Cleaner Engineering and Technology 16 (2023) 100672

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Cleaner Engineering and Technology

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Modelling and optimisation of intermediate pyrolysis synthesis of bio-oil

production from palm kernel shell
Imhade P. Okokpujie a, b, *, Anthony O. Onokwai c, **, Ejiroghene Onokpite d, Kunle Babaremu e,
Emmanuel S.A. Ajisegiri d, Christian O. Osueke a, f, Stephen A. Akinlabi g, Esther T. Akinlabi g
a
Department of Mechanical and Mechatronics Engineering, Afe Babalola University, Ado Ekiti, Nigeria
b
Department of Mechanical and Industrial Engineering Technology, University of Johannesburg, Johannesburg, 2028, South Africa
c
Mechanical Engineering Department, Bells University of Technology, Ota, Ogun State, Nigeria
d
Mechanical Engineering Department, Landmark University, Omu-Aran, Kwara State, Nigeria
e
Department of Mechanical Engineering Science, University of Johannesburg, Auckland Park Kingsway Campus, South Africa
f
Department of Mechatronics Engineering, Bowen University, Iwo, Osun State, Nigeria
g
Department of Mechanical and Construction Engineering, Faculty of Engineering and Environment, Northumbria University, Newcastle, UK

A R T I C L E I N F O A B S T R A C T

Keywords: A Palm Kernel Shell (PKS) is an enclosed shell obtained as residue from processing palm kernel. Its regarded as
Bio-oil production lignocellulosic biomass that serves as an abundant renewable energy source. The thermal and physicochemical
Optimisation behaviour was investigated, and results showed a low Fixed Carbon (FC) (22.60 wt%), high Volatile Matter (VM)
Palm kernel shell
(74.60 wt%), and high Higher Heating Value (HHV) of 19.78 MJ/kg. The elemental results showed the presence
Pyrolysis
Renewable energy
of C (48.70 wt%), H (5.58 wt%), N (0.23 wt%), O (45.02 wt%), and S (0.04 wt%). The fixed-bed pyrolysis reactor
was utilised for the decomposition of the PKS to produce an optimum bio-oil of 47.10 wt% at temperature
(520 ◦ C), reaction time (15 min), nitrogen (175 cm3/min), particle size (0.70 mm), and heating rate (22.5 ◦ C/
min). The efficient Response Surface Methodology (RSM) via Central Composite Design (CCD) was employed to
model and optimise the operating parameters. P<0.05, a high F-value for bio-oil makes the established model
predicted, suitable, responsive, and reliable. The actual and predicted value for the quantity of bio-oil produced
showed clearly that the data is reasonably in consonance with the predicted value. Screening with FT-IR revealed
that the peak of 3339.7, 1416 cm− 1 attributed to O–H stretching vibrations depicted the presence of alcohol and
carboxylic acids, respectively, the resent, while the peak at 1636.3, 1274.7 was due to C–H bend and C–O stretch
indicating the presence of aromatic compounds and aromatic ester respectively. The most significant element in
the bio-oil obtained via Gas Chromatography–Mass Spectrometry (GC–MS) analysis is phenol, 9, 17 – octa­
decadienoyl, oleic acids, 2-cyclo pentane-1-one, and pent ethylene glycol are the by-products in the sample.
Hence, the bio-oil produced is suitable for high-speed diesel engines, vehicle locomotion, powering heavy ma­
chines, marine equipment, manufacturing industries, and mining types of machinery. This is a significant
contribution in the field of bio-oil production and application.

1. Introduction and energy security. Onokwai et al. (2022a) Reported that even though
the overall recognition of renewable energy has been increasing, the
Environmental concerns about the emission of greenhouse gas average contribution to the world energy reserves remains limited
(GHG) and oil crises from burning fossil fuel steered increased study into Fahmy et al. (2020) and Nnomdi et al. (Nnodim et al., 2022). Challenges
a renewable, sustainable, and clean energy source, which plays a sig­ and uncertainties arise from various techniques or methods of convert­
nificant role in future energy supply Efetobor et al. (2023). These ing renewable energy into fuels Dhanavath et al. (2019). Amongst these
renewable energy sources are already proposed as significant energy are solar, hydro, wind, biomass, etc., the waste and virgin biomass have
supply options and address the world energy demand, climate change, the advantage of their non-zero carbon footprint and abundant

* Corresponding author. Department of Mechanical and Mechatronics Engineering, Afe Babalola University, Ado Ekiti, Nigeria.
** Corresponding author.
E-mail addresses: [email protected], [email protected] (I.P. Okokpujie), [email protected] (A.O. Onokwai).

