CHAPTER 2

A. Banana (Musa paradisiaca)

Banana is a long and slightly curved fruit with creamy colored soft flesh and a skin that turns
from green to yellow when ripe. Bananas are popular for aroma, texture, and easy to peel and
eat, besides rich in potassium and calcium and low in sodium content (Mohpharta, 2010).

Banana (Musa sp.) is one of the most common and widely grown fruit crops in the
Philippines. It is also one of the countrys major dollar earners and banana ranked next to
coconut oil and prawn in terms of value earning during the last five years.

Musa paradisiaca grows to as tall as 20 feet; fruit is angular; has thick peel that is green
when unripe, yellow when ripe; flesh is white when ripe; gestation period is 15 to 16 months
(Department of Agriculture. 2010).

The ripe banana fruit is pureed, candied and preserved in various forms when not eaten fresh.
Its extract is used in the manufacture of ketchup, vinegar and wine. The unripe fruit is powdered
and chipped. In rural areas the young leaves are pounded and applied to injuries to suppress
bleeding. The leaves are also used widely as packing materials for fruits and vegetables in
market centers. Banana fiber is woven into rope, and mat. Sheets of paper and paper boards are
also made from banana peel. Banana blossom is exported, dried and usually added to meat
recipes (Department of Agriculture, 2010).

A.1. Banana Peel
The peel of banana represents forty percent of the total weight of the fruit, however
unutilized (Alkarkhi and others, 2010). These peels are usually discarded as waste after the
inner fleshy portion has been eaten (Oladiji and others, 2010). Banana peel waste is normally
disposed in municipal landfills, which contribute to the environmental problems
(Wachirasiri, 2009).

Recycling of fruit peel wastes will not only help lessen solid waste problems but also
help discover important substances that may prove to have vital use. The peel wastes from
Saba may contain the same valuable components generally found in banana flesh. These
valuable substances may be used to formulate preparations with pharmacologic or medicinal,
nutritive, and energy values (Solidum, 2011).

A.2. Chemical Composition
The following are the major composition of banana peel: Natural moisture 83.8 %,
Protein 6.1%, Ether extract 8.7%, Crude Fibre 10.0%, total sugar 22.0%, total ash 12.1%,
Soluble ash 11.7%, Calcium 0.35%, Magnesium 0.23%, Sodium trace, Potassium 5.72%,
Phosphorus 0.32%, Sulfur trace, Chlorine 0.64% (Shemg and Yiming ,2011).

B. Oil from banana peel

B.1. Soxhlet Extraction
Extraction includes two steps: (1) Contact of the solvent with the solid to be treated so as
to transfer the soluble constituent or solute to the solvent, and separation or washing of the
solution from the residual solid. (2) Solid liquid extraction (leaching) is the process of
removing a solute or solutes from a solid by using of liquid solvent. Process may come in
three parts: (1) Diffusion of the solvent through the pores of the solid, (2) diffused solvent
dissolves the solutes (i.e. transfer the solute to liquid phase), and (3) transfer of solution from
porous solids to the main bulk of the solution (Gibbs, unknown date).

The process begins with a solvent vapor, which is generated by gently heating the
reservoir, condenses and is allowed to drip back onto the porous sample cup. The liquid
condensate that drips onto the sample performs the extraction which then passes through the
container and back into the reservoir. The cycle is repeated continuously and can be
sustained as long as needed. As it progresses the oil is concentrated in the reservoir
(CHEMO, 2003).




C. Biodiesel
C.1. Description
Biodiesel refers to fatty acid methyl ester or mono-alkyl ester derived from vegetable oil,
or animal fats and other biomass-derived oils that shall be technically proven and approved
by the DOE (Department of Energy) with quality specifications in accordance with the PNS
(Philippine National Standards) (Corpuz, 2010).

