterization results confirmed high volatile matter (~ 79.8 wt%) and
high heating value (16.85 MJ/kg) of pistachio shell. Thermogravimetric analysis (TGA) is performed at four different heating
rates of 10, 20, 30, and 40 °C/min under nitrogen gas flow rate from ambient temperature to 900 °C. TGA results show the three-
stage pyrolysis reaction which involves removal of moisture and light volatiles, degradation of cellulose and hemicellulose, and
decomposition of lignin. The result also reveals that maximum degradation occurred in the temperature range of 200–400 °C. For
calculating the kinetic (activation energy and pre-exponential factor) and thermodynamic parameters (enthalpy, entropy, and
Gibbs free energy), different iso-conversional models, i.e. Flynn-wall-Ozawa (FWO), Kissinger–Akahira–Sunose (KAS),
Starink, and Friedman, are employed which gives the average value of activation energy as 168.86, 165.80, 166.29, and
190.10 kJ/mol, respectively and the pre-exponential factor values lie in the range of 107-1021 s−1. The average values of Gibbs
free energy calculated for FWO, KAS, Starink, and Friedman methods are 182.09, 182.15, 182.13, and 181.42 kJ/mol, respec-
tively. Criado method and Z plot are showing complex reaction mechanism. The results of kinetics and thermodynamic study
reveal pistachio shell is an efficient biomass for bioenergy production.

Keywords Pistachio shell . Thermogravimetric analysis . Kinetics . Reaction mechanism . Thermodynamic study

