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Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology


Chemical Engineering Department

BASE-CATALYZED TRANSESTERIFICATION OF
GUYABANO (ANNONA MURICATA) SEED OIL DERIVED
THROUGH SOLVENT EXTRACTION FOR THE
PRODUCTION OF FATTY ACID METHYL ESTER

Submitted by:

DE DIOS, Mary Jane T.

GUY, Erick Kristonne R.

LIM, Kassandra Charmaine C.

LOVERES, Shania Faith R.

GROUP 3

BS ChE 3-1

Submitted to:

Engr. Milagros R. Cabangon

Date Submitted:

February 24, 2017

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TABLE OF CONTENTS

Base-Catalyzed Transesterification Of Guyabano Seed Oil Derived Through


Solvent Extraction For The Production Of Fatty Acid Methyl Ester

I. Introduction
II. Statement of the Problem
III. Objectives
IV. Significance of the Study
V. Background of the Study
Review of Related Literature
Review of Related Studies
VI. Procedure
VII. Summary of Equivalent Unit Operations
VIII. Summary of Parameters
IX. Summary of Process Flow Diagram
X. Conclusion
XI. Recommendation
XII. References

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BASE-CATALYZED TRANSESTERIFICATION OF GUYABANO SEED OIL


DERIVED THROUGH SOLVENT EXTRACTION FOR THE PRODUCTION OF
FATTY ACID METHYL ESTER

I. INTRODUCTION

Soursop (Annona muricata L.), also known as graviola, guyabano,


guayabano guanabano and babana, is a shrub or small tree 3-10 meters in
height. It is adapted to warm, humid tropical climate, and can tolerate both
drought conditions and partial shade. The fruit consists of about 67.5% edible
white pulp with a pleasing fragrance and flavor. It is a good source of vitamins
B and C with some calcium and phosphorus. (Bareja, 2010)

Soursop continues flowering year around but the peak is May to June.
The fruits are harvested when fully developed and still green. They are
considered mature when their spines are set far apart and the shiny green
color turns dull-green or yellowish green. Selective harvesting is practiced
because the fruits on a tree do not mature at the same time.

The fruit contains significant amounts of vitamin C, vitamin B1 and


vitamin B2. The compound annonacin, which is contained in the seeds of
soursop, is a neurotoxin associated with neurodegenerative disease. The leaves
of Annona muricata contain annonamine, which is an aporphine-class alkaloid
featuring a quaternary ammonium group. (Philippine Medical Plants, 2016)

Soursop seeds constitute 20% - 25% mass of the fruit and have potential
to produced 33.87% oil with nutritional and functional properties highly
similar to those of edible oils (Okoro, 2013).

TRANSESTERIFICATION PROCESS

In the transesterification process a glyceride reacts with an alcohol in the


presence of a catalyst, forming a mixture of fatty acids esters and an alcohol.
Using triglycerides results in the production of glycerol.

The end products of the transesterification process are raw biodiesel and
raw glycerol. After a cleaning step biodiesel is produced. The purified glycerol

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can be used in the food and cosmetic industries, as well as in the oleochemical
industry (EBTP, 2011).

FATTY ACID METHYL ESTER

Fatty Acid Methyl Ester (FAME) is produced from vegetable oils, animal
fats or waste cooking oils by transesterification. Transesterification is a
reversible reaction and is carried out by mixing the reactants. A strong base or
a strong acid can be used as a catalyst.

FAME characteristics include high boiling points, good lubricity and


excellent solubility in organic solvents. Fatty acid methyl esters are versatile
products covering a wide range of product uses including: lubricants,
metalworking fluids, solvents, fuels, agriculture, surfactants, polymers,
coatings and plasticizers.

Pure vegetable oils have been considered as alternatives for diesel fuel,
but the high viscosity at room temperature made them unsuitable for diesel
engines. However, fatty acid methyl esters (FAME) have lower viscosity than the
pure oils, and as such are promising alternatives. While the focus has been
mostly on oils like soybean, rapeseed, and sunflower (Lang et al., 2001), which
are essentially edible in nature, biodiesel has also been produced from non-
edible sources such as used frying oil and greases (Alcantara et al.,2000;
Canakci and Gerpen, 2001; Mittelbach et al., 1992).

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II. STATEMENT OF THE PROBLEM

Guyabano seeds are reported to be poisonous. Some toxicants are found


in the seeds and the seed coat of the guyabano. The seeds contain 45% of a
yellow non-drying oil which is an irritant poison, which can cause eye
inflammation. According to Fasakin et. al., the seeds are found to have 3.7 mg
of cyanide per kg of the seeds. The seeds also contain 620.5 mg phytate and
2.6 mg of tannin per 100 g sample seeds. Guyabano seed coat, however,
contain 4.9 mg tannin and 188 mg phytate per 100 g seeds and 10.8 mg
cyanide per kilogram seeds.

The US Federal Drug Administration has banned the import of certain


soursop juices as the suppliers did not properly separate the seeds from the
juice while pressing. Two studies done in the French West Indies suggested
that there may be a link between symptoms similar to acute Parkinsons
Disease and the consumption of graviola. In 2010 the French food safety
agency, Agence franaise de scurit sanitaire des produits de sant, concluded
that, based on the available research findings, "it is not possible to confirm that
the observed cases of atypical Parkinson syndrome ... are linked to the
consumption of Annona muricata," calling for further study on potential risks
to human health.

The United States Food and Drug Administration published an import


alert last July 2, 2014 regarding the detention without physical examination of
guanabana (soursop). In February 1990, thirty-four adults and children drank
"Rain Drop" Guanabana Drink from Mexico and within 15 minutes they began
vomiting. Dallas district laboratory performed microscopic examination of the
product and found some seed cells in all "suspect" codes examined. The
literature indicates the seeds are toxic and an oil expressed from the seeds has
been used as an insecticide and fish poison. According to the Mexican
authorities, the product is only manufactured for exportation and not
consumed in Mexico. Due to this incident, list of firms and their products
subject to detention without physical examination under this import alert were
released. Philippines was one of the countries listed under the said alert. In
July 2013, Profood International Corporation, located in Cebu City, was noted
that their aseptic guyabana puree contain toxic material from the fruit seed
was incorporated into the finished product during the manufacturing process.
In September 2009, Summer Fruit Inc. Marsman-Drysdale Group, both

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factories located at Cavite and Makati, were noted that the fruit juices or
concentrated of guanabana contain toxic material from the fruit seed
incorporated into the finished product during the manufacturing process.

