INTRODUCTION
Noriel: The demand for biodiesel increases and has been considered one of the alarming
issues due to the industrialization, urbanization, and population growth of the world. Based on
an article published by Foreign Agricultural Service (FAS), the demand was estimated to
increase up to 250 million liters. Additionally, the Biofuels Act of 2006 in the Philippines was
implemented requiring that biofuels should be combined with commercially available fuels.
Meanwhile, domestic producers can only meet half of the bioethanol demand. Therefore, there
is a need for alternative sources of biodiesel.
Shena: The possible raw materials for biodiesel production are oil extracted from vegetables,
animal fats, algae, and fungi. Align with this, there is a high probability of competition between
food and fuel which may result in a price increase for both biodiesel and food-derived oil. Thus,
there is an increasing interest in finding alternative feedstock for biodiesel fabrication.
Almira: Align with this, waste cooking oil (WCO) is also a source of triglyceride, showing a
potential competition to virgin oils because of the price difference. The utilization of waste
cooking oil promotes the reduction of its disposal concern. The demand for biodiesel is high as
well as the amount of waste cooking oil produced, it can reduce the scarcity of biodiesel. As a
result, the WCO-derived biodiesel answers three problems: pollution control, food, and energy
security.
Bern: The most renowned process of synthesizing biodiesel from WCO is known as
transesterification. It includes the reaction of oil and alcohol in the presence of a catalytic
medium. The important parameters to be considered for the said process are alcohol and oil
type, catalyst type and amount, and the ratio of oil to alcohol. With this, the reaction can be
carried out using a homogeneous or heterogeneous catalyst and the selection of the most
effective approach varies on the oil's FFA level.
Noriel: Unfortunately, homogeneous catalysts might result in soap production, gel formation,
produce water when dissolved in an alcohol reaction and absorb moisture while being stored.
As a result, interest is increasing in different heterogeneous catalysts because it is
non-corrosive, can be reused, can be easily separated from the product, and can be applied in
continuous processes. Hydroxyapatite (HAp) is a heterogeneous catalyst derived from calcium
phosphate which has the capability to speed up the transesterification process for biodiesel
production.
Shena: Fishbone is considered food waste and has caused several environmental concerns
such as organic odor and disposal issues. On the other hand, it is a natural calcium source that
can be utilized in deriving calcium phosphate, which is prominent in the making of
hydroxyapatite
Almira: In specific, yellowfin tuna (Thunnus albacares) is abundant in tropical countries and
widely consumed in the Philippines. Its fishbone contains high calcium and phosphor which
makes it notable for hydroxyapatite synthesis. In this study, fishbones of yellowfin tuna (Thunnus
albacares) will be used as a source of hydroxyapatite which will act as a heterogeneous catalyst
for the transesterification of waste cooking oil to biodiesel.
STATEMENT OF THE PROBLEM
Bern: Environmental concerns related to food wastes result in the degradation of ecological
quality. For this reason, there is a need for alternative applications where it can be recycled for
better use.
The demand for biodiesel is continuously increasing. The common raw materials for biodiesel
production are vegetables and animal oil, however, it results in a dilemma between food and
fuel.
Noriel: An alternative to this, waste cooking oil has qualities suitable to be a source of biodiesel.
However, transesterification involving WCO is a slow process, hence there is a need for a
catalytic medium.
Shiena: The common catalyst used is homogeneous, which is non-renewable, and is not
feasible to be recovered. Thus, researching a more sustainable catalyst is necessary.
This study generally aims to synthesize hydroxyapatite which is a heterogeneous catalyst from
waste fishbone of yellowfin tuna. In specific, it aims to answer the following questions:
*read slide*
NULL HYPOTHESES
Almira: In this study, the following null hypotheses will be tested:
*read slide*
SIGNIFICANCE OF THE STUDY
Bern: In this study, the researchers will synthesize hydroxyapatite from fishbone, which will be a
great potential catalyst for WCO-based biodiesel production in order to meet and to sustain the
increasing demand for this type of fuel.
In particular, significance of this study lies in the following beneficiaries:
Noriel: To the Energy Regulatory Agencies. The study may benefit them through widening of
the energy sources array, specifically their origin, and process of production.