1 Introduction nowadays [1]. Biomass is one of the promising renewable

In the context of current scenario of the energy crisis, the
reckless use of fossil fuels (non-renewable energy resource)
and a great hike in the population demands an alternative to
fulfill and meet the energy requirements for the future gener-
ation. Fossils like petrol, natural gas, and coal are present in
limited quantity and these resources also create a threat to the
ecosystem as the burning of these fuels results in the emission
of harmful and toxic gasses (CO2, SOX, NOX). This leads to
increase in global warming which is a worldwide concern
* Monoj Kumar Mondal
mkmondal13@yahoo.com
1
Department of Chemical Engineering and Technology, Indian
Institute of Technology (Banaras Hindu University),
Varanasi 221005, India
resources for the energy production because of its sustainabil-
ity, easy availability, and environmentally friendly nature [2].
Unlike fossil fuels, biomass is a lignocellulosic material that
intakes carbon dioxide released during combustion by photo-
synthesis, thus neutralizing the carbon cycle with zero CO2
emission. It mainly consists of cellulose, hemicellulose, and
lignin with minor traces of sulfur, nitrogen, and metals
resulting in minute emission of toxic gasses during combus-
tion of biofuel. Enormous availability of biomass worldwide
in the form of agricultural residue, forest waste, municipal
waste, animal waste, water-based plants, and vegetation waste
receives significant attention to use it as a substitute of fossils
for further energy production [3, 4]. Apart from biofuel pro-
duction, biomass can also be used for the production of hy-
drogen gas as it is rich in volatile content, which on thermal
degradation release hydrogen-rich gas or syngas which on
further reforming produces hydrogen [4–6].
4848
The extraction of energy from biomass can be done by
different methods like biochemical, chemical, and thermo-
chemical processes [7]. Biochemical process mainly involves
fermentation or anaerobic digestion which uses bacteria and
enzymes to break down biomass into biofuel, but due to its
sluggish nature, this process does not draw much attention.
Thermochemical conversion of biomass seems to be better
than the former because of rapid reaction and high throughput.
Combustion, gasification, liquefaction, and pyrolysis are the
various methods of the thermochemical process [8].
Combustion is an exothermic chemical reaction between an
oxidant and a fuel escorted by the release of a large amount of
heat and harmful gasses. Gasification is a complex multi-stage
partial oxidation process which occurs at elevated temperature
and involves expensive initial setup while liquefaction re-
quires high pressure for conversion of biomass into biofuel.
Pyrolysis is a thermal degradation process that occurs in the
absence of oxygen or requires an inert medium to transform
biomass into bio-oil, solid char, and non-condensable gas. It is
performed at moderate temperature, low-pressure process as
compared to gasification and liquefaction [9]. Pyrolysis plants
are also flexible, easy to operate, efficient, and less polluting,
thus considering being the best thermochemical conversion
route for the bio-oil generation. Bio-oil obtained as a pyrolysis
product is a complex mixture of oxygenated compound and
various functional groups like carbonyl and phenol carboxyl.
which can be used to generate CHP (chemical, heat, and pow-
er) and find applications in boiler, furnaces, turbine, and diesel
engine. Pyrolytic gas mainly consists of H2, CH4, and CO
which acts as an alternative fuel for IC engines and industrial
combustion process [10]. Solid char obtained as a product
after biomass pyrolysis can also be used for subsequent
gasification.
Basic knowledge about the biomass behavior and its suit-
ability towards the pyrolysis reaction along with different ki-
netic and thermodynamic parameters is necessary for the eco-
nomical and feasible design of the pyrolysis plant.
Thermogravimetric (TG) analysis and derivative thermogra-
vimetric (DTG) analysis are the two widely used techniques to
analyze the thermal degradation of biomass and pyrolysis re-
action mechanism [2, 11]. TG analysis involves mass loss data
as a function of temperature at controlled heating rate and the
TG curve obtained can be further used for finding kinetic
parameters. After taking the first derivative of the TG curve,
DTG curve is obtained, which also act as a useful tool for
further kinetic and thermodynamic analyses. TG analysis
can be operated in both isothermal and non-isothermal modes.
But because of fewer calculations and straightforward ap-
proach, non-isothermal (dynamic) approach is preferred [1].
The understanding of kinetics and thermodynamics is neces-
sary for adequate bioenergy generation from pistachio shell
[12]. The knowledge of these parameters is necessary for the
prediction and simulation of complex degradation process, for
Biomass Conv. Bioref. (2022) 12:4847–4861
the estimation of energy required, and also for energy balance.
A deeper understanding of reaction kinetics and thermody-
namic aspect is essential for the feasibility analysis of the
process as well as for the scale up of the pyrolysis system.
Previously, researches have been done to investigate the
thermal suitability of different biomass including agricultural
waste, woody biomass, and fruit nut shells [13–16] towards
bioenergy generation. However, each biomass has its charac-
teristics and composition, thus exhibit different nature of ther-
mal decomposition. In this research work, pistachio shell is
considered a biomass feedstock for bioenergy production be-
cause they are sustainable energy resource [17] and satisfy the
quality criteria of low moisture content, high volatile matter,
and low ash content required for bioenergy generation. In
addition, high cellulose content and moderate lignin in pista-
chio shell are suitable for bio-oil and biochar production.
Apart from this, pistachios are a great source of healthy fats,
fiber, protein, antioxidants, and various nutrients including
vitamin B6 and thiamine [18, 19]; thus, these nuts are popular
snacks and ingredient in cookies, confectionery, sweets, and
etc. all around the world. In 2017, approximately 11.44 thou-
sand metric tons of pistachio nuts were consumed in India,
which has increased by about 43% over the past 3 years
(https://www.statista.com/statistics/872339/india-pistachio-
nut-comsumption/). India consumes 4.5 million kg of
pistachio per year, of which pistachio shell accounts for
about 47% of its total weight which is of no importance and
has negligible economic or market value resulting in excess
shell waste which creates disposal problem as well. Therefore,
pistachio shell can be considered a suitable biomass feedstock
for bioenergy production, thereby minimizing the pistachio
shell waste. Isitan et al. [20] performed the pyrolysis of
pistachio shell to investigate the effect of temperature on the
bio-oil production. Analysis of the quality of products (bio-oil,
char, and gas) was also done. The study showed that biochar
produced can efficiently work as an activated carbon because
of high surface area and micropore volume. Likewise,
Acikalin et al. [21] also investigated the pistachio shell pyrol-
ysis on fixed bed reactor along with various characterizations
of products. Effect of temperature, reaction time, and N2 gas
flow rate on the bio-oil yield was also studied. Varol et al. [22]
studied the slow pyrolysis of pistachio shell in a fixed bed
reactor. The effect of temperature on bio-oil yield and compo-
sition was studied. Characterization results of the product
showed a close similarity of bio-oil and char concerning con-
ventional fuels. Acikalin [23] performed the kinetic study of
pistachio shell by TG analysis using model-fitting methods
along with the initial pyrolytic characterization of biomass.
Silva et al. [24] also studied the thermal decomposition kinet-
ics of pistachio shell under an oxidative atmosphere.
The present study mainly focuses on the thermal and kinet-
ic suitability of pistachio shell towards pyrolysis reaction for
its bioenergy potential. In present study, the initial
Biomass Conv. Bioref. (2022) 12:4847–4861
characterizations of pistachio shell like proximate, ultimate,
higher heating value (HHV), and compositional analysis were
performed using standard protocols. Further, TG analysis was
performed at four different heating rates to find the thermal
characteristics and kinetic variables like activation energy and
frequency factor by using four iso-conversional models, i.e.
FWO, KAS, Friedman, and Starink methods. The reaction
mechanism for pistachio shell degradation was studied by com-
paring with various diffusion and power-law models of solid-
state biomass pyrolysis. Thermodynamic parameters like en-
thalpy, Gibbs free energy, and entropy were also calculated
for gaining enhanced knowledge of pyrolysis reaction kinetics.
2 Materials and methods
2.1 Raw material
The pistachio shell was collected from the regional market of
Varanasi and shells were removed gently from the pistachio
nut. Then, it was washed 3-4 times with tap water to remove
impurities and sand particles adhered on its surface, followed
by washing two times with distilled water. The shells were
dried in sunlight for about 1 day for removal of surface mois-
ture. Then, it was kept in an oven at 105 °C for 12 h for further
removal of the moisture trapped inside the shells. The oven-
dried shells were crushed into small pieces by disintegrator
and were converted to powdered form by a mixer grinder.
Collected powder was sieved with 60 mesh size and retaining
on 85 mesh size to get the particle size in the range of 0.177–
0.250 mm. The pistachio shell sample was collected in a con-
tainer and kept in the desiccator for further experimental work.
2.2 Characterization of pistachio shell
The proximate, ultimate, HHV, and compositional analyses
are the most important characteristics for any biomass to be
used for bioenergy generation. Proximate analysis of pistachio
shell was done to obtain the moisture content, ash content, and
volatile matter present in it by adopting standard ASTM
E-871, ASTM E-1755, and ASTM E-872 methods [25] re-
spectively. Equation 1 below is used to determine the fixed
carbon content of pistachio shell:
Fixed carbon ¼ ½100−ðmoisture content þ ash content þ volatile matterÞ%
The ultimate analysis was done to find the elemental com-
position such as (CHNS) carbon, hydrogen, nitrogen, and sul-
fur by using elemental analyzer (EURO EA, EURO ECTOR
instruments and software, Italy). Oxygen content was evalu-
ated by using Eq. 2:
O ¼ ½100−ðC þ N þ H þ SÞ%
4849
Compositional analysis (hemicellulose, cellulose, and lig-
nin) for pistachio shell was done following the methods of
Van Soest [26]. Bomb calorimeter (Rajdhani Scientific
Instts. Co., New Delhi, India) was employed for determining
the HHV of pistachio shell. All the experiments were per-
formed in triplicate and average values have been reported
along with the standard deviation.
2.3 Thermogravimetric experiment
TG experiments were done to examine the thermal degrada-
tion and the pyrolysis characteristics of the pistachio shell by
means of TG analyzer (NETZSCH 449 F3 Jupiter, Germany).
Dried powdered pistachio shell sample was kept in the cruci-
ble. The mass of the samples used for the TGA analysis were
10.691 mg, 7.782 mg, 8.922 mg, and 11.014 mg at the
heating rates of 10, 20, 30, and 40 °C/min, respectively.
Nitrogen gas at a constant flow rate of 100 mL/min was
supplied at four different heating rates of 10, 20, 30,
and 40 °C/min from ambient temperature to 900 °C.
Furthermore, the mass loss versus temperature data at
each heating rate was analyzed.
2.4 Kinetic modeling
TG and DTG results were used to find out the kinetic and
thermodynamic variables to check the suitability of pistachio
shell for thermochemical conversion. The general pyrolysis
reaction scheme for biomass is prescribed as follows:
Biomass→biochar þ bio−oil þ non−condensable gasses
Generally, the solid decomposition rate in non-isothermal
condition is expressed by the following equation:
dα
¼ k ðT Þ:f ðαÞ ð3Þ
dt
where t represents the time, T represents the absolute temper-
ature, f(α) serves as the function of conversion independent of
temperature [27]. and α is the fractional conversion of bio-
mass, which can be expressed as:
m0 −mt
a¼ ð4Þ
m0 −m f
ð1Þ where m0, mt, and mf represent the initial mass of biomass,
mass of biomass at time t, and finamass of biomass
respectively.
k(T) is the reaction rate constant dependent on temperature.
The temperature dependency is shown by the Arrhenius equa-
tion expressed as follows:
 
