MODULE 3

VEGETABLE OILS AND BIOFUELS

Vegetable Oil Industry

Introduction
Vegetable oils are obtained from plants. They are important ingredients in many foods, and
can be hardened through a chemical process to make, for example, margarine. They can also
be used as fuels, for example as biodiesel. Emulsifiers are food additives that prevent oil and
water mixtures in food from separating. Vegetable oils are natural oils found in seeds, nuts
and some fruit. These oils can be extracted. The plant material is crushed and pressed to
squeeze the oil out. Olive oil is obtained this way. Sometimes the oil is more difficult to
extract and has to be dissolved in a solvent. Once the oil is dissolved, the solvent is removed
by distillation, and impurities such as water are also removed, to leave pure vegetable oil.
Sunflower oil is obtained in this way.
Vegetable oils are usually extracted from the oilseeds using hexane because of its high
extraction power and low boiling point. In the first stage of extraction, a mixture of 70–
75 wt% solvent and 25–30 wt% oils is obtained. The crude vegetable oils have to undergo oil
refining to remove undesirable components such as solvent, water, dust, gums, and trace
elements (iron, copper, and sulfur) to meet the properties required for their commercial
applications (Firman et al., 2013).
Some of the most common liquid vegetable oils used in the food industry include soybean,
canola, sunflower, cottonseed, and corn. If properly refined, all of these oils work well in most
of the general home cooking applications. However, in industrial food manufacturing, where
food matrices can be complex, unit operations rigorous, and finished products require certain
minimum stability to last through the supply chain and the eventual consumption, the oils used
in the formulations often require additional oxidative stability.
Several factors impact the oxidative stability of native oils, including, among others, the level of
unsaturation and the amount and types of natural antioxidants present in the oil. The level of
unsaturation, as expressed by iodine value, is a function of the fatty acid profile of the oil. The
higher the ratio of saturated fatty acids, like stearic and palmitic acids, and mono unsaturated
fatty acids, like oleic acid, the higher the stability. The higher the ratios of polyunsaturated fatty
acids, like linoleic and linolenic acids, the lower the stability. Natural antioxidants,
like tocopherols, tocotrienols, and others, also greatly influence the oxidative stability.
Structure of vegetable oils
Molecules of vegetable oils consist of glycerol and fatty acids. In the diagram below you can

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see how three long chains of carbon atoms are attached to a glycerol molecule to make one
molecule of vegetable oil.

1. Vegetable oils have higher boiling points than water. This means that foods can be
cooked or fried at higher temperatures than they can be cooked or boiled in water.
Food cooked in vegetable oils: cook faster than if they were boiled have different
flavours than if they were boiled. However, vegetable oils are a source of energy in
the diet.
2. Food cooked in vegetable oils releases more energy when it is eaten than food cooked
in water. This can have an impact on our health. For example, people who eat a lot of
fried food may become overweight.
Fats and Oils
The fatty acids in some vegetable oils are saturated: they only have single bonds between
their carbon atoms.
1. Saturated oils tend to be solid at room temperature, and are sometimes called
vegetable fats instead of vegetable oils. Lard is an example of a saturated oil. The
fatty acids in some vegetable oils are unsaturated: they have double bonds between
some of their carbon atoms.
2. Unsaturated oils tend to be liquid at room temperature, and are useful for frying food.
They can be divided into two categories: monounsaturated fats have one double bond
in each fatty acid polyunsaturated fats have many double bonds. Unsaturated fats are
thought to be a healthier option in the diet than saturated fats.

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Vegetable oils do not dissolve in water. If oil and water are shaken together, tiny droplets of
one liquid spread through the other liquid, forming a mixture called an emulsion.

Emulsions
1. Emulsions are thicker (more viscous) than the oil or water they contain. This makes
them useful in foods such as salad dressings and ice cream.
2. Emulsions are also used in cosmetics and paints. There are two main types of
emulsion:
a. oil droplets in water (milk, ice cream, salad cream, mayonnaise)
b. water droplets in oil (margarine, butter, skin cream, moisturising lotion).
3. If an emulsion is left to stand, eventually a layer of oil will form on the surface of
the water. Emulsifiers are substances that stabilise emulsions, stopping them
separating out. Egg yolk contains a natural emulsifier. Mayonnaise is a stable emulsion
of vegetable oil and vinegar with egg yolk.

