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Jezza Faith H. Bitang1, Jessa Mae B. Cabeza1, Erwin Roi S. Pacot1, and
Karyn Chrislene A. Vitor2*
Department of Teacher Education1, Department of Arts and Sciences Education2, UM Tagum
College, Tagum City, Philippines
*Corresponding author: [email protected]
ABSTRACT
Improper disposal of waste cooking oil is a growing problem in many urban countries along
with hazardous and solid wastes. In this study, waste cooking palm oil (WCO) was used to
produce alternative fuel resources such as biodiesel. The raw waste cooking oil was collected
from a local chicken establishment of Tagum City, Davao del Norte. Through
transesterification, potassium hydroxide (KOH) and sodium hydroxide (NaOH) were used as
catalysts in two (2) different reaction times, 60 minutes and 120 minutes. Percentage volume
yield was obtained. T-test was used to determine significant differences between the catalysts
in 60-minute and 120-minute reaction time. The production of biodiesel from a low-cost WCO
was successful. Research findings showed that the volume yield of biodiesel using NaOH and
KOH within 60-minute reaction time were 36.5% and 70.17%, respectively. The biodiesel
yield obtained using NaOH and KOH within 120-minute reaction time were 50.5% and
58.67%, respectively. T-test revealed a significant difference between NaOH and KOH
catalysts within a 60-minute reaction time but no significant difference within 120-minute
reaction time. It is recommended that policies must be locally adapted to enhance waste
reduction.
INTRODUCTION
Fossil energy is the primary energy contributor globally for industrial, technological, social,
and economic progress (Yildiz, 2018). Crude oil is the most abundant energy source among
varieties of fossil fuels accounting for roughly 33.1%, followed by coal with 27.0%, natural
gas with 24.2%, and others with 15.7% of fossil energy as of 2019. Despite its positive impact
on global change, it has been the dominant source of air pollution, which results in the
greenhouse effect and global climate crisis (Perera, 2017). In 2017, according to the Global
Carbon Project (GCP), the annual CO2 emission is largely contributed by Asia with 53% global
emission, where China produces 10 billion tons a year, representing more than a quarter of the
annual global emissions, followed by the USA in North America with 18% of global emissions.
Africa and South Africa account for 3-4% global emission, relatively small in value. The
Philippines has had a steady increase in CO2 emission since 2011 with 83.53 million tons of
CO2, and in 2017, it reached 127.61 million tons of CO2 (Le Quéré et al., 2018). The Fifth
Assessment Report (2013) of the International Panel on Climate Change (IPCC), the perpetual
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greenhouse gas emission will extend above the pre-industrial level. There was a recorded
average increase of global temperature of 0.85˚C from 1880 to 2012, and the Arctic ice is
continuously melting with 1.07 × 106 km² of ice loss per decade since 1979. In effect, polar
ice will continuously melt and they predict that the sea level will rise 40 -63 cm by the end of
the century (Quinn et al., 2013).
International organizations like the United Nations (UN) and the European Union (EU) suggest
countries imposing policies to lessen carbon emission and reduce reliance on fossil fuels as
energy system sources (da Silva, 2015; Ghazouani et al., 2020). The Philippines contributes
0.35% of the total CO2 emission globally however, it is one of the most affected countries to
the effects of climate change. As a member state of the UN, the Philippines is committed to
lowering the carbon footprint together with other member states convened in the Conference
of Parties. The transportation sector was emphasized the highest on CO2 emission contribution
compared to the manufacturing sector. This is due to the vulnerability of the Philippine
economy from the effects of climate change (Durana, 2017).
The fossil fuel reserves are limited and expected to diminish until fully consumed (Owusu &
Asumadu-Sarkodie, 2016). The concern on the depleting fossil fuel resource and the urgency
of the global climate crisis has led the Environmental advocate to suggest the EU on banning
crop-based fuels and resort to second-generation biofuels- biofuels made from wastes oils and
algae, instead of the first-generation biofuels which are made from raw feedstock (Keating,
2019). The steady increase in global consumption of biofuel expects to consume 12% of coarse
grain, 28% of sugarcane, and 14% of vegetable oil of the total global production of these crops
by 2023. It implies that with the increase of biofuel consumption, food security is at risk due
to competition of food and fuel over a limited land area (da Silva, 2015; Najeeb, 2021). As a
result, alternative fuels have been widely developed for fossil fuel replacement (Reijnders,
2009). These alternative fuels include straight vegetable oils (SVOs), bioethanol, glycerol,
hydrogen, Coal to Liquid technology (CTL), and biodiesel (Sangeeta, et al., 2014).
