Chapter II Biodiesel

CHAPTER II
REVIEW OF RELATED LITERATURE
The chapter present a review of conceptual and research literature that
the researchers made as the framework.
CONCEPTUAL LITERATURE
1. Rambutan
Figure 2: Rambutan
Fruit
Source:
Healthachieved, 2015
The Rambutan (Nephelium lappaceum) is a medium-sized tropical tree in
the family Sapindaceae.It is closely related to several other edible tropical
fruits including the lychee, longan, and mamoncillo. The rambutan is native to
Malaysia and commonly cultivated throughout the archipelago and southeast
Asia. Many years ago, Arab traders introduced it into Zanzibar and Pemba. There
are limited plantings in India, a few trees in Surinam, and in the coastal lowlands
of Colombia, Ecuador, Honduras, Costa Rica, Trinidad and Cuba. Some fruits are
being marketed in Costa Rica. The Rambutan was taken to the Philippines from
Indonesia in 1912. Further introductions were made in 1920 (from Indonesia) and
1930 (from Malaya), but until the 1950's its distribution was rather limited. Then
popular demand brought about systematic efforts to improve the crop and
resulted in the establishment of many commercial plantations in the provinces of
Batangas, Cavite, Davao, Iloilo, Laguna, Oriental Mindoro and Zamboanga.

Production and Evaluation of Biodiesel from Rambutan Chapter II
(Nephelium lappaceum) Seed Oil Review of Related Literature
Aguila, A.M.,Arellano, J.C.M., Panganiban, K.D.D.
Seeds were imported into the United States from Java in 1906 but the species is
not grown in this country. (Integrated Taxonomic Information System, 2010)

1.1 Types of Rambutan Grown in the Philippines
1.1.1 Seematjan
Tree has an open crown and long, flexible branches. Fruits are
dark-red with spines to 3/4 in (2 cm) long. It is cultivated in the Philippines
where it has averaged 16 lbs/acre (16 kg/ha). There are 2 forms: (1)
Seematjan besar with small fruit, thin rind, spines fairly far apart; very
sweet; (2) Seematjan ketjil the fruit has soft, tough, and less sweet flesh to
which the seed coat does not tightly adhere. (Morton, 2002)
1.1.2 Seenjonja
Tree low-growing; has a drooping crown. Fruit nearly ovoid, about 1
1/2 in (4 cm) long and 1 1/5 in (3 cm) wide; dark wine-red with slender,
flexible spines about 2/5 in (1 cm) long. Flesh clings firmly to the seed. In
the Philippines has yielded on the average 41 lbs/acre. (Morton, 2002)

1.1.3 Maharlika
In the Philippines, two cultivars of rambutan are recognized by their
seed. The normal rambutan seed and natural product are hard to
separate, while the 'Maharlika Rambutan', that has yielded 21 lbs/ acre in
the Philippines, isolates neatly from its seed. The taste and size of these
two cultivars are indistinguishable, yet the 'Maharlika Rambutan' is more
well-known with a higher cost.
1.2 Rambutan Seed Composition
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Figure 3. Rambutan
Seeds
Source: Growplants, 2011
Rambutan seeds are non-
toxic and contains carbohydrates,
fats, proteins, which can meet the needs of the body of nutrients. Rambutan seed
polyphenols also quite high in fat. Composition of chemical substances in
rambutan seeds produced hypoglycemic properties (lowering blood sugar levels)
so that the seeds of rambutan is widely used for alternative treatments to
normalize blood sugar levels of people with diabetes. The local fruit seed of
rambutan is a has also a potential feedstock for biodiesel production due to its
high lipid content and easily available. (Dion, 2005)
Table No. 1
Fatty Acid Profile of Rambutan Seeds
Properties Composition
Fatty Acid 34.7%
Oleic Acid 45.3%
Stearic Acid 13.8%
Ericosenoic Acid 4.2%
Palmitic Acid 2%
Source: National Clonal Germplasm Repository, 2005
1.3 Rambutan seed oil

Oils from local fruit seeds like rambutan has a potential feedstock for
biodiesel production due to their high lipid contents and easily available. In
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the present study rambutan seed oils were extracted via soxhlet apparatus
using n-hexane and the oil yields were in between 3440% (Wong, 2006)
Table No. 2
Composition of Rambutan seed oil
Properties Composition
Oil analysis 38.9%
Proteins 12.4%
Carbohydrates 48.1%
Ash 2.26%
Moisture 3.31%
Water Activity 0.73
Saponification Value, SV 157.07
Iodine Value, IV 37.64

Free Fatty Acid, FFA 0.37
Source: Rambutan Composition, 2006
1.4 Properties of Rambutan Seed Oil