C.2 Impact and Issues
The United Nations Food and Agriculture Organization estimated in 2008 that biofuels
accounted for approximately ten percent of the recent food price increases around the world.
The key success factors for the future of biofuels will be gradual expansion in cultivated land
and considerable increases in agricultural productivity. This will require a broad political
commitment, including introduction of badly needed land reforms, better irrigation, and use
of fertilizers and further development of transport infrastructure. The development of second-
generation biofuels that can help to limit the direct competition between food and biofuel that
is associated with mostly first generation biofuels should be a priority for sustainability of
biofuels (World Energy Council, 2010).
There is a continuous debate around the world about biofuels production and its impact
on traditional agriculture and the perceived competition for land and the risk of displacing
production of human and animal food by biofuels. Land availability for food production
could be reduced by the land devoted to fuel production. It is important to ensure that
biofuels are developed in areas that do not affect the use of the basic resources of agricultural
ecosystems such us soil, water, air and biodiversity. Large-scale production of biofuels could
increase the price of agricultural commodities. This would benefit farmers, but might
increase food prices (World Energy Council, 2010).




C.3.Biofuels Act - RA 9367
The Philippine biofuels program (RA 9367) has three policy objectives, namely:
1. Reduce dependence on imported oil
2. Mitigate toxic and greenhouse gas (GHG) emissions, and
3. Increase rural employment and incomes.
Moreover, it has one caveat with three elements: the production of biofuels should be
achieved without any detriment to the natural ecosystem, biodiversity and food reserves of
the country.

C.4. Methods of Preparation
C.4.1. Transesterification
In the transesterification of vegetable oils, a triglyceride reacts with an alcohol in the
presence of a strong acid or base, producing a mixture of fatty acids alkyl esters and
glycerol. The overall process is a sequence of three consecutive and reversible reactions,
in which di and monoglycerides are formed as intermediates. The stoichiometric reaction
requires one molecule of a triglyceride and three molecules of the alcohol. However, an
excess of the alcohol is used to increase the yields of the alkyl esters and to allow its
phase separation from the glycerol formed (Schuchardt and others, 1998).

C.4.1.1 Centrifugation
Centrifugation is a process by which solid particles are sedimented and separated
from a liquid using centrifugal force as a driving force. Depending on the rotational speed
and distance from the axis of rotation, the centrifugal force can be many times greater
than the force of gravity, allowing even very small particles or particles slightly denser
than the fluid to settle.





C.4.1.2 Distillation
Distillation is a commonly used method for purifying liquids and separating mixtures
of liquids into their individual components. It relies on differences in the boiling points of
the component liquids to be separated.

D. Analysis of Biodiesel
D.1. Flash Point
D.1.1 Method of Determination
Flash point will be determined using the Flasky-Martens method.

D.1.2. Significance of Parameter
The flash point temperature is one measure of the tendency of biodiesel to form a
flammable mixture with air under controlled laboratory conditions. Flash point is used in
shipping and safety regulations to define flammable and combustible materials. This test
method should be used to measure and describe the properties of biodiesel in response to
heat and an ignition source under controlled laboratory conditions and should not be used
to describe or appraise the fire hazard or fire risk of materials, products, or assemblies
under actual fire conditions. However, results of this test method may be used as
elements of a fire risk assessment which takes into account all of the factors which are
pertinent to an assessment of the fire hazard of a particular end use (ASTM D 93).

D.2. Water and Sediment
D.2.1 Method of Determination
Water and sediment content will be determined by centrifugation procedure where
equal volumes of biodiesel and water-saturated toluene are placed into a cone-shaped
centrifuge tube. After centrifugation, the volume of the higher density water and sediment
layer at the bottom of the tube is read.

D.2.2. Significance of Parameter
The water and sediment content of crude oil is significant because it can cause
corrosion of equipment and problems in processing. A determination of water and
sediment content is required to measure accurately net volumes of actual oil in sales,
taxation, exchanges, and custody transfers (ASTM D 4007).

D.3. Kinematic Viscosity
D.3.1. Method of Determination
The time is measured for a xed volume of liquid to ow under gravity through the
capillary of a calibrated viscometer under a reproducible driving head and at a closely
controlled and known temperature. The kinematic viscosity (determined value) is the
product of the measured ow time and the calibration constant of the viscometer. Two
such determinations are needed from which to calculate a kinematic viscosity result that
is the average of two acceptable determined values.

D.3.2. Significance of Parameter
The viscosity of many biodiesel is important for the estimation of optimum storage,
handling, and operational conditions. Thus, the accurate determination of viscosity is
essential to many product specifications (ASTM D445 - 11a).

