1.

INTRODUCTION:

1.1 OVERVIEW:

An Adoption of Alternative Energy Solutions will be a step in the right direction.

India, a nation which is in constant move towards progress, must deal with a wide
variety of forms of pollution such as vehicle emissions and factories sewage as
well as the pollution that comes from agriculture practices. According to the last
WHO reports, several towns in India are among the world’s most polluted ones
with beyond the limit air and water pollution levels having adverse effects on the
population's health.

The situation gets more serious due to the heavy reliance on coal and oil for
generating electric power. Such combustion pollutes atmospheric air with carbon
dioxide (CO) and electric carcinogens like sulphur dioxide (SO), nitrogen oxides
(NOx), and suspended particulates, so triggers the clocking of Particulate Matter
(PM), acid rain, and adverse effects on human health. Although attempts are
shifted toward cleaner energy, fossil fuels are yet to be out of the scene and
continue to be mainly contributor to the greenhouse effect in the country due to
which several emissions are emitted.

To negate the negatives of pollution and to be less dependent on the finite

corresponding fossil fuel reserves, the need to discover alternate energy sources
and innovative technologies for sustainability can't be timely pressed.

1.2 PYROLYSIS:

Through pyrolysis biomass and plastics can be converted to fuels superbly

valuable thus providing a possible solution to the current waste dilemma we have
in our hands. because of them, the environmental issues concerning environmental
pollution and waste management will be very well dealt with. In pyrolysis, organic
materials are exposed to an oxygen-less high-temperature environment, often
inducing chemical devaluation and the production of bio-oil biochar and not to
forget syngas [3].

1
The selection of the right feedstocks, which determines a large share of the
performance in the pyrolysis processes, is vital to enrich and increase product
yields and properties. Areca nut husk fiber has been employed as it is a byproduct
of areca nut industry which is therefore plenty in its cellulose content. On the other
hand, polypropylene is the polymer which is widely used for packaging. Moreover,
they are catalysts for manufacturing through different ways and they are
assembled for their various properties and product blending that comes in pyrolysis
processes.

1.3 CO-PYROLYSIS:

Co-pyrolysis is the process of pyrolyzing various feedstock at once and begins with
a simple but powerful advantage: combined benefits compared to stand-alone
pyrolysis which for the most will be to go faster, save energy, or increase bio-oil
yield among others [8].

The blend of biomass and natural fiber like betel nut husk with polypropylene in
the co-pyrolysis aim to make product quality and use less energy at the same time
reduce environmental impacts.

It is the product of an action of the equivalent feedstocks’ features, which produces

a synergistic effect. As a natural catalyst, betel nut husk is the best alternative to
speed up the disintegration of polypropylene and stimulate the generation of
valuable compounds used for hydrocarbon production.

Thermogravimetric analysis (TGA) and kinetic analysis are the two focal processes
in the complex investigation of different type feedstocks and the maximisation of
process optimization. TGA demonstrates kinetic data that represents the weight
loss and thermal degradation of both betel nut husks and polypropylene, thus
facilitating the design of efficient co-processing systems [9].

In conclusion, the co-pyrolysis provides a possible exit from the conflict of

sustainability waste management and energy creation challenges in India. The
incorporation of wastes from biomass and plastic into pyrolysis. which is a co-
pyrolysis technology, is a very viable approach of fighting pollution, addressing
global warming and of enhancing efficiency in energy resource use.

2
2. LITERATURE REVIEW:

Gokul et al. [1] conducted a review on pyrolysis behaviour of areca nut husk. In
this research they discovered that there is a research gap in the areca nut husk’s
thermal degradation kinetics. There was a huge mass loss between 220°C ~370
ºC, the average activation energy was found out to be 230.707 kJ/mol. This
indicates the possibility of using areca nut husk as an alternative energy.

Tipboonsri et al. [2] studied the pultrusion process for making long glass fiber-
reinforced polypropylene (PP) pellets. Ponlapat performed TGA to find the
manufacturing process and properties of long fiber-reinforced thermoplastics. The
purpose of referring to this article is to find the TGA analysis of polypropylene.

Aboulkas et al. [3] aimed to demonstrate the utility of kinetic analysis methods in
determining the activation energy of thermoplastics' pyrolysis. They employed
different methods without prior assumptions regarding the reaction model, focusing
on HDPE, LDPE, and PP. The activation energy for PP was found to be in the
range from 179 to 188 kJ/mol. The purpose of referring to this article is to find the
activation energy of polypropylene (PP).

Deepak et al. [4] review underlines the imperative of innovative feedstock types
and conversion strategies because of non-renewable fossil resources exhaustion
and environmental concerns. The authors point to biomass and polymer co-
pyrolysis as well as the most prospective methods since the bio-oil characteristics
enhancement and valuable compounds generation are demonstrated.
Nevertheless, the issues of coking and catalyst deactivation require more in-depth
investigation, to evaluate feasibility for commercial use. The purpose of studying
this paper is to understand the co-pyrolysis process in depth.

Ekta Chaturvedi et al. [5], co-pyrolysis of waste Shorea robusta species and rice
husk was explored in the pursuit of qualitative and quantitative upgrading of the
produced oil. They discovered that the co-pyrolysis increased oil yields to a
maximum of 75% for rice husk and 69.9% for waste leaves. The TGA study implies
that the plastics decompose faster than biomass materials. The co-pyrolysis oil

3
contains about 75% aromatic fraction and 14% hydrocarbons. This paper was
referred to select suitable biomass feedstock.