https://doi.org/10.1016/j.clet.2023.100672
Received 11 May 2023; Received in revised form 27 July 2023; Accepted 17 August 2023
Available online 19 August 2023
2666-7908/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

availability Kumar et al. (2019). optimise pyrolysis yields. At the same time, in this study, 5 par meters
Biomass is recognised as an alternative eco-friendly renewable were used to avoid errors due to insufficient consideration of pertinent
source for bioenergy production and is readily available globally parameters. The parameters employed for the study are temperature,
Onokwai et al. (2022c). Biomass utilisation is receiving great attention reaction time, nitrogen flow rate, heating rate, and particle size on the
in mainstream energy because of the increased global demand for en­ dispersal of the parameters of pyrolysis would be examined and opti­
ergy and environmental considerations. It is complex and contains a mized to improve bio-oil yield using central composite design (CCD) by
small percentage of ash, nitrogen, and sulphur. Hence, biofuel com­ focusing on the intermediate pyrolysis of palm kernel shell via a fixed-
bustion yields less harmful gas emissions like soot, SO2, and NOX. While bed reactor. Also, FTIR and GC-MS tech were used to study the func­
CO2 emissions when producing bio-oil could be recycled for plant use tional group and chemical composition of the obtained palm kernel shell
Onokwai et al. (2022a). bio-oil sample. This study is impactful in enhancing the use of bio-oil in
Several countries have biomass in large quantities that could be used various applications.
as energy resources. Various classes of biomass resources are commonly
and readily available from sludge from wastewater treatment plants and 2. Source of materials
municipal solid wastes, forestry wastes such as bark, sawdust, and wood
chips, etc., agricultural wastes like wheat straw, rice husk, and palm Oil palm shell was sourced from a local mill in Omu-Aran metropolis,
kernel shell, etc, have reasonably high energy content Go et al. (2019). Kwara State, Nigeria, with geographical coordinate: Latitude
However, the palm kernel shell among these categories of agricultural 8◦ 08ʹ18.85ʺN and Longitude 5◦ 06ʹ9.36ʺE), between early November to
residues represents an important potential for developing the bioenergy late December 2020. The raw PKS was transported to the Civil Engi­
industry Demirbas et al. (2006). neering Laboratory, Landmark University, Omu-Aran, Kwara State, for a
Besides Malaysia, Nigeria produces enormous quantities of palm treatment process that includes cleaning, crushing, and sieving. The
shells from palm oil industries Sumathi et al. (2008). The major crushed PKS was sun-dried indoors to prevent contaminants at room
advantage of using the palm kernel shell is that it can be produced in temperature for ten working days. It was further dried in an oven for
large amount as residues from the processed facility and have no sig­ about 5.5 h at 105 ◦ C ± 5 to aid milling. Then pulverised in a ball mill
nificant market value. Additionally, the composition of the waste con­ and sieved to varying particle sizes of 0.1–0.20, 0.2–0.40, 0.40–0.60,
cerning carbon and hydrogen is higher than other available agricultural 0.6–0.80, and 0.8–1.00 mm. Before analysis, the sample was stored at
residues. It was reported by Abnisa et al. (2011) that the quantity of room temperature in a Zip locked bag by Oyebanji et al. (2023).
palm shell waste in 2009 was approximately 5.2 million tonnes.
Generally, they are not fully used; some amounts are burnt without 2.1. Characterization of the PSK sample
recovering the energy. Meanwhile, turning this waste to bio-oil through
a thermochemical process affords more potency and benefits to replace The proximate analysis was performed on the oven-dried sample in
fossil fuels. Hence, many researchers have explored its potency for en­ accordance with the ASTM methods using a carbolite muffle furnace
ergy with encouraging results Onokwai et al. (2022b). Biomass con­ (Model: CWF1223–230SN+&02-3216P1). Volatile matter (VM), ash,
version into bio-oil involves thermochemical conversion processes and moisture content were evaluated in accordance with ASTM
Balogun et al. (2019). Thermochemical conversion is biomass break­ E872-82, ASTM D1102-84, and ASTM E 1358 – 97 standards, respec­
down at elevated temperatures above 150 ◦ C under controlled oxidation tively (Oyebanji et al., 2023). While the fixed carbon (FC) content is
or heating for bio-oil production, bio-char, and syngas Hassan et al. obtained by difference using Equation (1);
(2017). The thermochemical conversion processes, as reported by
Chowdhury et al. (2017) include, among others, combustion, gasifica­ FC=100-(MC wt% + VM wt% +Ash wt%). (1)
tion, and pyrolysis. Similarly, the gasification process is effective but The elemental analysis evaluates nitrogen, hydrogen, oxygen,
requires a high investment cost, while combustion is the most popular
sulphur, and carbon content percentage using the Elemental analyser
and simplest conversion route; however, it poses several environmental LECO CHN 2000 model per ASTM D5373-21 methods. While sulphur is
risks Laouge et al. (Sahoo et al., 2021). But the pyrolysis route offers a
obtained by difference. The compositional analysis was done to deter­
cheaper and simple operation for decomposing biomass to biofuels mine lignin, hemicellulose, and cellulose. Conclusively, HHV was ana­
without oxygen Gautam and Chaurasia (2020). Depending on the
lysed with Mohan Brother Bomb Calorimeter based on ASTM D2015-00
heating rate, it could be grouped as slow, fast, and flash pyrolysis Guedes methods.
et al. (2018). Comparatively, fast pyrolysis is more efficient for pro­
ducing high amounts of bio-oil within the temperature and heating rate
2.2. Experimental design
ranges of 300–700 ◦ C and 10–200 ◦ C/s, respectively, Onokwai et al.
(2023a).
The RSM was employed based on a central composite design in this
Reportedly, pyrolysis operating parameters like heating rate and
work for the experimental design. It is a statistical tool often used for
temperature have been studied to influence bio-oil yield; hence it is
fitting quadratic models and is highly reliable when the behaviour of
almost important to study the best operating conditions to maximise its
multiple operating parameters on the final results is considered by
yield. Interestedly this concern has been of interest to most researchers
Hossain et al. (2017). Firstly, the design of the experiment starts with a
Kumar et al. (Park et al., 2019). Therefore, an optimisation tool response
layout of the design matrix that explains the factors and the response
surface methodology (RSM) for experimental design is engaged to ach­
Savasari et al. (2015). The analysis was performed with bio-oil as the
ieve this task. It is a mathematical and statistical tool for exploring the
single response in the CCD and N2, temperature, reaction time, particle
correction between one or more responses introduced in 1951 by Box
size, and heating rate as the five operating parameters. Each parameter
and Wilson Onokwai et al. (2023b). The RSM operation defined the
is considered at levels 1, -1, 0, α, and –α Laouge et al. (2020). The values
effect of independent variables, making room for each parameter to be
-α and + α were evaluated using Equation (2), whose value is displayed
determined and their interactions Mohammed et al. (2017). Many in­
at − 2 and +2 where n represents the operating parameters.
vestigations centred on a single parameter by maintaining operating
parameters as constant. Regrettably, this approach involves many 1
(2)
/
α = [2n ] 4
experimental runs and consumes so much operational time, which could
yield incorrect experimental results. Hence, the optimisation method is y = f (x1 , x2 , x3 , ………….xn ) (3)
referred to in this research to investigate palm kernel shell bio-oil yield.
Several authors only combined 3 or 4 parameters to model and Equation (3) is used to institute a mathematical connection between the