Sixty per cent (60%) of energy is produced from fossil fuel in the Philippines. Primary diesel
imports are from countries such as the United Arab Emirates (UAE) and Russia, where they
provided 35% in 2013, according to U.S. Energy Information Administration (2014). Gasoline
and diesel are the most common types of fuel imported in the country where alternative
resources are produced within the country with its natural resources. Like any other country,
the energy demand of the Philippines is increasing with time such that fuel consumption of the
country will also increase (Mondal, 2018). Policies and programs have been imposed to address
the demands of the biodiesel industry in the Philippines. The Biofuel act of 2006 (RA 9367)
was passed into law to reduce the country’s dependence on imported fuels. It includes the
mandate to adopt sustainable and renewable local biodiesel and encourage investors to do so
through incentives in producing and utilizing locally produced biofuel (Official Gazette of the
Republic of the Philippines, 2007; Philippine Board of Investments, 2011).
Despite the law mandating the 10% minimum blend of bioethanol for all liquid fuels in the
Philippines by the year 2011, there has been no recommendation from National Biofuel Board
(NBB) for the Department of Energy (DOE) to increase its blend as specified on Section 5.2
of the said act. The 5% minimum bioethanol blend was not implemented in 2015 due to high
coconut oil prices, which would lead to an increase of fuel in the market. The United Nations
Conference on Trade Development (UNCTAD) identified the Philippines as “likely remains a
net importer of fuel” since local oil companies have been importing ethanol from Thailand to
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be consistent with the 10% ethanol blend requirement. It implies that the Biofuel Act of 2006
has not been able to meet its intended outcome (Olchondra, 2014; Corpuz, 2018).
In general, waste cooking oils (WCO) refers to a mixture of oils and fats used for cooking in
food processing industries, fast food restaurants, and households (Raqeeb & Bhargavi, 2015).
In most fast-food chains, oils are used to deep-fry foods like French fries and fried chicken
(Zhang et al., 2012). As cited by Xu et al. (2020), Frying is done within the range of 160 to
200°C and is one of the oldest methods for food preparation. It is a complex process wherein a
series of physical and chemical reactions occur, such as heat and mass transfer. Ideally, cooking
oils should be used at a minimum temperature of 35˚C and in a maximum of 180˚C (Santos et
al., 2013; De Alzaa et al., 2018) because cooking on low temperature would lead to an increase
in fat uptake of fried foods (Brown et al., 2017). The rise of food establishments due to high
human consumption increases considerable waste cooking oil. This could lead to
uncontrollable disposal and may negatively impact the environment (De Feo et al., 2020; Goh
et al., 2020). In this regard, instead of disposing of WCO, it is recycled to produce animal feeds,
manufacture of soaps, and biodegradable lubricants (Panadare, 2015; Mannu et al., 2019).
Several reports are found on the recycling of WCO to produce transportation fuel that are
environmentally sustainable such as in Thailand (Pleanjai et al., 2009), Singapore (Chua et al.,
2010), Mexico (Sheinbaum-Pardo et al., 2013), Portugal (Caldeira et al., 2015), Indonesia
(Pasae et al., 2019). To date, current techniques for the treatment, recovery and conversion of
waste oil has grown rapidly (Mannu et al., 2020) such as transesterification (Zhang et al., 2003;
De Paola et al., 2009; Gashaw & Lakachew, 2014;) ultrasound-assisted transesterification
(Carmona-Cabello et al., 2019), and hydrotreating (De & Luque, 2014; Wang et al., 2019).
The concern about energy supply has driven the transport industry to use vegetable oil as an
alternative to petrodiesel (Li et al., 2012) then Europe began to improve and started the
biodiesel industry in 1980 until it was commercialized in 1990 (Yarkasuwa et al., 2013). In
2005, the global production of biodiesel reached about 3,762 million liters where 85% is
produced in Europe, 7% is produced in the USA and 8% is produced in some countries
predominantly in China and Brazil (Goto et al., 2010).