Sakthivel Rajamohan et al. [6] provided the key and meaningful results of the
thermodynamics, and kinetic study of Tamarindus indica shell through the
thermogravimetric analysis (TGA). Our paper presents a detailed description of the
techniques and formulae used in kinetic analysis, therefore becoming a good
reading material for the research study we are conducting. This work served as a
guide to our investigation because it involved not only the principle but also
technique of TGA-based kinetic analysis, which contributed to more rigor and
accuracy.

Kaur et al. [7] employed thermogravimetric analysis (TGA) to determine kinetic

parameters. Their work provides valuable insights into applying TGA for kinetic
analysis, which served as a foundation for the present study on the betel nut husk
and polypropylene blend.

Moalin Hussein et al. [8], studied the mixing of both waste tires and plants to
generate liquid fuel. They tested different mixtures and found out that more fuel
and better quality are obtained by using both the materials together. They think
waste tires can help manage trash better. They tried mixing waste tires with walnut
shells to use the high lignin present in the shells. The purpose of referring to this
article is to find alternate biomass and plastic compositions for our project.

Sunarno et al. [9] researched how to improve bio-oil. They used palm oil waste
and old tires. They added calcium oxide to help. They found that bio-oil increases
by 1-3% with calcium oxide, but it drops after 3%. Co-pyrolysis at 400-500 °C
makes more bio-oil. The analysis found 94.01% hydrocarbon and 5.99%
oxygenated compounds in the bio-oil. This research helps us study using catalysts
in co-pyrolysis and explore different biomass and plastic combinations for our
project.

Huei Yeong Lim et al. [10], the co-pyrolysis of various wastes and plastics with
the intent of discovering liquid biofuels from the process of testing for high bio-oil
productions. An important observation from all that, the the residual wax formation
is also observed. Besides, the thermo-gravimetric analysis shows co-pyrolysis

4
promotes the formation of nitrogen-derived carbon dioxide and oxygen-trace
elements with only nitrogen as a tracer fluid while air sweeping is conducted during
the process. Such a measure entails an endeavor to reduce the expense of care
of a pure form of nitrogen or other than a neutral gas.

Bardalai et al. [11] studied the production and characteristics of biochar using
areca catechu tree dust through pyrolysis. Later, the biochar had higher heating
value (22.93 MJ/kg) due to the increase in the carbon content. Besides, the biochar
showed alkaline nature and a high pH value. From the FTIR analysis it was found
that it contains aromatic hydrocarbons. The BC's thermal decomposition
commenced at temperatures above 300 °C already, with limited degradation below
600 °C to yield lignin-rich composite. The XRD result was consistent with the
amorphous structure of the cellulose pad, displaying localized crystalline cellulose
and some traces of inorganic compounds. The review of this paper was to gain
knowledge about the areca nut plant.

Yusriah et al. [12] made an analysis of the physical, thermal, mechanical and
morphological properties of BNH fiber. They experimented the water content in
raw, ripe and mature betel nut husk. They performed TGA of the three cases and
found the weight loss over temperature change. This paper provides good insight
about the properties of betel nut husk such as moisture content, tensile strength,
mass loss, residue char% etc.,

Sun et al. [13] studied the pyrolysis of corn starch and PP, then they analysed the
co-pyrolysis of the both with and without using Zn-Al co-modified MCM-41 as a
catalyst. They found out that the activation energies with and without catalyst were
provided, showed a decrease of 28.07% for CS and 50.03% for PP, which
indicated that the catalytic effect reduced the activation energies.

Kalargaris et al. [14] experimented about the pyrolysis of polypropylene (PP) at

temperatures two temp. 700 °C and 900 °C and analysed the combustion and
emission of the resulting oils in a diesel engine. This study aimed at finding the
optimum pyrolysis temperature for polypropylene. The test concluded that both the
PP700 and PP900 oils were responsible for a stable engine operation and the
PP900 oil seemed to have a slightly better performance in such regard.

5
Nevertheless, even though both oils had longer ignition delay periods, lower brake
thermal efficiencies, they had worse emission of NOX, UHC, and CO relative to
diesel. However, a small amount of diesel in the blends boosted the performance
of them thus making them viable for long term use in diesel engines, still a higher
blending ratio of diesel was necessary for the PP 900 75 blend. This paper helped
at understanding Polypropylene and to gain insight about the real time use of bio-
oil from pyrolysis.

Nardella et al. [15] experimented the co-pyrolysis of lignocellulose and plastic

using the EGA-MS method. They found out that the activation energy of biomass
did not change by plastic presence, except for fir: polystyrene mixtures, where it
decreased by over 50%. Additionally, they found that the activation energies of
polyethylene mixed with wood was less than pure polyethylene, suggesting
biomass influence. They highlighted varying effects of biomass on polyethylene
and polystyrene and their thermal stability. The paper provided knowledge on co-
pyrolysis produced synergistic effects, thermal behavior.

