Results in Engineering 19 (2023) 101233

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Results in Engineering
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Natural adsorbent of corncob (Zea mays L.) powder capability in

purification of used cooking oil with shaking operation based on turbidity
Bode Haryanto *, Ilham Taufik Nasution, Aflah Fadliani Polem, Rondang Tambun,
Vikram Alexander
Department of Chemical Engineering, Universitas Sumatera Utara, Padang Bulan, Medan 20155, Indonesia

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

Keywords: In the purification process of used cooking oil, an adsorption technique utilizing corncob as the adsorbent can be
Adsorption applied. To optimize the purification, the shaking speed, adsorption time, and turbidity vary. Therefore, this
Corncob study was conducted in batch operation to determine the effect of suitable adsorption and reactions on shaking
Cooking oil
speed with variations in mass, size, and the contact time of the adsorbent for 5 h. During the experiment, the used
Shaking
Turbidity
cooking oil was subjected to the adsorption process using 100 mL of adsorbent, with mass variations of 2 g, 3 g,
and 4 g. The surface morphology of the adsorbent was characterized by modeling corncob and the oil compo­
nents of chemical compounds contained in the used cooking oil were examined before and after purification. The
parameters observed were measured using Scanning Electron Microscope-Energy Dispersive X-Ray (SEM-EDX),
Gas Chromatography-Mass Spectrometry (GCMS), Fourier-Transform Infrared Spectroscopy (FTIR), and
Brunauer-Emmett-Teller (BET). The results showed that the adsorbent with a size of 100 mesh, a shaking speed of
140 rpm, and a mass of 4 g exhibited a higher surface area and greater adsorption capacity. Furthermore, the
adsorbent also influenced the turbidity value of the used cooking oil, and prolonged contact between the
adsorbent and oil led to an increase in turbidity, particularly when using adsorbents of sizes 50 and 70 mesh.

1. Introduction contributing to the circular economy. It is projected that agricultural

In developing countries, a significant amount of food waste is
improperly handled, leading to environmental contamination daily. In
Indonesia, for example, 4.15 million hectares of land can be used for
corn cultivation, resulting in a net production of 15.79 million tons with
a moisture content of 14% [1]. Such high corn production inevitably
generates substantial waste, particularly in the form of corncobs. Sub­
sequently, corncobs, a lignocellulosic material with high potential can
be processed into various products. They consist of 41% cellulose, 36%
hemicellulose, and 16% lignin. Corn has emerged as a popular com­
modity, surpassing rice, due to its significant contribution as a primary
source of carbohydrates and protein. With their high cellulose content
and active compounds, corncobs have found utility as an adsorbent
capable of adsorbing various substances such as metals, dyestuffs, etc.
[2]. Cellulose in plants is a carbohydrate with a molecular weight of
2000–3000 glucose, formed from polysaccharides consisting of 1,4-
poly-glucose [3]. The utilization of biosorbents in adsorption offers
numerous benefits, such as enhancing economic sustainability and
waste biomass, including corncobs, will experience an annual growth
rate of 10% due to increasing global demand for agricultural products.
The annual production of corn cobs from agricultural waste currently
amounts to 230 million tons [4].
In this study, the materials used were corncob obtained from the
local market in Namo Pinang Village, Delitua, Sumatera Utara, and
waste cooking oil collected at Medan City, Indonesia, as shown in Fig. 1.
The average corn productivity in North Sumatra, Indonesia, in 2021
was projected to reach 63.00 (kw/ha), with a harvested area of 273.703
(ha) and production of 1.724.398 tons [5]. Corn recording will be very
dynamic, influenced by the rising oil prices. The demand for corn as an
alternative energy source, industrial raw material feed, and industrial
food will continue to increase in the future. The changes in the pattern of
demand for corn in the future need to be used as a reference in shopping.
Considering Indonesian vast territory, almost all regions have the po­
tential for corn cultivation. The extent to which corn crops are grown in
a particular area depends on the local population’s consumption habits.
Moreover, the utilization of corn cobs is hindered by the lack of

* Corresponding author.
E-mail address: bode.haryanto@usu.ac.id (B. Haryanto).

https://doi.org/10.1016/j.rineng.2023.101233
Received 20 March 2023; Received in revised form 12 June 2023; Accepted 12 June 2023
Available online 22 June 2023
2590-1230/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
B. Haryanto et al. Results in Engineering 19 (2023) 101233