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

operating parameters and the responses. Where y represents the value of consists of a cylindrical insulated reactor with an electrically heated
the response, f the function of the response that is unknown, the oper­ furnace with 4 kW power and a condensing unit. It has an installed
ating parameters are represented as x1 , x2 , x3 , ………….xn and the external PID controller that controls the temperature inside the reactor.
number of operating parameters designated as n, as previously used by The reactor has two openings at the top, one through which N2 enters
Tripathi et al. (Oyebanji et al., 2023). and the other for hot vapours exiting the reactor into the condenser to
Step two used a quadratic expression to evaluate the coefficients (e. condense hot vapours. In the condenser is a circulation of ice-cooled
g., quadratic, linear, constant, and interactive) in a model resented in water used as a medium of cooling through the pump. The liquid that
Equation (3). The importance of the mathematical expression concern­ is condensed with the aid of a measuring cylinder was collected and
ing the P-value (alpha) constraint and the R2, which is the coefficient of weighed. The reactor was then allowed to cool down at the end of the
determination, was used to select the second-order mathematical model. process and solid char that remained as the residue was collected and
The choice to optimise is founded on the preferred desirable constraints, weighed. While the non-condensable produced was estimated by ma­
like maximising bio-oil production while minimising the reaction time, terial balance.
etc.
∑
k ∑
k k ∑
∑ k 2.4. Experimental procedure
y = β0 + βi xi + βii x2i + βij xi xj + εi (4)
The pyrolysis process investigates the influence of operating pa­
i=1 i=1 i=1 j>1

Where xi and represent independent variables like the heating rate, rameters on the products and obtains optimum operating parameters for
particle sizes, operating temperature, and residence time. This research optimum bio-oil production. The PKS sample was fed into the reactor
engaged the Design Expert software 7.0.3 version (Stat-Ease) to solve the and then closed tightly at a pre-set variables temperature, T ranges of
interactions automatically, of xi and xj , the quantity y stands for the 320, 420, 520, 620, and 720 ◦ C, heating rate (H) of 7.5, 12.5, 17.5, 22.5,
responses. While β0 represents the constant coefficient for linear (βi ), particle size (P) of 0.1–0.2, 0.2–0.4, 0.4–0.6, 0.6–0.8, and 0.8–1.0 mm,
quadratic (βjj ) and interactive effects (βij ). And the value k stands for the reaction time (R) of 5, 10, 15, 20 and 25 min, a, and 27.5 ◦ C/min, ni­
trogen flow rate (N) at 25, 75, 125, 175, and 225 cm3/min as a carrier
number of process parameters, and εi is the error term.
gas. The vapour was separated automatically into the water and bio-oil
50 runs were performed to support the results obtained from the RSM
Oyebanji et al. (2021). Fig. 2 shows the experimental procedure of the
using the CCD as presented in Equation (5) by Kshirsagar et al. (Kshir­
study.
sagar and Kalamkar, 2020).