1.4.1 Density
The density is a mass measurement per volume unit and has a
direct influence on the volumetric fuel consumption. Lower density
lowers the emission of particulate matter, hydrocarbons and carbon
monoxide. The changes in the fuel density may also contribute to the
emission increase by causing improper operation of the exhaust gases
recirculation system which regulates recirculation degree depending on
the fuel dose (Bochenska & Gis, 2011)

1.4.2 Fatty Acid Profile
Fatty acid is a carboxylic acid with a long aliphatic chain, which
is either saturated or unsaturated. Most naturally occurring fatty acids
have an unbranched chain of an even number of carbon atoms, from 4
to 28. Fattyacids are usually derived
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from triglycerides or phospholipids. Fatty acids are important sources
of fuel because, when metabolized, they yield large quantities of ATP.

1.4.3 Free Fatty Acid
Free fatty acids (FFA) are produced by the hydrolysis of oils and
fats. The level of FFA depends on time, temperature and moisture
content because the oils and fats are exposed to various environments
such as storage, processing, heating or frying. Since FFA are less
stable than neutral oil, they are more prone to oxidation and to turning
rancid. (Bochenska & Gis, 2011)

1.4.4 Saponification Value
The number of milligrams of potassium hydroxide required
to saponify one gram of a given ester, especially a glyceride. Expand
Also called saponification value. The saponification number and
acid number are both very low, but a fatty oil is present. (Bochenska &
Gis, 2011)
1.4.5 Moisture and Volatile matter
The Moisture and Volatiles Determination procedure is designed
to help Fat, Oil, Grease, and Biodiesel attain useful information
regarding primarily methanol and water content quickly and
inexpensively on-site. This test is based on the principal that you can
heat a material to remove (vaporize) volatile components, and that the
change in mass can be used to determine the amount of volatile matter
that was originally present. (Bochenska & Gis, 2011)

1.5 Oil Extraction Method
1.5.1 Soaking Extraction
Soaking Extraction is a procedure to remove lipids from food
and oils from seeds. In a Glass container, samples are soaked using a
solvent. The sample is dried and ground and placed in a Glass
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Container with the solvent. The yield of the oil defends on the soaking
time. After it was soaked the sample and the solvent was separated
using fine cloth and then the separated solvent was subjected to a
Rotary Evaporator to extract the oil. (Labcom, 2011)

Most Commonly Used Solvent
A. Ethanol
Ethanol is an important industrial ingredient. It has widespread
use as a precursor for other organic compounds such as
ethyl halides, ethyl esters, diethyl ether, acetic acid, and ethyl amines.
B. n-Hexane
Hexanes are chiefly obtained by refining crude oil. The exact
composition of the fraction depends largely on the source of the oil
(crude or reformed) and the constraints of the refining. The industrial
product (usually around 50% by weight of the straight-chain isomer) is
the fraction boiling at 6570 C
1.5.2 Steam Distillation

Steam distillation is a special type of distillation (a separation
process) for temperature sensitive materials like
natural aromatic compounds. It once was a popular laboratory method
for purification of organic compounds, but has become obsolete
by vacuum distillation. Steam distillation remains important in certain
industrial sectors. (Labcom, 2011)

1.5.3 Fractional Distillation
Fractional distillation is the separation of a mixture into its
component parts, or fractions, separating chemical compounds by
their boiling point by heating them to a temperature at which one or
more fractions of the compound will vaporize. It
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uses distillation to fractionate. Generally the component parts have
boiling points that differ by less than 25 C from each other under a
pressure of one atmosphere. If the difference in boiling points is
greater than 25 C, a simple distillation is typically used.

2. Biodiesel
Figure 4. Biodiesel
Source: BiodieselQuality, 2011
Biodiesel is a renewable and biodegradable diesel fuel extracted from
plant oil. It is less harmful to the environment for it contains practically no sulfur
and substantially reduces emission of unburned hydrocarbon (HC), carbon
monoxide, sulfates, polycyclic aromatic HC (PAH) and particulate matter.
Biodiesel is typically made by chemically reacting lipids with an with an alcohol. It
has a technical definition as a mono-alkyl ester or fatty acid methyl ester.
Biodiesel works well with new technologies such as catalyst (which can reduce
the soluble fraction of diesel particulates but not solid carbon fraction), particulate
traps and exhaust gas re-circulation. It can be produced from any kind of oil both
vegetable and animal source. (Renewable, 2007)

2.1 Biodiesel Fuel Feedstocks
Biodiesel is a renewable fuel that can be manufactured from vegetable
oils, animal fats, algae or recycled restaurant greases. It is one of the
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easiest alternative fuels to use. This study will focus on biodiesel
feedstock. (Renewable, 2007)