Anca-Couce et al. [16] found that the variations of 20-30 kJ/mol for cellulose,
hemicellulose and beech wood pyrolysis led to the development of a method for
the reliable characteristic’s determination. Employing this technique decreased
deviations of activation energy to 10 kJ/mol or lower in all fragments overall except
lignin. The activation energy of the cellulose of beech wood, which is about 180
kJ/mol, is relatively lower than the pure cellulose. The hemicellulose showed the
activation energy of 150 KJ/mol and lignin with the activation energy value more
than 200 KJ/mol. This paper helped to gain insights about the TGA and methods
(KAS & FW0) to find the activation energies.

Bach et al. [17], the paper on Pyrolysis characteristics and kinetics of microalgae
involves microalgae samples of 5-20 mg, inert gas flow rates of 50-200 mL/min,
and heating rates of 5-40 °C/min. Many research groups utilize thermal-free
models to derive activation energy and pre-exponential factors, which makes it
difficult to accurately simulate thermogravimetric curves and provides mechanism
of reaction clarification. Since several cell reactions are more adequate as models
for decomposition of microalgae, they give a better fit and explain the reactivity of
microalgal components. The series reaction model is off the beaten track as it tries

6
to fit in TGA only for isothermal studies therefore, the DAEM is off the beaten track,
but it shows promise.

Prakash Parthasarathy [18] aimed to demonstrate that the selected feedstock

samples are capable of being used in pyrolysis to produce biochar. They performed
thermogravimetry Analysis 50 °C/min to degrade from ambient temperatures to
950 °C. Then they undergo the pyrolytic kinetics of the CD, DS, and CD-DS blend
were determined by using the Friedman, FWO, KAS, and Starink methods at α
ranging from 0.1 to 0.8. The purpose of referring to this article is to gain knowledge
about various kinetic analysis methods.

Katarzyna Slopiecka et al. [19] invoived Poplar TGA analysis done with different
heating rates. Then they show the determination of differential thermogravimetric
data. And involved in Determination of kinetic constants describing biomass
devolatilization. The purpose of this article is to show the Thermal decomposition
of poplar wood proceeds in three steps as water evaporation, passive and active
pyrolysis. It was found that the mainly pyrolysis process occurred at about 450–
740 K.

Soria-Verdugo et al. [20] the research explores how Pyrolysis kinetics changes
while using TGA at different heating rates. Over that, it interests the researcher
how the heating rate impacts the agricultural biomass pyrolysis. The fourth
contents consist of biomasses which were examined at the nine values of heating
(10-40 K/min). Unknown thermo-reaction temperatures and heating rates
contribute to kinetic parameter uncertainty.

Lemaire et al. [21] investigated coal and poplar wood co-pyrolysis using
thermogravimetric analysis (TGA). Their findings revealed a significant decrease
in reaction temperature and activation energy with the addition of wood to coal,
suggesting potential synergistic effects. Further studies are recommended to
derive adapted kinetic parameters for simulating high heating rate devolatilization
processes.

Wang et al. [22] investigated co-pyrolysis models for Polylactic Acid (PLA) and
wood composites. They used poplar wood, PLA, and PLA/wood composites with

7
mass ratios of 1:3, 1:1, and 3:1 for TGA and cone calorimeter tests. The results
showed that PLA/wood composites reduced the peak temperature of co-pyrolysis
by 21.7–23.7 K compared to neat PLA. Three methods accurately predicted the
measured Heat Release Rates (HRRs). Micro-scale TGA tests at heating rates of
5, 10, and 20 K min^−1 and bench-scale cone calorimeter experiments at heat
fluxes of 20 and 35 kW m^−2 were conducted.

Singh et al. [23] analyzed

pyrolysis and co-pyrolysis of corn cob (CC) and polyethylene (PE) using TGA. They
found a 50% reduction in residue during co-pyrolysis compared to CC pyrolysis
alone. Activation energy was determined through iso-conversional methods. Third
order reaction, 3D diffusion Jander, and Ginstling–Brounshtein (D4) models fit best
for CC pyrolysis, PE pyrolysis, and co-pyrolysis, respectively.

Fardi et al. [24] investigated the co-pyrolysis of potato peel and Sargassum
angastifolium to enhance fuel yield and quality. TGA conducted at heating rates of
5, 20, and 50 °C/min revealed increased bio-oil production, peaking at 27.1 wt% in
a blend of 25% Sargassum angastifolium and 75% potato peel. GC-MS analysis
showed improved bio-oil quality, particularly with a 75% Sargassum angastifolium
blend where acidity levels halved. The onset of pyrolysis decreased to 233.5 °C
with Sargassum angastifolium addition, enhancing char removal efficiency.

Kyu Choi et al. [25] investigated the pyrolysis of coffee grounds, a promising
biomass feedstock with high calorific value. They explored enhancing oil quality by
mixing with synthetic polymers like polyethylene or polystyrene. Their research
employed a tilted-slide reactor for fast pyrolysis with a feeding capacity of 20 kg/h,
notable for its absence of fluidizing gas for hot sand conveyance. While elemental
composition and moisture content remained stable with increasing polystyrene
ratio, the transformation of polystyrene into vapor phase during pyrolysis conditions
requires further investigation. The simulation results are expected to inform the
scale-up of polystyrene pyrolysis in reactors.