Ea
ð2Þ k ðT Þ ¼ Aexp − ð5Þ
RT
4850 Biomass Conv. Bioref. (2022) 12:4847–4861
   
where A represents the pre-exponential or frequency factor AE a Ea
lnðβÞ ¼ ln −5:311−1:052 ð10Þ
(min−1), Ea represents the activation energy (J/mol), T repre- RgðαÞ RT
sents the reaction temperature (K), and R represents the uni-
versal gas constant with a value of 8.314 J/mol K. where g (α) is constant at particular conversion α, and β
By substituting the rate constant expression of Eq. 5 denotes the heating rate. The linear plot of ln (β) vs. 1/T gives
in Eq. 3, general expression for solid decomposition rate a negative slope of 1.052Ea/R at different temperature and
can be written as: conversion data points for all heating rates from which activa-
tion energy has been calculated.
 
dα Ea
¼ Aexp − : f ðαÞ ð6Þ
dt RT 2.4.2 Kissinger–Akahira–Sunose method

TG experiment was performed at a constant heating rate, β KAS is also a model-free technique in which oversimplified
which is expressed in linear form: temperature integral approximation is used [29] which is rep-
resented by Eq. 11 below:
β ¼ dT=dt ð7Þ
   
β AE a Ea
By putting the value of β in Eq. 6 ln 2 ¼ ln − ð11Þ
T RgðαÞ RT
 
dα A Ea
¼ exp − :f ðαÞ ð8Þ Activation energy is evaluated by the negative slope of ERa
dT β RT
on plotting the graph between ln (β/T2) and 1/T at four differ-
Integrating both sides of Eq. 8 gives: ent heating rates with four sets of data points obtained at
  particular conversion.
α dα A T Ea
g ðαÞ ¼ ∫ 0 ¼ ∫ exp − dT ð9Þ
f ðαÞ β 0 RT 2.4.3 Starink method
where g(α) represents the integral function of conversion
It is also an integral iso-conversional method which is a com-
and f(α) represents the algebraic expression describing the
bination of KAS and FWO methods [1]. Equation 12 predicts
kinetic model of solid-state decomposition [25]. Functional
the linear expression;
forms of f(α) and g(α) are listed in Table 1 which represents
   
different reaction models. β Ea
There are basically two approaches to find out the kinetic ln 1:92 ¼ const:−1:0008 ð12Þ
T RT
parameters for the non-isothermal degradation of biomass, i.e.
model-fitting and model-free method. The model-fitting ap- On comparing with the straight line equation and fitting the
proach requires the knowledge of reaction mechanism and data points, activation energy calculation from the negative
fitting the data into a particular model and estimating the re- slope of (1.0008Ea/R) was made.
action order. But iso-conversional methods are independent of
the reaction model as this approach describes the complex 2.4.4 Friedman method
reaction mechanism with increasing conversion and requires
TGA data at different heating rates instead of assuming reac- Friedman method requires the derivative conversion
tion order [1]. data, termed as differential iso-conversional method
Solid-state biomass decomposition is a complex multi-step for estimating kinetic parameters. Equation 13 below
reaction mechanism which makes the selection or prediction represents the linear expression for this method, ob-
of reaction model very tedious. In order to analyze the kinetic tained by rearranging Eq. 9 and by taking its logarithm
parameters deeply, this research work mainly focuses upon [29, 30].
the model-free methods. Four iso-conversional methods were  
dα Ea
used for estimating the kinetic parameters i.e. Flynn–wall– ln β ¼ ln½A f ðαÞ− ð13Þ
Ozawa (FWO) method, Kissinger–Akahira–Sunose (KAS) dT RT
method, Starink method, and Friedman method.
By comparing the expression with straight line equation


plot a graph between ln β dT dα
and 1/T at four different
2.4.1 Flynn–wall–Ozawa method
heating rates for different values of temperature and
conversion data and fitting it into straight line, the neg-
It is an iso-conversional (integral) method for finding activa-
tion energy at different heating rates [28]. The following ex- ative slope of ERa gives the activation energy at different
pression represents it: conversions.
Biomass Conv. Bioref. (2022) 12:4847–4861 4851

2.5 Reaction modeling 2.6 Thermodynamic study

Prediction of reaction mechanism or reaction model for solid- After estimating the activation energy by four models at four
state thermal degradation of pistachio shell was made by Z different heating rates, pre-exponential factor (A) and thermo-
master plot which is given by Criado method [25] as shown dynamic properties like enthalpy (H), Gibbs free energy (G),
in Eq. 14. and entropy (S) were evaluated by using subsequent equations
below [32]:
 2

Z ðαÞ f ðαÞ  g ðαÞ Tα ðdα=dT Þα A ¼ β E a exp ðEa =RT m Þ= RT m 2 ð15Þ
¼ ¼  ð14Þ
Z ð0:5Þ f ð0:5Þ  g ð0:5Þ T 05 ðdα=dT Þ0:5
ΔH ¼ E a −RT ð16Þ
ΔG ¼ Ea þ RT m ln ½ðK B =T m Þ=ðh AÞ ð17Þ
f ðαÞgðαÞ
The term f ð0:5Þgð0:5Þ is calculated from different solid-
ΔS ¼ ðΔH−ΔGÞ=T m ð18Þ
state reaction models as listed in Table 1 which gives
 2
Here, Tm represents the peak temperature from DTG curve
17 different theoretical plots and the term TT05α 
at particular heating rate, Boltzmann constant with a value of
ðdα=dT Þα
ðdα=dT Þ0:5 is derived from the experimental value at a 1.381 × 10−23 J/K is represented by KB, and h denotes the
particular heating rate which gives single curve [25, plank constant (6.626 × 10−34 J s).
31]. The plot obtained from the above equation is re-
ferred as master plot which does not require information
of any kinetic parameter like activation energy and pre- 3 Results and discussion
exponential factor. The term Tα denotes the temperature
at particular conversion α and T0 · 5 signifies the temper- 3.1 Physiochemical properties of pistachio shell
ature at 50% conversion. The reference value of α = 0.5
is taken at which the term Z ðαÞ
reduces to the value of Physical and chemical properties of pistachio shell are listed in
Z ð0:5Þ
Table 2 and compared with the properties of other biomass.
1 for the entire theoretical and experimental curve. These results revealed that pistachio shell contains high
From this, we can predict the reaction mechanism of amount of volatile matter, low moisture, and low ash content
the experimental curve by comparing the theoretical which is favorable for the pyrolysis of pistachio shell. The
curve which gives the closest fitting. amount of moisture content, volatile matter, ash content, and

Table 1 Fitting performance of various kinetic models with different values of f (α) and g (α)