Noriel: To the Community. They may have an insight on the production process of biodiesel, its
benefits and effects, and energy consumption.
Shiena: To the Researchers. It would be beneficial in terms of information dissemination of
renewable sources of energy which is also valuable in terms of human life and environment.
Aside from the awareness, the researchers may contribute the outcome of the project to the
local agencies whose focus is on sustainable energy, environment, and health.
Amira: To the Future Researchers. This study may include information that benefits future
researchers, such as usage of the local wastes, catalysts, and biodiesel production. Also, this
study may be used for future references as methodology improvement and outcome quality
enhancement.
SCOPE AND LIMITATIONS
Bern: The study only focuses on the synthesis of a natural and renewable heterogeneous
catalyst, hydroxyapatite, from waste fishbones and its utilization for WCO-based biodiesel
production. Moreover, the calcium-source samples will only be limited to waste fishbones,
specifically from yellowfin tuna which will only be gathered from the local markets and
households in the province of Batangas. Meanwhile, the waste cooking oil samples will only be
gathered from the restaurants, fast food chains, and households also of the specified province.
The catalyst and biodiesel produced will only be tested according to the given and specified
parameters.
Noriel: The data in this study will be limited by the availability of the formerly specified fish
species and by the quantity of the samples that will be gathered from the local province. There
is a rare possibility that these species are seasonal and limited for some causes such as in
crisis, short in supply, and affected by local disasters and calamities. Moreover, the quantity of
waste cooking oil would limit the study in a way that some restaurants and households reused
their cooking oil.
CONCEPTUAL FRAMEWORK
Shiena: The conceptual framework of the study is hinged on the concepts that convert waste
cooking oil to biodiesel through association of a heterogeneous catalyst, specifically
hydroxyapatite.For this study, the input variables for WCO-based biodiesel production are waste
cooking oil, waste fishbones, potassium hydroxide solution, and phosphoric acid solution. These
were vital for the processes involved which are preparation and purification of the raw materials,
catalyst synthesis, transesterification process, design of experiment, and further data
analyses.The expected output of this study were fishbone-derived hydroxyapatite, WCO-based
biodiesel, glycerol, a model equation, statistical results, and the optimized condition of
transesterification among the predetermined runs.
CONCEPTUAL LITERATURE
Almira Biodiesel
Biodiesel is a clean-burning renewable fuel substitute for traditional petroleum-based fuels.
There are 3 different feedstocks used in biodiesel production: first-generation biofuel-feedstocks
are extracted from crops which are used for food consumption. Second-generation
biofuel-feedstocks were synthesized from crops but from those that were not used for human
consumption. Third-generation biofuel-feedstocks are from waste or used oils. Accordingly, the
yielded biodiesel should conform with the requirements set by the United States Environmental
Protection Agency (EPA), in accordance with section 211 of the Clean Air Act, for fuels and fuel
additives and the standard of the American Society of Testing and Materials
Bern WCO
New developments in the technology that transforms used cooking oil into high-quality refined
oil have encouraged the expansion of the market, as a whole. Almost 15 million tons of cooking
oil are generated annually, an enormous amount that, if converted, could partially meet the need
for biodiesel around the world. The generation of biodiesel from WCOs enables savings of 96%
of fossil energy and 21% of crude oil. WCOs can be turned into biodiesel at very high yields per
kilogram. Transesterification process alters the physicochemical characteristics of WCO to
make it better suited for compression ignition engines. Prior to biodiesel production, the
properties of the WCOs should be determined to assess if these can have an adverse effect on
the production of biodiesel.
Shiena YELLOWFIN TUNA
The Yellowfin Tuna (Thunnus albacares) is characterized by its torpedo-like shape, dark metallic
blue dorsal area, yellow sides, and silver belly. The two species with the highest catch rates in
the Philippines are yellowfin and skipjack tuna. In the study of Nam et al. in 2019, fishbone of 4
species including tuna was compared to assess the amount of HAp it can synthesized. Table
2.6 shows that the samples are mostly composed of calcium and phosphorus, with an average
Ca/P molar ratio of roughly 1.80. This ratio exceeds the stoichiometric one found in human
bone, which is 1.67.