8
3. MATERIALS AND METHODS

3.1 FEEDSTOCK PROCESSING:

3.1.1 BETEL NUT HUSK:

Digging into betel nut husk (BNH), sheathing material of betel nut or areca nut, is
not the only option available but it is rather a great one to associate co-pyrolysis
processes with polypropylene. The deliberate choice of betel nut husk as a
feedstock is the outcome of premeditation towards its properties, availability, and
destructive effects on the co-pyrolysis process among others.

Dried betel nut husk, shown in Fig. 3.1 is a biomass available as a residue of the
industry, especially in areas where betel nut cultivation occupies a primary position,
for example, Southeast Asia and partly Africa. The wide availability of it provides a
good opportunity for its use in a cost-effective and sustainable manner in the
biomass utilization sector [1].

Betel nut husk is highly content in cellulose, a compound that is complex in its
nature and serves as a carbon source in the process of thermochemical
conversion. Materials that happen to be cellulose-based can be considered ideal
precursors for co-pyrolysis reaction as these feedstocks tend to produce
substantially high yields of oil, char, and syngas as bio-products. The chemical
composition of the betel nut husk is shown is Table 3.1.

Beneath its unique cellular structure, betel nut husk can be efficiently decomposed
enabling it to remain as one of the principal feedstocks for pyrolysis. Its fibrous
structure is responsible for rapid heat transfer and uniform heating across the
biomass feedstock. As a result, improved kinetic and yield of products are obtained
because of the process.

9
 Fig. 3.1: Betel Nut Husk

Utilization of betel nut husk fibre for fuel synthesis through co-pyrolysis not only
elevates the fuel dependence on fossil fuel thereby reducing the combustion waste
accumulation. Joint pyrolysis or gasification of ready-to-use fibers from betel nut
husks and polypropylene would not only reduce the greenhouse gases in a manner
but also promote a circular economy by this conversion of biomass into essential
bio-based products.

Bio oil from betel nut husk fibre and polypropylene mixed pyrolysis can be
employed as a full suite of renewable feedstock for the chemical industry e.g.
biofuel production, chemical synthesis and the biorefinery. The char produced
during the pyrolysis process can serve as a soil amendment that will enhance the
soil fertility and carbon sequestration and thereby help us achieve sustainable
farming practices.

The conclusion in totality is that a combination of betel nut husk combustion

(biomass utilization) and the production of bio-based compounds from (co-
pyrolysis) opens the door to sustainable biomass utilization and the manufacturing
of bio-based products. It is rich; its high cellulose content, key synergy with
polypropylene, and environmental benefits suggest that it is a resourceful material
that can be employed for the development of biomass conversion technologies!

10
 Composition Average amount (%)

α-Cellulose 35.22

Hemicellulose 28.89

Lignin 19.08

Extractives 16.81

Table 3.1: Chemical composition of betel nut husk [1].

Taking data from Gokul et al. (2019), the TGA graph shown in Fig 3.2 of areca nut
husk [1]. This graph offers insights into the thermal behaviour and kinetics of
pyrolysis of areca nut husk. This helps in comparing the results with the co-
pyrolysis of betel nut husk alongside other materials [12].

Fig. 3.2: TGA of betel nut husk [1]

11
The pyrolysis behaviour of areca nut husk investigated using thermogravimetric
analysis. The major mass loss (44.4 wt%) of AH was found to be in the temperature
range of 220–370ºCwherein rapid decomposition of AH took place. The kinetic
parameters for the pyrolysis of arecanut husk, viz. distribution curve of activation
energy, f(E), and the activation energy dependent frequency factor, k0(E), were
determined by the distributed activation energy model (DAEM). The Peak of f(E)
curve for the areca nut husk is obtained at 240 kJ/mol, whereas the activation
energy ranged from upto 514.08 kJ/mol. [1]

3.1.2 POLYPROPYLENE:

Polypropylene is one of the first thermoplastics worldwide that is utilized to produce

packaging, screws, construction, and only consumer products. Its abundance
being not delectable, as it is erroneously streamed from different industrial
processes and consumer activities.

Propene, a polypropylene constituent, is mostly carbon and hydrogen atoms thus

it serves as a low-value carbon basis for pyrolysis. In co-pyrolysis, polypropylene
gets heated resulting in the formation of hydrogen-rich products which are
unsuitable being used in many industrial boilers!

Disability in melting nature of polypropylene from polypropylene at the time of co-

pyrolysis is the reason which does narrow the process and handling. The high
melting point and low fluidity of inorganic materials at high temperature limit molten
metal infiltration as well as the interaction of the biomass feedstocks which lead to
non-heating and decreased outputs!

The bio-oil, biochar, and syngas generated by co-pyrolysis of combined

polypropylene and biomass other feedstocks has multiple ways of utilisation in
various industrial applications [5]. Among many other things, bio-oil can be
processed as aviation fuel or chemical intermediates, while biochar can be.

12
 Fig. 3.3: Polypropylene

In fact, the graph of the thermogravimetric analysis of polypropylene in the

research paper by Tipboonsri et al., [2] allows us to draw the line of the thermal
stability of the material under different temperatures. One can refer to the
decomposition behavior and thermal properties of polypropylene as to the subtext
of your insert overarching study or discussion. Consequently, we can use this
graph to suggest new information regarding thermal performance.

Fig. 3.4: TGA of polypropylene [2]

The research paper on Thermal degradation behaviors of polyethylene and

polypropylene. Part I: Pyrolysis kinetics and mechanisms by A. Aboulkas, K. El
harfi and A El Bouadili found out the activation energy of PP as 179–188 kJ/mol.
[3].