process should possess a high cellulose content, allowing it to be syn­

thesized in solid form and reducing the free fatty acid (FFA) content of
used cooking oil [16]. In this study, the adsorption process was carried
out using corncob as an adsorbent.
Adsorption can also be carried out by mixing the adsorbent with oil,
followed by stirring, filtering, and refining [17]. During this process, the
adsorbent adheres to the surface of used cooking oil by shaking at speed
variation, which is related to the activation energy needed. Meanwhile,
excessive shaking at high speed can cause the adsorbate to be released,
resulting in reduced adsorption capacity. The shaking process also fa­
cilitates the contact between the surface of used cooking oil and the
adsorption compounds, thereby increasing the concentration efficiency
of the adsorbent by homogenizing the mixture [18].
Previous studies revealed that adsorption and equilibrium of adsor­
bate could occur on the surface of the adsorbent monolayer. The
adsorbent also interacts on its surface through a multilayer mechanism
with secondary interactions between dye molecules and the surface of
Fig. 1. Map of the study area in chemical engineering operations laboratory
the biosorbent. During this process, the dye will interact secondarily
and used cooking oil collected around universitas sumatera utara,
with the surface of the biosorbent through lignin-cellulose molecules
medan, Indonesia.
[19].
To optimize the process of oil purification, filtration and varying the
commercial industrial processing methods that could transform this
shaking speed with the adsorption time can be used. These variables are
plant waste into value-added products.
related to the energy required for the adsorbent to adhere to the surface
The recent population growth has led to an increase in the envi­
of used cooking oil. Meanwhile, excessive-high shaking speed can lead
ronmental problem, amount of energy released, and food consumption
to the release of adsorbate, leading to a decrease in the adsorption power
such as household cooking oil. Data shows that the consumption of
of the adsorbent. When the shaking process takes longer time, it will
cooking oil in Indonesia has increased by 1.1% from approximately 17.3
delay the separation process and the filtering results to be imperfect. The
million to 18.4 million tons per year [6]. Subsequently, this high con­
shaking process aims to provide ample time for the surface of used
sumption rate has led to large quantities of cooking oil production. This
cooking oil to come into contact with the adsorption compounds,
is because cooking oil serves as a more effective source of energy derived
thereby enhancing the efficiency of adsorbent concentration by creating
from plants and animals, which can also be made synthetically through a
a homogenous mixture with different particle sizes [18]. Therefore, this
refining process. Previous investigations established that 1 g of oil could
study aims to optimize the absorption of impurities in used cooking oil
produce 9 kcal/g, while carbohydrates and protein only generated 4
for turbidity and shaking speed by using corncob as an adsorbent.
kcal/g. The quality of the oil is largely determined by the fatty acids,
water content, impurity content, and whitening ability [7]. Contami­
2. Materials and methods
nated cooking oil can affect the quality, nutritional value, and appear­
ance of fried food. Therefore, the application of purified used cooking oil
In this study, the materials used are corncob obtained from the local
will significantly help industries that use the commodity for production
market in Namo Pinang Village, Delitua, Sumatera Utara (3◦ 55′North
[8].
98◦ 85′East) and 5 L of waste cooking oil collected from Medan,
One uncommon alternative source of energy and food that can be
Indonesia (3◦ 35′North 98◦ 40′East). The instrument used is aluminum
reused as fuel is purified used cooking oil. Based on its composition, used
foil, sieve tray (RLS Test Sieve Analysis Mesh Mart’l S/Steel 50 mesh, 70
cooking oil contains carcinogenic compounds that are formed during the
mesh, 100 mesh), cutter, ball mill (using Hawker Siddeley Brook
frying process. Additionally, the chemical and physicochemical
Crompton Parkinson Motors), beaker glass, measuring cup, digital bal­
composition has a significant effect on its nutritional value and quality
ance (Mettler Toledo, ME 2014, 0.0001 accurate), pH meter, filter
of consumption [9]. To ensure the effective recycling of used cooking
paper, oven (Memmert), shaker (SWB–B Biobase), Scanning Electron
oil, it is crucial to purify the intermediate regeneration base obtained
Microscope-Energy Dispersive X-Ray (SEM-EDX, JEOL JSM-6510LA),
from the previous step [10]. The purification process involves the use of
Gas Chromatography-Mass Spectrometry (GC-MS, Shimadzu GCMS-
an adsorption technique employing an adsorbent such as corncob, with
OP2010 SE), Brunauer Emmett Teller (BET) Surface Area (Quantach­
variables such as shaking speed, adsorption time, and turbidity.
rome Autosorb-IQ), Fourier Transform - Infra Red (FTIR, PerkinElmer
To improve the quality of vegetable oil, the refining process usually
UATR Spectrum Two) and Turbidity meter (ORION AQ4500). This study
includes degumming, adsorption, alkali neutralization, bleaching,
was carried out in June 2022 in Chemical Engineering Operations
deodorization, and dewaxing [11]. However, traditional degumming
Laboratory with ambient temperature and standard atmospheric tem­
techniques used in the vegetable oil industry require high temperatures
perature, Universitas Sumatera Utara, Medan, Indonesia.
and consume more energy. This makes it necessary to develop green
purification techniques [12].
2.1. Preparation of corncob adsorbent
In purification applications, the use of adsorbents is indispensable
because the cost is relatively low. Generally, adsorption is also consid­
To cleanse the corncob samples, they were washed with water until
ered an economical and effective method because it is inexpensive,
the pH of the washing solution reached neutrality. Subsequently, the
regenerative, and simple [13]. Furthermore, it can be carried out by
corncobs were dried in an oven at 60 ◦ C to until a constant weight was
using natural polymers, activated carbon, synthetic polymers, tea resi­
achieved [20]. The corncob was crushed into powder [21] by ball mill
dues, orange and charcoal peels, as well as pomelos, and even shellfish
and filtered using a sieve tray with sizes of 50, 70, and 100 mesh to
shells are also used for removing Pb, Zn, and Cu from rainwater [14].
obtain the weight of 2 g, 3 g, and 4 g. Meanwhile, a beaker glass was
Various types of locally made bio-adsorbents derived from plant
filled with 100 mL of used cooking oil. The sample was allowed to stand
biomass, such as Colocasia esculenta leaves, active biochar, mangrove
and the turbidity was measured every 20 min for 5 h [22].
leaf residue, tea powder from rubber leaf waste, and neem leaf powder
can be applied [15]. An effective adsorbent used in the purification