In attempt to utilize the guyabano seeds without harming human health,


the researchers proposed the study entitled, Base-Catalyzed
Transesterification of Guyabano Seed Oil Derived Through Solvent
Extraction For The Production Of Fatty Acid Methyl Ester.

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III. OBJECTIVES

A. General Objective
To produce fatty acid methyl ester used in the production of biodiesel
under the process of transesterification of guyabano seed oil which will
conform to the properties of the standard fatty acid methyl ester.

Properties of Fatty Acid Methyl Acid


Standard Existing
Appearance Liquid Liquid
Color Yellow Yellow
Flash Point 120 deg C >101 deg C
Density 860-900 kg/m3 860-900 kg/m3
Viscosity 3.5-5.0 mm2/s 3.5-5.0 mm2/s
Lower Heating
- 37.1 MJ/kg
Value

*(For the existing properties, Shell 2014)

B. Specific Objectives

To determine the parameters which will provide the production its


properties that will conform to the properties of the standard fatty acid
methyl ester.
To identify the solvent and catalyst which will provide the highest
amount of seed oil.
To determine the ratio of methoxide to the seed oil that will produce the
highest yield of fatty acid methyl ester.

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IV. SIGNIFICANCE OF THE STUDY

This study entitled Base-Catalyzed Transesterification Of Soursop


(Annona Muricata) Seed Oil Derived Through Solvent Extraction For The
Production Of Fatty Acid Methyl Ester is expected to be significant to the
following fields:

To the guyabano plantation owners

The study utilizes guyabano seeds as its major raw material for the
production of fatty acid methyl ester. This will provide guyabano tree plantation
owners a potential market for fatty acid methyl ester rather than ending up the
guyabano seeds as waste.

To the chemical industry

This study promotes an environment-friendly chemical industry as it will


provide bio-based routes in the production of fatty acid methyl ester. Also, it
promotes the establishment of local production that will potentially minimize
the volume of Philippine importation on fatty acid methyl ester.

To the business field

Both the materials and procedure of this study could be utilized and
developed by other institutions and could be a reason for a local production of
fatty acid methyl ester from the raw material. Moreover, this study would help
create jobs for local citizens since fatty acid methyl esters are versatile products
covering a wide range or industry like agriculture, fuels, solvents, polymers,
and food industry.

To the chemical engineering profession

This study may serve as an additional reference for related and similar
studies of fellow researchers. Chemical engineers could help in conducting
further research and study of the process involved in the production of fatty
acid methyl ester. With the help of this field, scientific and economic condition
in the country could be improved.

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V. BACKGROUND OF THE STUDY

REVIEW OF RELATED LITERATURE

A. RAW MATERIALS

Soursop (Guyabano)

The Soursop tree (Annona Muricata),


indigenous to the rainforest regions, is a
broadleaf, evergreen tree that produces flowers
and fruit. The trees grow in areas with high
humidity and warm temperate winters. (Bareja,
2010)

The Soursop designation is the name of the fruit produced by the


Soursop tree. The fruit appears in large, heart-shaped forms with a yellow-
green, spiky skin and white fleshy interior. Much like the name implies the
fruit is fairly acidic with a taste that resembles a mix of strawberry and
pineapple. (Philippine Medical Plants, 2016)

The nature green fruits are used as a vegetable and for making sweet
meats, while the ripe one is eaten off hand or as dessert. Its juice is used for
flavoring ice cream, sherbets, canning and for preparation of refreshing drinks.
It may also be processed intro preserve, candies, jam and jelly. Guyabano also
possess some medicinal properties. (Agribusiness, 2017)

Guyabano production in the Philippines from year 2010 to 2015

Guyabano SU Production
2010 6,922
2011 7,007
2012 7,305
2013 7,579
2014 7,150
2015 7,671

*SU Supply

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Guyabano production in the Philippines in the year 2015

Guyabano (2015) Amount in metric tons


SU Production 7,671
SU Gross Supply 7,671
UT Seeds 0
UT Feeds and Waste 460
UT Processing 0
UT Total Net Food Disposable 7,211

*SU Supply *UT Utilization

Source: Philippine Statistics Authority (PSA)

Based on BAS crop statistics of 2003; a total land area of 3,016 has.
were planted to guyabano with the following as the five leading producing
regions: Western Visayas (705 has.); Region IV-A (643 has.); Cagayan Valley
(400 has.); Central Visayas (169 has.); and Central Luzon (165 has.).

Guyabano seeds

There are two strains presently grown.

1. Aguinaldo Fruit, 1kg; peel, yellow green; flesh,


juicy, sub-acid, 78% of fruit weight; seeds, 70 per fruit.

2. Davao Fruit, 1.7 kg; peel, light green; flesh,


moderately juicy, pleasantly sub-acid, 82% of fruit weight; seeds, 82 per fruit.
(Agribusiness, 2017)

For the dried seeds, they are tolerant of the moisture extraction, showing no
problems for long-term storage under reasonable
conditions.

The image shows a guyabano seed after


hammering. Guyabano seeds are tough. Automatic seed
remover and blenders force might be enough to break
the seed apart resulting to mixture to finish products in

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the guyabano processing plants. If teeth could tear a seed apart, the more the
heavy-duty machines can. (Foodrecap, 2013)

Figure 1 Compositional analyses of the seed of sour sop, Annona muricata L., as a potential
animal feed supplement (Fasakin, et.al. 2008)

B. PROCESS

Solvent Extraction

Being a conventional method, solvent extraction is the most widely used


technique owing to its high efficiency in oil recovery (Sharma, et.al.,2004). The
use of solvent extraction over other methods includes higher recovery, larger
processing capacity and gives oil that many considered to be of lower losses
(Lager, 2006; Robellen et. al., 1989).