13
3.2 ANALYSIS METHODOLOGY:

3.2.1 THERMOGRAVIMETRIC ANALYSIS:

Thermogravimetric analysis (TGA) was done (by means) of SHIMADZU DTG-60

apparatus. The experiment involved subjecting the samples to four distinct heating
rates: 20, 25, 30, and 35 °C/min respectively — starting from normal temperature
and going up to 900°C. The DSC-TGA setup was first loaded with 10 mg of the
sample and properly aligned in an alumina microbalance of the latest technology.
Nitrogen gas served as the sweeping gas, maintaining a flow rate of 200 ml/min
throughout the analysis.

3.2.2 KINETIC MODELING:

To explore the kinetic behaviour of the feedstock, different model-free iso-

conversional methods, namely the KAS, Starink, and Ozawa-Flynn-Wall models,
were selected. The discrepancies observed in their results were analysed and
presented. The thermal decomposition of the feedstock is given by the Equation 1.
𝑑𝛼
= 𝑘𝑓 (𝛼 ) (1)
𝑑𝑡

Here, α = mass transfer rate given by Equation 2,

k = The reaction rate given by the Arrhenius equation given in Equation 3,
f(α) is a kinetic model function and varies depending on the model used.
𝑚𝑖 −𝑚𝑡
𝛼= (2)
𝑚𝑖 −𝑚𝑓

𝐸𝑎
𝑘 = 𝐴𝑒 − 𝑅𝑇 (3)
Where T = Temperature in Kelvin,
A = pre-exponential factor,
Eα = activation energy,
R = universal gas constant.
Kissinger-Akahira-Sunose (KAS) method is based on the Eq.4
𝐸𝑎
𝐴𝑅𝑇2
𝑔 (𝛼 ) = 𝑒 (−𝑅𝑇) (4)
𝛽𝐸𝑎

On solving Eq.4 by rearranging and taking natural logarithms on both sides, we get
Eq.5

14
 𝛽 𝐴𝐸 𝐸
ln (𝑇2 ) = ln (𝑅𝑔 (𝑎𝑎)) − 𝑅𝑇 (5)

We are now able to generate a diagram using ln (β/T2) as the ordinate and 1/T as
the abscissa. The activation energy (Ea) can then be obtained from the slope of
the plot.

For the cycle of LTE, the FWO (Flynn-Wall Ozawa) method takes this link to be
Eq.6.

1.052𝐸𝑎
𝐴 (− )
𝑔 (𝛼 ) = 𝛽 0.00484𝑒 𝑅𝑇 (6)

On solving Eq.6 by rearranging and taking natural logarithms on both sides, we get
Eq.7
𝐴𝐸 𝐸
𝑙𝑛(𝛽 ) = 𝑙𝑛 𝑅𝑔 (𝛼) − 5.331 − 1.052 𝑅𝑇𝑎 (7)

Applying in situation of activation energy is possible via utilizing two factors. i.e. the
plot of ln(β) and 1 / T, the slope of which gives the value of activation energy (Ea).

Integral rate method known from the Starink model as given in (Eq.8).

𝛽 1.0008𝐸𝑎
𝑙𝑛 ( ) = 𝑐𝑠 − (8)
𝑇1.92 𝑅𝑇

This approach has demonstrated superior accuracy compared to both the KAS and
FWO methods. A plot of ln (β/T0.8) vs 1/T renders the activation energy (Ea).

3.2.3 THERMODYNAMIC ANALYSIS:

Thermodynamic parameters like enthalpy (ΔH), entropy (ΔS), and Gibbs free
energy (ΔG) are crucial in assessing the thermal characteristics of the feedstock
during co-pyrolysis. These values are essential for evaluating the viability of
utilizing the feedstock in co-pyrolysis and heat generation [7]. Equations 9 to 11
are employed to compute these thermodynamic parameters.
𝛥𝐻 = 𝐸𝑎 − 𝑅𝑇 (9)
𝐴ℎ
∆ 𝑆 = 𝑅 ∗ ln ( 𝐾𝑇) (10)

𝛥𝐺 = 𝛥𝐻 − 𝑇𝛥𝑆 (11)

15
In this context, K represents Boltzmann’s constant (1.38 × 10-23 J K-1), h stands for
Planck’s constant (6.63 × 10-34 J.s), Ea denotes the activation energy determined
from graphical analysis, and A signifies the pre-exponential factor.

3.3 FEEDSTOCK PREPARATION:

The procedure performed was the filling in of the feedstock for the TGA analysis
by preparing betel nut husk and polypropylene and feeding them into the TGA
machine.

3.3.1 PREPARATION OF BETEL NUT HUSK:

The coarse fibre of betel nut husk had to be grinded into a fine powder before
subjected to thermogravimetric analysis (TGA). The initial stage was subjecting the
betel nut husk to a hydraulic machine where high pressure was applied to the husk
using a press. This gentle pounding action of the striker generated through the
press broke the stubborn exterior otherwise the betel nut pod and so began the
process of further processing of it.