Biodiesel is claimed to be a fast-growing alternative fuel in the world because of the number
of benefits it holds towards the environment (Dincer, 2008). Analysis of particulate matter and
carbon monoxide emission of biodiesel is found to be lesser (Rashid et al., 2010; Rubianto et
al., 2013). Carbon monoxide and nitrogen oxide produce smog during hot days which causes
respiratory illnesses to the public (Manisalidis et al., 2020). Biodiesel also provides sustainable,
renewable, and cost-effective fuel which can compensate for the shortage of petroleum (Kumar
et al., 2020). It offers a good economic impact and environmental effect in the coming future
(Nunez, 2019).
In 2007, the Philippines grasped the development of biofuels to attain future energy security,
increase the farmer's income, and generate rural employment, according to the Philippines
Biofuels Activities. Production of biofuels in the Philippines is currently limited to biodiesel
where coconut oil is the primary feedstock. A total of 257 million liters of biodiesel per year
were produced by seven (7) biodiesel plants in the country. In the same year, blending of
coconut methyl ester (CME) in petrodiesel started upon the implementation of R.A. No. 9367
or the Biofuels Act of 2006 (Ison, 2019) in 2007. A minimum of one percent (1%) biodiesel
by volume shall be blended into all diesel engine fuels, according to this act. B1 (1% biodiesel
and 99% petrodiesel) has been successfully used by thousands of vehicles in the Philippines
since 2002. It was increased to two (2) percent in 2007 and has remained at that level since.
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The Philippine Department of Energy reported in 2012 that the biodiesel production for the
Philippines reached 137.88 million liters. Its latest energy plan has recommended maintaining
the current ethanol and biodiesel blends (10 and 2 percent, respectively) through 2019, and
revisit blend targets through 2040 due to feedstock concerns and pricing (Corpuz, 2018). In
2011, the Philippine Board of Investments (BOI) created a program to support mechanisms to
have an adequate supply of feedstock and adopt technologies that use alternative fuels such as
biodiesel. A development plans and programs following a framework that covers feedstock,
technology, and industry development, industry promotion, guidelines, and standards
enforcement and evaluation, and industry promotion with financial support from the Land Bank
of the Philippines (LBP) and the Development Bank of the Philippines (DBP) on renewable
and agri-based energy source projects (Philippine Board of Investments, 2011). The statistics
published by Statista Research Department (2019) shows the total biodiesel consumption in
the Philippines from 2009 to 2017. In 2017, the total biodiesel consumption amounted to
approximately 204 million liters, indicating a decrease of 14 million liters compared to 2016.
Tagum City’s effort to decrease its carbon emission is consistent with its commitment to reduce
CO2 emission. The local government has approved fourteen (14) environmental policies since
1990. In 2014, Resolution No. 567 was passed to mitigate carbon emission in the city which
paved way for the establishment of waste-to-energy through pyrolysis in 2015 at Barangay San
Agustin (Lim, 2014). However, there have been no reports on disposal of waste oils, treatment
facilities for WCO, and permits to transport WCO to nearby cities where waste oils are used
for treatment. Improper disposal of WCOs can substantially harm the environment. It can cause
contamination of potable water and drastically drop the oxygen level affecting the freshwater
ecosystem. Hence, this paper is presented as an attempt to yield biodiesel from waste cooking
products using potassium hydroxide and sodium hydroxide as catalysts.
This study followed strict compliance with the waste management protocol and biohazard
precautionary measures provided under Section 11 of Republic Act (RA) 6969 (Toxic
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Substances and Hazardous and Nuclear Wastes Control Act of 1990) and Section 22 of RA
9003 (Ecological Solid Waste Management Act of 2000). Proper bottling, labelling, and
storage for WCO, distilled water (Di H2O), KOH, NaOH, phenolphthalein, H2SO4, and ethanol,
were made as part of the general safety measures for handling chemicals. Storage of the
collected WCO was within the laboratory premises, where the experiment is conducted. All
reagents and materials used were within the laboratory premises and were never transported
elsewhere. All materials used in this study were disposed properly following the standard rules
and regulations determined by the DENR under RA 9003.