Base Catalyzed Transesterification

Transesterification of vegetable or fruit seed oils is conventionally carried


out by subjecting the pre-extracted oil to the treatment with the appropriate
alcohol, in the presence of an alkaline catalyst. Selecting a suitable alcohol,
catalyst, amount of catalyst, oil to solvent ratio, reaction time (Refaat,2010).

Base-catalyzed transesterification which falls under homogenous


transesterification is the action of one alcohol from a strong base displacing
another from an ester, referred to as alcoholysis.

Transesterification is a reversible reaction and is carried out by mixing


the reactants. A strong base or a strong acid can be used as a catalyst. At the

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industrial scale, sodium or potassium methanolate is mostly used. The


following reaction occurs:

The production of biodiesel is relatively simple from a technical


standpoint, also allowing the construction of small decentralised production
units without excessive extra costs. This limits the need to transport raw
materials long distances and permits operations to start with modest-sized
installations. (EBTP, 2011)

C. PRODUCT

Fatty Acid Methyl Ester (FAME)

Fatty Acid Methyl Esters (FAME) are esters of fatty acids. The physical
characteristics of fatty acid esters are closer to those of fossil diesel fuels than
pure vegetable oils, but properties depend on the type of vegetable oil. A
mixture of different fatty acid methyl esters is commonly referred to as
biodiesel, which is a renewable alternative fuel. FAME has physical properties
similar to those of conventional diesel. It is also non-toxic and biodegradable.
(EBTP, 2011)

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For the properties of FAME:

Figure 2 Shell. 2014.

FAME is produced from vegetable oils, animal fats or waste cooking oils
by transesterification. In the transesterification process a glyceride reacts with
an alcohol in the presence of a catalyst, forming a mixture of fatty acids esters
and an alcohol. Using triglycerides results in the production of glycerol. (EBTP,
2011)

Rapeseed, sunflower, soybean, palm oils, UCO and animal fat are the
most common raw materials being used for the production of biodiesel. Using
methanol in the transesterification process has the advantage that the
resulting glycerol can be separated simultaneously during the
transesterification process. When using ethanol during the process the ethanol
needs to be free of water and the oil needs to have a low water content as well
to achieve an easy glycerol separation. (EBTP, 2011)

The end products of the transesterification process are raw biodiesel and
raw glycerol. After a cleaning step biodiesel is produced. The purified glycerol

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can be used in the food and cosmetic industries, as well as in the oleochemical
industry. The glycerol can also be used as a substrate for anaerobic digestion.
(EBTP, 2011)

Uses of FAME

Fatty acid methyl esters are products that are produced by an alkali-
catalyzed reaction between fats or fatty acids and methanol. In biodiesel, fatty
acid methyl esters are the primary constituent, usually obtained from vegetable
oils by transesterification.

In solvent applications, they are known as green solvents because fatty


acid methyl esters are biodegradable, produce low volatile organic compounds
(VOCs), and are non-toxic to humans.

Characteristics include high boiling points, good lubricity and excellent


solubility in organic solvents. Fatty acid methyl esters are versatile products
covering a wide range of product uses including: lubricants, metalworking
fluids, solvents, fuels, agriculture, surfactants, polymers, coatings and food.

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REVIEW OF RELATED STUDIES

A. PROCESS

Biodiesel Production Process Optimization from Soursop Seed Oil (Annona


Muricata) and Its Characterization (2014)

In the production process of biodiesel, the effects of process parameters


such as alcohol to oil molar ratio, catalyst concentration, reaction time, and
reaction temperature have been studied and optimized. the fuel properties of
produced biodiesel have been investigated and compared with the standard
specifications for assessing their feasibility to substitute the petroleum fuels.

The emphasis of present work is to produce biodiesel from Soursop seed


oil by transesterification process using methanol and sodium hydroxide (NaOH)
as catalyst and to study the effect of process parameters such as alcohol to oil
molar ratio, reaction time, and reaction temperature on the yield of biodiesel.
Further the physicochemical properties of produced biodiesel are investigated
and compared with diesel and standard specifications of biodiesel to assess its
feasibility to replace the petroleum fuel.

The transesterification reaction mechanism is as shown in Figure below.

Figure 3 source: https://www.hindawi.com/journals/jre/2015/148587/fig2/

And for the data gathered and the comparison for the standard and
commercially available properties of Biodiesel or FAME:

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Figure 4 source: https://www.hindawi.com/journals/jre/2015/148587/tab3/

Solvent Extraction of Oil from Oil Seeds (1997)

In order to improve the yield of oil and the quality of remaining protein
various attempts have been made to alter the basic steps of cooking, pressing
and extracting the oil from oil bearing seeds and nuts. One approach is
disclosed in the patent to Drenning, U.S. Pat. No. 2,629,722 wherein it is
taught that if best results are to be achieved in oil production then the
moisture content of the cooked seeds must be closely controlled, evaporation
prevented, and the time and temperature of the cooking reduced. Thus, a
process is disclosed in which oil bearing seeds and nut meats are first flaked
and then treated prior to extraction of the oil by raising the moisture content of
the seeds to a value of between 12 and 20% by the addition of steam or water
and then cooking the seeds for a period of time between 7 and 20 minutes at a
temperature between 190 and 215 F under such conditions as to ensure that

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evaporation does not reduce the moisture in the seed nut meats below 12%.
The oil may then be extracted from the treated (cooked) seed by a combined
process involving mechanized presure followed by solvent extractions. This
process is said, among others, to produce a meal of high nutritional value
above that obtained from a standard high temperature processing and to
achieve higher oil yields.

