247

A publication of

CHEMICAL ENGINEERING TRANSACTIONS

VOL. 97, 2022 The Italian Association
of Chemical Engineering
Online at www.cetjournal.it

Guest Editors: Jeng Shiun Lim, Nor Alafiza Yunus, Jiří Jaromír Klemeš
Copyright © 2022, AIDIC Servizi S.r.l.
DOI: 10.3303/CET2297042
ISBN 978-88-95608-96-9; ISSN 2283-9216

The Residence Time and Slow Pyrolysis Temperature Effect

on Chemical Composition Pyrolysis Gas Product of Durian
(Durio Zibethinus Murr) Skin
Rizka Wulandari Putria,*, Rahmatullaha, Sri Haryatia, Budi Santoso a, Alek A Hadib
Chemical Engineering Department, Engineering Faculty, Sriwijaya University, South Sumatera, Indonesia
a

Mining Engineering Department, Engineering Faculty, Sriwijaya University, South Sumatera, Indonesia
b

[email protected]

Durian (Durio Ziberthinus Murr) is a commodity fruit in Southeast Asia especially in Malaysia, Thailand and
Indonesia. Durian skin contains lignin, cellulose, and hemicellulose and is the potential to be converted into
several solid, liquid, and gas products by a slow pyrolysis process. This work strived to observe the effect of
residence time and temperature on pyrolysis-gas product composition. Durian skin (DS) in size 4-5 cm was
pyrolyzed in a fixed bed pyrolysis reactor with natural zeolite inside at the temperature range of 300 °C - 400 °C
for 10 min and 30 min. The yield of pyrolysis gas products and gas product components was determined in this
work. The pyrolysis gas product was analyzed using Gas Chromatography (GC) to determine the components
of gas such as CO, CH4 and H2 along with CO2 gas. The best performance was achieved at 300 °C for 30 min
residence time with gas products 29.8 ng/ul CO2, 30.89 ng/ul CO, 13.08 ng/ul CH4 and 8.17 ng/ul H2. The
characteristics of the zeolite used were analyzed by X-ray Diffraction (XRD) to determine the effect of activation
and pyrolysis product on the catalyst crystal transformation.

1. Introduction
Durian (Durrio zubethinus Linn) is a famous fruit in Southeast Asia, especially in Malaysia, Thailand and
Indonesia. People of these countries consume durian flesh (20.92 %) and waste the remaining seeds and skin
(79.08 %) (Wahidin et al., 2014). Durian skin (DS), as the wasted part of the fruit, has significant potential to
become an alternative fuel. DS mainly contains lignin, cellulose, and hemicellulose. It embodies 50 % - 60 % of
high cellulose, 5 % of lignin, and 5 % of low starch (Prabowo, 2009). The DS will become the alternative energy
source when its high lignocellulose content undergoes the thermochemical process. The thermochemical
process is a conversion method by thermal for converting biomass into fuel or chemical products (McKendry,
2002). During thermochemical conversion (combustion, pyrolysis, and gasification), biomass turns into solid,
liquid, and gaseous forms, which can be synthesized through chemical processes or used directly (Basu, 2010).
During the thermochemical process, the three main components of DS will undergo a decomposition process
at different temperatures. Lignin, hemicellulose, and cellulose will decompose at 160 - 900 °C, 220-315 °C, and
315 - 400 °C (Yang et al., 2010).
One of the most effective lignocellulose decomposition processes is pyrolysis. Pyrolysis is part of the
thermochemical method in the absence of oxygen. Pyrolysis splits into three categories based on the heating
rate and heating temperature; slow, medium, and fast pyrolysis. Slow pyrolysis occurs at low temperatures (300
- 400 °C) with >15 min of heating time and 50 °C/min of heating rate. Then, the medium one happens at a
moderate temperature (500 °C) with 200 °C/min of heating rate. Fast pyrolysis exists at high temperatures from
600 – 700 °C with <5 min of heating time and 10 – 1000 °C/min of heating rate (Zeng et al., 2017).
Many researchers have conducted studies on pyrolysis. Kampegowda and Pongchan (2008) investigated the
slow pyrolysis on rice straw and produced a charcoal product with 4337 kcal/kg of Low High Value (LHV). Slow
pyrolysis of rice straw was examined in a bench-scale fixed bed pyrolysis reactor. Shakita (2021) researched
the effect of pyrolysis temperature (300, 400, 500, and 600 °C) and residence time (1, 2, and 3 h) on product
yield distribution and energy yield and discovered that the concentration of CO and CO2 decreased gradually