2.1.1 Virgin Oil Feedstock
Rapeseed and soybean oils are most commonly used raw
materials for biodiesel fuel. Soybean oil alone accounts for about
ninety percent of all biodiesel fuel feedstock in the US. It can be
acquired from field pennycress and jatropha. Many other crops like
mustard, flax, sunflower, palm oil, coconut, hemp are good resources
of soybean oil
2.1.2 Waste Vegetable Oil
The waste vegetable oil (WVO) discarded from a restaurant is
getting popular as feedstocks for biodiesel fuel. Many supporters
propose that waste vegetable oil is the best raw material for biodiesel
production.
2.1.3 Animal Fats
Tallow, lard, yellow grease, chicken fat and the by products of
the production of omega-3 fatty acids from fish oils increasingly used in
biodiesel fuel feedstocks.

2.1.4 Algae
Algae can be grown using waste materials such as sewage and
without making use of land used for food production. They are also
looked upon as a good source of biodiesel feedstocks.

2.1.5 Oil from Halophytes
Other feedstocks for biodiesel fuel are halophyte such as
salicorniabigelovii, which can be grow using saltwater in coastal areas
where conventional crops cannot be grown. They produce yields of
soybeans and other oilseeds grown using freshwater irrigation.

2.2 Biodiesel Properties
2.2.1 Physical Properties
Density
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The relative fuel density is a mass measurement per volume
unit and has direct influence on the volumetric fuel consumption. Lower
density lowers the emission of particulate matter, hydrocarbon and
carbon monoxide. The changes in the fuels density may also
contribute to the emission increase by causing improper operation of
the exhaust gases recirculation system, which regulates improper
degree depending on the fuel dose (Bochenska & Gis, 2011)

Kinematic Viscosity
Kinematic viscosity is the measure of the resistance flow of
liquid under gravity, the pressure head being proportional to the density
of the fluid, for gravity flow under a given hydrostatic head, the
pressure head is of a liquid is proportional to its density. For any
particular viscosity the flow od a fixed volume of liquid is directly to its
kinematic viscosity. (ASTM, 1985)

2.2.2 Thermal Properties
Distillation
The distillation characteristics of hydrocarbons have an important
effect on their safety and performance, especially in the case of fuels
and solvents. The boiling range gives information on the composition,
the properties, and the behavior of the fuel during storage and use.
(ASTM d86-12)
Flash point
The most reduced temperature at which the fuel will touch off if
presented to a fire is alluded to as its flash point. ASTM confirmed
B100 must have a flash point more prominent than 266F (130C). The
flash point is the temperature to which a combustible liquid must be
heated to give off sufficient vapor to form momentarily a flammable
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mixture with air when a small flame is applied under specified
conditions. Lowering the flash point represents a potential safety
hazards as the fuel may need to be treated more like gasoline, which
also has a low flash point than diesel fuel. Hence, flash point will
fluctuate because of various feedstocks and different variables. Some
biodiesel has flashpoints more prominent than 300FThe higher flash
point makes it a much more secure substance than petroleum diesel to
have around. (Biodiesel Flashpoint, 2008)

Pour Point
It is the lowest temperature at which it will pour or flow under
prescribed conditions. Pour Point, or Gel Point as it is called by home
brewers, is the temperature where biodiesel gets to be strong and can
never again be pumped. That temperature is a decent piece colder
than the frosty channel stopping point. It is a rough indication of the
lowest temperature at which oil can be pumped. Also, the pour point
can be defined as the minimum temperature of a liquid, particularly a
lubricant, after which, on decreasing the temperature, the liquid ceases
to flow. (Da Tech, 2016)

2.2.3 Chemical Properties
Cetane Number
Cetane Number is utilized to assess fuel start quality dictated
when between begin of infusion and begin of burning. Higher CN
shows shorter time after the infusion. CN is mostly controlled by the
fuel piece and can influence motor startability, commotion and
discharge qualities. By and large, biodiesel has a higher CN than
mineral diesel. This can be credited to the more extended carbon chain
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length of biodiesel. Unsaturation and carbon chain length are the most
two compelling elements of CN. Higher immersion degree and more
unsaturated fat anchor length can prompt a lower CN. The positions of
concoction gathering may likewise impact the CN. The CNis the most
astounding when the carbonyl gathering is toward the end of the
carbon chain and least amidst the carbon chain. What's more, a larger
amount of hydroperoxides expands CN and a shorter chain length of
the liquor moiety may likewise build CN (Schnborn et al., 2009).

2.3 Biodiesel Blend
Blends of biodiesel and conventional hydrocarbon-based diesel
are products most commonly distributed for use in the retail diesel fuel
marketplace. Much of the world uses a system known as the "B" factor to
state the amount of biodiesel in any fuel mix. Biodiesel can be blended
and used in many different concentrations such as, 100% biodiesel is
referred to as B100, 20% biodiesel, 80% petrodiesel is labeled B20, 5%
biodiesel, 95% petrodiesel is labeled B5, 2% biodiesel, 98% petrodiesel is
labeled B2 and 1% biodiesel, 99% petrodiesel is labeled B1.