Solvent Extraction of Oil from Soursop Oilseeds & Its Quality


Characterization (2014)

Soursop seeds constitute 20% - 25% mass of the fruit and have potential
to produced 33.87% oil with nutritional and functional properties highly
similar to those of edible oils (Okoro, 2013). Previous researchers applied
solvent extraction technique for the extraction of oils from different plant
oilseeds due to it cost effectiveness, simplicity, remarkable reduction in solvent
volume and short time needed for the extraction (Tan et al., 2009; Betiku and
Adepoju, 2012; Bimakr et al., 2012; Adepoju et al., 2013).

The study showed that the Soursop seed is a good source rich in oil.
Also, this work demonstrated Response Surface Methodology is a good tool for
optimization in oil extraction processes. The maximum seed oil yield of 34.
6074% (w/w) was established at the optimal condition of extraction time, 38.10
min, sample weight, 30.0 g and solvent volume, 100 ml. The optimized
condition was validated with the actual seed oil yield of 33.593% (w/w). The
fatty acid profile of the seed oil showed it is highly unsaturated (73.42%).

For the drying process:

According to Ebewele et al. (2010), the optimum moisture content of


soursop seed oil extraction is 12%. They also reported that higher oil yield was
observed at a lower moisture content of 7% up to 10 to 13% with exceptional to
very low or higher temperature. This is because, during the extraction process,
the moisture in the seeds acts as a heat transfer medium and helps in
coagulation of protein for oil yield. Therefore, too high or too low temperature
may disturb the function of the moisture in oilseed processing.

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And from the stated above study Solvent Extraction of Oil from Oil
Seeds by Ayres et al. (1997) a process is disclosed in which oil bearing seeds
and nut meats are first flaked and then treated prior to extraction of the oil by
raising the moisture content of the seeds to a value of between 12 and 20% by
the addition of steam or water and then cooking the seeds for a period of time
between 7 and 20 minutes at a temperature between 190 and 215 F under
such conditions as to insure that evaporation does not reduce the moisture in
the seed nut meats below 12%.

For the Solvent Extraction:

According to the study Biodiesel Production Process Optimization


from Soursop Seed Oil (Annona Muricata) and Its Characterization by
Hebbal et al., they also reported that easy solvent recovery from the meal is
also an important trait of an ideal solvent. The ideal solvent should be non-
flammable or has a narrower range of explosive limits to avoid or reduce the
possibility of fire or explosion during extraction. The extraction solvent also
should be non-reactive to the meal or oil, as well as the extraction equipment.
On the other hand, ideal solvents should also have high purity to exhibit more
uniform operating characteristics, as well as having low solubility in water for
easier separation. Ultimately, an ideal solvent should be easily available at low
prices.

For the Base-Catalyzed Transesterification:

Base catalyzed transesterification will be employed in the study due to


the fact that guyabano seed was reported to have high free fatty acid content of
17% (Pandey, 2008). Conventionally, it must undergo acid catalyzed
esterification before base catalyzed transesterification to reduce the FFA
content, which would yield greater amount of biodiesel (Ribeiro et al., 2011).
Since this study focuses more on yielding less ester and more glycerol, base
catalyzed transesterification will be employed in this study.

For transesterification, the usual base catalyst used are sodium


hydroxide, potassium hydroxide, and calcium hydroxide. This catalyst has
varying effects in the yield of biodiesel and glycerol. Biodiesel with the best
properties was obtained using potassium hydroxide as catalyst in many studies
(Refaat et al., 2008). In the case of the alcohol, most of the time, methanol is
used as solvent for transesterification. Ethanol is less stable than methanol,

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being a hydrophilic this interferes in the reaction which leads to lesser yield if
the product. Among these solvents, methanol works best because it has the
least molecular weight. The molecular weight of methanol is 32.05g/gmol while
the molecular weight of ethanol and propanol are 46.08 and 60.11 g/gmol
respectively. Increasing the chain length of RO-(alcohol) group results in the
increase of reaction rate and causes steric hindrance which prolonged the
reaction.

B. PRODUCT

Biodiesel Quality, Standards and Properties. (2011)

The main criterion of biodiesel quality is the inclusion of its physical and
chemical properties into the requirements of the adequate standard. Quality
standards for biodiesel are continuously updated, due to the evolution of
compression ignition engines, ever stricter emission standards, reevaluation of
the eligibility of feedstocks used to produce biodiesel, etc.

The biodiesel standards in Brazil and the U.S. are applicable for both
fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE), whereas the
current European biodiesel standard is only applicable for fatty acid methyl
esters (FAME).

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Figure 5 European Standard FAME Properties (EN 14214)

Biodiesel Production Process Optimization from Soursop Seed Oil (Annona


Muricata) and Its Characterization (2014)

In the production process of biodiesel, the effects of process parameters


such as alcohol to oil molar ratio, catalyst concentration, reaction time, and
reaction temperature have been studied and optimized. the fuel properties of
produced biodiesel have been investigated and compared with the standard
specifications for assessing their feasibility to substitute the petroleum fuels.

The emphasis of present work is to produce biodiesel from Soursop seed


oil by transesterification process using methanol and sodium hydroxide (NaOH)
as catalyst and to study the effect of process parameters such as alcohol to oil
molar ratio, reaction time, and reaction temperature on the yield of biodiesel.
Further the physicochemical properties of produced biodiesel are investigated
and compared with diesel and standard specifications of biodiesel to assess its
feasibility to replace the petroleum fuel.

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The transesterification reaction mechanism is as shown in Figure below.