Fig. 3.5 Betel nut husk powder

The means of further processing is also a grinding mill in which crushed betel nut
shells are being grounded. Moreover, the grinding of the crushed swelling was of

16
utmost importance to change in homogeneous enormous chunks into an even
powder with appropriate sizes as shown in Fig. 3.5. The TGA machine takes the
finely powdered betel nut husk that was produced through the grinding process
and additionally uses this powder to play a role of adding surface area of biomass.
This enhancement in the reaction surface could take an important part of the entire
exposure of all biomass constituents to improve the level of the pyrolysis reaction.
Hence, its performance is high and precise.

3.3.2 PREPARATION OF POLYPROPYLENE:

While the husk fiber of betel nuts was processed in a similar way, polypropylene,
a thermoplastic polymer, also underwent intermediary steps to render it suitable
for co-pyrolysis studies. Much like the residue from betel nuts, the polypropylene
needs to be powdered to be fit for analysis by TGA. The fine grinded polypropylene
powder is shown in Fig. 3.6.

Fig. 3.6 Grinded Polypropylene Powder

This was feasible by grinding the polypropylene material in the special milling unit.
The grinding process became the method of the production of polypropylene
microparticles with a high degree of material size uniformity [13]. The direction of
particle size consistency, which helped in the uniform mixing of polypropylene with
betel nut husk during co-pyrolysis experiments, was attributed to uniform mixing.
In addition to that, the conversion of polypropylene to powder particles enhanced

17
the sample’s response to the thermal decomposition of biomass components,
therefore, it is evident that synergistic effects existed between the feedstock
materials [15].

After a series of steps, the Betel-nut husk fibres and polypropylene underwent a
chemical transformation, turning them into fine powders to be used for the complex
TGA analysis and further co-pyrolysis work.

3.4 PREPARATION AND MIXING OF FEEDSTOCK MATERIALS:

Crushing the fibers of betel nut husk and polypropylene equally were done and the
weights were further measured using a precision weighing machine. The aim was
to keep an equal ratio of these two feedstock materials, enabling the use of a
balanced blend for subsequent experiments and subsequent ones. Each feedstock
material was weighed to achieve a total mass of 5 grams, with 5 grams of betel nut
husk and 5 grams of polypropylene used in a 1:1 ratio.

3.5 THERMOGRAVIMETRIC ANALYSIS SETUP AND PROCEDURE:

The betel nut husk and polypropylene powders were well blended together which
might achieve an ideal homogeneous mixture after being thoroughly mixed. The
critical mixing step of these two feedstock materials was necessary to achieve the
uniform distribution of the sample through the material surface and the same
thermal decomposition behaviour during the TGA experiments.

Once the blended powders of betel nut husk and polypropylene were meticulously
prepared and mixed, they were subjected to thermogravimetric analysis (TGA)
using a dedicated instrument. TGA is a powerful analytical technique employed to
investigate the thermal decomposition behavior of materials under controlled
temperature and atmosphere conditions.

In this experiment, the blended powders were loaded into the sample holder of the
TGA instrument, which operates under an inert atmosphere of nitrogen gas. The
use of nitrogen gas ensures an oxygen-free environment, preventing oxidation
reactions and accurately characterizing the pyrolysis behavior of the feedstock
materials.

18
 Fig. 3.7 Thermogravimetric Analyzer

The TGA instrument shown in Fig. 3.7 then subjected the sample to a programmed
temperature ramp, gradually increasing the temperature from ambient conditions
to elevated levels [22]. As the temperature increased, the thermal decomposition
of the blended powders commenced, leading to the release of volatile products
and subsequent weight loss.

During the TGA experiment, the instrument continuously measured the weight of
the sample as a function of temperature or time, providing valuable data on the
thermal stability, decomposition kinetics, and mass loss profiles of the blended
feedstock. The resulting thermogravimetric curve depicted the weight percentage
as a function of temperature, revealing distinct decomposition stages and
characteristic thermal events associated with the pyrolysis process [19].

By employing TGA under nitrogen atmosphere, the experiment aimed to elucidate

the synergistic effects between betel nut husk and polypropylene during co-
pyrolysis. The obtained TGA data served as a crucial tool for understanding the
thermal behavior of the blended feedstock and optimizing process parameters for
efficient conversion of biomass-plastic mixtures into valuable energy products.

19
4. RESULT AND DISCUSSION:

4.1 THERMAL ANALYSIS:

In this project, the feedstocks, consisting of betel nut husk and polypropylene in a
1:1, weighted, ratio, were carried through by thermogravimetric analysis (TGA),
which involved the use of a temperature-controlled heating process. In contrast to
the TGA illustrated in this drawing, different heating rates encountered included 20,
25, 30, and 35 °C per minute with nitrogen as the inert material [22].

Implementation of the TGA turns out to be very essential as it highlights the

temperature dependent decomposition behaviour of the blended feedstock, and
subsequently used in describing the pyrolysis kinetics. While the control of heating
rates affected the high temperature feedstock was surprisingly measurable.

The TGA analysis was performed to examine the thermal degradation temperature
of the combined betel nut husk fibre and polypropylene feedstock under different
temperatures' rises (20˚C/min, 25˚C/min, 30˚C/min, and 35˚C/min) for the blended
composite materials.

At a heating rate of 20°C/min, a substantial weight loss of approximately 98.8%

was observed at 900°C, signifying significant decomposition. Figure 4.1 illustrates
the conversion of biomass into volatile products, evident from the sharp curve
observed between 250°C to 500°C, indicating pronounced weight loss during rapid
pyrolysis [17].