The WCO samples were collected from a local chicken establishment in Tagum City, Davao
del Norte, Philippines. Entry protocols were obtained prior the collection of samples from
Country’s Fried Chicken (CFC). WCO was stored in a plastic container and transported from
the store to the Chemistry Laboratory of the University of Mindanao Tagum College, Mabini
Street, Tagum City, Philippines.
The FFA content of WCO was determined by titration using phenolphthalein as an acid-base
indicator (Banani, et al., 2015; Yusuff et al., 2018). This method was replicated thrice to get
the average KOH volume (Alam et al., 2016). The acid value of WCO was taken using KOH
as the titrant (Yusuff, Adeniyi, Olutoye, & Akpan, 2018; Luu, et al., 2014). The reference
solution was prepared by dissolving 5.6 grams of KOH, diluted to 1L Di H 2O with 50 ±0.05
ml in a titration set-up (Ebenaza & Vinoth, 2015). Phenolphthalein (C20H14O4) indicator was
prepared by dissolving 0.5g of phenolphthalein powder in 10 ml of ethanol and 50 ml of Di
H2O (Ebenaza & Vinoth, 2015). 1 mL of WCO was mixed with 10 mL of ethanol and 2-3 drops
of phenolphthalein solution were added into the mixture in each flask (Ebenaza & Vinoth,
2015). The reference solution was added drop by drop from the burette to the mixture until it
turned into a light pink solution and the final reading was recorded. Phenolphthalein changes
color from colorless to pink at a pH range of 8.3-10. The solution was tested with the use of
pH paper to see if it fits the pH range which ensures that the titration process was completed.
The same process of titration was repeated for two samples. The different values of titration
were recorded (T1, T2, and T3). The final value was calculated by taking the average of the
three values (Alam et al., 2016). Acid value was calculated after the average volume of KOH
was obtained. With the acquired acid value, the %FFA present in the oil can be determined.
The percentage FFA in the sample is approximately equal to half the acid value and calculated
using E2 (Banani et al., 2015). Since the %FFA of the oil was <2%, there is no need for the oil
to undergo acid esterification process.
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glycerol (Chinni et al., 2015; Wicaksono et al., 2019). Raw biodiesel from phase I have
undergone washing for purification (Rahadianti et al., 2018). FAEE was separated from the
glycerol, a warm Di H2O (approx. 50°C) was carefully added, and the volume of the water was
50% of the total volume of the raw biodiesel (Bashir et al., 2018). Washing of the impure
biodiesel was continued until the pH neutrality (7.25) was obtained (Udeh, 2017). Purified
biodiesel was dried to remove the excess amount of water from washing (Gupta et al., 2014;
Bateni et al., 2017). The biodiesel was removed from the separatory funnel into a 250 ml beaker
and placed on the top of a hot plate magnetic stirrer. The solution was slowly heated at a range
temperature of 100°C to 110°C (Arenas et al., 2021) for 30 min until the cloudiness gradually
disappeared as the water evaporated. Biodiesel was allowed to cool down and transferred to a
±1.0 ml graduated cylinder for measurements.
For the analysis of data, the biodiesel yield from transesterification was calculated. Percentage
volume yield (Abbah et al., 2016) is calculated using this equation:
The average (x̄) volume yield by catalyst within 60-min and 120-min reaction time was
calculated. T-test was used to determine if there is a significant difference between the catalysts
within 60-min and 120-min reaction time at p<0.05 (Kim, 2015).
In this study, biodiesel production by transesterification of waste cooking oil with 95% ethanol
was studied in a homogeneous catalyst system. The optimal conditions for transesterification
were an ethanol/oil molar ratio of 12:1, NaOH and KOH amount (1% wt/wt of oil) with a range
temperature of 55-60°C. In order to study the effects of the mixture catalyst on the biodiesel
production yield, the mixture of the KOH and NaOH was mixed in an equal molar ratio of 1:1
with the same amount of WCO and alcohol. The biodiesel was produced successfully from
low-cost waste cooking oil using the KOH and NaOH as catalyst.