Paper Received: 25 May 2022; Revised: 30 July 2022; Accepted: 4 August 2022
Please cite this article as: Putri R.W., Rahmatullah .., Haryati S., Santoso B., Hadi A.A., 2022, The Residence Time and Slow Pyrolysis
Temperature Effect on Chemical Composition Pyrolysis Gas Product of Durian (Durio Zibethinus Murr) Skin, Chemical Engineering
Transactions, 97, 247-252 DOI:10.3303/CET2297042
248

from 41.81-29.66% and 54.02-38.46%, while H2 and CH4 increased from 1.9-19.22% and 2.3-10.54%. Suhendi
et al. (2021) studied the influence of natural zeolite on palm oil shell pyrolysis at 500 °C. The employment of
activated natural zeolite catalysts increased CO, CH4, and H2 gas levels by decreasing CO2 with a gas yield of
around 46%, which was better than the one without zeolite (44 %) (Suhendi et al., 2021).
The present study focuses on the natural zeolite application as the catalyst to enhance pyrolysis performances
at low temperatures. Zeolite is an alumina silicate crystal with a microporous structure and utilized as a catalyst
with particular characteristics in its pore size, pore distribution, and ion exchange capabilities. Zeolite catalyst
brings efficiencies in the slow pyrolysis process and allows reactions to emerging more quickly or at lower
temperatures due to change it triggers in reagents (Oyeleke et al., 2021).
In this study, slow pyrolysis of DS was processed at 300 - 400 °C with natural zeolite as the catalyst in 10 min
and 30 min residence time. The yield of the pyrolysis product was measured, and the gas product components
were analyzed to show the best performance of zeolite in the slow pyrolysis process

2. Methods
This research transpired in several stages of the procedure, including raw material preparation and the slow
pyrolysis process. The yield of gas product was calculated, and the gas product components were analyzed
using gas chromatography (GC). The zeolite characterization during pre-activation, post-activation and after the
pyrolysis reaction was analyzed to determine the effect of activation and pyrolysis reaction on the size and
intensity of zeolite crystals.
2.1 Raw material preparation
This research began by preparing the raw material for durian skin (DS) from Prabumulih, South Sumatera. DS
was washed with distillate water and reduced to 4-5 cm with a grinder machine. DS was dried in the sun until
reached constant weight. The 300 g of dried DS was placed in the pyrolysis reactor.
Table 1 displays the proximate and calorific value analysis results. Those tests were to predict the possibility of
DS becoming an alternative fuel. This research calculated the calorific value using bomb calorimeter Model-IKA
C2000, placed the sample into the bomb, and chose determination on the operation menu for coal samples or
standardization for Benzoic AC ID. As the temperature on the heater stabilized at ± 30 °C, the process
proceeded. Table 1 reveals that durian skin is likely alternative fuel due to its high calorific value (15.89 MJ/kg)
compared to one in palm oil plants (14.77 Mj/kg) (Satria et al., 2016). (Satria et al, 2016).

Table 1: Proximate analysis and calorific value of DS

Proximate analysis (wt% in dry at room temperature) Calorific Value
Fixed Carbon Volatile Matter Ash Moisture (MJ/kg)
10.38 64.04 8.14 10.38 15.89

2.2 Slow pyrolysis process

The 300 g of dried DS went into a fixed bed reactor containing 4 % wt natural zeolite. The zeolite was prepared
for activation by calcined at a temperature of 450 °C for 4 h to open the pores and active site of zeolite (Kusuma
et al., 2013). Slow pyrolysis was carried out at a temperature of 300 – 400 °C with variations in 10 min and 30
min residence time, as stated by Jouhara’s statement (2018). The output product proceeded to the holding tank,
and the yield of product pyrolysis gas was calculated and sent for gas chromatography analysis.
2.3 Gasification product analysis
The chemical composition analysis of the gas produced from the gasification process of DS was used GC-TCD
type variant 4000 with a carbon molecular sieve column (Carboxen1010 PLOT Capillary GC Column) to
determine the gas product components. The sample was injected into the GC without an intermediary and using
an autosampler with Helium as the carrier gas. Afterwards, the sample evaporated, and the gas passed through
the column in a GC oven at 50 °C for 2 min. Based on the percent composition of CO, CH4 and H2, the percent
yield gas is calculated using Eq (1):
Gas Comb = (Y CO + Y CH4 + Y H2 ) x 100 % (1)
where Y CO is the mole fraction of CO; Y CH4 is the mole fraction of CH4; and Y H2 is the mole fraction of H2
(Sanjaya et al., 2018).
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2.4 Characterization of Zeolite