Almira HYDROXYAPATITE
In the fields of energy and environmental protection, as well as the production of chemicals and
refinery operations, there is a growing interest in the creation of a new generation of solid
catalysts. Moreover, an inexpensive mineral catalyst for the production of biodiesel is
hydroxyapatite. When synthetic and natural hydroxyapatite are compared, Natural
hydroxyapatite differs from synthetic hydroxyapatite in a way that it possesses disordered
nanostructures, nonstoichiometric composition, and a lower hydroxyl content. Thus, it is
reasonable to anticipate that biological hydroxyapatite will yield better results as a functional
material if its nanoscale properties are maintained. For the case of biodiesel production, an
appropriate quantity of catalyst can enhance the reaction's efficiency and minimize
saponification
Bern TRANSESTERIFICATION
In this process, triglycerides from oils or fats are reacted with alcohol, usually methanol, to form
fatty acid methyl esters (FAMEs), also known as biodiesel, and glycerol. The reaction requires
three moles of alcohol for every one mole of triglyceride to produce one mole of glycerol and
three moles of FAMEs. Methanol is favored due to its low cost, chemical properties (shortest
alcohol chain), and physical properties (polarity) in chemical reactions. Based on Figure 2.10, in
transesterification, ester bonds in triglycerides are broken and replaced with alcohol to yield fatty
acid methyl esters (FAMEs). It is important to note that a higher ratio of methanol to oil usually
results in a faster reaction rate and higher production of FAMEs but it may also cause an
increase in the formation of glycerol and soap byproducts.
Noriel REFLUX
Reflux method is useful in chemical synthesis because it allows the reactions to be carried out
at higher temperatures and for longer periods of time rather than simple heating. In this case,
Fishbone waste was used as a source of Calcium, and the reflux method was used to produce
hydroxyapatite by bonding the Calcium with Phosphate from the solution.
Shiena 3-Factor
It is used to create a mathematical connection between process parameters and their
corresponding response. Its main objective is to identify the optimal value combination of these
parameters through statistical analysis. According to Daniyan et al., in terms of biodiesel
production, the use of Central Composite Design (CCD) has the potential to benefit the
production such that it can aid in biodiesel yield prediction and achieve a high conversion rate of
vegetable oil to biodiesel, as well as providing a means for process control.
RESEARCH LITERATURE
*basahin na lang asa table*
METHODOLOGY
Almira Before the actual conduct of the experiment, a pre-laboratory will be conducted to
ensure the accuracy of set levels for each factor. From the result of the pre-laboratory, several
considerations will be made to obtain a cost-effective product but will also ensure its quality.
Bern Collection of Raw Materials
For the collection of waste fishbone and WCO, the researchers will be dealing with partnerships
within the local restaurants, fast food chains, and local market. The collected materials will be
stored properly in an enclosed container to avoid additional contaminations.
Noriel Purification of WCO
Food particles and debris will be filtered out from the waste cooking oil (WCO) through the
filtration process. To remove the water component of the oil, it will be heated in an oven at a
temperature of 110 ℃ for about half an hour. The remaining water after heating was allowed to
settle at the bottom, after that the water will be removed through decantation. After this, purified
WCO will be produced.
After purification, samples will be sent to the DOST testing center to assess its viscosity,
moisture content, acid value, saponification value, and free fatty acid (FFA) content.
Shiena Preparation of Waste Fishbone
To free the samples from debris and fats, they will be boiled in water for ten (10) minutes at a
temperature of 100 ℃. The boiled fishbones will be dried in an oven at a temperature of 90 ℃
for about an hour and 40 minutes and will proceed through the process of crushing and
pulverization using mortar and pestle. Further drying of the powder will be done using a dry-heat
oven for 24 hours at 60 ℃. To obtain the fine powder, high-energy ball milling will be utilized for
another 24 hours. Milled fishbone powder will be dried once more using a microwave oven at a
temperature of 60 ℃. Once dried, it will be placed on a desiccator to maintain its dry condition.