Upon heating the initial sample weight at 100% with a heating rate of 25°C/min, at
901°C the sample weight loss strives to 100% with only 98.7% remaining. The
illustration indicated rapid pyrolysis kinetics with 87% of the feedstock being
converted into volatile products between 230℃ to 550℃ with the variation in the
given range.

Similary during 30°C/min heating rate of the feedstock, only 86.6% remained at
901°C, thereby strongly suggesting depolymerization and volatilization of the
feedstock components. The graphical plots illustrated a sharp fall in weight loss in

20
the temperature range 230°C to 550°C, indicating extremely fast kinetics within the
said range [22].

Fig. 4.1 TGA at different heating rates

With the highest heating speed of 35°C/min, the initial temperature of the sample
is 47.86°C, the total sample weight taken as 8.52 grams in 1:1 ratio. Under that
given temperature the sample would begin to lose its mass which began to
decrease gradually [. As the temperature was close to 901°C the weight loss was
almost 100%. The diagram (Figure 4.1) illustrated the most considerable reduction
in weight loss between 300 °C and 500°C, which renamed a vital stage of pyrolysis
where there is a high rate of degradation of feedstock.

The TGA experiments provided valuable insights about the weight loss at different
temperature range which is shown in Table 4.1 and also the thermal decomposition
behaviour of the biomass-plastic feedstock. Moving forward, these results will be
used to calculate the kinetics of the co-pyrolysis process and determine
thermodynamic parameters.

21
 Fig 4.2 DTG curve for various heating rate

From DTG curve shown in figure 4.2 we can analyse many features. The
temperature at which pyrolysis is about to start is called initial temperature.
The peak maximum temperature is simply the temperature at the peak of the
DTG curve is noting the temperature at which maximum weight loss occurs.
It was stipulated peak temperature was at 500 ˚°C and derivative weight of
0.013 %/ ˚C.

Table 4.1. Weight Loss% at different temperature range

Heating rates
Temp. range 20°C/min 25°C/min 30°C/min 35°C/min
0-200°C 3.03% 3% 3.02% 4%
200-550 °C 79.7% 80.5% 77% 55.86%
550-900°C 10.6% 3.6% 6.6% 8.11%

22
4.2 KINETIC ANALYSIS:

To obtain an accurate activation energy of the feedstock (a mix comprising betel

nut husk and polypropylene in 1:1 ratio), we employed some models in line with
the recommendations of ICTAC at different heating rates. Applying equation (5) of
the Kissinger-Akahira-Sunose (KAS) method, we plotted the 1000/T vs ln(ß/T²)
graph in figure 4.3. The activation energy could be determined from this graph [15].

Fig. 4.3 KAS plot at various conversion ratios

The other one is the Flynn-Wall-Ozawa method of Equation (7) which was we used,
to sketch a diagram between (1000/T) and ln(β) on figure 4.4 for activation energy
calculation.

23
 Fig. 4.4 OFW plot at various conversion ratios

Furthermore, by applying the Van-der-Waals-Linek combination with equation (8)

they drew a curve between 1000/T and in(β/T1.8) to determine the activation energy
show in figure 4.5.

24
 Fig. 4.5 Starink plot at various conversion ratios

Since these methodologies employ experimental data at identical conversion

levels, they are collectively referred to as iso-conversional techniques. The main
benefit of iso-conversional methodologies lies in their capacity to consider
variations in both the reaction mechanism and activation energy, in addition to
conversion levels.

25
 Fig. 4.6 Change in Ea across all conversion ratio

Figure 4.6 illustrates the variation of activation energy across all iso-conversional
models at different conversion ratios. Notably, both the KAS and Starink methods
produce similar results, while the OFW method shows slightly higher values.
However, all three methods ultimately converge to comparable outcomes. The data
indicates no substantial deviation compared to other iso-conversional model-free
methods [20]. Particularly, a notable variation in activation energy range is
observed within the conversion ratio range of 0.4 to 0.6, as evident from Figure
4.6.

26
Table 4.2. Variation of activation energy of Betel Nut Husk and Polypropylene
found using iso-conversional model-free methods.

KAS STARINK FWO

Conversion
ratio (α) Ea Ea Ea
R2 R2 R2
(kJ/mol) (kJ/mol) (kJ/mol)

0.2 257.98 0.88 258.27 0.88 272.65 0.89

0.3 249.42 0.97 255.12 0.97 255.66 0.97
0.4 266.19 0.9 266.39 0.9 264.75 0.91
0.5 214.33 0.91 191.42 0.79 254.47 0.98
0.6 213.66 0.91 214.29 0.92 215.27 0.92
0.7 191.22 0.87 194.16 0.88 195.2 0.89
0.8 179.16 0.8 179.74 0.8 182.48 0.81
0.9 143.41 0.95 144.21 0.95 148.57 0.96

Average 214.42 0.89 212.95 0.88 223.63 0.91

The average activation energies found in our research was 214.42 kJ/mol by using
KAS method, 213.9 kJ/mol by applying Starink model, and 223.63 kJ/mol by
employing FWO method. All this data is shown in Table 4.2. Interestingly, they do
not greatly differ amongst themselves reflecting the similarity in the results obtained
from all methods. The R2 in the equation would indicate how well the fit worked
whereas a higher value in the R2 near 1 will show that the fit has been good.
Table:4.2 indicates that there is maximum R2 value between 0.3 to 0.6 indicating it
has a good fit [15].