As the catalyst, zeolite characterization occurred in pre-activation, post-activation, and after the pyrolysis
process. In this process, the X-ray Diffraction (XRD) type Rigaku Mini Flex analyzed the crystals, and the zeolite
characterization determined their morphological form (shape and size). Next, zeolite samples (before activation,
after activation, and after pyrolysis) were pulverized into powders and pressed. Then, the powdered zeolite
sample was placed in the sample holder and X-rayed with Cu Kα radiation of 1.541 A) at a speed of 3o/second
(Intarapong et al., 2013). Identification to determine the crystal size with a certain phase used a modification of
the Deybe Scherrer Equation (Monshi et al., 2012) as in Eq (2):
𝑘𝑘𝑘𝑘
𝐷𝐷 = (2)
𝛽𝛽 cos 𝜃𝜃

Where D is Crystal size (nm), k is Crystal form factor (0.9-1), λ is X-ray wavelength (0.15406 nm), β is Value of
Full Width at Half Maximum (FWHM) (rad ), and θ = Angle of diffraction (degrees).
XRD instruments were to monitor the process of chemical reactions and material synthesis. The specificity of
the diffraction pattern of a compound changed if it reacted to other compounds. Changes in the diffraction pattern
were the principle of analysis-synthesis process using XRD (Fuentes, et al., 2001). The diffractogram pattern
was the series of diffraction peaks with relative intensity varying along a certain 2θ value.

3. Result and discussion

Experimental conditions and procedures like variations in temperature and residence time affected he product
yield. The gas composition of the pyrolysis product also indicated different results in each variation of
temperature and resident time.
3.1 The effect of temperature on pyrolysis gas component
Thermal decomposition of biomass happens through four stages of pyrolysis, namely drying stages (100 °C ),
initial stage (100 -300 °C ), intermediate stage (>200 °C or 200 – 600 °C ), and final stage (300 – 600 °C ). The
dissimilarity of temperatures at each stage refers to the different decomposition of biomass components (Basu,
2010). During the decomposition process, the lignocellulose structure will release gas. Therefore, when the
pyrolysis decomposes various biomass components (such as hemicellulose, cellulose, and lignin), variants of
gas components will be released. At temperatures 350 and 400 °C, the gas composition produced is
CO2>CO>CH4>H2, indicating CO2 gas is dominant in the cellulose decomposition, and CO was more prominent
than CH4 and H2 (Quan et al., 2016). On the other hand, the temperature of 300 °C assembles CO>CO2>CH4>H2
composition, implying that hemicellulose decomposition occurs at this heat. The effect of temperature variation
on the amount of gas product at 10 and 30 min of this study is revealed in the Figure 1 below.

(a) 50 (b) 70
60
Ammount (ng/ul)

Ammount (ng/ul)

40
CO 50 CO
30 40
20 CO2 30 CO2
10 20
CH4 10 CH4
0 0
300 350 400 H2 300 350 400 H2
Temperature (°C) Temperature (°C)

Figure 1: (a) The effect of temperature variation on the amount of gas product at 10 min (b) The effect of
temperature variation on the amount of gas product at 30 min

Figure 1 displays the composition of the pyrolysis gas products of this study. The CO2 gas from the pyrolysis
process fluctuates in temperature variation, and CO gas changes insignificantly. As seen in Figure 1b, at 300
°C, the gas composition produced is CO>CO2>CH4>H2 with CO, CO2, CH4, and H2 values are 30.89 ng/ul, 29.8
ng/ul, 13 ng/ul, and 8.17 ng/ul. Meanwhile, at temperatures above 315 - 400 °C, the gas composition is
CO2>CO>CH4>H2 (Figures 1a and 1b). This condition was in line with Yang's (2010) statement mentioning that
hemicellulose occurred at the temperature of 220 - 315 °C with the gas component of CO>CO2>CH4>H2, and
cellulose decomposition occurred at the temperature of 315 - 400 °C with the gas component of
CO2>CO>CH4>H2.
250

3.2 The effect of residence time to pyrolysis gas products

From Figure 1b, the best pyrolysis performance in this study was achieved at a temperature of 300 °C and a
residence time of 30 min. At these conditions, the lowest CO2 gas produced was 30.8 ng/ul, and the highest
combustible gases CO, CH4 and H2 (29.8 ng/ul, 13.1 ng/ul and 8.18 ng/ul). The result indicated that long
residence time and low heating temperature directed gas production increases (Bridgewater, 2012). In Figure
3, the composition if combustible gas was calculated with eq (1) which was the sum of the yields of CO, CH4
and H2 gases. The combustible gases (CO, CH4 and H2) decreased as the temperature increased.