Moreover, blending Biodiesel with petroleum diesel may be
accomplished by mixing in tanks at manufacturing point prior to delivery to
tanker truck. Splash mixing in the tanker truck (adding specific
percentages of biodiesel and petroleum diesel). In-line mixing, two
components arrive at tanker truck simultaneously. Metered pump mixing,
petroleum diesel and biodiesel meters are set to X total volume, transfer
pump pulls from two points and mix is complete on leaving pump.
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2.4 Standard Specification of Biodiesel
The primary criterion for biodiesel quality is adherence to the
appropriate standard. In the Philippines, the standard specification is the
National Philippine Standard for Coco Methyl Ester. Generally, the fuel
quality of the biodiesel can be influenced by several factors such as the
quality of the feedstock, fatty acid composition of the animal oil or
vegetable oil, production process and other material used in the process.
Table 4
Philippine National Standard Specification of
Coco Methyl Ester (B2 & B100)
Specifications B2 B100
Density @ 15 C, kg/L 0.82 0.86 0.87 0.89
Kinematic Viscosity @ 40 C 2.0 4.5 2.0 4.5
(mm^2/s)
Flash point, C 55 minimum 100 minimum
Cloud point, C Report Report
Pour point, C Report 9 maximum
Acid number, mg KOH/g, max 0.5 maximum 0.5 maximum
Carbon Residue, % mass 0.30 maximum 0.05 maximum
Cetane Number, min 50 minimum 42
Free Glycerin, % mass 0.02 maximum 0.02 maximum
Total Gylcerin, % mass 0.24 maximum 0.24 maximum
Sulfur Content, % mass (ppm) 0.30 maximum 0.05 maximum
Source: Department of Energy, 2007
Presented in Table 3 is the Philippine National Standard for
Coco Methyl Ester (B2 & B100) used as reference in the country. The
Department of Energy made Coconut Methyl Ester as the standard for
biodiesel characterization because of its good properties nearly similar to
the petrodiesel. It also promoted by the government.
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2.5 Biodiesel Process

2.5.1 Acid Esterification
Esterification increases the yield of biodiesel. When oil
feedstocks contain an excess of free fatty acids they have to go
through the process of esterification. The key to effectively preparing
for the esterification process is to make sure the feedstocks have been
sufficiently filtered by removing all contaminants and water. Upon
filtration the feedstocks are fed to the acid esterification process. The
catalyst, sulfuric acid, is dissolved in methanol and then mixed with the
pretreated oil. Once the mixture is heated and stirred, the free fatty
acids are converted to biodiesel. The final step of esterification is to
dewater and feed the product to the transesterification.
(Biodeiselflasvegas, 2012)
2.5.2 Transesterification
Transesterification is a chemical reaction for conversion of
vegetables oil to biodiesel. In this process, vegetable oil is chemically
reacted to alcohol like methanol or ethanol in the presence of catalyst
like lye. This a chemical reaction can cause the breaking down of
vegetable oil and form compounds. Oil containing small amount of free
fatty acids are fed directly to the transesterification process. The
catalyst, potassium hydroxide, is dissolved In methanol and then mixed
with the pretreated oil. The co-products of this reaction are biodiesel
and glycerin. (Biodeiselflasvegas, 2012)

Three Process of transesterification
A. Acid Catalyzed Transesterification
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Figure 5. Acid Catalyzed Transesterification Reaction

Source: ScienLo, 2012
Transesterification by acid catalysis is much slower than that by
alkali catalysis, requiring typically high temperature above 100 C.
Generally employed acid catalysts for transesterification are HCl,
H2SO4, BF3 and sulfonic acids. (Pharm, 2015)
B. Based Catalyzed Transesterification
Figure 6. Base Catalyzed Transesterification Reaction
26

The Based Catalyzed transesterification reaction yield higher
conversion of methyl ester at shorter reaction time when compared
with acid catalyzed Transesterification reaction. The based Catalyzed
transesterification favored a temperature of 55 C with (Oil: Methanol)
molar ratio of 1:8 and sodium hydroxide at 2% w/w (oil basis). (Gerpen,
2005)
The majority of Biodiesel produced via Base Catalyzed
Transesterification is methanol as the alcohol and Sodium Hydroxide
or Potassium hydroxide as the catalyst due to its high yield of
Biodiesel.
C. Enzymatic Catalyzed Transesterification
Figure 7. Enzymatic Catalyzed Transesterification Reaction