4.3 THERMODYNAMIC ANALYSIS:

The thermodynamic parameters like enthalpy, entropy and Gibbs free energy of
the feedstock (betel nut husk and polypropylene) using the equations (9), (10), and
(11) can be applied in computations. The variation of these thermodynamic
properties concerning iso-conversational model-free methods at different

27
conversion ratios is depicted in the plotted Figures 4.7, 4.8 and 4.9 respectively.

Fig. 4.7 Change in ΔH across all conversion ratio

28
 Fig. 4.8 Change in ΔS across all conversion ratio

The fluctuation in enthalpy illustrates the difference in energy needed to break

bonds versus the energy released from the formation of new bonds during
chemical reactions. The downward trend depicted in Figure 4.8 suggests a
decreased energy requirement to break bonds as the conversion ratio rises,
indicating the exothermic nature of the reaction. This observation corresponds to
the downward trend observed in Figure 4.9 for Gibbs free energy, which is also
verified in [6]. Conversely, the shift in entropy indicates the level of instability within
the system. The negative ΔS value at higher conversion ratios indicates minimal
resistance and reduced disorderliness.

29
 Fig. 4.9 Change in ΔG across all conversion ratio

It is observed that the average ΔH, ΔS and ΔG values using KAS method was
found out to be 208.13 kJ/mol, 23.79 J/mol K and 190.75 kJ/mol respectively.
Similarly, ΔH, ΔS and ΔG were found out to be 206.66 kJ/mol, 23.08 J/mol K and
189.77 kJ/mol for Starink method and 217.3 kJ/mol, 33.07 J/mol K and 192.9
kJ/mol respectively for OFW method respectively. The similarity in the obtained
thermodynamic values indicates the credibility of results which is clearly depicted
in Table 4.3.
Table 4.3: Consolidated Results

KAS STARINK OFW AVERAGE

Ea (kJ/mol) 214.42 212.95 223.63 217
ΔH (kJ/mol) 208.13 206.6 217.4 210.71
ΔS (J/mol K) 23.79 23.08 33.07 26.64
ΔG (kJ/mol) 190.75 189.77 192.9 191.14

30
4.4 SYNERGETIC EFFECT:

A synergistic effect is a phenomenon of action when the combined action of two or

more components results in an outcome that is greater than a sum of the results
of the components [15]. In other words, it suggests that the combination of various
biomass mates or the adding of additives can significantly increase the
effectiveness of the process, as well as the goods quality of the pyrolysis process
[21].

This project focused into the feasibility of utilizing a novel biomass blend of betel
nut husk and polypropylene, as a potential fuel source. Comparative analysis
between the pyrolysis of betel nut husk alone and the co-pyrolysis of betel nut husk
and polypropylene revealed intriguing insights. While the activation energy for betel
nut husk alone was notably high at approximately 515 kJ/mol, the incorporation of
polypropylene in the Feedstock significantly reduced this value to around
214.kJ/mol. This substantial reduction underscores the synergistic effect of
blending polypropylene, which appears to enhance the thermal decomposition
efficiency of the feedstock. Furthermore, the calculated thermodynamic variables,
including enthalpy (ΔH), entropy (ΔS), and Gibbs free energy (ΔG), reinforced the
superiority of Feedstock as a biomass fuel, with favourable values indicating its
potential for efficient biofuel transformation. In summary, our findings underscore
the promise of Feedstock as a competitive alternative for biofuel production,
offering a sustainable solution towards mitigating environmental challenges.

31
5. CONCLUSION:

With the focus on Feedstock, a novel biomass of betel nut husk and polypropylene,
this thesis explored the possibility of using this resource as a fuel through a thermo-
kinetic analysis. The research shows that the switching of Feedstock is indeed
feasible for this project.

By thermogravimetric analysis (TGA) method, the decomposition was investigated.

The analysis revealed a three-stage decomposition process: the course of
decomposition is divided into 3 stages, namely: the first one - moisture loss (40-
230 °C), the second - volatile compound decomposition (250-550 °C) and the third
one - carbonization (above 550 °C).

The activation energy, as a key parameter to explain the decomposition kinetics,

was calculated through a series of equations and found out that it was much lower
for Feedstock – Betel nut husk and Polypropylene (about 214 kJ/mol) than that of
using betel nut husk only (around 515 kJ/mol). This significant reducing process
shows that the Feedstock decomposition is already favorable and hence, this
Feedstock can be easily transformed into biofuels.

In addition, thermodynamic variables of enthalpy (ΔH), entropy (ΔS), and Gibbs

free energy (ΔG) were also calculated for Feedstock, which provided further
evidence for its superiority as a biomass fuel. As a result, the enthalpy, entropy
and free energy for the feedstock were estimated to be around 210 kJ/mol, 26.64
J/mol K and 191.14 kJ/mol respectively.

Therefore, this study has successfully outlined the possibility of Feedstock (betel
nut husk and polypropylene blend) as an alternative and competitive biofuels
option due to its positive degradation features and thermodynamic properties. This
lays a foundation for further research and development that leads to the use of
Feedstock as an alternative to biofuel production which creates a sustainable
environment.

32
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