Solid-state process Mechanism f (α) g (α)

One-dimensional diffusion D1 1/(2α) α2

Two-dimensional diffusion (Valensi model) D2 [− ln (1 − α)]−1 (1 − α) ln (1 − α) + α
Three-dimensional diffusion (Jander model) D3 3/2 (1 − α)2/3 [1 − (1 − α)1/3]−1 [1 − (1 − α)1/3]2
Three-dimensional diffusion (Ginstlinge-Brounshtein model) D4 3/2 [(1 − α)1/3 − 1]−1 1 − 2/3α − (1 − α)2/3
Contracting cylinder F2 2(1 − α)1/3 1 − (1 − α)1/2
Contracting sphere F3 (1 − α)2/3 1 − (1 − α)1/3
Power law P2/3 2/3α−1/2 α3/2
Power law P2 2α1/2 α1/2
Power law P3 3α2/3 α1/3
Power law P4 4α3/4 α1/4
Avrami-Erofeev A1 1/2 (1 − α) [− ln (1 − α)]1/3 [− ln (1 − α)]2/3
Avrami-Erofeev A2 2 (1 − α) [− ln (1 − α)]1/2 [− ln (1 − α)]1/2
Avrami-Erofeev A3 3 (1 − α) [− ln (1 − α)]2/3 [− ln (1 − α)]1/3
Avrami-Erofeev A4 4 (1 − α) [− ln (1 − α)]3/4 [− ln (1 − α)]1/4
1st-order random nucleation having one nucleus on individual particle R1 (1 − α) [− ln (1 − α)]
2nd-order random nucleation having two nucleus on individual particle R2 (1 − α)2 (1 − α)−1 − 1
3rd-order random nucleation having three nucleus on individual particle R3 (1 − α)3 1/2 [(1 − α)−2 − 1]
4852 Biomass Conv. Bioref. (2022) 12:4847–4861

Table 2 Physiochemical properties of pistachio shell along with comparison with other biomass

Physicochemical properties Pistachio shell Cotton stalk [33] Rice husk [33] Walnut shell [33] Corn stover [33] Corn cob [33] Sorghum
stalk [33]

Moisture content 5.72 ± 0.32 8.9 9.8 10.6 8.3 10.2 8.7
Volatile matter 79.80 ± 1.13 71.0 64.0 63.0 73.0 80.0 66.0
Ash content 1.97 ± 0.16 3.5 17.4 10.5 11.1 5.7 8.8
Fixed carbon 12.51 ± 0.97 16.6 8.8 15.9 7.9 4.2 16.5
Carbon 45.31 ± 0.3 46.8 39.8 41.7 45.7 44.2 44.4
Hydrogen 5.49 ± 0.22 6.4 5.7 5.0 6.3 5.9 6.2
Nitrogen 0.28 ± 0.06 0.3 0.5 0.4 0.4 0.4 0.5
Oxygen 48.92 ± 0.14 46.8 39.8 41.7 45.7 44.2 44.4
H/C 1.45 ± 0.07 1.64 1.72 1.44 1.65 1.60 1.68
O/C 0.81 ± 0.01 0.75 0.75 0.75 0.75 0.75 0.75
Cellulose 51.18 ± 0.53 39.4 32.4 36.6 28.3 32.2 35.4
Hemicellulose 21.55 ± 0.24 19.2 13.9 18.9 16.4 29.0 17.4
Lignin 21.51 ± 0.30 24.8 27.8 22.2 23.8 18.4 21.3
Extractives 5.76 ± 0.40 7.8 9.1 13.0 20.5 15.12 25.9
HHV (MJ/kg) 16.85 ± 0.58 19.2 15.5 17.4 17.9 13.3 17.1

fixed carbon present in the pistachio shell lies in the range of
lignocellulosic biomass [34, 35] which indicates the similar
nature of thermochemical degradation of pistachio shell as
compared to another lignocellulosic biomass. Ultimate analy-
sis result showed high carbon, low nitrogen, and sulfur con-
tent below detection range which indicates less emission of
toxic gasses during thermochemical degradation which
confirms the process to be eco-friendly. The compositional
analysis showed pistachio shell contains good amount
of cellulose and moderate amount of hemicelluloses
and lignin. HHV of pistachio shell was 16.85 MJ/kg
that lies in the range of other biomass [33, 36]. This
also determines the amount of heat evolved during the
process.