Emulsifier molecules have two different ends: a hydrophilic end - 'water-loving' - that forms
chemical bonds with water but not with oils a hydrophobic end - 'water-hating' - that forms
chemical bonds with oils but not with water. Lecithin is an emulsifier commonly used in foods.
It is obtained from oil seeds and is a mixture of different substances. A molecular model of
one of these substances is seen in the diagram.

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The hydrophilic 'head' dissolves in the water and the hydrophobic 'tail' dissolves in the oil. In
this way, the water and oil droplets become unable to separate out.

Bromine Water Test

Unsaturated vegetable oils contain double carbon-carbon bonds. These can be detected using
bromine water (just as alkenes can be detected).
1. Bromine water becomes colourless when shaken with an unsaturated vegetable oil,
but it stays orange-brown when shaken with a saturated vegetable fat.
2. Bromine water can also be used to determine the amount of unsaturation of a
vegetable oil. The more unsaturated a vegetable oil is, the more bromine water it can
decolourise.

Hydrogenation
Higher tier Saturated vegetable fats are solid at room temperature, and have a higher melting
point than unsaturated oils. This makes them suitable for making margarine, or for
commercial use in the making of cakes and pastry. Unsaturated vegetable oils can be
‘hardened’ by reacting them with hydrogen, a reaction called hydrogenation. During
hydrogenation, vegetable oils are reacted with hydrogen gas at about 60ºC. A nickel catalyst
is used to speed up the reaction. The double bonds are converted to single bonds in the
reaction. In this way unsaturated fats can be made into saturated fats – they are hardened.

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The structure of part of a fatty acid.

Methodology

Rural vegetable oil production

Rural oil extraction usually occurs near the areas of raw material production. This provides the
smallscale processor with access to raw materials, helps to ensure that perishable oil crops are
processed quickly, and reduces transport costs. For rural communities and the urban poor,
unrefined vegetable oils contribute significantly to the total amount of oil consumed. Crude oils
are affordable to low-income groups and serve as important sources of b -carotene and
tocopherols.

To maintain the quality of the raw material, care is needed during and after the harvesting of
oilbearing fruits that are perishable and susceptible to fat breakdown. Bruising of fresh palm
fruits accelerates lipase activity leading to fat degradation. Oil-bearing crops such as sheanuts
are prone to mould infestation during storage. This is curtailed by heat treatment: steaming or
boiling, coupled with sun-drying to reduce the moisture content.

1. Storage

The moisture content of oil seeds and nuts influences the quality of raw materials over time.
In most rural operations, sun-drying reduces the moisture content of oil seeds to below 10
percent. Adequate ventilation or aeration of the seeds or nuts during storage ensures that
low moisture levels are maintained and microbial development is avoided. This is important
in the storage of groundnuts which are highly susceptible to aflatoxin contamination through
the growth of Aspergillusflavus. Since aflatoxins and pesticides are not removed by rural

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extraction techniques, microbial contamination and the application of insecticides should be

avoided. There is a need for storage practices which are affordable and available to the
small-scale processor. Perishable raw materials such as palm fruits should be processed as
soon as possible after harvesting.

In humid developing countries, the sun-drying of oil seeds with a high moisture content, such
as mature coconut, is slow and inefficient. Such conditions promote mould growth which results
in high free fatty acid levels and poor organoleptic qualities. Coconut oil for human consumption
should be obtained soon after harvest.

2. Pre-treatment.

The first operation after harvesting involves sterilization and heat treatment by steaming
or boiling, this inactivates lipolytic enzymes which could cause rapid degradation of the
oil and facilitates the pulping of the mesocarp for oil extraction. "Sterilised" palm fruits
are pulped in a wooden pestle and mortar or mechanised digestor.