2
B. Haryanto et al. Results in Engineering 19 (2023) 101233

2.2. Turbidity of used cooking oil in shaking treatments [29].

(C0 − Ce )V
Preparation of the waste cooking oil obtained was allowed to stand qe = (1)
W
for 20 min to settle by gravity [22], 100 mL sample was taken and
poured into a beaker glass. The sample was mixed with 2 g, 3 g, and 4 g Information:
of corncob adsorbent in the form of non-activated powder with particle qe = Absorption Capacity (mg/g).
sizes of 50, 70, and 100 mesh, respectively [23]. Then the beaker glass Co = Initial Concentration (mg/L).
was placed on a shaker for 3 h with variations in shaking speeds of 70, Ce = Final Concentration (mg/L).
100, and 140 rpm, as shown in Fig. 2. V = Volume of Solution (L).
Fig. 2 shows the scheme of the corncob preparation process for use as W = Weight of Adsorbent (g).
an adsorbent in the purification of used cooking oil through shaker-
batch adsorption and turbidity measurement. A total of 5 mL sample 2.4. Determination of adsorption kinetics model
was taken every 20 min and the turbidity was measured with a turbidity
meter for 5 h. Subsequently, the adsorbent with the best adsorption The kinetic models were widely used to analyze the dynamic
power was tested using the Scanning Electron Microscope-Energy adsorption behaviors in a batch system and identify the mass-transfer
Dispersive X-Ray (SEM-EDX) and Brunauer-Emmett-Tellers (BET) anal­ mechanisms. This was carried out to identify the curve characteristics
ysis. Moreover, various studies showed the effectiveness of adsorption as of the kinetic models and determine the optimum model by error
a treatment method [4,24–27]. These showed that these adsorbents functions [30]:
could be utilized to efficiently remove impurities or pollutants, thereby
V (C0 − Ce )
offering an optimal solution. qt = (2)
m

2.3. Determination of adsorption capacity with variations in mass and Where:

size of adsorbents
To determine the adsorption capacity with variations in the mass and
size of the adsorbents, batch adsorption studies were conducted using
different initial parameters, adsorbent mass, kinetics, and capacity [24].
The adsorption capacity was estimated to determine the ability of an
adsorbent to adsorb an adsorbate [28]. The equation below was used to
calculate the number of substances adsorbed with corncob adsorbent
qt = adsorption capacity at time t (mg/g).
V = volume of used cooking oil (L).
Co = initial concentration of cooking oil (mg/L).
Ce = final concentration of cooking oil (mg/L).
m = mass of dissolved adsorbent (g).
The first-order kinetic equation is determined using the equation
below [31]:

Fig. 2. Scheme of corn cob preparation as adsorbent for used cooking oil purification. in Shaker-Batch Adsorption and Turbidity Measurement.