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Enzymatic Transesterification is the use of lipases as
biocatalysts for biodiesel production due to their favorable conversion
rate obtained in gentle conditions and relatively simple downstream
processing steps for the purification of biodiesel and by-products.
However, comparatively to conventional chemical processes, the major
obstacles for enzymatic production of biodiesel remain the cost of
lipases, the relatively slower reaction rate and lipases inactivation
caused by methanol and glycerol. (Roman, 2012)
2.5.3 Methanol Recovery

Methanol is usually removed after the biodiesel and glycerin
have been separated into two layers, preventing reaction reversal. The
methanol is then and recycled back to the beginning of the process.
(Biodieselflasvegas, 2012)
2.5.4 Biodiesel Refining
Once separated from the gylcerin, the biodiesel goes through a
purification process, removing all remaining alcohol and catalyst. It is
then dried and stored. To guarantee the biodiesel is without color, odor
and sulfur, an additional distillation process maybe implemented.
(Biodieselflasvegas, 2012)
2.6 Biodiesel Production
Biodiesel is commonly produced by the Transesterification of the
vegetable oil or animal fat feedstock. There are several methods for carrying
out this transesterification reaction including the common batch process,
supercritical processes, ultrasonic methods and even microwave methods.
(ebiofuel, 2012)
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The based catalyzed production of biodiesel generally occurs
using the following steps.

A. Pre-treatment of oil/fat
In this step, unwanted stuff like impurities and moisture are
removed by filtration and evaporation respectively. This unwanted particles
and moisture may affect the quality of the biodiesel produced.

B. Mixing of alcohol and catalyst
The catalyst is typically sodium hydroxide or potassium
hydroxide. It is dissolved in the alcohol usually methanol using standard
agitator or mixer.
C. Reaction
The alcohol/catalyst mix is then charged into a reaction vessel
and the oil or fat is added. Recommended reaction time varies from 1 to 8
hours, and some system recommended the reaction take place at room
temperature. Excess alcohol is normally used to ensure total conversion of
the fat or oil its esters. Care must be taken to monitor the amount of water
and free fatty acids in the incoming oil or fat. F the free fatty acid level or
water level is too high it may cause problems with soap formation and the
separation of the glycerin by- product downstream.

D. Separation
Once the reaction is complete, two major product exist: gylcerin
and biodiesel. Each has a substantial amount of excess methanol that
was used in the reaction. The reacted mixture is sometime neutralized at
this step if needed. The gylcerin phase is much denser than biodiesel
phase and two can be gravity separated with glycerin simply drawn off the
bottom of the settling vessel. In some cases, a centrifuge is used to
separate the two materials faster.

E. Methyl Ester wash.
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Once separated from glycerin, the biodiesel is sometimes
purified by washing gently with warm water to remove residual catalyst or
soaps, dried and sent to storage. In some processes this step is
unnecessary. This is normally the end of the production process resulting
in a clear amber yellow liquid with a viscosity similar to petrodiesel. In
some systems the biodiesel is distilled in an additional step to remove
small amount of color bodies to produce a colorless biodiesel.
Figure 8. Biodiesel Production

Source: ebiofuel, 2012
2.7 Application of Biodiesel

2.7.1 Engine Fuel
Biodiesel can also be blended in any
proportion with diesel in the diesel
engines of modern
automobiles. It is used to lessen the greenhouse gasses emitted by the
vehicles. And also using blended biodiesel can prevent clogging in the
engine since biodiesel has good lubricity which is better in engine fuels
for efficient burning of fuel. It has an added advantage of efficiency
enhancement and less cost in maintenance. (Ezinearticle, 2001)

Types of Fuel Analysis
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A. Engine Emission Test

Engine Emission Test is a protocol contained in an
emission standard to allow repeatable and comparable
measurement of exhaust emission for different engines.

B. Engine Combustion Test
Engine Combustion Test use to test the output of energy
input in the form of fuel. It gives the efficiency with which the
chemical energy of fuel is converted into mechanical work.

2.7.2 Household Chores
Biodiesel can be used as a home heating oil in domestic and
commercial boilers. While a 20% biodiesel blend B20 can be used
without modification, higher blends may affect rubber seats and
gaskets in older equipment. High blends of biodiesel will also clean out
fuel pipes, which can improve heating efficiency but may initially cause
fuel filter clogging. (HChores, 2011)

2.8 Biodiesel Advantages and Disadvantages
Compared to other alternative fuels, biodiesel supports some
unique features and qualities. Unlike any other alternatives fuels, it has
successfully passed all the health effects testing requirements, meeting the
standards of the 1990 Clean Air Act Amendments. (Berkeley Biodiesel,2011)