Fig. 1 TG-DTG curve of pistachio shell at heating rate of a 10, b 20, c 30, and d 40 °C/min
Biomass Conv. Bioref. (2022) 12:4847–4861
Fig. 2 FWO integral model for
activation energy calculation of
pistachio shell
3.2 Thermogravimetric analysis
TG and DTG curves obtained at each heating rates (10, 20, 30,
and 40 °C/min) are depicted in Fig. 1 (a)-(d), respectively.
These curves were the result of the TG analysis of pistachio
shell at a constant nitrogen flow rate of 100 mL/min that
shows the pyrolytic nature and thermal degradation of pista-
chio shell at increasing temperature. Like other biomass, pis-
tachio shell also contains cellulosic and hemicellulosic com-
ponents along with lignin, considering it to be lignocellulosic
biomass [19]. According to previously reported literatures, the
thermal decomposition of every component of lignocellulosic
biomass occurs at different temperature range; i.e., hemicellu-
lose decomposes in the range of 210–325 °C, cellulose de-
composes between 310 and 400 °C, and lignin degrades over
a wide range of temperatures i.e. from 160 to 900 °C [2, 37].
By considering the TG/DTG curve obtained at the heating rate
of 10 °C/min, the following observations were made.
The whole degradation process has been divided into three
zones i.e. drying, devolatilization, and charring [38, 39]. The
first zone indicates the removal of moisture, whereas the
Fig. 3 KAS integral model for
activation energy calculation of
pistachio shell
4853
second and third zones depict the thermal decay of
holocellulose (combination of cellulose and hemicellulose)
and lignin respectively. TG curve revealed that the initial mass
loss of around 5 wt% occurs from ambient temperature to 120
°C. This mass loss at low temperature indicates the removal of
moisture present inside the shells along with some light vola-
tile compounds present in it [27]. Similar nature is explained
by a small peak in the DTG curve on the very left-hand side of
the curve. Thereafter, the TG curve became stable up to 200
°C showing negligible degradation. The second zone depicts
the high rate of devolatilization from 200 to 400 °C which
indicates the breakdown of hemicellulose and cellulose pres-
ent in the pistachio shell. This zone is further subdivided into
two temperature range as slope changes beyond 320 °C. From
200 to 320 °C, degradation of mainly hemicellulose occurs
which can be depicted in the DTG curve as the first peak at
around 298 °C. As the biomass has moderate amount of hemi-
celluloses, thus a separate peak in the DTG curve was ob-
served. Beyond 320 °C, breakdown of cellulosic constituent
starts along with various complex reactions until 400 °C. The
second peak in the DTG curve at 353 °C indicates the
4854
Fig. 4 Starink integral model for
activation energy calculation of
pistachio shell
decomposition of cellulose as it is the most abundantly avail-
able in the pistachio shell. This whole stage can be referred as
an active pyrolysis zone as maximum devolatilization (around
70 wt%) occurred in this zone due to the complexity and
multi-step reaction mechanism [23, 40]. Since both hemicel-
luloses and cellulose are more easily degraded than lignin,
thus this major volatile release is due to degradation of these
two components of biomass. A wide range of volatile com-
pounds are released in this stage owing to breakdown of the
polymeric fraction that comprises the lignocellulosic biomass.
The third zone can be referred as a lignin decomposition zone
which occurs from 400 °C and continued up to 900 °C. Until
600 °C, further slow decomposition of biomass occurs
resulting in the release of more volatile components present
in it while beyond 600 °C, there is a long tail indicating neg-
ligible release of volatiles. Tailing section in the DTG curve
represents the degradation of lignin which occurs over a wide
range of temperature because of complexity and heterogeneity
in the structure of lignin [34]. These TG/DTG curves act as a
useful tool for finding the optimum temperature zone for ther-
mochemical conversion and for further calculation of kinetic
parameters. From the above observations, we can say that the
Fig. 5 Freidman differential
model for activation energy
calculation of pistachio shell
Biomass Conv. Bioref. (2022) 12:4847–4861
pyrolysis of pistachio shell can be done effectively in the
temperature range of 200–400 °C.
Similar trends of thermal degradation were also observed at
another three heating rates of 20, 30, and 40 °C/min as pre-
sented in Fig. 1 (b)-(d) with a slight increase in temperature as
the increase in heating rate occurs. The similarity in the nature
of the TG curves is at different heating rates indicating that the
reaction mechanism is not altered with change in the heating
rate. The maximum temperature of mass loss was predicted by
DTG curve which is represented by Tm, playing an important
role in finding thermodynamic parameters as presented in Eqs.
15-18. The value of Tm was 352.92 °C, 363.93 °C, 381.91 °C,
and 389.62 °C for heating rates of 10, 20, 30, and 40 °C/min
respectively calculated from the particular DTG curve.
Various researches on different biomass confirm this right
shift in DTG curve [38, 41, 42]. This increment in temperature
with increase in heating rate suggests that the characteristic
time for the devolatilization is low which results in random
degradation, ultimately decreasing the heating rate efficiency
as compared to low heating rate where gradual heat effects
occur with improved and effective internal heating of biomass
[23]. Increase in the heating rate contributes to the
Biomass Conv. Bioref. (2022) 12:4847–4861 4855

Table 3 Activation energy as a function of conversion at four different iso-conversional models

α (%) FWO Ea (kJ/mol) R2 KAS Ea (kJ/mol) R2 Starink Ea (kJ/mol) R2 Friedman Ea (kJ/mol) R2

10 114.07 0.983 111.01 0.981 111.30 0.981 139.40 0.995

15 132.36 0.974 129.89 0.967 129.78 0.968 168.96 0.989
20 126.46 0.967 122.06 0.959 123.95 0.963 142.59 0.946
25 125.78 0.975 122.71 0.971 122.96 0.971 150.21 0.976
30 150.70 0.993 148.82 0.991 149.08 0.992 186.68 0.981
35 180.24 0.996 179.94 0.996 180.09 0.996 229.32 0.991
40 174.01 0.996 173.41 0.996 173.67 0.996 200.15 0.989
45 201.20 0.977 201.58 0.971 201.43 0.972 204.47 0.917
50 181.34 0.954 181.00 0.948 180.88 0.949 215.22 0.962
55 183.61 0.956 184.71 0.955 183.61 0.953 204.37 0.983
60 189.71 0.968 188.05 0.965 189.96 0.966 177.99 0.991
65 166.34 0.965 163.12 0.961 164.43 0.960 147.96 0.976
70 187.59 0.787 151.26 0.973 151.98 0.972 164.87 0.978
75 166.85 0.955 165.68 0.955 165.58 0.952 241.61 0.958
80 252.68 0.932 263.88 0.931 265.77 0.932 277.74 0.937
Average 168.86 - 165.80 - 166.29 - 190.10 -

deceleration of thermal degradation processes towards high
temperatures because of thermal lag.
3.3 Kinetic study
TG analysis results were used to obtain the kinetic parameters
for thermal degradation of pistachio shell. For the effective
design and better functionality of any pyrolysis plant, the es-
timation of kinetic parameters is necessary. Due to the com-
plexity, heterogeneity, and multi-step reaction mechanism of
whole pyrolysis process, model-free methods were used for
the kinetic analysis as these methods do not require the pre
assumption of reaction mechanism [31].
Four iso-conversional models (FWO, KAS, Starink,
Friedman) were employed for determining the activation en-
ergy of the thermal decay process of pistachio shell at temper-
ature ranging from ambient to 900 °C in nitrogen environ-
ment. The present study shows the plot of four models in
Figs. 2, 3, 4, and 5 calculated from Eqs. 10-13 with increase
in conversion extending from 10 to 80% with a small

Table 4 Activation energy comparison with other biomass

Biomass Gas medium Heating rate (°C/min) Model Average activation energy (kJ/mol) Reference

Maize cob N2 5, 10, 20 FWO 186.06 [1]