Figure 6 source: https://www.hindawi.com/journals/jre/2015/148587/fig2/

And for the data gathered and the comparison for the standard and
commercially available properties of Biodiesel or FAME:

Figure 7 source: https://www.hindawi.com/journals/jre/2015/148587/tab3/

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Solvent Extraction of Oil from Oil Seeds (1997)

In order to improve the yield of oil and the quality of remaining protein
various attempts have been made to alter the basic steps of cooking, pressing
and extracting the oil from oil bearing seeds and nuts. One approach is
disclosed in the patent to Drenning, U.S. Pat. No. 2,629,722 wherein it is
taught that if best results are to be achieved in oil production then the
moisture content of the cooked seeds must be closely controlled, evaporation
prevented, and the time and temperature of the cooking reduced. Thus, a
process is disclosed in which oil bearing seeds and nut meats are first flaked
and then treated prior to extraction of the oil by raising the moisture content of
the seeds to a value of between 12 and 20% by the addition of steam or water
and then cooking the seeds for a period of time between 7 and 20 minutes at a
temperature between 190 and 215 F under such conditions as to insure that
evaporation does not reduce the moisture in the seed nut meats below 12%.
The oil may then be extracted from the treated (cooked) seed by a combined
process involving mechanized pressure followed by solvent extractions. This
process is said, among others, to produce a meal of high nutritional value
above that obtained from a standard high temperature processing and to
achieve higher oil yields.

Solvent Extraction Of Oil From Soursop Oilseeds & Its Quality


Characterization (2014)

Soursop seeds constitute 20% - 25% mass of the fruit and have potential
to produced 33.87% oil with nutritional and functional properties highly
similar to those of edible oils (Okoro, 2013). Previous researchers applied
solvent extraction technique for the extraction of oils from different plant
oilseeds due to it cost effectiveness, simplicity, remarkable reduction in solvent
volume and short time needed for the extraction (Tan et al., 2009; Betiku and
Adepoju, 2012; Bimakr et al., 2012; Adepoju et al., 2013).

The study showed that the Soursop seed is a good source rich in oil.
Also, this work demonstrated Response Surface Methodology is a good tool for
optimization in oil extraction processes. The maximum seed oil yield of 34.
6074% (w/w) was established at the optimal condition of extraction time, 38.10
min, sample weight, 30.0 g and solvent volume, 100 ml. The optimized

Project Study 22
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condition was validated with the actual seed oil yield of 33.593% (w/w). The
fatty acid profile of the seed oil showed it is highly unsaturated (73.42%).

For the drying process:

According to Ebewele et al. (2010), the optimum moisture content of


soursop seed oil extraction is 12%. They also reported that higher oil yield was
observed at a lower moisture content of 7% up to 10 to 13% with exceptional to
very low or higher temperature. This is because, during the extraction process,
the moisture in the seeds acts as a heat transfer medium and helps in
coagulation of protein for oil yield. Therefore, too high or too low temperature
may disturb the function of the moisture in oilseed processing.

And from the stated above study Solvent Extraction of Oil from Oil
Seeds by Ayres et al. (1997) a process is disclosed in which oil bearing seeds
and nut meats are first flaked and then treated prior to extraction of the oil by
raising the moisture content of the seeds to a value of between 12 and 20% by
the addition of steam or water and then cooking the seeds for a period of time
between 7 and 20 minutes at a temperature between 190 and 215 F under
such conditions as to insure that evaporation does not reduce the moisture in
the seed nut meats below 12%.

For the Solvent Extraction:

According to the study Biodiesel Production Process Optimization


from Soursop Seed Oil (Annona Muricata) and Its Characterization by
Hebbal et al., they also reported that easy solvent recovery from the meal is
also an important trait of an ideal solvent. The ideal solvent should be non-
flammable or has a narrower range of explosive limits to avoid or reduce the
possibility of fire or explosion during extraction. The extraction solvent also
should be non-reactive to the meal or oil, as well as the extraction equipment.
On the other hand, ideal solvents should also have high purity to exhibit more
uniform operating characteristics, as well as having low solubility in water for
easier separation. Ultimately, an ideal solvent should be easily available at low
prices.

Project Study 23
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

For the Base-Catalyzed Transesterification:

Base catalyzed transesterification will be employed in the study due to


the fact that guyabano seed was reported to have high free fatty acid content of
17% (Pandey, 2008). Conventionally, it must undergo acid catalyzed
esterification before base catalyzed transesterification to reduce the FFA
content, which would yield greater amount of biodiesel (Ribeiro et al., 2011).
Since this study focuses more on yielding less ester and more glycerol, base
catalyzed transesterification will be employed in this study.

For transesterification, the usual base catalyst used are sodium


hydroxide, potassium hydroxide, and calcium hydroxide. These catalyst has
varying effects in the yield of biodiesel and glycerol. Biodiesel with the best
properties was obtained using potassium hydroxide as catalyst in many studies
(Refaat et al., 2008). In the case of the alcohol, most of the time, methanol is
used as solvent for transesterification. Ethanol is less stable than methanol,
being a hydrophilic this interferes in the reaction which leads to lesser yield if
the product. Among these solvents, methanol works best because it has the
least molecular weight. The molecular weight of methanol is 32.05g/gmol while
the molecular weight of ethanol and propanol are 46.08 and 60.11 g/gmol
respectively. Increasing the chain length of RO-(alcohol) group results in the
increase of reaction rate and causes steric hindrance which prolonged the
reaction.

Project Study 24
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

VI. EXPERIMENTAL PROCEDURE

A. PREPARATION OF RAW MATERIALS


I. Raw Material

The main raw material, soursop (guyabano) seeds, is collected from


Cenmaco Inc located at Mariano Marcos Street,
San Juan Metro Manila.

II. Reagent

Table 2 presents the reagents that were used for the experimental
method. They were purchased from local chemical supplier Tough Stone
Lab Enterprises, which is located at Bambang, Manila; and was used
without further purification.

Table 2. Reagents Used in the Experimental Methodology

Reagent Chemical Molecular Boiling Density


Formula Weight Point
(g/mole) (C)

C6H14 86.18 68 655 kg/m3

Hexane

Project Study 25
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

CH4OH 32.04 64.7 792 kg/m3

Methanol

2.13
NaOH 39.997 1,388
g/cm3
Sodium Hydroxide

KOH 56.1056 1,327 2.12 g/cm

Potassium Hydroxide

2.21
Ca(OH)2 74.093 580
g/cm3

Calcium Hydroxide

Project Study 26
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

B. DRYING OF SOURSOP SEEDS

Drying the soursop moisture content before it proceeds to the next


process for maintaining control over the necessary quality. Under drying of
soursop seeds leads to reduction of percent yield or degrading the quality of
the acid. Over-drying it leads to energy losses.