Decortication or shelling separates the oil-bearing portion of the raw material and
eliminates the parts that have little or no nutritional value. Small-scale mechanical
shellers are available for kernels and nuts although manual cracking is still prevalent.

Most oil seeds and nuts are heat-treated by roasting to liquify the oil in the plant cells
and facilitate its release during extraction. All oil seeds and nuts undergo this treatment
except palm fruits for which "sterilization" replaces this operation.

To increase the surface area and maximize oil yield, the oil-bearing part of groundnuts,
sunflower, sesame, coconut, palm kernel and sheanuts is reduced in size. Mechanical
discattrition mills are commonly used in rural operations.

3. Extraction

In oil extraction, milled seed is mixed with hot water and boiled to allow the oil to float
and be skimmed off. The milled oil seed is mixed with hot water to make a paste for

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kneading by hand or machine until the oil separates as an emulsion. In groundnut oil
extraction, salt is usually added to coagulate the protein and enhance oil separation.

A large rotating pestle in a fixed mortar system can be powered by motor, humans or animals
to apply friction and pressure to the oil seeds to release oil at the base of the mortar. Other
traditional systems used in rural oil extraction include the use of heavy stones, wedges, levers
and twisted ropes. For pressing, a plate or piston is manually forced into a perforated cylinder
containing the milled or pulped oil mass by means of a worm. The oil is collected below the
perforated chamber. A variety of mechanical expellers have been designed. The pre-heated raw
material is fed into a horizontal cylinder by a wormshaft. By means of an adjustable choke,
internal pressure which is built up in the cylinder ruptures the oil cells to release the oil.

4. Dehydration

By boiling in shallow pans, traces of water in crude oil are removed after settling. This is
common in all rural techniques which recognize the catalytic role of water in the development of
rancidity and poor organoleptic qualities.

5. Pressing cakes

A by-product of processing, the pressed cake, may be useful depending on the oil extraction
technique applied. Cakes from water-extracted oil are usually depleted of nutrients. Other
traditional techniques, for instance, those used for groundnut and copra ensure that the by-
products, if handled with care, are suitable for human consumption.

Large-scale production

1. Storage.

Many steps in industrial processing find their origin in the traditional processes. In large-scale
operations, oilseeds are dried to less than 10 percent moisture. They may be stored for
prolonged time periods under suitable conditions of aeration with precautions against insect and
rodent infestation. Such storage reduces mould infection and mycotoxin contamination and

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minimizes biological degradative processes which lead to the development of free fatty acids
and colour in the oil.

Oil-bearing fruits such as olive and palm are treated as quickly as possible. Palm is sterilized as
a first step in processing. Adipose tissues and fish-based raw materials (that is, the body or
liver) are rendered within a few hours by boiling to destroy enzymes and prevent oil
deterioration.

2. Processing.

Oilseeds are generally cleaned of foreign matter before dehulling. The kernels are ground to
reduce size and cooked with steam, and the oil is extracted in a screw or hydraulic press. The
pressed cake is flaked for later extraction of residual fat with solvents such as "food grade"
hexane. Oil can be directly extracted with solvent from products which are low in oil content,
that is, soybean, ricebran and corn germ.

After sterilization, oil-bearing fruits are pulped (digested) before mechanical pressing often in a
screw press. Palm kernels are removed from pressed cakes and further processed for oil.
Animal tissues are reduced in size before rendering by wet or dry processes. After autoclaving,
tissues of fish are pressed and the oil/water suspension is passed through centrifuges to
separate the oil.

3. Oil Refining

Refining produces an edible oil with characteristics that consumers desire such as bland flavour
and odour, clear appearance, light colour, stability to oxidation and suitability for frying. Two
main refining routes are alkaline refining and physical refining (steam stripping, distillative
neutralisation) which are used for removing the free fatty acids.

The classical alkaline refining method usually comprises the following steps:

Step 1.
Degumming with water to remove the easily hydratable phospholipids and metals.

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Step 2.
Addition of a small amount of phosphoric or citric acid to convert the remaining non-hydralable
phospholipids (Ca, Mg salts) into hydratable phospholipids.