3
B. Haryanto et al.
k1
log(qe − qt ) = log qe − t (3)
2.303
Where:
Qe = adsorption capacity at equilibrium (mg/g).
Qt = adsorption capacity at time t (mg/g).
k1 = pseudo-first-order adsorption rate constant (min− 1).
The second-order kinetic equation is determined by the following
equation [31]:
1 1 1 value of used cooking oil on natural adsorbents decreases constantly.
= + t (4)
qt k2 q2e qe
Where:
Qe = adsorption capacity at equilibrium (mg/g).
Qt = adsorption capacity at time t (mg/g).
K2 = pseudo-second-order adsorption rate constant (g.mg− 1. min− 1).
2.5. Calculation of removal percentage
The percentage removal of waste from cooking oil was calculated by
using the following Equation (5) [32].
(Ci − Ce)100%
Percentage removal = (5)
Ci
Where Ci = the initial concentration (mg/l).
Ce = the equilibrium concentration (mg/l).
3. Result and discussion
3.1. Effect of adsorbent surface area on turbidity
The availability of absorption is influenced by various factors, as
indicated in a previous study. These factors include the surface area,
which is determined by the particle size and the total amount of
adsorbent [33]. Therefore, the smaller the particle size, the larger the
surface area, and a larger area led to the adsorption of more substances
[34]. The relationship between turbidity and time is shown in Fig. 3 to
determine the effect of the adsorbent surface area on decreasing the
turbidity of used cooking oil.
Fig. 3 illustrates the relationship between turbidity and time with a
speed of 140 rpm. In the experiment, the adsorbent mass was 4 g, with
size variations of 50, 70, and 100 mesh. The measurement of the
turbidity of used cooking oil was carried out for 5 h with a time interval
of every 20 min. The initial turbidity recorded at the start of the process
was t0 = 122 NTU.
The graph demonstrates a significant difference in turbidity with and
without the presence of the adsorbent. At t = 20 min, the turbidity was
measured at 51.8 NTU for the variation of the 50 mesh adsorbent, and
Fig. 3. Turbidity of used cooking oil along time with Corncob adsorbent mass of 4 g
and Shaker Speed of 140 rpm.
4
Results in Engineering 19 (2023) 101233
37.5 NTU was obtained after the adsorption process for t = 5 h. At 70
mesh size adsorbent and t = 20 min, the turbidity was 43.2 NTU and
recorded at 28.6 NTU at t = 5 h after the adsorption process. For 100
mesh size adsorbent, t = 20 min the turbidity was 30.5 NTU and 15.8
NTU at t = 5 h after the adsorption process.
Based on the graph above, it can be concluded that the size of the
adsorbent also influenced the turbidity of the used cooking oil. The data
suggest that the 100 mesh size adsorbent possesses a larger surface area
compared to the 50 and 70 mesh sizes. At several points, the turbidity
This showed that the use of adsorbents will have a significant impact on
surface and particle absorption. A natural adsorbent with a 100 mesh
size exhibits a larger surface area, resulting in enhanced adsorption
capacity by creating active adsorbent pores, thereby promoting greater
absorption [35]. A reduction in the diameter of the adsorbent will in­
crease the surface area, widening the surface area, and improving the
adsorption process. Subsequently, it was also reported that adsorption
d as the mesh size increases [36]. This was because a larger mesh size
reduced adsorbent particle size, yielding greater surface area for
adsorption [37]. Previous investigations explored the relationship be­
tween adsorbent surface area and adsorption, such as the use of chem­
ical AgNPs for the adsorption of methylene blue and malachite green as
photocatalysts for the degradation of cationic dyes [38] and the appli­
cation of water hyacinth and arum shoot powders for Cr and Cu removal
from tannery effluents [39]. This result was in line with the previous
theory, stating that the adsorption power was directly proportional to
the increase in the surface area of the adsorbent.
3.2. Effect of mass of natural adsorbent on the adsorption ability to
reduce the turbidity of used cooking oil
The relationship between turbidity and the amount of adsorbent can
be established, and this aimed to determine the effect of adsorbent mass
on decreasing the turbidity of used cooking oil. The adsorbent was used
for the adsorption of impurities in oil or triglyceride compounds.
Therefore, the weight of the adsorbent was determined to identify the
effect of additional weight on the adsorption capacity. Based on the
results, the increase in brightness and yellowness of the oil was caused
by a higher surface area. This was because, with the wider surface area
of the adsorbent, more impurities in the oil were absorbed, thereby
increasing the clarity, brightness, and yellowness [40].
This study was carried out using variations in sizes of the adsorbent,
specifically 100 mesh, which were used with masses of 2 g, 3 g, and 4 g,
along with a stirrer speed of 140 rpm (See Fig. 4). From the graph, it was
discovered that at t = 20 min, the turbidity was 35.0 NTU and became
19.5 NTU after reaching the final time t = 5 h. At 3 g of adsorbent mass
with a speed of 140 rpm, the final turbidity obtained at t = 5 h was 17.0
NTU. Meanwhile, for a mass of 4 g at a speed of 140 rpm, the final
turbidity obtained at t = 5 h was 15.8 NTU. The heavier the adsorbent
B. Haryanto et al.
Fig. 4. Turbidity of used cooking oil along time graph with 100 mesh Corncob natural adsorbent size and 140 rpm shaker speed and waste cooking oil sample.
used, the higher the value of the adsorption efficiency on ions. This was
because an increase in adsorbent weight was proportional to the number
of particles and surface area. This will also increase the number of
binding sites for metal ions and the adsorption efficiency [41].
The graph above presented the result of an experiment with varia­
tions in mass, adsorbent size, and stirrer speed. The optimum weight
obtained was the adsorbent with a mass of 4 g, a turbidity level of 8.97
NTU, size of 100 mesh at a speed of 70 rpm. This was followed by 7.8
NTU, size 100 mesh at 100 rpm, and 6.56 NTU at 100 rpm, size 100 mesh
with a speed of 140 rpm. This study aligned with the theory that an
increase in the adsorbent leads to a higher adsorption value.
3.3. Determination of adsorption capacity with variations in mass and
size of adsorbents
Fig. 5 showed the results obtained from an experiment using a
sample in the form of used cooking oil with variations in shaking speed.
For the adsorbent with a mass of 4 g, size 100 mesh, and a stirrer speed of
70 rpm for 5 h, the adsorption capacity was 11.828 mg/g. Similarly, a
sample with a mass of 4 g, a size of 100 mesh, and a stirrer speed of 100
rpm exhibited an adsorption capacity of 12.102 mg/g, while a speed of
140 rpm yielded 12.372 mg/g.
Adsorption kinetics involves studying the rate at which an adsorbent
absorbs an adsorbate, providing insights into the adsorption ability of
the adsorbent. In this study, first-order pseudo-kinetic modeling (PFO)
and second-order pseudo-kinetic modeling (PSO) were used. The PFO
model establishes a relationship between the adsorption rate and the
number of accessible adsorption sites on the adsorbent, while the PSO
model is used to describe how the adsorption capacity of the adsorbent
material varies with time [24].
The discussion of the results was evaluated using first-order and
second-order kinetics models, which show the relationship between log
Fig. 5. Adsorption capacity value with the variation of shaking speed and
Corncob adsorbent mass of 4 g and 100 mesh size.
5
Results in Engineering 19 (2023) 101233
(qe – qt) and t (minutes) as well as t
qt and t (minutes), respectively.
First- and Second-Order Pseudo Kinetic Models on 100 mesh Natural
Adsorbent with a Speed of 140 rpm are presented below.
Figs. 6 and 7 were first-order and second-order pseudo modeling
graphs, respectively, focusing on 100 mesh natural adsorbents with a
speed of 140 rpm. Fig. 6 showed the value of the correlation coefficient
(R2) on the 4 g, namely R2 = 0.2228 value. The value of t/qt increased
with the addition of time due to the ability of the adsorbent to absorb
used cooking oil during the adsorption process. The shaking process was
used to ensure effective contact between the adsorbent particles and the
compounds present in the used cooking oil [42].
Fig. 7 showed the value of the correlation coefficient (R2) on the 4 g
adsorbent, namely R2 = 0.9979 value. The closer the value to 1, the
better the regression value [43]. From these two graphs, the
second-order pseudo modeling displayed higher precision in the
adsorption data compared to the first-order model, as evident from the
improved correlation coefficient (R2). This indicates that the
second-order pseudo modeling was the right adsorption data. Therefore,
it can be concluded that the adsorption process involved chemical in­
teractions (chemisorption) between the adsorbent and the adsorbate
characterized by a higher correlation coefficient of second-order.
The kinetics of adsorption influenced the changes in turbidity of the
adsorbent over time. The reduction in turbidity indicated the successful
activation of the adsorbent’s chemical composition and the formation of
active sites [44]. From the experimental results, the adsorbent mass of 4
g and the size of 100 mesh with a stirrer speed of 140 rpm had the largest
capacity. This showed that the weight of the adsorbent played an
important role in adsorption capacity because an increase in the amount
of adsorbent also improved the adsorption capacity [41]. The speed of
Fig. 6. First-order pseudo modeling on 100 mesh Corncob natural adsorbents
with a shaker speed of 140 rpm.
B. Haryanto et al. Results in Engineering 19 (2023) 101233