N = 2k + 2k + nc = 25 + 2(5) + 8 = 5 (5) 3. Results and discussion

Where N stands for the actual runs; nc = 8 represents the number of 3.1. Bio-oil characterization
repeated identical runs at the centre points of the CCD; k represents the
number of parameters. 2k indicates the factorial number. Table 1 presents the mean values of the proximate, elemental,
compositional, and high heating value analyses. The results present an
2.3. Experimental setup understanding of the behaviour of the PKS sample when decomposed. It
was observed that the VM (74.60 wt%) and FC (21.60 wt %) which is
The setup of the fixed bed reactor plant is presented in Fig. 1. It close to that presented by Acevedo et al. (2019). In the same vein, the

Fig. 1. Exploded view of the pyrolysis plant in 2D.

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

Fig. 2. Modelling and optimisation flow chart of the Bio-oil analysis.

Onokwai et al. (2023c). Likewise, the low AC, sulphur, and nitrogen
Table 1 could help limit harmful chemicals deposited in the reactor compart­
PKS characterization.
ment, consequently, reduce maintenance of the pyrolysis plant. The low
Analysis Wt% sulphur and nitrogen could lead to reducing SOx and NOx gases Ayeni
Proximate analysis (wt%) et al. (2018).
MC 0.31 ±0.01
VM 74.60 ± 0.40
3.2. Experimental design format for bio-oil yield
FC 22.60 ± 0.21
Ash 3.49 ±0.02
Ultimate analysis (wt%) The yields obtained from combining different parameters at five
C 48.70 ± 1.14 levels provided by the Design Expert software are shown in Table 2. The
H 5.58 ± 0.01 software suggested fifty experimental runs with the same operating
N 0.23 ± 0.01
parameters and their combination. And the experimental results ob­
O 45.02 ± 0.12
S 0.04 ± 0.001 tained were used as input variables to the software to predict the yields.
Structural composition analysis (wt%) At the initial stage, the bio-oil yield was low due to incomplete thermal
Cellulose 28.72 ± 0.14 decomposition of the biomass at a lower temperature (<350) caused by
Hemicellulose 26.21 ± 0.22
conservative minor devolatilisation of the cellulose and lignin contents
Lignin 44.41 ± 0.32
Heating value analysis (MJ/kg) of the biomass in the reactor Onokwai et al. (2023b), Varma et al.
HHV 19.78 ± 0.53 (Varma and Mondal, 2017), Alvarez et al. (2018). The bio-oil produced
LHV 18.90 ± 0.31 improved as the temperature moved from 320 to 520 ◦ C until optimum
yield (47.10 wt%) was attained at reaction time (R), temperature (T),
nitrogen flow rate (N), heating rate (H), and particle size (P of 15 min,
elemental analysis obtained agrees with the work of Okoroigwe et al.
520 ◦ C, 175 cm3/min, 22.5 ◦ C/min, and 0.70 mm respectively. The
(2014). Similarly, the compositional analysis results obtained in this
increased bio-oil yield was attributed to the primary decomposition of
research are within the range of that reported by Baffour-Awuah (Baf­
the PKS and the secondary degradation of the biochar residue at a higher
four-Awuah et al., 2021). Then the increase in the heating value of the
temperature Encinar et al. (1998). A decrease in the bio-oil was
sample could be attributed to the high FC and low MC, which makes the
observed, with a further increase from 520 ◦ C due to secondary reactions
sample appropriate for the pyrolysis process for high bio-oil production
such as thermal cracking, repolymeriation, and recondensation caused

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

Table 2
Experimental design matrix and the corresponding bio-oil yield.
Run Factor A: Temperature Factor B: Reaction time Factor C: Heating rate(oC/ Factor D: Nitrogen flow rate Factor E: Particle size Response 1: Bio-oil(w
(oC) (min) min) (cm3/min) (mm) %)