1.1 Materials and Apparatus

Soursop Seeds Analytical Balance

Oven Timer

1.2 Procedure
1. Weigh the initial moist soursop seeds.
2. Dry the seeds until a constant weight or negligible change in mass.
3. Place the first set over the oven tray.
4. Dry the soursop seed for 30 minutes.
5. After drying, weigh the dried soursop seeds.

1.3 Data and Results

Mass of Soursop Seeds 82 grams

The mass of dried soursop came out 82 grams.

Equivalent Unit Operation

Unit Operation Lab Scale Plant Scale


Drying Oven Rotary Dryer

Project Study 27
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

C. Size Reduction of Soursop Seeds

After drying the soursop seeds, the next process is size reduction. It is
necessary to reduce the size of the seeds to increase the rate of reaction for
the next process.

1.1 Materials and Apparatus

Dried Soursop Seeds Timer

Blender

1.2 Procedure
1.From the drying process, place the dried seeds in the blender.
2. Grind the seeds for 3 minutes.
3. Weigh the ground soursop seeds.

1.3 Data and Results

Mass of Soursop 81.6 grams


Seeds

The mass of ground soursop came out 81.6 grams.

Equivalent Unit Operation

Unit Operation Lab Scale Plant Scale


Size Reduction Blender Grinder

D. OIL EXTRACTION OF SOURSOP SEEDS

Being a conventional method, solvent extraction is the most widely used


technique owing to its high efficiency in oil recovery (Sharma, et.al.,2004).
The use of solvent extraction over other methods includes higher recovery,
larger processing capacity and gives oil that many considered to be of lower
losses (Lager, 2006; Robellen et. al., 1989).

Project Study 28
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

1. Determination of Time of Settling


1.1 Materials and Apparatus

Ground Soursop Seeds Funnel

Erlenmeyer Flask Filter Paper

Graduated Cylinder Distillation Set-up

Rubber Stopper Analytical Balance

Fume hood

1.2 Procedure

1. Weigh 25 g of dried crushed soursop seeds and place it on a


250-mL Erlenmeyer flask.

2. Add the 100-mL of hexane to the flask and put a rubber stopper
to prevent the hexane from evaporating.

3. Separate the filtrate (solvent containing oil) from the residue


(crushed seeds) using a filter paper and funnel rested on a 250-mL
Erlenmeyer flask.

4. Distill the solution to separate the oil from the hexane (B.P. 60-
70 C) with its temperature varying from 55, 65, and 75C. Note:
Recover the solvent and water to recycle.

5. Weigh the oil extracted and the hexane recovered.

6. Repeat procedure substituting hexane with a different solvent


per procedure: ethanol and methanol.

Project Study 29
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

1.3 Data and Results


Mass of seeds Mass of Solvent Time Weight of Oil
25 g 100 g 30 minutes 4.5 g
25 g 100 g 45 minutes 6.3 g
25 g 100 g 60 minutes 7.2 g

MASS OF OIL
7.5
MASS OF GUYABANO OIL,

7
6.5
6
GRAMS

5.5
5
4.5
4
30 45 60
SETTLING TIME, MINUTES

Mass of Oil

Figure 1. Mass of Oil Depending on the Settling Time

1.4 Conclusion

The amount of oil that can be extracted from the seed varies with the
time it takes for the solvent to fully absorb the oil present in the seed. At
60-minute mark, 7.2 grams of oil are extracted from 25 g of sample
crushed soursop seeds

Project Study 30
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

DOCUMENTATION

Equivalent Unit Operation

Unit Operation Lab Scale Plant Scale


Filtration Funnel, Filter Paper Filter Press
Distillation Distillation Apparatus Distillation Column

Project Study 31
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

E. PREPARATION OF METHOXIDE

Transesterification of vegetable or fruit seed oils is conventionally carried


out by subjecting the pre-extracted oil to the treatment with the appropriate
alcohol, in the presence of an alkaline catalyst. Selecting a suitable alcohol,
catalyst, amount of catalyst, oil to solvent ratio, reaction time (Refaat,2010).

1. Determination of Catalyst Used

1.1 Materials and Apparatus

Soursop Seed Oil Watch Glass

100-mL Beaker Analytical Balance

1.2 Procedure

1.Weigh 10 g of methanol and place it in a 100-mL beaker.

2. Cover the beaker with a watch glass.

3. Prepare three sets of 0.15 grams of NaOH, KOH, Ca(OH)2)


separately.

4. Weigh 0.15 g of the first set of catalyst and add it on the


methanol. Note: This solution is toxic; use preventive measures to
limit exposure.

5. Repeat procedure for the remaining two sets.

1.3 Data and Results


Mass of Mass Mass of Tempe Mass of Methyl
Catalyst Time
catalyst of Oil Methanol rature Ester
30
NaOH 0.15 g 30 g 10 g 60 C 13.8 g
minutes
30
KOH 0.15 g 30 g 10 g 60 C 10.2 g
minutes
30
Ca(OH)2) 0.15 g 30 g 10 g 60 C 8.4 g
minutes

Project Study 32
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

Best Catalyst
14
MASS OF OIL, GRAMS

13
12
11
10
Best Catalyst
9
8
7
NaOH KOH Ca(OH)2)
CATALYSTS

Figure 2. Mass of Oil Depending on the Catalyst Used

1.4 Conclusion

The amount of methyl ester that can be obtained from oil depends
on the catalyst used and its type. Among three basic catalyst used,
sodium hydroxide (NaOH) yields the highest amount of oil weighing
13.8 grams of Methyl Ester using only soursop seeds.