Effect of Mass, Size, and Surface Area

turbidity level of the cooking oil,

Results of Present Study (Corncob)

2 g, 3 g, 4 g, and 50, 70,100 mesh

• The corncob 100 mesh and 140

modeling was (R2) close to 1.

of Natural Adsorbent Ability to

• The best adsorption kinetics

rpm effectively reduced the

the optimum weight of 4 g,

Reduce the Turbidity of UCO
Shaking (3 h)

140 rpm
Corncob

70,100,

• Best batch adsorption experiment at pH 7,

(COD) use first and second-order pseudos.

ZnO dose 4.0 g, 120 min, 200 rpm, color
removal is 75% (N), 69 (NH3), and 79%
Use of zeolite adsorbent to remove 80% of
Fig. 7. Second-order pseudo modeling on 100 mesh Corncob natural adsorbent

Waste water from the rubber processing

with a shaker speed of 140 rpm.

shaking in the adsorption process also played an important role, there­

106–150 μm dried at 105 ◦ C

fore, the lower the speed, the slower the adsorption, and vice versa [45].

pollutants several samples

Table 1 provide information about previous investigations on cooking
oil adsorption by using various adsorbents.

Dried at 24 h
Zeolite [44]
3.4. Characterization and analyses

industry
3.4.1. Results of scanning electron microscope (SEM) and Energy
Dispersive X-ray (EDX)

Original bio adsorbent adsorption

• The highest removal (93.75%)

with an optimum dose of 23.9

• The R2 value obtained is 0.99

industrial effluents with (OFAT)
SEM-EDX is used to determine the morphology, elemental compo­

capacity for dye removal from

Particle size 0.053–0.075 mm

mg/100 mL with a shaking

Charcoal, and Rice Husk Ash
sition, and density of particles emitted from a sample [48] based on the
results of the Energy Dispersive X-Ray (EDX). Meanwhile, SEM is used to

(black and white) [43]

observe the surface of the adsorbent with high resolution, most of which

time of 356 rpm.