1 520 10 17.5 125 0.5 43.1

2 520 15 17.5 125 0.5 46.5
3 520 5 17.5 125 0.5 43.2
4 720 25 27.5 225 0.1 38.6
5 320 5 7.5 25 0.9 36.9
6 520 15 17.5 125 0.5 46.1
7 520 15 12.5 125 0.5 43.3
8 720 5 7.5 25 0.9 38.5
9 720 5 27.5 25 0.9 40
10 320 25 27.5 25 0.9 38.1
11 320 25 27.5 25 0.1 37.1
12 420 15 17.5 125 0.5 39.9
13 520 15 17.5 125 0.5 46.3
14 320 5 7.5 25 0.1 36.9
15 320 25 7.5 25 0.1 37.4
16 520 15 17.5 75 0.5 43.1
17 720 25 27.5 225 0.9 40.2
18 720 25 7.5 225 0.1 36.5
19 320 5 27.5 25 0.1 37.1
20 320 25 27.5 225 0.9 37.1
21 520 15 17.5 125 0.5 46.2
22 320 5 27.5 25 0.9 36
23 720 5 27.5 225 0.9 39.6
24 320 25 7.5 25 0.9 36.3
25 520 15 17.5 125 0.3 43.2
26 720 5 27.5 225 0.1 39.6
27 320 5 7.5 225 0.9 36.8
28 520 15 17.5 125 0.5 46.4
29 520 15 22.5 175 0.7 44.4
30 720 5 27.5 25 0.1 40
31 720 25 7.5 25 0.9 40.8
32 520 15 17.5 125 0.5 43.5
33 320 5 7.5 225 0.1 36.2
34 520 15 17.5 25 0.5 43.7
35 720 25 27.5 25 0.1 39.6
36 320 25 7.5 225 0.1 37.2
37 620 15 17.5 125 0.5 38.7
38 720 25 7.5 25 0.1 38.6
39 520 15 17.5 125 0.5 43.4
40 720 5 7.5 225 0.1 39.9
41 520 15 17.5 225 0.5 44.2
42 720 5 7.5 25 0.1 39.7
43 320 5 27.5 225 0.1 36.5
44 320 5 27.5 225 0.9 36.2
45 320 25 7.5 225 0.9 36.4
46 720 25 7.5 225 0.9 40.8
47 720 20 7.5 225 0.9 40.1
48 720 25 27.5 25 0.9 39.5
49 520 15 17.5 125 0.5 43.6
50 320 25 27.5 225 0.1 36.9

Table 3
ANOVA for the produced bio-oil.
Source Sum of Squares Degree of freedom (df) Mean Squares F-value P-vale probability > F Remark

Model 504.719 11 50.47 233.57 <0.0001 Significant

A-Temperature 6.748 1 6.748 30.62 <0.0001 Significant
B-Reaction time 1.053 1 1.053 4.96 0.032 Significant
C-Heating rate 1.241 1 1.241 5.84 0.02 Significant
D-N2 flow rate 1.152 1 1.152 5.25 0.028 Significant
E-Particle size 0.864 1 0.864 4.07 0.051 Not Significant
A2 39.695 1 39.695 187 <0.0001 Significant
C2 6.469 1 6.469 30.47 <0.0001 Significant
AB 1.672 1 1.672 7.88 0.008 Significant
AD 1.247 1 1.247 5.94 0.02 Significant
BC 0.911 1 0.911 4.29 0.045 Significant
CD 1.051 1 1.051 4.95 0.032 Significant
Residual 8.279 39 0.212
Lack of fit 7.759 32 0.242 3.26 0.054 Not Significant
Pure error 0.52 7 0.074
Cor Total 513 50

R2 =98.65%; Adjusted R2 =97.73%; Predicted R2 = 83.73%; CV% = 5.41.

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

by longer vapour removal residence time Onokwai et al. (2023a), Park 3.3. The statistical equation for the produced bio-oil
et al. (2019); hence, increase production of non-condensable gas from
22.50 to 34.70 wt%. Furthermore, minimum bio-oil production (40.10 The statistical equation to predict the bio-oil produced is presented
wt%), was noticed at temperature, heating rate, reaction time, particle in Equation (6), while the ANOVA for the second-order RSM is shown in
size, and nitrogen 720 ◦ C, 27.50 ◦ C/min, 25 min, 0.10 mm, and 225.0 Table 3.
cm3/min, respectively.
YBO = − 0.22.99 + 0.3226A + 0.0451B − 2.165C − 0.00093D − 0.000303A2
The optimum bio-oil yield (47.10 wt%) obtained in this study was
higher than the bio-oil yield (46.4 wt%) from fast pyrolysis of palm + 0.0621C2 + 0.000089AB + 0.000002AD + 0.00065BC − 0.000063CD
kernel shell reported by Abnisa et al. (2011) at a temperature (500 ◦ C), 6
reaction time (60 min), particle size (2 mm) and nitrogen flow rate (2
l/min) and bio-oil yield (39.0 wt%) at temperature, heating rate and Where YBO is the bio-oil produced (wt%), A, B, C, D, and E represent the
nitrogen flow rate of 600 ◦ C, 75◦ C/ min and 200 ml/min, respectively as coded value of Temperature (T) (oC), Reaction time (R) (min), Heating
reported by Waluyo et al. (2018). rate (H) (oC/min), Nitrogen flow rate (N) (cm3/min), and Particle size
(P) (mm) respectively.
The F-value specifies the relationships between the mean square
values in the regression model developed and that of the error term. The

Fig. 3. (a) 2D contour plot for temperature and reaction time on bio-oil and (b) 3D response surface plot for temperature and reaction time on bio-oil.