2. Determination of Amount of Catalyst Used

2.1 Materials and Apparatus

Soursop Seed Oil Watch Glass

100-mL Beaker Analytical Balance

2.2 Procedure
1.Weigh 10 g of methanol and place it in a 100-mL beaker.
2. Cover the beaker with a watch glass.
3. Prepare three sets of NaOH with 0.10, 0.15 and 0.20 grams
separately.

Project Study 33
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

4. Weigh the first set of catalyst and add it on the methanol. Note:
This solution is toxic; use preventive measures to limit exposure.
5. Repeat procedure for the remaining two sets.

2.3 Data and Results


Mass of Mass of Mass of Mass of Methyl
Temperature Time
NaOH Oil Methanol Ester
0.10 g 30 g 10 g 60 C 30 minutes 12.6 g
0.15 g 30 g 10 g 60 C 30 minutes 17.3 g
0.20 g 30 g 10 g 60 C 30 minutes 15.4 g

DETERMINATION OF AMOUNT OF
CATALYST
20
MASS OF OIL, GRAMS

19
18
17
16 DETERMINATION
15 OF AMOUNT OF
14 CATALYST
13
12
0.1 0.15 0.2
MASS OF CATALYST, GRAMS

Figure 3. Mass of Oil Depending on the Amount of Catalyst Used

2.4 Conclusion

Using same masses of methanol, the 0.15 g trial of NaOH


yielded the highest amount of Methyl Ester formed amounting to 17.3
grams per 30 grams of soursop seeds.

Project Study 34
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

3. Determination of Amount of Methanol Used


3.1 Materials and Apparatus

Soursop Oil Watch Glass

100-mL Beaker Analytical Balance

3.2 Procedure
1. Measure 10 g of Methanol and place it on a 100-mL beaker,
cover it with a watch glass.
2. Weigh 0.15 g of NaOH and add it on the Methanol. Take note
that this solution is toxic; use preventive measures to limit
exposure.
3. Weigh 30g of oil and place it on a 250 ml Erlenmeyer flask.
Preheat it to 60 C. Add the prepared Methanol-catalyst to the
preheated oil. Continue heating the oil with constant
temperature of 60 C with continuous stirring for 30 minutes.
4. Set the solution aside until warm to touch (about 25 30 C).
Transfer the solution to a separatory funnel to completely cool
and to settle the produced mixtures (soap and FAME).
5. Separate the solutions by discarding the formed soap and
keeping the produced Fatty Acid Methyl Ester.
6. Repeat steps 1-5 using 5 grams and 7.5 grams of Methanol.

3.3 Data and Results

Mass of Mass of Mass of Mass of Methyl


Temperature Time
NaOH Oil Methanol Ester
0.15 g 30 g 5g 60 C 30 minutes 15.1 g
0.15 g 30 g 7.5 g 60 C 30 minutes 17.4 g
0.15 g 30 g 10 g 60 C 30 minutes 16.9 g

Project Study 35
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

WEIGHT OF METHANOL
18
17.5
MASS OF OIL, GRAMS

17
16.5
16
15.5 WEIGHT OF
15 METHANOL
14.5
14
13.5
5 7.5 10
MASS OF METHANOL

Figure 4. Mass of Oil Depending on the Weight of Methanol Used

3.4 Conclusion
The 7.5 grams of methanol yielded the highest weight of Methyl
Ester using 0.15 g of the Sodium Hydroxide (NaOH) catalyst.

Equivalent Unit Operation

Unit Operation Lab Scale Plant Scale


Mixing Beaker Methoxide Mixing Tank

Project Study 36
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

F. TRANSESTERIFICATION OF METHOXIDE AND SOURSOP OIL

Base catalyzed transesterification will be employed in the study due to


the fact that guyabano seed was reported to have high free fatty acid
content of 17% (Pandey, 2008). Conventionally, it must undergo acid
catalyzed esterification before base catalyzed transesterification to reduce
the FFA content, which would yield greater amount of biodiesel (Ribeiro et
al., 2011). Since this study focuses more on yielding less ester and more
glycerol, base catalyzed transesterification will be employed in this study.

1. Determination of Preheating and Constant Temperature

1.1 Materials and Apparatus

Soursop Oil Extract Stirring Rod

100- mL Beaker Erlenmeyer Flask

Electric Stove Separatory Funnel

Thermometer Timer

1.2 Procedure

1.Weigh 30 g of oil and place it on a 100-mL beaker.

2. Preheat the oil in a 60C temperature.

3. Add the prepared methoxide to the preheated oil.

4. Continue heating the oil with constant temperature of the same


temperature used in preheating with continuous stirring for 30
minutes.

5. Set the solution aside until warm to touch (about ambient).

6. Transfer the solution to a separatory funnel to completely cool


and to settle the produced mixtures (soap and FAME).

Project Study 37
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

7. Separate the solutions by discarding the formed soap and


keeping the produced Fatty Acid Methyl Ester (FAME).

8. Weigh the FAME extracted.

9. Repeat procedure using different temperatures: 75 and 90 C.

1.3 Data and Results


Mass of Mass Mass of
Temperature Time Mass of Methyl Ester
NaOH of Oil Methanol
0.15 g 30 g 10 g 60 C 30 minutes 19.7 g
0.15 g 30 g 10 g 75 C 30 minutes 22 g
0.15 g 30 g 10 g 90 C 30 minutes 21.6 g

TEMPERATURE
22.5
MASS OF OIL, GRAMS

22
21.5
21
20.5
20 TEMPERATURE
19.5
19
18.5
60 75 90
HEATING TEMPERATURE, DEGREE CELCIUS

Figure 5. Mass of Oil Depending on the Preheating Temperature

1.4 Conclusion

As seen on the graph, at 75 C, the soursop seed oil will


produce the highest amount of methyl ester amounting to 22 g of
methyl ester. This means that at 75 C, the maximum yield of methyl
ester can be achieved.