60
10 min
Combustible Gas (%)

50
30 min
40
30
20
10
0
300 350 400
Temperature (℃)

Figure 2. Comparison of combustible gas on residence time 10 min and 30 min

Based on Figure 2, during 10 min of residence time, the temperature of 300 °C produced 31.59 % combustible
gas, and the temperature 350 °C increased slightly to 35%. Meanwhile, at a temperature of 400 °C, the
combustible gas decreased by 22.27 % because high temperature tended to form majority CO2 gas. On the
other hand , at a residence time of 30 min, the most combustible gas produced at a temperature of 300 °C with
a value of 52.15 %. It was supported by Al (2018) stated that for methane and other combustible gas favored
low temperatures. In many cases, the syngas was also highly dependent on feedstock used as well as
temperature (Jouhara et al., 2018).
3.3 The effect of activation and pyrolysis process on zeolite characteristics
The natural zeolites are low in crystallinity. Therefore an activation is needed to improve the crystal size (Suhendi
et al., 2021). The crystal size value (D) was obtained with the Eq (2). The result showed the crystal size of
zeolite in the range 144.18 to 156.62 nm. The comparison of the crystal size of the natural zeolite catalyst before
activation (BA), after activation (AA), and zeolite after the pyrolysis process (AP) was calculated using the
modified Eq (2). The results of the crystal sizes comparison of zeolite shown in Table 2

Table 2. Crystal size of zeolite in variant condition

Sample Crystal size (nm)
Before activation (BA) 156.62
After activation (AA) 144.18
After pyrolysis (AP) 155.77

Table 2 represented the decrease in crystal size on the zeolite sample before activation, after activation and
after pyrolysis. This phenomenon indicated that the activation process in natural zeolite could be reduce the
crystal size, where the smaller crystal size provided a larger surface area of natural zeolite and increased the
active site (Qiang, et al., 2017).
The results of this study are also translated into a diffractogram pattern. The diffractogram pattern is a series of
diffraction peaks with relative intensity varying along a certain 2θ value. The relative intensity of the series of
peaks depended on the number of atoms or ions present and their distribution within the unit cell of the material
(Chook, et al., 2012). The diffraction peak of zeolite crystals after activation increased compared to pure,
inactivated zeolite. The top peak of zeolite after activation was 36.10 o and then decreased after the pyrolysis
reaction to 30.64 o. The before-activation process represented the peaks with the sharp intensity that occurred
in the 2Ө region of 10.06 o, 22.57 o, 25.98 o, and 28.07 o. On the other hand, the after-activation revealed that
increased peaks with sharp intensity occurred in the 2Ө region at 19.78 o, 22.61 o, 26.02 o, 27.98 o,and 36.10 o.
In the after-pyrolysis process, the intensity peaks of zeolite decreased with sharp intensity occurring in the 2Ө
region at 10.17 o, 22.60 o, 26.00 o, 28.37 o, and 30.64 o (See Figure 3)
 251

(a)

(b)

(c)

Figure 3. (a) XRD result of zeolite before activation (BA) (b) XRD result of zeolite after activation (AA) (c) XRD
result of zeolite after pyrolysis process (AP)

XRD peak positions are identical because chemical compositions, physical properties, and chemical properties
are similar. The crystals become smaller with the increase of XRD relative intensity. On the contrary, large
crystal has less broadened peaks (Inoue and Izumi, 2013). Based on Figure 3, the BA zeolite has a higher
intensity representing a bigger crystal size of about 156.56 nm and causing the smaller surface area of the
crystal. The activation process leads to the decrease of intensity from 650 cps to 500 cps. Broader crystal
surface area is more effective in expanding the active site due to the crystal size reduction to 144.18 nm. The
pyrolysis process causes the intensity of AA zeolite to increase from 500 cps to 600 cps. This conditions implied
damage to the carbon composition, which reduced the crystal surface area when the crystal size expanded to
155.77 nm. In other words, the carbon composition changes on the degree of activation (Lee et al., 2021).

4. Conclusions
The slow pyrolysis process was conducted at 300 - 400 °C and 10 and 30 min of residence time. The best
performance with the maximum combustible gas product occurred at a temperature of 300 °C and a residence
time of 30 min. The gas products were 29.8 ng/ul CO2, 30.89 ng/ul CO, 13.08 ng/ul CH4 and 8.17 ng/ul H2. The
results conclude that a long residence time and low heating temperature increased gas production with 52.15
% of gas combustible that revealed similar results to the previous related research of Al (2018). The zeolite
activation process is able to maximize the surface area (contact area) due to the decrease of crystal size during
the activation process about 144.18 nm.

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