Many petroleum products, and some non-petroleum materials, are used as lubricants,
and the correct operation of the equipment depends upon the appropriate viscosity of the
liquid being used. In addition, the viscosity of many petroleum fuels is important for the
estimation of optimum storage, handling, and operational conditions. Thus, the accurate
determination of viscosity is essential to many product specications (ASTM D 445).

D.4. Sulfated Ash
D.4.1. Method of Determination
Sulfated ash will be determined by igniting and burning the sample until only ash and
carbon remain. After cooling, the residue is treated with sulfuric acid and heated at 775
C until oxidation of carbon is complete. The ash will be cooled, re-treated with sulfuric
acid, ad heated at 775 C to constant weight.


D.4.2 Significance of Parameter
The sulfated ash can be used to indicate the concentration of known metal-containing
additives in new oils. When phosphorus is absent, barium, calcium, magnesium, sodium
and potassium are converted to their sulfates and tin (stannic) and zinc to their oxides.
Sulfur and chloride do not interfere, but when phosphorus is present with metals, it
remains partially or wholly in the sulfated ash as metal phosphates.

D.5. Total Sulfur
D.5.1 Method of Determination

D.5.1. Significance of Parameter
Some process catalysts used in biodiesel and chemical refining can be poisoned when
trace amounts of sulfur bearing materials are contained in the feedstocks. This test
method can be used to determine sulfur in process feeds sulfur in finished products, and
can also be used for purposes of regulatory control (ASTM D5453 09).

D.6. Copper Strip Corrosion
D.6.1. Method of Determination

A polished copper strip is immersed in a specic volume of the sample being tested
and heated under conditions of temperature and time that are specic to the class of
material being tested. At the end of the heating period, the copper strip is removed,
washed and the color and tarnish level assessed against the ASTM Copper Strip
Corrosion Standard.

D.6.2. Significance of the Parameter
This test method is suitable for setting specifications, for use as an internal quality
control tool, and for use in development or research work on industrial aromatic
hydrocarbons and related materials. It also gives an indication of the presence of certain
corrosive substances which may corrode equipment, such as acidic compounds or sulfur
compounds.
D.7. Cetane Number
D.7.1 Methods of Determination
Cetane Number is usually measured directly using a test engine.

D.7.2. Significance of Parameter

Cetane Number is a measure of the readiness of a fuel to auto-ignite when
injected into a diesel engine. It relates to the delay between when fuel is injected into the
cylinder and when ignition occurs. Also, there is a direct relationship between exhaust
emissions and cetane number of diesel fuel.

D.8. Cloud Point
D.8.1. Methods of Determination
D.8.2. Significance of Parameter
The cloud point of petroleum products and biodiesel fuels is an index of the lowest
temperature of their utility for certain applications. Wax crystals of sufficient quantity
can plug filters used in some fuel systems (ASTM D738 11).

D.9. Carbon Residue
D.9.1. Methods of Determination
The carbon residue is determined when a weighed quantity of sample is placed in a
glass vial and heated to 500 C under an inert (nitrogen) atmosphere in a controlled
manner for a specic time. The sample undergoes coking reactions, and volatiles formed
are swept away by the nitrogen. The carbonaceous-type residue remaining is reported as a
percent of the original sample as carbon residue (micro).

D.9.2. Significance of Parameter
The carbon residue value of the various petroleum materials serves as an
approximation of the tendency of the material to form carbonaceous type deposits under
degradation conditions similar to those used in the test method, and can be useful as a
guide in manufacture of certain stocks. However, care needs to be exercised in
interpreting the results.

D.10. Acid Number
D.10.1. Methods of Determination
D.10.2. Significance of Parameter
New biodiesel may contain acidic constituents that are present as additives or as
degradation products formed during service, such as oxidation products. The relative
amount of these materials can be determined by titrating with bases. The acid number is a
measure of this amount of acidic substance in the oil, always under the conditions of the
test. The acid number is used as a guide in the quality control of lubricating oil
formulations. It is also sometimes used as a measure of lubricant degradation in service.
Any condemning limits must be empirically established (ASTM D664).