The average yield of KOH is slightly higher compared to NaOH. The mean volume yield of
NaOH is 36.5% while KOH is 70.17% in a 60-min reaction time. Presented in Figure 3 is the
volume yield by the two catalysts within 60-min reaction time. The average yield of the product
using NaOH and KOH as catalysts are 36.50 ±0.05 mL and 70.17 ±0.05 mL, respectively
(Figure 1).
Figure 1. Percentage volume yield catalyst at 60-minute and 120-min reaction time.
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The percentage yield of NaOH (50.50%) is slightly low compared to KOH (58.67%) in a 120-
min reaction time. As shown in Figure 3, the volume yield of the biodiesel product within
120min. The average yield of the product using NaOH and KOH as catalysts are 50.50 ±0.05
mL and 58.67 ±0.05 mL, respectively. During the process, it was observed that the
transesterification reaction was very slow as oils and alcohols are not completely miscible
without mixing. Chozhavendhan et al. (2020) stated that the increase in stirring speed will
shorten the reaction time and increase the conversion. Ideally, the maximum mixing speed for
60-minute and 120-minute reaction time is 600 revolutions per minute (rpm) (Mashkour et al.,
2016). Yield of biodiesel could be influenced by the stirring speed. This parameter was not
determined due to the insufficiency of laboratory equipment such as the chemical agitator,
hence agitating was made manually. Basically, agitating the solution is necessary to promote
the transesterification reactions to take place (Trejo-Zaragga et al., 2017). A related study from
Alamsyah et al. (2010) produced a yield of 80% biodiesel using a blade agitator reactor within
60-min reaction. A 97.3% conversion of triglycerides that matched with the EN biodiesel
standards was achieved by Hosseine et al. (2012) using a helical ribbon-like agitator.
Meanwhile, a maximum yield of 49% biodiesel that met the quality standard of Standard
Nasional Indonesia (SNI) was attained using a static mixer with a mechanism of agitator blades
(Rahmat et al., 2013). A bench reactor with a mechanical agitator was used by Colombo et al.
(2017) to obtain a yield of 96% biodiesel.
Biodiesel conversion also depends on the concentration of the catalyst. It was observed that
utilizing a high concentration of catalysts resulted in the formation of soap thus reducing the
yield of the biodiesel production. In addition, above 1% amount of catalyst was found to be
difficult to eliminate during washing of the impure biodiesel. According to Changmai et al.
(2020) using vegetable oil with low FFA content as a feedstock in making biodiesel, a small
amount of catalyst (<0.5%) is needed.
Analysis of volume yield by catalyst using T-test showed that there is a significant difference
(at p>0.05) within a 60-min reaction time as presented in Table 3. The results of this study
showed KOH had higher results compared to NaOH. Table 1 showed the significant difference
on volume yield of biodiesel by catalyst, and when analyzed by 60-min reaction time, NaOH
showed a significant (p < 0.05) result compared with KOH.
This finding could be attributed to the nature of the NaOH as an alkali catalyst. According to
Efavi et al., (2018), a higher concentration of NaOH will lead to the triglycerides forming soap
thereby, reducing the yield of the biodiesel production. Nevertheless, Gnanaprakasam (2013)
referred NaOH as the fastest catalyst among other alkali catalysts. Ejikeme et al. (2010) found
out that NaOH requires low temperature and less reaction time and converts oil to biodiesel
directly. Also, Kawentar & Budiman (2013) and Nasreen et al. (2018) pointed out that NaOH
74
is the most preferable catalyst for biodiesel production due to its low temperature and
atmospheric pressure requirement, and high conversion rate in lower reaction time than any
other alkali catalysts. However, Hossain & Mazen (2010) stated that there are no clear
explanations between NaOH and KOH as good catalysts, instead, emphasizing that based on
several studies, performance of different catalysts are dependent on the oil used. For this
research work, the oil used is palm oil collected from a local fried chicken store. The result of
this study is similar to the findings of Gumahin et al. (2019) which conclude that KOH gives
the highest yield of biodiesel at 60-min time reaction with a maximum yield of 93%. Karabas
(2013) also concludes that the optimum reaction time using KOH is 60min, which provides
98% biodiesel from canola oil. Saleh & Kulkarni (2014), using KOH catalyst, showed that the
biodiesel yield and conversion obtained were higher than using NaOH. This is due to the
formation of soap during the reaction, nevertheless, with KOH catalyst, less soap formation
was obtained. However, with catalyst concentration higher than 1%, the ester content available
for the conversion decreased due to soap formation. Anisah et al. (2018) obtained 56.60% of
biodiesel using NaOH at a 12:1 molar ratio of alcohol to oil within 60-minute time reaction. It
was observed that the optimum reaction time has been achieved within 60 minutes. However,
Efavi et al. (2018) suggested that the suitable reaction time for NaOH is somewhere between
90 min to 120 min. It also shows that the excess reaction time at about 150 min will lead to a
reduction in the product yield due to the backward reaction of transesterification thus, resulting
in losing some of the esters available for the conversion.