A. Advantages of biodiesel fuel
The main advantage of biodiesel fuels is it being a renewable
energy source like petroleum-based diesel. One of the main biodiesel fuel
advantages that concerns the environment is that it is less polluting than
petroleum diesel. The lack of sulfur in 100% biodiesel that exhibits an extend
life of catalytic converters is another great advantage in terms of engines.
Another of the advantages of biodiesel fuel is that can also be blended with
other energy resources and oil. Biodiesel fuel can also be used in existing oil
31
heating system and diesel engines without making any alterations. And lastly,
it can also be distributed through existing diesel fuel pumps, which is another
biodiesel fuel advantage over other alternatives fuels

B. Disadvantages of biodiesel fuel
At present, biodiesel fuel is about one and half times more expensive
than petroleum diesel fuel. It requires energy to produce biodiesel fuel from
soy crops, plus there is the energy of sowing, fertilizing and harvesting.
Another biodiesel fuel disadvantage is that it can harm rubber hoses in some
engines. As biodiesel cleans the dirt from the engine, this dirt can then get
collected in the fuel filter, thus clogging it. So, filters have to be changed after
the first several hours of biodiesel use. Biodiesel fuel distribution
infrastructure needs improvement, which is another of the biodiesel fuel
disadvantages.
RESEARCH LITERATURE
Presented here are the studies of foreign and local setting research
involving Rambutan (Naphelium lappaceum) seed Biodiesel.
FOREIGN SETTING
A study entitled Biodiesel Production by Enzymatic
Transesterification of Papaya Seed Oil and Rambutan Seed Oil by Wong et
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al. (2015) presented papaya and rambutan seed oils extracted via soxhlet
apparatus using n-hexane and yields were in between 3440% of oil. The
extracted oils were subjected to enzymatic transesterification by the immobilized
Candida rugosa lipase as a catalyst under room temperature with varies molar
ratios of methanol to oil. The highest biodiesel yield for papaya seed oil and
rambutan seed oil was found to be 96% and 89% at methanol-to-oil ratios of 6:1
and 8:1, respectively. Results also showed a higher biodiesel yield using lipase
immobilized on the magnetic particles as the heterogeneous catalyst compared
to the yield obtained using free enzyme as the homogeneous catalyst. The
properties of biodiesel such as Density, Acid Value, Iodine Value, Cloud Point,
Kinematic Viscosity, Flash Point, Sulfur content, Glycerin Content and Cetane
Number were analyzed and found to meet the European Standard of Biodiesel.
The study shows that papaya and rambutan seed oils have the potential to be
used as alternative feedstock for biodiesel production than the full dependence
on palm oil in Malaysia.
Aransiola et al. (2012) conducted a study entitled Biodiesel
Production from Non-Edible Oil seeds which is a comparative study that
utilized two kinds of non-edible seed oils to compare which of the oils when used
for biodiesel production is more environmentally friendly and cheaper. The
optimum reaction time for transesterification process, FAME yield, viscosity was
also investigated. From their results, they conclude that the optimum reaction
time is 3 hours and it has no significant effect on FAME yield and viscosity
values.
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A study was conducted by Florina Karen Ak Jones (2008) entitled
Blending effects of biodiesel with pure diesel that has the main objective of
improving biodiesel properties by blending it with pure diesel and to measure the
basic properties of waste palm oil biodiesel-diesel fuel blends according to the
standard specifications of diesel fuels. Therefore, effects of blending biodiesel
with petrodiesel are analyzed. Neat fuels are designated as B100 and B0,
respectively. The samples of biodiesel petrodiesel blends consist of B0, B5, B10,
B20, B30, B40, B50, B60, B70, B80, B90, and B100. The total blended fuel was
taken for 25 ml for all analysis except for combustion test where it requires 1.5 L
of the blended fuel. All these samples have gone through five types of fuel
analysis namely viscosity test, moisture content, acid value, TLC test and
combustion test. From the results of the analysis, it is found out that optimum of
volume ratio mixing in order to improve the cold flow properties if biodiesels are
used under severe winter conditions. The most optimum range for biodiesel-
diesel blending is from B20 until B50. Range from B20 to B50 gives the most
optimum condition for engine fuel. Fuels below B20 have a better quality as they
contain as less moisture content as possible where most of them have moisture
content below than 0.05%. On the other hand, blended fuels above B50 that
contain more amount of biodiesel increases the amount of methyl ester, more
than 0.68 conversions. The emission particulates can also be improved when
optimum amount of biodiesel is blended to the v petrodiesel. The amount of O2 is
more than 8.3% starting form B20 onwards. The amount of CO2 was able to be
reduced from 9.4% downwards starting from B20 until B100. Oppositely, the
34
amount of NOx was the highest at B100 which is 31 ppm and the lowest at B0
which is 3 ppm. The amount of free fatty acid also increases as the volume ratio
of biodiesel increase. At B0, there is no presence of free fatty acid. At B100, the
value of free fatty acid is the highest which is 0.62 ml NaOH/g and 1.3 ml
NaOH/g for acid value.
Venkata Ramesh Mamilla et al. (2012), analyzed the Biodiesel
Production from Palm oil by transesterification method of which utilized the
crude oil with methanol in the presence of NaOH as catalyst. Important fuel
properties of methyl esters of biodiesel produced from palm oil like viscosity,
flash point, fire point, calorific value etc., were determined and was compared to
the properties of Indian standard biodiesel. This research studies about the basic
properties of palm oil biodieseldiesel fuel blends were measured according to