and (30 ± 0.5 ◦ C)
are equipped with an EDX detector to enable a fast elemental analysis of
the adsorbent. EDX provides qualitative and quantitative information on
the composition of the sample [49]. It can also be used to determine lost

method
chemical elements during the adsorption process. The morphology and
elemental content of natural adsorbents before and after treatment are –
shown in Fig. 8 (a) and (b). –

activated charcoal of breadfruit peel and

Improved cooking oil quality (%) change in
FFA content, peroxide, and color change of
Based on the results of SEM in Fig. 8(a) and (b), the surface shape of

the market in reducing free fatty acid

levels in used cooking oil from frying
• Difference between the adsorbent of
the natural adsorbent before and after treatment with the distance be­
tween pores shows a difference. However, the pores of the adsorbent
before treatment are slightly more open with small elongated round
shapes containing used cooking oil and are cleaner after treatment. In
Fig. 8(a), the SEM image shows the surface of the corncob adsorbent
Bread fruit skin [47]

oil after purification

before adsorption, displaying an irregular structure with numerous

Previous investigations on cooking oil adsorption by using various adsorbents.

small pores. These pores appear as small elongated round shapes con­
taining remnants of used cooking oil. Conversely, Fig. 8(b) displays the
SEM image of the corncob adsorbent’s surface after adsorption. This is
because the adsorbent has reacted with the used cooking oil. The pres­
ence of cellulose in the adsorbent, characterized by –OH ions, contrib­
–

–
–

utes to the adsorption process. This proves that the adsorption process
(1.5, 2.5, 3.5, 4.5, 5.5, 6.5, and 7.5) g in 50

• The mass yield of activated charcoal is

5.5 g (80 min) with a water content of

can improve the ability to adsorb impurities in used cooking oil, and this
Reduction of peroxide number, water

indicated that the more pores formed, the larger the surface area of the
content, and Free Fatty Acid in used

peroxide 2.4617 meq/kg 89.15%

0.0559% of 97.91% (capacity)A

adsorbent produced. The loss of substances from the used cooking oil
can cause the pores to be united and increase the adsorption ability [50].
Furthermore, the temperature and contact time influence the effective
Ironwood sawdust [46]

surface area represented by the pores [51]. The elemental content of the
40, 60, and 80 min.

adsorbent is presented in Table 2.

Previous Studies

The EDX analysis results revealed the presence of several chemical

reduction

elements in the unpurified natural adsorbent of corncob, including

cooking

carbon (C), oxygen (O), potassium (K), and copper (Cu). However, after
purification, corncob absorbed two other elements, silica (Si) and zinc
g

(Zn). The presence of the element Si was attributed to SiO2 of corncob

and the Zn element was obtained from the content of used cooking oil.
Mass, Size, and
Temperature

Speed Shaking

Based on Table 2, carbon compounds (C) had higher weight and

Hypothesis
Parameter

Adsorbent

atomic percentages before and after purification compared to other

Table 1

Result
Time

compounds, namely 69.79% and 75.66%, as well as 74.28% and

79.64%, respectively. These carbon compounds contribute to enhanced

6
B. Haryanto et al. Results in Engineering 19 (2023) 101233

Fig. 8. (a) SEM result of corncob adsorbent surface morphology before adsorption with 1000 times magnification, (b) SEM result of corncob adsorbent surface
morphology after adsorption with 1000 times magnification.

drying process before using EDX analysis, leading to a reduction in the

Table 2
oxygen content of the adsorbent.
EDX analysis results on corncob adsorbent before and after adsorption of used
The weight and atomic percentages of K and Cu elements also
cooking oil at 1000 time magnification.
decreased after purification, indicating an improvement as they were
No Chemical % Weight % Atom
impurities present in the used cooking oil. Table 2 demonstrates that
Compounds
Before After Before After corncob can be applied as an adsorbent for used cooking oil to be pu­
Adsorption Adsorption Adsorption Adsorption rified using a shaker for treatment. The table also showed the SEM re­
1 C 69.79 74.28 75.66 79.64 sults of corncob adsorbent surface morphology before adsorption with
2 O 29.79 25.12 24.23 20.22 1000 times magnification. Based on the EDX analysis, corncob can be
3 K 0.20 0.07
– –
applied as an adsorbent to adsorb compounds in used cooking oil.
4 Cu 0.24 0.33 0.05 0.07
5 Si – 0.08 – 0.03
6 Zn – 0.19 – 0.04 3.4.2. Results of Gas Chromatography-Mass Spectrometry (GCMS)
GCMS is a tool used to detect the main compounds of oil components
and volatile compounds with high separation efficiency as well as sen­
adsorption power and improved efficiency of the adsorbents [52]. On sitive detection with various components [53]. In this study, the GCMS
the other hand, the weight and atomic percentages of Si in the purified was applied to analyze the compounds in the sample before purification
natural adsorbent were the lowest at 0.08% and 0.03%, respectively. and the results were presented in Fig. 9.
The reduced oxygen (O) content of the corncob adsorbent was due to the

Fig. 9. Results of GCMS analysis for used cooking oil (a) before purification and (b) after purification with Corncob natural adsorbents.