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

p-value from the regression analysis was found acceptable and reliable cm3/min) as a result of complete thermal decomposition of the biomass
by Kumar et al. (2019). The higher the F-value, the more reliable, bonds caused leading to rapid devolatilisation of the biomass in the
responsive, and reproductive the regression model. Similarly, the reactor at a high-temperature Onokwai et al. (2023c). There was a
p-value should be meaningfully low to give a more reliable model remarkable decrease in bio-oil produced, with further increase in tem­
Nizamuddin et al. (2016). The regression model generated was found to perature from 520 to 720 ◦ C and reaction time from 15 to 25 min,
have a high F-value (233.57) with a p-value lower than 0.05 for all probably due to secondary cracking reactions of the heavy-molecular
feedstock investigated, signifying that the model is significant. From weight compounds in the volatile dominated and longer volatile
Table 3 the model terms A, B, C, D, A2, C2, AB, AD, BC, and CD were all removal residence time Fernandex et al. (2022); Bridgwater, (Bridg­
significant. Hence, they positively impact bio-oil production. The lack of water et al., 1999). The impacts of the interaction of nitrogen and re­
Fit (0.054) displays that the expression produced could reproduce and action time on bio-oil are indicated in Fig. 4(a–b). 44.26 wt% of
predict the experimental data. maximum bio-oil was reported at constant temperature (520 ◦ C), heat­
ing rate (17.50 ◦ C/min), and particle size (0.50 mm). The bio-oil
3.4. Effect of operating parameters on the yields generated reduced from (46.98–44.43 wt%) with an increase in reac­
tion time (15–25 min) and nitrogen flow rate (5–225 cm3/min) as a
Fig. 3(a–b) to 6(a-b) illustrate the combined impact of the two most result of an increase in secondary reactions such as thermal cracking,
important process parameters essential to bio-oil yield. Fig. 3(a–b) recondensation, repolymerisation, caused by longer vapour removal
showed that the highest bio-oil (44.30 wt%) was attained with a tem­ residence time from the hot pyrolysis zone Guedes et al. (2018).
perature increased from 320 to 520 ◦ C at a constant heating rate Furthermore, the impact of particle size interaction with tempera­
(17.5 ◦ C/min), particle size (0.50 mm), and nitrogen flow rate (125 ture on the bio-oil yield is also presented in Fig. 7(a–b). An increase in

Fig. 4. (a) 2D contour plot for temperature and nitrogen flow rate on bio-oil and (b) 3D response surface plot for temperature and nitrogen flow rate on bio-oil.

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

Fig. 5. (a) 2D contour plot for effect reaction time and heating rate on bio-oil and (b) 3D response surface plot for reaction time and heating rate on bio-oil.

particle sizes increases the temperature gradient inside the biomass 3.5. Optimized operating parameters for bio-oil yield
particle, thereby increasing the distance between the biomass particle
surfaces to its centre. This resulted in an incomplete pyrolysis process The results obtained from the qualitative analysis (experimental
due to the low heat transfer between the hot and cold material and runs) were inputted into the design expert software to model and opti­
decreased volatile matter formation Ogunkanmia et al. (2018); Tripathi mise pyrolysis operating parameters such as temperature, heating rate,
et al. (2016). Hence, a reduction in bio-oil yield (Fig. 7(a) and b). The particle sizes, and reaction time for maximum bio-oil yields. The sig­
contour flag shows the value of the interactions with the parameters and nificance of this analysis is to obtain a better relationship between the
the various colour to see the effects of the parameters on the bio-oil operating parameters and the response (bio-oil yield), predict the
yields. Maximum bio-oil (45.43%) was achieved at constant reaction qualitative experimental values, and establish the optimal conditions of
time (15 min), heating rate (17.50 ◦ C/min), and nitrogen flow rate (125 the pyrolysis process using the response surface methodology. The
cm3/min). This study agrees with the findings of Gautam and Chaurasia optimisation is vital for a forecast for the better future accuracy of
(2020). experimental pyrolysis runs, developing new processes, reducing waste,
reducing the bottle in carrying out rigorous experimental runs, optimi­
sation of future plants performance, enhancement of pyrolysis plant
design and formulation of new products Onokwai et al. (2022d),

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

Fig. 6. (a) 2D contour plot for nitrogen flow rate and heating rate on bio-oil and (b) 3D response surface plot for nitrogen flow rate and heating rate on bio-oil.