KAS 185.39
Friedman 197.63
Starink 185.80
Corn stover N2 10, 20, 30, 40 FWO 191.57 [31]
KAS 181.66
Typha latifolia N2 10, 30, 50 FWO 182.67 [13]
KAS 184.58
Deodar sawdust N2 10, 25, 50, 100 FWO 180.60 [14]
KAS 179.20
Deodar sawdust Air 10, 25, 50, 100 FWO 95.3 [14]
KAS 89.9
Poplar wood N2 2, 5, 10, 15 FWO 158.58 [15]
KAS 157.27
Pistachio shell N2 10, 20, 30, 40 FWO 168.86 Present work
KAS 165.80
Starink 166.29
Friedman 190.10
4856
Fig. 6 Activation energy as a function of conversion at different iso-
conversional models
increment of 5% to get better results. The conversion below 10
and above 80% was disregarded to reduce the effect of mois-
ture and ash content. The activation energies were calculated
from the slope of trendline obtained at different conversions
for all four methods which are listed in Table 3. The value of
regression coefficient (R2) lies between 0.932 and 0.996
which was high enough representing appropriate fitting of
the model. The average value of activation energy computed
from four model-free methods (FWO, KAS, Starink,
Friedman) was 168.86, 165.80, 166.29, and 190.10 kJ/
mol, respectively. These activation energy values were
in close agreement with other biomass as compared in
Table 4. However, it was also noted that the activation
energy in the present work was much lower as com-
pared to other biomass which signifies the thermal de-
composition of pistachio shell occurred at lower temper-
ature (with minimum energy requirement) and proves
pistachio shell an appropriate biomass for bioenergy
generation through pyrolysis.
The nature of kinetic plot for all the iso-conversional
models was similar and it proves to be an acceptable method
for activation energy calculations. Figure 6 shows that the
activation energy from all the models was different with
Fig. 7 Correlation between
activation energies and
pre-exponential factors of
pistachio shell
Biomass Conv. Bioref. (2022) 12:4847–4861
conversion indicating that the thermal decomposition process
does not occur in single step. This is a complex, multi-stage
reaction scheme process in which a different degree of energy
is required as reaction proceeds [43]. Initially, activation en-
ergy increases up to 15% conversion then decreases and again
there was an increase in activation energy at 40%, then de-
creased up to 60% and again increased. This increase in the
activation energy beyond 60% suggests that less cellulose and
more lignin component is getting degraded in this zone. This
increasing-decreasing trend of activation energy with increase
in conversion shows the integrity and complexity in the nature
of biomass. Simultaneous change in reaction mechanism and
different degree of cracking or volatilization of pistachio
shell at different temperature and heating rates confirms
much reliance on activation energy upon conversion
[44]. Given that pyrolysis engrosses a bulk of different
reactions that occur simultaneously at each point of con-
version, each single point reaction contributes to the
overall reaction mechanism.
3.4 Compensation effect
Figure 7 demonstrates the relationship between Ea and loga-
rithmic pre-exponential factors (ln A) assessed at different
values of fractional conversion for pistachio shell degradation
based on FWO model results. A compensation effect is clearly
seen from the start to the final values of α with excellent fitting
factor. Generally, at the molecular level, increase in tempera-
ture enhances the vibration among the particles that leads to
the rise in stretching and bending of molecules. Moreover, at
higher temperature nucleation reaction weakens and diffusion
reaction dominates owing to an increase in biomass porosity.
The relationship between ln A and Ea is believed to be linear as
the reaction rate is assumed to follow an Arrhenius-type law
[45, 46]. The plot shows the linear trend with high fitting
accuracy (R2 = 1) signifies the validity of calculated kinetic
parameters.
Biomass Conv. Bioref. (2022) 12:4847–4861
3.5 Reaction mechanism
Biomass pyrolysis presents a multi-stage intricate reaction
phenomenon in which a series of side reactions occur simul-
taneously [47]. Estimating the single reaction model for the
whole process is somewhat challenging as complete reaction
follows different kinetics and mechanism with the change in
conversion as reaction proceeds [40]. However, efforts have
been made for predicting the reaction mechanism of solid-
state biomass pyrolysis of pistachio shell at the heating rate
of 10 °C/min by employing Criado method and Z master plot.
The experimental and theoretical curves were plotted at con-
version ranging from 10 to 80% by using Eq. 14, and reaction
models were selected from Table 1.
Figure 8 compares the experimental curve obtained with
the theoretical curves of 17 models. By comparing the nature
of the experimental curve with the different theoretical curves,
a close prediction of reaction mechanism has been made. It
can be analyzed that in up to 50% conversion, experimental
curve closely matches the theoretical curve with R2 and R3
mechanisms; thus, thermal degradation of pistachio shell fol-
lows the process of the 2nd-order and 3rd-order random nu-
cleation possessing two and three nucleus on particular parti-
cles respectively. During thermal degradation of biomass, as
conversion increases, cleavage of some weaker bonds occurs
as a result of devolatilization of cellulose components (studied
in TGA results) forming the chain of low molecular mass
which may serve as an active site for the growth of nucleus
and decomposition to occur [25]. As conversion increased up
to 70%, the experimental curve had the similarity with the D4
and P4 mechanisms which corresponds to the 3rd-order dif-
fusion model and power-law model respectively, as conver-
sion increases at high-temperature diffusion of gaseous prod-
ucts may take place [48]. Again in up to 80% conversion,
degradation of biomass follows R3 model corresponding to
the 3rd-order random nucleation. Based on the above
Fig. 8 Experimental and
theoretical plot for estimating the
reaction mechanism of solid-state
decomposition of biomass
4857
observations, it can be inferred that the pyrolysis reaction of
pistachio shell follows more than one reaction mechanism for
the overall conversion. The results showed good harmony
with previously reported results by Doddapaneni et al. [49],
Poletto et al. [50], and Vlaev et al. [51].
3.6 Thermodynamic study
The estimation of thermodynamic parameters is also a signif-
icant step along with kinetic parameters for the effective de-
sign of pyrolysis plant, as these parameters impart the basic
idea about the energy requirement, energy barrier, and ther-
modynamic equilibrium during pyrolysis reaction of biomass.
The pre-exponential factor A along with thermodynamic prop-
erties (enthalpy ΔH, Gibbs free energy ΔG, entropy ΔS) was
calculated from Eqs. 15-18 based on apparent activation en-
ergy at heating rate of 10 °C/min for all four iso-conversional
models (FWO, KAS, Starink, Friedman) in an inert atmo-
sphere. In addition, the purpose of the selection of the lowest
heating rate was to lessen the influence of interaction among
the components during thermal degradation reaction [1]. The
calculated results of all the parameters are listed in Table 5.
The frequency factor, often termed as pre-exponential fac-
tor, signifies the frequency of collision between reactant mol-
ecules along with the nature of complex formed. The values of
pre-exponential factor for different model-free methods were
in the range of 1.92 × 107–1.56 × 1019, 1.04 × 107–1.40 ×
1020, 1.10 × 107–2.03 × 1020, and 3.05 × 109–2.12 × 1021 s−1
for FWO, KAS, Starink, and Friedman methods respectively.
This broad variation in pre-exponential factor with increasing
conversion exhibits the complicated and heterogeneous nature
of biomass along with the indication of complex multi-step
reaction mechanism [28]. Pre-exponential factor having low
values (< 109) denotes closed complex formation and easier
decomposition, whereas high values (> 109) denote loose
complex formation [27]. The empirical frequency factor value
4858 Biomass Conv. Bioref. (2022) 12:4847–4861