7
B. Haryanto et al. Results in Engineering 19 (2023) 101233

Fig. 9(a) and (b) display the results of GCMS chromatography anal­ Table 4
ysis for used cooking oil before and after purification, respectively. The GCMS analysis compounds results contained in used cooking oil after
chromatograms revealed that four fatty acid compounds exhibited the purification.
highest peaks, namely peak numbers 6 and 9 for used cooking oil before Number Peak Time Area Highest Components of Chemical
purification and with natural adsorbents, respectively. The number of Retention (Minutes) % Peak Compounds
peaks indicated the number of compounds contained in the used cooking 2 41.824 13.04 6,277,464 Hexadecanoic acid, methyl
oil before the purification. However, peaks with a small area were ester (CAS)
ignored because they were very few. The 5 peaks in the chroma tog had 4 45.984 16.80 7,904,827 9-Octadecenoic acid (Z)-,
methyl ester (CAS)
different retention times, which indicated 5 various compounds. The
6 50.349 16.75 6,955,969 Hexadecanoic acid, 2-hy­
area of each peak also showed the percentage of the compound. droxy-1,3-propanediyl
Based on the chroma tog above, the comparison between the fatty ester (CAS)
acid compounds of used cooking oil before and after purification with 9 53.995 34.21 10,185,769 9-Octadecenal, (Z)- (CAS)
natural adsorbents is presented in Tables 3 and 4.
Tables 3 and 4 showed that both the pre-purified and post-purified
results in Fig. 10(a) showed that comparison before the adsorption of
samples of used cooking oil, treated with natural adsorbents, con­
used cooking oil contained C–H stretching groups at wave peaks of
tained various types of compounds. However, they shared three com­
3006.01 cm− 1, 2922.13 cm− 1, and 2853.17 cm− 1, the C– – O group
mon fatty acid compounds, namely Hexadecanoic acid, methyl ester
stretching at the peak of the 1743.53 cm− 1, the C–H bending group at
(CAS), 9- Octadecenoic acid (Z)-, methyl ester (CAS), and Hexadecanoic
the wave crests was 1461.83 cm− 1 and 1375.97 cm− 1. There was also
acid, 2-hydroxy-1,3-propanediyl ester (CAS). Among these compounds,
C–O group stretching at wave crests 1235.81 cm− 1, 1160.04 cm− 1, and
9-Octadecenal,(Z)- had the highest retention time and area for used
1116.21 cm− 1, group = C–H bending at the crests 721.68 cm− 1, the C–Br
cooking oil before purification, namely 53.984 min and 27.21%. After
group stretching at the peak of the 587.94 cm− 1, and the C–I group
the purification process with natural adsorbents, the compound 9-Octa­
stretching at the wave crest of 458.56 cm− 1. Based on Fig. 10(b), it was
decenal, (Z)- (CAS) displayed a retention time of 53.995 min, an area of
discovered that used cooking oil contained C–H stretching groups at
34.21%, and the highest peak at 10,185,769. Based on the GCMS
wave peaks of 3005.92 cm− 1, 2922.17 cm− 1, and 2853.18 cm− 1, the
analysis, the efficiency of compound removal was determined based on – O group stretching at the peak of the 1743.54 cm− 1, the C–H bending
C–
percentage removal (calculated using equation (5)). The analysis
group at the wave crest of 1461.82 cm− 1 and 1375.95 cm− 1, C–O group
revealed an efficiency of 28.08% for the 9-Octadecenoic acid (Z)-, methyl
stretching at wave crests 1235.86 cm− 1, 1160.11 cm− 1, and 1116.11
ester (CAS) compound and 24.37% for hydroxy-1,3-propanediol ester
cm− 1, group = C–H bending at the wave crest of 721.73 cm− 1, the C–Br
(CAS) compound.
group stretching at the peak of the 583.71 cm− 1 wave, and the C–I group
In the second test, it was found that the oil contained free fatty acid
stretching at the crest of the 458.00 cm− 1 wave. The wavelength values
compounds, including methyl ester compounds, can be utilized as bio­
on corncobs after adsorption are found to be smaller compared to the
diesel. Methyl ester compounds can contribute to environmental pro­
wavelength values on cellulose compounds after adsorption. Cellulose is
tection because they are biodegradable, non-toxic, and produce fewer
a biopolymer used in the process of separation or purification. The
emissions of sulfur oxides and greenhouse gases [54]. According to SNI
disparity in the spectra between the two substances is attributed to
7709: 201,217, the standard content of free fatty acids in the oil should
intermolecular interactions occurring during the adsorption process.
not exceed 0.3% [55]. The refining process of used cooking oil through
The FTIR reading ranging from 400 cm− 1 to 4000 cm− 1 are then
shaking proved effective in removing impurities, thus making it useful
matched accordingly with the classification of the types of functional
when processed appropriately.
groups based on their wavelength. The post-adsorption results indicate
an increase in wavelength and functional group content on the adsor­
3.4.3. Results of the Fourier Transform infrared (FTIR)
bent, specifically the presence of –CH, –OH, and –CO functional groups,
FTIR spectroscopy is an effective tool to characterize and identify the
showing the effectiveness of corncobs as an adsorbent. In a previous
structure of organic molecules for studying oil and fat. Furthermore, it
study, FTIR analysis successfully identified a reduction in functional
can also be used to determine the presence of chemical functions in the
groups in Graphene oxide (GO) and reduced graphene oxide (rGO)
molecule [56]. In this study, FTIR analysis was carried out to determine
synthesized from graphite powder while comparing their adsorption
the functional groups contained in used cooking oil before and after
properties towards a cationic dye called methylene blue (MB) [57].
purification. The IR transmittance spectrum was shown in Fig. 10(a) and
Therefore, it can be concluded that used cooking oil before and after
(b).
adsorption contains the same functional groups, namely alkanes, al­
After purification, the corncob powder exhibits an increase in the
kenes, esters, alcohols, and alkyl halides.
wavelength value of the –CH, –OH, and –CO groups compared to before
purification because the group reacted with cellulose. The spectral
3.4.4. Results of Branauer Emmett Teller (BET)
The results of the Branauer Emmett Teller (BET) were used to
determine the surface area, and pore volume [24]. The BET equation is
Table 3
used for determining the surface area of solids from the nitrogen tem­
GCMS analysis compounds results contained in used cooking oil before
peratures. However, the equation can be used with a wide range of other
purification.
gases, as well as vapors at ambient temperature and pressure [58]. Most
Number Peak Time Area Highest Components of Chemical
solids have cavities inside their structure known as porosity and are
Retention (Minutes) % Peak Compounds
classified by size, type, and shape as a whole. Effective or useful porosity
4 41.820 18.13 13,691,721 Hexadecanoic acid, methyl consists of interconnected cavities capable of passing fluids with a ratio
ester
of the volume of cavities to the total volume of matter [59].
5 45.840 6.12 4,423,406 9,12-Octadecadienoic acid
(Z, Z)-, methyl ester Fig. 11(a) showed the BET result before adsorption, in which the
6 45.978 22.15 16,083,179 9-Octadecenoic acid (Z)-, surface area was 7.977 m2/g, the pore volume was 0.014 cc/g and the
methyl ester pore radius Dv(r) was 19.110 Å (Table 5). After the adsorption process,
9 50.336 15.02 9,745,806 Hexadecanoic acid, 2-hy­
Fig. 11(b) showed the BET result, with a surface area of 3.002 m2/g, a
droxy-1,3-propanediol
ester pore volume of 0.008 cc/g, and a pore radius Dv(r) of 15.268 Å. The data
13 53.984 27.21 12,777,490 9-Octadecenal, (Z)- presented in Fig. 11 (a) and 11(b) were obtained at a Nitrogen