D.11. Free Glycerin and Total Glycerin
D.11.1. Methods of Determination
D.11.2.Significance of Parameter
Free and bonded glycerin content reflects the quality of biodiesel. A high content
of free glycerin may cause problems during storage, or in the fuel system, due to
separation of the glycerin. High total glycerin content can lead to injector fouling and
may also contribute to the formation of deposits at injection nozzles, pistons, and valves
(ASTM D6584 - 10ae1).

D.12. Phosphorous
D.12.1. Methods of Determination
D.12.2. Significance of Parameter

D.13. Density
D.13.1. Methods of Determination
D.13.2. Significance of Parameter

E. Related Studies
E.1. Banana Related
Musa sapientum peels were analysed for minerals,nutritional and anti-nutritional
contents. The result of mineral content indicate the concentrations of potassium, calcium,
sodium, iron, manganese, bromine, rubium, strontium, zirconium and niobium. The study of
the anti-nutrient content of the peel indicates generally low values except saponins. If the
peels are properly exploited and process, they could be a high quality and cheap sourdce of
carbohydrates and minerals for livestock (Anhwange,2008).
Composition of fatty oil in two different varieties of banana peels Musa Cavendis and
Musa Sapientum was determined. Solvent extraction of the peel powder yields 10% oil in the
case of Musa Cavendis variety, while 7.50% in the case of Musa Sapientum variety. From the
data it is clear that peel of Musa Cavendis variety yields oil more than that of Musa
Sapientum variety (Hassan et al, 2010).

Oil extracted from ripe peel of Musa paradisiaca (plantain) was analyzed for
physicochemical properties and fatty acid constituents using standard methods. The
percentage yield of the oil from the peel of M. parasidiaca fruit was 6%. The component
phospholipids of the peel oil included phosphatidyl glycerol and diphosphoglycerol while the
neutral lipids were free fatty acids and cholesterol esters. Overall, the results suggest that the
oil from the ripe peel of Musa parasidiaca may not be a good candidate for conventional oil
and may not be a good raw material for soap, paint and food industries (Oladiji et al, 2010).

Four different preparation methods of banana peel, dry milling, wet milling, wet milling
and tap water washing, and wet milling and hot water washing were investigated on their
effects on the chemical composition and properties of the banana peel dietary fibre
concentrate (BDFC). The dry milling process gave the BDFC a significant higher fat, protein,
and starch content than the wet milling process, resulting in a lower water holding capacity
(WHC) and oil holding capacity (OHC). Washing after wet milling could enhance the
concentration of total dietary fibre by improving the removal of protein and fat. Washing
with hot water after wet milling process caused a higher loss of soluble fibre fraction,
resulting in a lower WHC and OHC of the obtained BDFC when compared to washing with
tap water. Wet milling and tap water washing gave the BDFC the highest concentration of
total and soluble dietary fibre, WHC and OHC (Wachirasiri et al, 2009).

E.2. Biodiesel Related
Biodiesel production from crude Jatropha curcas with a high content of free fatty acids
has been investigated. A technique to produce biodiesel from crude Jatropha curcas seed oil
having high free fatty acids has been developed. A two-stage transesterification process was
selected to improve the methyl ester yield. The high free fatty acids level of the said fruit was
reduced to less than one percent by a two-step pre-treatment process which was the first
stage. The second stage, alkali base catalysed transesterification process gave 90% methyl
ester yield (Berchmans and Hirata, 2008).

Biodiesel is an important new alternative diesel fuel that is produced from vegetable oils
and animal fats. Conventional processing involves an alkali catalyzed process, but this is
unsatisfactory for lower cost high free fatty acid feedstock due to soap formation. Processes
have been developed to allow biodiesel production from high free fatty acid feedstock, such
as recycled restaurant grease, animal fats, and soap stock which are often considered as waste
(Gerpen, 2005).

The fuel properties of biodiesel are strongly influenced by the properties of the individual
fatty esters in biodiesel. Important fuel properties of biodiesel that are influenced by the fatty
acid profile and, in turn, by the structural features of the various fatty esters are cetane
number and ultimately exhaust emissions, heat of combustion, cold flow, oxidative stability,
viscosity, and lubricity. Generally, these properties of fatty compounds increase with
increasing chain length and decrease with increasing unsaturation. It appears reasonable to
enrich certain fatty ester with desirable properties in the fuel in order to improve the
properties of the whole fuel (Knothe, 2005).