Table 5 Pre-exponential factor and thermodynamic parameters for Table 5 (continued)

FWO, KAS, Starink, and Friedman methods of pistachio shell pyrolysis
FWO method
FWO method
α (%) A (s−1) ΔH (kJ/mol) ΔG (kJ/mol) ΔS (J/mol K)
−1
α (%) A (s ) ΔH (kJ/mol) ΔG (kJ/mol) ΔS (J/mol K)
70 3.72 × 1010 146.76 182.48 − 57.05
10 1.92 × 107
109.65 183.97 − 118.71 75 5.53 × 1011 160.28 182.03 − 34.74
15 7.48 × 108 127.80 183.20 − 88.48 80 2.03 × 1020 260.23 179.57 128.84
20 2.3 × 108 121.83 183.43 − 98.39 Average - 161.36 182.13 − 33.18
25 2.01 × 108 121.10 183.46 − 99.60 Friedman method
30 2.89 × 1010 145.96 182.52 − 58.39 10 3.05 × 109 134.98 182.92 − 90.18
35 1.01 × 1013 175.43 181.59 − 9.84 15 1.08 × 1012 164.40 181.92 − 31.96
40 2.94 × 1012 169.15 181.77 − 20.16 20 5.75 × 109 137.96 182.81 − 80.58
45 6.3 × 1014 196.25 181.02 24.34 25 2.62 × 1010 145.53 182.54 − 65.76
50 1.25 × 1013 176.33 181.56 − 8.35 30 3.59 × 1013 181.94 181.41 0.94
55 1.96 × 1013 178.54 181.49 − 4.71 35 1.59 × 1017 224.51 180.33 76.31
60 6.54 × 1013 184.58 181.32 5.20 40 5.13 × 1014 195.29 181.04 24.38
65 6.43 × 1011 161.16 182.01 − 33.30 45 1.20 × 1015 199.52 180.93 31.25
70 4.3 × 1013 182.37 181.38 1.58 50 9.97 × 1015 210.21 180.67 49.04
75 7.12 × 1011 161.55 181.99 − 32.64 55 1.18 × 1015 199.30 180.93 30.12
80 1.56 × 1019 247.14 179.83 107.51 60 6.45 × 1012 172.86 181.65 − 14.25
Average - 163.92 182.04 − 28.93 65 1.68 × 1010 142.78 182.62 − 63.91
KAS method 70 4.81 × 1011 159.65 182.05 − 35.67
10 1.04 × 107 106.59 184.11 − 123.82 75 1.78 × 1018 236.31 180.06 88.28
15 4.57 × 108 125.33 183.29 − 92.58 80 2.12 × 10 21
272.20 179.34 139.39
20 9.54 × 107 117.43 183.62 − 105.71 Average - 185.16 181.42 3.83
25 1.09 × 108 118.03 183.59 − 104.71
30 1.99 × 1010 144.08 182.59 − 61.50
35 9.49 × 1012 175.13 181.60 − 10.33 generally lies in the range of 104-1018 s−1 for the first-order
40 2.61 × 1012 168.55 181.79 − 21.14 reaction mechanism. Beyond 25% conversion, high value of
45 6.79 × 1014 196.63 181.01 24.96 pre-exponential factor, that is, greater than 109, depicts slower
50 1.17 × 1013 175.99 181.57 − 8.90 decomposition; thus, more energy is required for the reaction.
55 2.44 × 1013 179.64 181.46 − 2.91 It can be analyzed that at low conversion rate, the low value of
60 4.71 × 1013 182.92 181.37 2.48 pre-exponential factor indicates lower energy requirement for
65 3.40 × 1011 157.94 182.11 − 38.61 decomposition and vice versa. Furthermore, it was also inves-
70 3.23 × 1010 146.04 182.50 − 58.24 tigated that as conversion increases, increasing–decreasing
75 5.64 × 1011 160.38 182.03 − 34.57 trend of pre-exponential factor follows the similar trend of
80 1.40 × 1020 258.34 179.60 125.76 activation energy; i.e., at high activation energy, pre-
Average - 160.87 182.15 − 33.99 exponential factor was high and vice versa. Pre-exponential
Starink method value of pistachio shell was low as compared to maize cob
10 1.10 × 107 106.89 184.10 − 123.34 (105–1023 s−1) [1] and acacia nilotica (1010–1025 s−1) [25] and
15 4.47 × 108 125.22 183.30 − 92.76 high as compared to typha latifolia (109–1015 s−1) [13] and
20 1.39 × 108 119.32 183.54 − 102.57 corn stover (1011–1016 s−1) [31].
25 1.14 × 108 118.28 183.58 − 104.30 Enthalpy, a thermodynamic property of system, represents
30 2.09 × 1010
144.34 182.58 − 61.07 the energy stored in the system. Change in enthalpy deter-
35 9.78 × 1012 175.28 181.60 − 10.09 mines the loss or gain in energy of the system. With respect
40 2.75 × 1012 168.81 181.78 − 20.72 to biomass pyrolysis, enthalpy can be defined as the amount of
45 6.6 × 1014 196.48 181.01 24.72 heat required to convert the biomass into products i.e. bio-oil,
50 1.14 × 1013 175.87 181.57 − 9.10 char, and gas or to bring the biomass from room temperature
55 1.96 × 1013 178.54 181.49 − 4.71 to 900 °C for thermal degradation. The average values of
60 6.87 × 1013 184.83 181.31 5.62 enthalpy calculated for FWO, KAS, Starink, and Friedman
65 4.41 × 1011 159.25 182.07 − 36.45 methods were 163.92, 160.87, 161.36, and 185.16 kJ/mol,
respectively. Enthalpy values for all iso-conversional models
Biomass Conv. Bioref. (2022) 12:4847–4861
were almost similar, except Friedman method as there was a
slight increase in value. However, the enthalpy change was
seen to be maximum beyond 70% of conversion; i.e., more
energy is required to degrade the pistachio shell as mostly
lignin is left after the degradation of cellulose and hemicellu-
loses. The positive nature of enthalpy makes the pyrolysis of
pistachio shell an endothermic process. It was also noted that
at particular conversion, there was a difference in enthalpy and
activation energy of about 4-5 kJ/mol for all models. This
potential barrier, often regarded as the difference between
the biomass reactant and activated complex, was very low
which favors the formation of the activated complex and
shows the reliability of the pyrolysis process for energy pro-
duction in an energy-efficient manner [52]. As compared to
the change in enthalpy of the pyrolysis process of other bio-
mass such as maize cob (180.58 kJ/mol) [1], typha latifolia
(179.42 kJ/mol) [13], and corn stover (181.5 kJ/mol) [31],
change in enthalpy of pistachio shell pyrolysis was low for
KAS method.
Gibbs free energy is another essential thermodynamic pa-
rameter which denotes the available energy of biomass that
can be used for the chemical transformation along with the
formation of the activated complex. The change in Gibbs free
energy depends upon the change in enthalpy and change in
entropy. The average values of change in Gibbs free energy
calculated for FWO, KAS, Starink, and Friedman methods
were 182.04, 182.15, 182.13, and 181.42 kJ/mol respectively.
The ΔG values for corn stover (171.5 kJ/mol) [31], deodar
sawdust (165 kJ/mol), and rice husk (165-176 kJ/mol) [14] are
low when compared to the present study of pistachio shell.
This high value of ΔG reveals that pistachio shell has enough
useful energy to be converted into products and acts as prom-
ising biomass for biofuel production.
Molecular disorder and randomness of the system are de-
fined by one of the thermodynamic properties, termed as en-
tropy. The change in entropy exhibits both positive and neg-