Mohammed et al. (2017). The bio-oil yield obtained at optimum pa­ 3.6. Physicochemical properties of produced bio-oil
rameters was utilised to extract bio-oil yield from palm kernel shell that
was characterised via GC-MS and FTIR techniques to check for ascer­ Table 4 illustrates the physical and ultimate properties of the bio-oil
taining the bio-oil produced at optimum conditions. Fig. 8 presents the yield from the pyrolysis of palm kernel shell at optimum conditions. The
optimisation plot from the RSM model, which defines the values of the higher heating value (21.23 MJ/kg) obtained in this study is slightly less
parameters necessary for the optimal production of bio-oil. The graphs than 29.46 MJ/kg reported by Shi et al. (2020), but higher than 11.94
produce the minimum, maximum, and optimum yield of pyrolysis MJ/kg reported by Abnisa et al. (2011). This value is also less than
products by interacting with all the operating parameters. The results gasoline (44–50 MJ/kg) and diesel (42-40 MJ/kg) reported by Oyebanji
displayed that varying the R, T, P, N, and H greatly affected the yields. It et al. (2023): Chukwuneke et al. (2019) This is probably due to an in­
could be inferred that the optimum yield of bio-oil of 47.20% was crease in moisture content (MC) in the bio-oil. The density of the bio-oil
achieved at Temperature (520 ◦ C), Heating rate (25/min), the flow rate at 40 ◦ C is 1.04. This agrees with the density specification of fuel oil of
of nitrogen (25 cm3/min), Particle size (0.10 mm), and Reaction time 0.90 g/cm3, heavy fuel oil of 0.99 g/cm3, and furnace oil (0.92 g/cm3)
(15 min). However, values not within this range will decrease the reported by Oyebanji et al. (Varma and Mondal, 2017). Bio-oil is suit­
quality and quantity of bio-oil production. The predicted values are able as transformers oil because of its greater than 0.92 g/cm3. The pH
closely packed around the regression line (Fig. 9), similar to Hossain level of 2.60 was attributed to free fatty acids like oleic, phenolic,
et al.‘s findings (Hossain et al., 2017). The experimental and predicted octadecanoic, carboxylic acids, etc. The bio-oil viscosity of 2.6 @ 40 ◦ C
values for bio-oil yield are in agreement. Hence, the model can repro­ helps to prevent partial ignition of the oil and poor atomisation Onokwai
duce the experimental results accurately. et al. (2023a).

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

Fig. 7. (a) 2D plot for particle size and temperature on bio-oil (b) 3D response surface plot for particle size and temperature on bio-oil.

Fig. 8. Optimisation plot.

3.7. FTIR of the produced bio-oil 4000 cm− 1 in the spectrum analysis, while Table 5 present the functional
group, molecular weight, transmittance and appearance extracted from
Fig. 10 depicts the spectra of Fourier Transform Infrared Spectros­ Fig. 5 through the aid of FT-IR bio-oil. FT-IR is a chemical analysis
copy (FTIR) of bio-oil yields from intermediate pyrolysis of PKS at op­ technique that detects the different functional groups and chemical
timum operating condition over a wavenumber range between 500 and bonds in the samples using infrared rays Oyebanji et al. (2022). The FTIR

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

the peak (831.2 cm− 1) is accredited to C–Cl stretching due to the pres­
ence of Halo compound. The medium peak 1416.4 is assigned to O–H
stretching vibration of the hydroxyl group, carboxylic acid, and water
impurities. The weak broad peak at 1636.3 indicates C–H bending
containing aromatic compounds. The peak (1274.7 cm-1) results from
the C–O bending of an aromatic ester. The peak at 1017.6 cm− 1 is due to
C–F stretching of the fluoro compound. The functional groups’ presence
is similar to Ogunkanmia et al. (2018) reported. The function group
presence in the bio-oil makes it useful as fuel in automobile vehicles,
furnaces, and marine equipment. It can also be utilised as a catalyst for
the production of drugs and plastic.