the corresponding Indian standards.
Davis et al. (2014), studied the Effect of biodieselbutanol fuel
blends on emissions and performance characteristics of a diesel engine
which has the purpose of investigating the effect of butanolbiodiesel blends on
the emissions and performance characteristics of a four-stroke, naturally
aspirated, water-cooled, indirect injection diesel engine (IDI). Testing was
performed comparing butanol blended with biodiesel, standard diesel (D100) and
neat biodiesel (B100) at four engine loads. The biodieselbutanol blends were
5%, 10%, and 20% butanol in volume basis (B95Bu5, B90Bu10, B80Bu20).
Compared to biodiesel, butanol blended fuels showed lower exhaust gas
temperatures and nitrogen oxides (NOx) emissions while exhibiting higher
35
carbon monoxide (CO) and unburned hydrocarbons (HC) emissions. Butanol
blended fuels produced lower CO and higher NOx emissions than diesel fuel for
low concentrations of butanol (5% and 10%), but there was no significant change
in terms of HC emissions. The biodiesel blend containing the highest
concentration of butanol (20%) caused higher CO and HC emissions and lower
NOx emission than diesel. Brake specific fuel consumption increased with
biodiesel and biodiesel blended fuels as compared to diesel.
LOCAL SETTING
A study under the title Alternative diesel fuel and diesel additive
from waste animal fat and used oil by Dela Cruz et al. (2009) compared the
property of the biodiesel produced from waste animal fats from different
rendering plants and used oil. The study used based catalyzed sodium hydroxide
as the base and methanol as the alcohol. The properties of the biodiesel from
animal fats obtained were density 0.840 g/mL, viscosity 3.770 cP, pH 6.630,
cloud point 11.33 C and freezing point 6 C.
Marasigan et al. (2007) conducted a study about Biodiesel produced
from tubang bakod oil via transesterification that involves following
procedures: filtration, evaporation, titration, sodium methoxide preparation,
heating and mixing, seetling and separation and washing and drying. The
properties of the oil and the biodiesel produced were compared with ASTM
standards and the PNS standard.
36
In a study of J.L. Garcia et al. (2012) entitled Characterization of
biodiesel from feather meal described the steps of purification of feather meal
biodiesel. The researchers obtained a two phase solution with the feather meal
methyl ester at the top and gylcerin at the bottom. It was then separated by
decantation and suing of seperatory funnel. The obtained feather meal methyl
ester still contained small amounts of methanol and gylcerin and was then
purified by washing. The pH pf the uncleaned methyl ester was then measured
using the pH paper. In order to get rid of the soap residues, the feather meal
methyl ester was washed with warm distilled water (40 45 C) containing a 0.5
% of its total volume, and then filled up with the biodiesel to be blended. After a
gentle stirring and 2 hours of setting, the oil and water was separated. The
cleaned oil was decanted out leaving the denser soapy water at the bottom. The
second and third washings were done with water alone. The pH of the finish
product was then checked also with a pH paper.
Escobar et al. (2008) study, Biodiesel Production from Jatropha
Curcas L. by Transesterification by hexane as a co-solvent, utilized the
hydraulic presser in extraction the oil from the Jatropha seeds and the two step
acid base transesterification using sulfuric acid and sodium hydroxide as the
catalysts. Results showed that sodium hydroxide as a catalyst is highly effective
at amount not lower than 1 % w/w of oil.
Payawans et al. (2010) study, the Transesterification of oil Extract
from Locally-Curcas using Heterogeneous Base Catalyst and
Determination of its Properties as a Viable Biodiesel, results showed that
37
solvent extraction using hexane of oil from Jatropha curcas nuts yielded 32.17%
crude oil. The acid value of the sample indicates a high free fatty acid content
which explains high yield of saponification products via the homogeneous base
catalyzed transesterification. Heterogeneous hybrid inorganic-organic base
catalyst for transesterification were designed and developed to facilitate a more
efficient conversion of Jatropha curcas oils to bio-based fuels.
SYNTHESIS
38
The above mentioned conceptual and research literature on biodiesel
production from Rambutan seeds will be used in this study as a reference to
produce Rambutan Biodiesel and consider the factors affecting its properties.
One of the bases in this study is the Biodiesel Production by Enzymatic
Transesterification of Papaya Seed Oil and Rambutan Seed Oil by Wong et al.
(2015). The study differs in the raw material and process that will be used in
converting Rambutan seed oil into Biodiesel. Wong et al. used Enzymatic-
Catalyzed Transesterification method while this study aims to utilize Rambutan
seeds only as its major raw material and the transesterification method be based
catalyzed, also formulation of a B2 (2% Biodiesel) in blending of Rambutan seed
Biodiesel with diesel as mandated by Department of Energy. The proponents will
be using n-Hexane for oil extraction under two methodologies, the soxhlet and
soaking extraction methods.
In addition to that, similar to the previous study are properties
measured, such as Acid Number, Cetane Number, Cloud Point, Density, Flash
Point, Gylcerin Content, Kinematic Viscosity and Sulfur Content. This study
compared the properties according to Philippine National Standard for Coco
Methyl Ester.
From the study of Biodiesel Production from Palm oil by
transesterification method by Venkata Ramesh Mamilla et al. (2012), the
researchers may adopt the transesterification process, but the current study
utilizes a different catalyst).
39
Furthermore, the previous study on the Effect of Biodieselbutanol fuel
blends on emissions and performance characteristics of a diesel engine by Davis
et al. (2014) is quite related since we have a test for emission for the biodiesel
blends.
40