At different temperatures, transesterification may occur depending on the alcohol used and the
type of catalysts (Taufiq-Yap et al., 2011). Temperature influences the reaction rate which can
be anchored to the theory of chemical reaction kinetics. Arnaut et. al. (2006) mentioned in their
book that this theory is affiliated to the theory of collision which explains how the reaction
rates of molecules are affected by the temperature. Lower (2020) stated that for a chemical
reaction to occur, temperature is needed as a source of energy. Thus, as the temperature of a
solution increases, the more the molecules collide and react with one another. This causes the
reaction to move faster. However, the temperature range maintained during the conduct of this
study was 55-60 °C using a bulb thermometer for the reason to prevent the alcohol from
evaporating. According to Refaat (2010), Allah & Alexandru (2016), Istiningrum et al. (2017),
and Saini (2017), the temperature for the reaction should not exceed the boiling point of any
alcohol to avoid evaporation of alcohol. In a related study by Abbah et al. (2016) using
methanol, increase in temperature results in decreased yield of biodiesel due to evaporation.
As cited, temperature increase results in increasing fraction of molecules with high speed, thus,
high kinetic rate. According to Degfie et al. (2019), the optimum temperature is 50°C which
increases biodiesel yield at 96% while higher temperature (70°C) decreases yield to 74% yield
within 90-min reaction time.
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Table 2. Significant Difference on Volume Yield by Catalyst (120-minute reaction time)
For most chemical reactions, the longer the reaction time, more interaction of molecules occurs
yielding to high results. However, expanding the reaction time in this process does not affect
fatty acid ethyl esters yield when the equilibrium is attained, which concurs with the results of
this study. The findings of this study are related to the findings of Anisah et. al. (2018) which
obtained 60-80% conversion at an increasing molar ratio of 1:3, 1:6, 1:12, and 1:15 with 1%
catalyst within 90-, 120-, and 150-min reaction time. They found out that the conversion rate
was stable with these increasing molar ratios and reaction time. They concluded that
accelerating the reaction time will not increase the conversion result. This is probably due to
the transesterification reaction as a reversible process in which the conversion of reactants to
products and products to reactants happens at the same time, as defined by Castillo-Gónzalez
et al. (2020). This infers that adding more time when the reaction equilibrium is reached does
not affect the volume yield unless adding excess alcohol to maintain a forward reaction yielding
to more biodiesel. Although the average yield in this study showed slightly higher results with
KOH, it is evident that the transesterification reaction equilibrium occurs in a 60-minute
reaction time (Anikeev & Ermakova, 2012; Trejo-Zarraga et al., 2017).
CONCLUSIONS
Biodiesel from waste cooking oil, particularly palm oil, is obtained by transesterification
process using two (2) different catalysts, sodium hydroxide (NaOH) and potassium hydroxide
(KOH), with corresponding reaction time of 60 minutes and 120 minutes. Catalysts play an
essential role in converting triglycerides into mono-alkyl esters by increasing the reaction rate.
On the other hand, the reaction time allowed the transesterification process to produce a high-
quality biodiesel with high yields. In summary, research findings from this study showed that
production of biodiesel from low-cost WCO was successful. Volume yield of biodiesel using
NaOH and KOH within 60-minute reaction time were 36.5% and 70.17%, respectively. The
biodiesel yield obtained using NaOH and KOH within 120-minute reaction time were 50.5%
and 58.67%, respectively. T-test revealed a significant difference between catalysts NaOH and
KOH within a 60-minute reaction time but no significant difference within 120-minute reaction
time.
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