Project Study 38
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

2. Determination of Heating Time

2.1 Materials and Apparatus

Soursop Oil Extract Stirring Rod

100- mL Beaker Erlenmeyer Flask

Electric Stove Separatory Funnel

Thermometer Timer

2.2 Procedure

1.Weigh 30 g of oil and place it on a 100-mL beaker.

2. Preheat it to 60C.

3. Add the prepared methoxide to the preheated oil.

4. Continue heating the oil with constant temperature of the same


temperature used in preheating with continuous stirring for three
sets of time, 30, 60, and 90 minutes.

4. Set the solution aside until warm to touch (about ambient).

5. Transfer the solution to a separatory funnel to completely cool


and to settle the produced mixtures (soap and FAME).

6. Separate the solutions by discarding the formed soap and


keeping the produced Fatty Acid Methyl Ester (FAME).

7. Weigh the FAME extracted.

8. Repeat procedure for the remaining two sets of time.

Project Study 39
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

2.2 Data and Results

Mass of Mass Mass of


Temperature Time Mass of Methyl Ester
NaOH of Oil Methanol
0.15 g 30 g 10 g 75 C 30 minutes 18.3 g
0.15 g 30 g 10 g 75 C 60 minutes 22.6 g
0.15 g 30 g 10 g 75 C 90 minutes 26.7 g

HEATING TIME
29
MASS OF METHYL ESTEER

27
25
23
21
HEATING TIME
19
17
15
30 60 90
HEATING TIME, MINUTES

Figure 6. Mass of Oil Depending on the Heating Time

2.3 Conclusion

There is an increasing trend when heating the oil-alcohol


mixture from 30 to 90 minutes. At 90 minutes of heating with
constant temperature of 75 C, the highest yield that can be obtained
is 26.7 grams.

Project Study 40
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Documentation

Equivalent Unit Operation

Unit Operation Lab Scale Plant Scale


Separation Separatory Funnel, Centrifuge
Erlenmeyer Flask

Project Study 41
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

SUMMARY OF EQUIVALENT UNIT OPERATIONS

(Laboratory Scale to Industrial Scale)

Unit Laboratory Industrial


Purpose
Operation Scale Scale
To remove
excess
moisture that
Drying Oven Rotary Dryer
may affect
succeeding
processes
To reduce the
size of the
soursop seed
oil to increase
Size Reduction Blender Crusher
the rate of
reaction in the
conversion
processes.
To filter the
Funnel, Filter solid ground
Filtration Filter Press
Paper seeds to the
filtrate.
To separate the
Distillation Distillation hexane and the
Distillation
Apparatus Column seed oil from
each other.
To add up the
Methoxide methanol and
Mixing Beaker
Mixing Tank the catalyst
used.
Separation Separatory Centrifuge To separate the

Project Study 42
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Funnel, soap and the


Erlenmeyer fatty acid
Flask methyl ester.

SUMMARY OF PARAMETERS

Unit Operations Parameters Values

Oil Extraction Time of Settling 60 minutes

Type of Catalyst to
NaOH
be Used
Mixing (Methoxide
Preparation) Amount of Catalyst
0.15 grams
Used

Amount of Methanol 7.5 grams


Preheating and
Constant 75 C
Separation Temperature
Time of Heating 90 minutes

Project Study 43
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

EXPERIMENTAL PROCESS FLOW DIAGRAM

100 g of peanut shells was placed evenly over the


oven tray. it was dried for 30 minutes to lower the
moisture content.
Drying

82 g of dried soursop seeds were size reduced


though a blender for 3 minutes.
Size
Reduction

82 g of the dried soursop are allowed to settle for


60 minutes. The ground seeds were weighed and
Oil filtered. 25 g is subjected to distillation for 60-
70C.
Extraction

0.15 g of the catalyst, NaOH, is added to the 7.5 g


methanol to be used for next process.
Methoxide
Preparation

30 g of oil is preheated to 75C. The methoxide


solution was then added and heated with the oil
using the same temperature. The solution was
Transesteri- transferred to the separatory funnel to separate
fication the soap to the fatty acid methyl ester.

Project Study 44
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

CONCLUSION

Before the extraction of oil process begins, the seeds (Soursop or


Guyabano) will be crushed to size reduce and increase the surface area
exposed to the solvent. The solvent used is Hexane which is a common solvent
and a strong solvent when extracting oils from seed or in fruits. Using 25
grams of crushed soursop seeds and bathing it to a 100 g of Hexane for 1 hour
(60 mins) will result to attraction of hexane molecules and oil molecules
present in the seeds. After settling it for 1 hour, the composition of oil and
hexane mixture will be distilled to separate different liquids condensing first
the solvent (b.p. 60-70) and can be recycled for future extraction. The
remaining solution in the distillate will be kept, this is the oil.

After extracting the oil, the methanol will be prepared for


transesterification process. Among three basic solutions, NaOH yielded the
most amount of methyl ester that can be obtained from the oil from solvent
extraction. This preparation needs 7.5 grams of methanol and 0.15 g of NaOH.
They will be mixed and be again mix with the preheated 30-gram soursop oil.
After 90 minutes of mixing and boiling the alcohol-oil mixture to 75 C, the
solution will be allowed to settle to form two visible liquids, one of which is the
glycerol and the other one is the Fatty Acid, Methyl Ester. Discard the glycerol
and the product will be kept.

Project Study 45
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

RECOMMENDATION

For the further improvement of the study, we suggest that:

1. For further efficiency of the final product, the researchers must use more
specific variations which do not rely only on numbers divisible by five
and ten.
2. The venue of the experiment must be fit for environment with standard
temperature and pressure so that in the manufacturing process for mass
production of this product is standardized.
3. As much as possible, the researchers must not rely on three to five
review of related literature and studies. This part must be plenty as
much as possible so that the best variation will be determined for the
experiment.
4. The researchers must determine and include the possible errors during
the experiment and make some assumptions on how it will be avoided.

Project Study 46
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

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Project Study 48
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

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Project Study 49

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