Chapter II Biodiesel

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Chapter II Biodiesel

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CHAPTER II

REVIEW OF RELATED LITERATURE

The chapter present a review of conceptual and research literature that

the researchers made as the framework.

the family Sapindaceae.It is closely related to several other edible tropical

Malaysia and commonly cultivated throughout the archipelago and southeast

resulted in the establishment of many commercial plantations in the provinces of

Batangas, Cavite, Davao, Iloilo, Laguna, Oriental Mindoro and Zamboanga.

not grown in this country. (Integrated Taxonomic Information System, 2010)

dark-red with spines to 3/4 in (2 cm) long. It is cultivated in the Philippines

the Philippines has yielded on the average 41 lbs/acre. (Morton, 2002)

In the Philippines, two cultivars of rambutan are recognized by their

two cultivars are indistinguishable, yet the 'Maharlika Rambutan' is more

well-known with a higher cost.

1.2 Rambutan Seed Composition

toxic and contains carbohydrates,

polyphenols also quite high in fat. Composition of chemical substances in

rambutan seeds produced hypoglycemic properties (lowering blood sugar levels)

so that the seeds of rambutan is widely used for alternative treatments to

high lipid content and easily available. (Dion, 2005)

1.3 Rambutan seed oil

Iodine Value, IV 37.64

1.4 Properties of Rambutan Seed Oil

direct influence on the volumetric fuel consumption. Lower density

lowers the emission of particulate matter, hydrocarbons and carbon

emission increase by causing improper operation of the exhaust gases

recirculation system which regulates recirculation degree depending on

the fuel dose (Bochenska & Gis, 2011)

is either saturated or unsaturated. Most naturally occurring fatty acids

have an unbranched chain of an even number of carbon atoms, from 4

to 28. Fattyacids are usually derived

from triglycerides or phospholipids. Fatty acids are important sources

of fuel because, when metabolized, they yield large quantities of ATP.

fats. The level of FFA depends on time, temperature and moisture

such as storage, processing, heating or frying. Since FFA are less

rancid. (Bochenska & Gis, 2011)

to saponify one gram of a given ester, especially a glyceride. Expand

Also called saponification value. The saponification number and

to help Fat, Oil, Grease, and Biodiesel attain useful information

regarding primarily methanol and water content quickly and

heat a material to remove (vaporize) volatile components, and that the

change in mass can be used to determine the amount of volatile matter

that was originally present. (Bochenska & Gis, 2011)

solvent. The sample is dried and ground and placed in a Glass

Rotary Evaporator to extract the oil. (Labcom, 2011)

use as a precursor for other organic compounds such as

composition of the fraction depends largely on the source of the oil

(crude or reformed) and the constraints of the refining. The industrial

product (usually around 50% by weight of the straight-chain isomer) is

the fraction boiling at 6570 C

1.5.2 Steam Distillation

process) for temperature sensitive materials like

natural aromatic compounds. It once was a popular laboratory method

for purification of organic compounds, but has become obsolete

by vacuum distillation. Steam distillation remains important in certain

industrial sectors. (Labcom, 2011)

component parts, or fractions, separating chemical compounds by

their boiling point by heating them to a temperature at which one or

more fractions of the compound will vaporize. It