Almira The catalyst will be synthesized through reflux method
Deproteinization
Starting with deproteinization, A 5% KOH solution will be utilized to deproteinize the powder
samples. The solution will be used to create a strong base solution that is efficient in the
hydrolyzation of the calcium and protein in the fishbones. The powder sample and the KOH
solution will be placed in a 500 mL beaker and will be boiled at a temperature of 130 ℃ for 18
hours.
Bern Reflux
After deproteinizing the samples, it will proceed in refluxing. The reflux will be utilizing H3PO4
(weak acid) with 2.33M as a source of PO43-, that would be the donor ion for hydroxyapatite
synthesis. The solution will be placed in a 500 mL beaker and will be boiled at a temperature of
130 ℃ for 12 hours.
Noriel Calcination
The refluxed sample will now proceed to the calcination process. It will be done using a
high-temperature furnace at 900 ℃ for 8 hours. After this, the resulting product will be the
hydroxyapatite.
After calcination, samples of yielded hydroxyapatite will be sent to DOST testing center for
characterization using X-ray Diffraction (XRD), scanning electron microscopy (SEM),
Transmission Electron Microscope (TEM) and Fourier Transform Infrared Spectrometry (FT-IR)
Shiena Transesterification
It will be done in a three‐necked 500 ml round‐bottom flask immersed in a water bath, to control
the temperature in the hot plate. The middle neck is used to insert a water-cooled condenser
and the other neck is fixed with a thermometer to control the reaction temperature. Waste
fishbone-derived hydroxyapatite was utilized in this procedure as a catalyst loading. Then, oil to
methanol ratio and HAp concentrations were measured simultaneously taking into consideration
the process parameters. Then, it was combined in a shake flask. The shaker's settings
remained constant at a reaction temperature of 65 °C, a reaction time of 4 hours, and a speed
of 300 rpm. The samples in the shaking flask were centrifuged at 4000 rpm for 10 minutes after
transesterification was finished. Following that, the samples were filtered through filter paper to
get rid of any contaminants and catalyst loading.
Shiena Reusability of Catalyst
It will be examined based on the amount of biodiesel yield at the optimal operating setup. The
filtered catalyst will be reused until there is a significant change in the duration of the
transesterification process and the amount of the yielded biodiesel.
Almira Biodiesel and glycerin separation
The biodiesel (FAME) and glycerol were separated after filtering by pouring the mixture into a
separator funnel. Moreover, the samples were divided into two layers after a short while. After
that, glycerol made up the bottom layer while biodiesel made up the top layer. The glycerol layer
was then taken off and thrown away. Then the remaining layer will be the unrefined biodiesel
Bern Washing of Methyl ester
The obtained biodiesel will be refined by washing because it will still contain trace amounts of
methanol and glycerine. Additionally, the separatory funnel will be filled with warm water, which
will then be added and will slightly be agitated to allow it to settle. The methyl esters will be
effectively separated from the water, which will then be drained out of the bottom. Moreover, the
process will be done several times until the water has a pH of 6-7 and no soap bubbles are
visible on it.
Sample of the yielded biodiesel will be sent to DOST testing center to assess specific
parameters in this study and the standard of ASTM and DOE
Noriel Yield Analysis
The biodiesel yield will be computed using the formula:
Biodiesel yield (%) = (volume of biodiesel / volume of WCO) * 100
After all of this, we will have the catalyst reusability analysis, biodiesel yield properties, and yield
analysis
Bern Design of Experiment
Response Surface Methodology (RSM) will be used to model and to optimize the
transesterification process parameters. The detailed analysis will be generated utilizing
Design-Expert version 12. Conversion of biodiesel and glycerol will be the process response
while the reaction variables are contact time, methanol to oil ratio, HAp dose, and temperature.
A total of 78 runs will be utilized in this study.
Almira Statistical Treatment of Data
In determining the statistical evaluation of the percent yield of biodiesel in varying conditions
multiple analysis of variance (ANOVA) will be used while one-way ANOVA will be utilized to
evaluate the reusability of HAp. In addition, T-test will be used in the comparison of the yielded
biodiesel and the B100.