ative values ranging from − 118.71 to 107.51 J/mol K, −
123.82 to 125.76 J/mol K, − 123.34 to 128.84 J/mol K, and
− 90.18 to 139.39 J/mol K calculated for FWO, KAS, Starink,
and Friedman methods respectively. The negative entropy
value symbolizes low intensity of randomness of the product
as compared to biomass. The negative value indicates some
structural changes needed to achieve a state of thermodynamic
equilibrium during the pyrolysis process [53]. The speed of
reaction kinetics and approach to thermodynamic equilibrium
may vary depending upon the change in the entropy. A low
value of entropy signifies the only physical and chemical
changes of material leading it to its own thermodynamic equi-
librium resulting in less chemical reactivity, whereas the high
value of entropy signifies increased reactivity and rapid for-
mation of the activated complex as the system is far enough
from thermodynamic equilibrium [32]. The value of entropy is
quite high as compared to values beyond 25% conversion
4859
which illustrates that at low conversion, the reaction rate is
faster as well as the decomposition, which is in agreement
with the pre-exponential factor values obtained. This co-
occurrence of both negative and positive values of ΔS with
the wide range also proves the complexity of the pyrolysis
process. These findings exemplify pistachio shell has a mas-
sive quantity of inherent energy and potential to be exploited
as a source for bioenergy production.
3.7 Future application
The present study confirms the potential of pistachio shell
towards bioenergy production via pyrolysis. The study can
be applied to get the optimum temperature range for pyrolysis
of pistachio shell for product generation. Pyrolysis basically
provides products in all three forms, i.e. bio-oil, biochar, and
non-condensable gas. However, the yield of products depends
upon the temperature chosen. The study reveals the produc-
tion of bio-oil to be high as compared to char and gas because
of high cellulose and high volatile content in pistachio shell.
These products find various applications as energy forms di-
rectly or indirectly. Bio-oil is mostly comprised hydrocarbons
and oxygenated compounds, so it can be used as a blend for
petrol or diesel and find applications in furnaces and diesel
engines. Bio-oil can also be further upgraded to reduce oxy-
gen content and can be used as stable lubricants. Solid bio-
char, which is also a by-product, finds application as a soil
additive in the form of manure and as a solid fuel or it can also
act as an efficient adsorbent for waste stream purification.
Non-condensable gasses also find application for further hy-
drogen production as mainly comprises syngas or as a fuel for
IC engines or boilers. The non-condensable gasses can also be
enriched for more hydrogen and carbon monoxide content
that can be used in Fischer-Tropsh synthesis for liquid hydro-
carbon production. The process describes the conversion of
waste to energy in the form of various products (bio-oil, bio-
char, and non-condensable gasses) which acts an energy
source for various industrial applications. The whole process
is feasible with respect to the economic point of view, as there
is a transformation of scrap i.e. pistachio shell (negligible eco-
nomic value, considering being waste) into the useful energy
products. Besides the energy generation, the advantage of
waste minimization can be made by reducing the landfill
scrap.
4 Conclusion
Non-isothermal TG analysis was performed to examine the
pyrolytic behavior and kinetics of pistachio shell pyrolysis at
four different heating rates (10, 20, 30, and 40 °C/min) in
nitrogen atmosphere from ambient temperature to 900 °C.
At the low heating rate, highest conversion was achieved at
4860
a particular temperature as compared to high heating rates. TG
curves showed three-stage thermal degradation processes
which are moisture removal, devolatilization, and lignin de-
composition. The optimum temperature range of 200–400 °C
was achieved where maximum mass decomposition takes
place. Iso-conversional models (FWO, KAS, Starink, and
Friedman) were employed for estimating the activation energy
and pre-exponential factors. The strong dependency of activa-
tion energy on conversion indicates the multi-stage reaction
mechanism of pyrolysis process. Prediction of the reaction
model was also done by Criado method which shows that
pistachio shell pyrolysis mainly follows the 2nd- and 3rd-
order random nucleation model along with the 3rd-order dif-
fusion model at different conversions. Thermodynamic prop-
erties (enthalpy, Gibbs free energy, and entropy) were
also calculated using four iso-conversional models.
Physiochemical properties, along with heating value,
were also calculated. HHV, low activation energy, and
low temperature range of maximum mass loss prove
pistachio shell a promising and potential lignocellulosic
biomass for production of biofuels with minimum ener-
gy requirements by adopting the principle of waste min-
imization. Further, high amount of volatile matter (~
80%) and low-temperature degradation range inferred
that pistachio shell can be used for hydrogen gas pro-
duction as well directly by pyrolysis or from steam
reforming of biofuel obtained from its pyrolysis.
Acknowledgments The authors are extremely obliged to the Chemical
Engineering and Technology department and Central Instrument Facility
Centre, Indian Institute of Technology, BHU, Varanasi for imparting
amenities towards the completion of this research study.
NomenclatureAcronyms HHV, Higher heating value (MJ/kg); TGA,
Thermogravimetric analysis; DTG, Differential thermogravimetry
Variables T, time (s); K, Reaction rate constant; Α, Fractional conver-
sion; mo, Initial mass of sample (mg); mt, Mass of sample at any time t
(mg); mf, Final mass of sample (mg); Ea, Activation energy (kJ/mol); A,
Pre-exponential factor (s−1); R, Universal gas constant; Β, Heating rate
(°C/min); T, Temperature (K); ΔH, Change in enthalpy (kJ/mol); ΔG,
Change in Gibbs free energy (kJ/mol); ΔS, Change in entropy (J/mol K);
K B , Boltzmann constant (1.381*10 −23 J/K); h, Plank constant
(6.626*10−34 J s)
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