3.8. Gas chromatography and mass spectrometry (GC-MS) analysis for

bio-oil yield

Fig. 11 presents the bio-oil chemical composition achieved using GC-

MS. At the same time, the different compounds were also detected and
recorded in Table 6, which agrees with that presented by Laouge et al.
(2020). The bio-oil is made up of oleic acid, phenol, octadecadienoic
acid, 9,17-octadecadienal. However, the most significant element in the
Fig. 9. Actual and predicted for Bio-oil yield. bio-oil is phenol, 9, 17 – octadecadienoyl, oleic acids, 2-cyclo
pentane-1-one, and pentamethylene glycol. Phenol presence in the
bio-oil was also found visible with the FTIR analysis. The presence of
Table 4
oleic acids, 9-12- octadecadienoyl chloride, and 9,17- octadecadienoyl,
Physico-chemical Properties of the bio-oil produced.
which are by-products in the sample, makes it suitable for high-speed
Properties PKS
diesel engines, vehicles locomotion, powering heavy machines, marine
Appearance Dark brown equipment, manufacturing industries, and mining types of machinery.
pH 2.6 For instance, more than 2.5 million tonnes of PKS are produced annually
Water content (wt%) 45
Density (g/cm3) 1.04
in Nigeria, where improper disposal endangers the environment
Iodine value (mgKOH/mg) 98.80 (Uchegbulam et al., 2022). Therefore, with this high volume of PKS
Viscosity @ 40 ◦ C (cst) 2.6 there can be a sustainable production of bio-oil from PKS.
Carbon (wt%) 41.2
Hydrogen (wt%) 8.61
Nitrogen (wt%) 0.3 4. Conclusions
Sulphur (wt%) 0.06
Oxygen (wt%) 49.83 This research uses Response Surface Methodology (RSM) to model
HHV (MJ/kg) 21.32 and optimise the parameters for bio-oil yield (obtained from palm kernel
Flash point 78
shell) improvement. It was observe from the results that the reaction
Pour point − 8
Cetane index 34.1 time, temperature, heating rate, Nitrogen flow rate, and the particle size
Conradson carbon residue (%) 2.41 significantly influenced the bio-oil yield. The high F-value (233.57), R2
(98.65) and p-value <0.05 indicated that the developed model was ac­
curate, responsive and can replicate the experimental data. The high
comprises different peaks with strong, medium, and weak intensities Bio-oil yield increased with increasing temperature from 350 to 520 and
corresponding to various bond levels in the bio-oil. The strong, broad
reduced with further temperature increase due to secondary reactions
peak in the wavelength range (2900-3700 cm− 1) is ascribed to the O–H such as thermal cracking, repolymerisation, and re-condensation of
stretching of Alcohol. The strong bond peak between 2050 and 2150 is
longer vapour removal residence time. Maximum bio-oil (47.20 wt%)
ascribed N–– C–– S stretching, indicating Isothiocyanate is present, while
produced was realised at a temperature (520 ◦ C), heating rate (12.10 ◦ C/

Fig. 10. FT-IR spectrum of bio-oil yield from pyrolysis of PKS.

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I.P. Okokpujie et al. Cleaner Engineering and Technology 16 (2023) 100672

Table 5
Functional group composition of bio-oil yield from pyrolysis of PKS.
Functional Group Wavelength (cm− 1) Molecular Motion % Transmittance Appearance

Range Actual

Alcohols 2900–3700 3339.7 O–H stretch 48.715 Strong broad

Isothiocyanate 2050–2150 2083.6 N–
–C– –S stretch 94.694 Strong broad
Aromatic compounds 1590–1730 1636.3 C–H bend 64.368 Weak broad
Carboxylic acids 1350–1450 1416.4 O–H bend 79.955 Medium broad
Aromatic Ester 1220–1320 1274.7 C–O stretch 85.246 Strong broad
Fluoro compound 980–1060 1017.6 C–F stretch 82.857 Strong broad

CRediT author statement

I.P. Okokpujie, A.O. Onokwai, E.Onokpite, K.Babaremu, E.S.A. Aji­

segiri, C.O. Osueke, S.A. Akinlabi, E.T. Akinlabi: Methodology, data
collection, and Visualization. I.P. Okokpujie, A.O. Onokwai, E. Onok­
pite, K. Babaremu, E.S.A. Ajisegiri, C.O. Osueke, S.A. Akinlabi, E.T.
Akinlabi: Conceptualization. I.P. Okokpujie, A.O. Onokwai, E. Onokpite,
K. Babaremu, E.S.A. Ajisegiri, C.O. Osueke, S.A. Akinlabi, E.T. Akinlabi:
Software, Investigation, and Validation. I.P. Okokpujie, A.O. Onokwai,
E. Onokpite, K. Babaremu, E.S.A. Ajisegiri, C.O. Osueke, S.A. Akinlabi,
E.T. Akinlabi: Data Curation. I.P. Okokpujie, A.O. Onokwai, E. Onokpite,
K. Babaremu, E.S.A. Ajisegiri, C.O. Osueke, S.A. Akinlabi, E.T. Akinlabi:
Project administration, Writing - Original Draft.

Declaration of competing interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence
the work reported in this paper.

Data availability

No data was used for the research described in the article.

Fig. 11. GC-MS of bio-oil compound produced from PKS.
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