8
B. Haryanto et al. Results in Engineering 19 (2023) 101233

Fig. 10. IR transmittance spectrum of used cooking oil (a) before purification and (b) after purification with corncob natural adsorbents.

9
B. Haryanto et al. Results in Engineering 19 (2023) 101233

Fig. 11. BET result (a) before adsorption, (b) after adsorption of Corncob adsorbent.

10
B. Haryanto et al.
Table 5
BET surface area (SBET) of prepared corncob adsorbents on used cooking oil purification.
No Surface Area (m2/g) P0 (Torr)
Before Adsorption After Adsorption Before Adsorption After Adsorption
1 773.12 772.40
2 7.977 3.002 773.13 772.23
3 773.15 771.60
temperature of 77.350 K, with a molecular weight of 28.013, a cross-
section of 16.200 Å, and a liquid density of 0.808 g/cc. Subsequently,
it was discovered that the surface area value decreased after the
adsorption process. This was because the pores of the adsorbent had
absorbed the adsorbate and become saturated.
4. Conclusion
The results showed that the corncob with a size of 100 mesh and a
speed of 140 rpm effectively reduced the turbidity level of the cooking
oil. This result can be attributed to its superior adsorption capacity and
larger surface area compared to other adsorbents with 50 and 70 mesh
sizes. Moreover, the optimum weight of 4 g yielded the best adsorption
kinetics modeling, which was obtained from the second-order kinetic
model with a correlation coefficient (R2) close to 1. This indicated that
corncob can be effectively used as a locally available adsorbent for used
cooking oil waste based on turbidity. For future investigations, it is
recommended to compare the adsorption method with continuous
processes to enhance the adsorption efficiency using corncob as an
adsorbent. Furthermore, the purifier oil should be further analyzed for
its potential use in biodiesel production.
Authors contributions
B.H. doing conceptualization, validation data and supervision. I.T.N
performing analysis and investigation. A.F.P collecting resources and
formal analysis. R.T. provides methodology and supervision. V.A. doing
writing, review and editing manuscript.
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
Data will be made available on request.
Acknowledgments
This paper is the result of PDUPT Research Project 2022 with No. 8/
UNS.2.3.1/PPM/KPDRTPM/TII/2022. The authors wish to express
sincere gratitude for the financial support for this research project to
Direktorat Riset, Teknologi, dan Pengabdian Kepada Masyarakat,
Kementerian Pendidikan, Kebudayaan, Riset dan Teknologi, with Proj­
ect contract No. 201/E5/Pg.02.00.PT/KPTALENTA USU/2022.
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