Step 3.
Neutralising of the free fatty acids with a slight excess of sodium hydroxide solution, followed
by the washing out of soaps and hydrated phospholipids.

Step 4.
Bleaching with natural or acid-activated clay minerals to adsorb colouring components and to
decompose hydroperoxides.

Step 5.
Deodorising to remove volatile components, mainly aldehydes and ketones, with low threshold
values for detection by taste or smell. Deodorisation is essentially a steam distillation process
carried out at low pressures (2-6 mbar) and elevated temperatures (180-220°C).

Market Trends, Issues and Drivers

As of 2016, the Philippines are one of the largest exporters of coconuts and coconut oil in the
world. However, coconut oil has now become a more export-oriented commodity and is used
less for domestic consumption purposes. It is gradually being replaced by palm oil in recent
years. The cooking oil market in the Philippines has increased on account of an increase in
food demand by a growing number of households and expanding health-conscious middle
class in the country.
The Philippines Cooking Oil Market is traditionally dominated by the unorganized sector on
account of providing the cooking oil at a lower cost than the organized players in the
Industry. The major organized players include Minola, Golden Fiesta, Baguio, Marca Leon, and
others. The organized players face tough competition from the unorganized market entities.
These organized players compete majorly on the basis of price, packaging, and types of
products offered.
Innovations and Researches
Many studies have directed efforts to the development of vegetable oils purification,
deacidification, discoloration, and solvent recovery methods to reduce costs and provide

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alternative economically sustainable processes. The viability of separating the oil from the
hexane using solvent-resistant NF membranes arises because of their unique characteristics,
properties, and other advantages when compared to the traditional separation techniques.
One of the advantages is that the separation process can be conducted at room temperature,
and it is therefore suitable for heat-sensitive products and can be used in almost all oil-
processing stages, as shown below.

Biofuels
Product Overview
Bioenergy is energy derived from biofuels. Biofuels are fuels produced directly or indirectly from
organic material – biomass – including plant materials and animal waste.
Overall, bioenergy covers approximately 10% of the total world energy demand. Traditional
unprocessed biomass such as fuelwood, charcoal and animal dung accounts for most of this
and represents the main source of energy for a large number of people in developing countries
who use it mainly for cooking and heating.
More advanced and efficient conversion technologies now allow the extraction of biofuels from
materials such as wood, crops and waste material. Biofuels can be solid, gaseous or liquid, even

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though the term is often used in the literature in a narrow sense to refer only to liquid biofuels
for transport.
Source
Biofuels may be derived from agricultural crops, including conventional food plants or from
special energy crops. Biofuels may also be derived from forestry, agricultural or fishery products
or municipal wastes, as well as from agro-industry, food industry and food service by-products
and wastes.

Biofuels generally come from a few common sources. The concept lies in the fact the energy
contained in raw materials, such as plants, originally came from the sun. Photosynthesis stores
energy in the plants’ cells through photosynthesis and is present in the following materials:

 Sugar crops: Sugar cane, sugar beet, and corn, maize, and other starches can be
fermented, which yields ethanol.
 Natural plant oils: Soybean, oil palm, or even algae can be burned. To produce power,
some diesel engines burn of these. You can also blend them with petroleum-based fuels.
 Wood/byproducts: They often convert these into ethanol, methanol, and other liquid
biofuels. They also form woodgas.
 Burned wood: You can use firewood as a solid fuel. If a furnace supports it, they use
chipped wood as a fuel-based biomass.

Kinds of Biofuels
1. Primary biofuels, such as fuelwood, wood chips and pellets, organic materials are
used in an unprocessed form, primarily for heating, cooking or electricity production.
2. Secondary biofuels result from processing of biomass and include liquid biofuels such
as ethanol and biodiesel that can be used in vehicles and industrial processes.

Types of Liquid biofuels for Transport

1. Ethanol is a type of alcohol that can be produced using any feedstock containing
significant amounts of sugar, such as sugar cane or sugar beet, or starch, such as maize
and wheat. Sugar can be directly fermented to alcohol, while starch first needs to be
converted to sugar. The fermentation process is similar to that used to make wine or
beer, and pure ethanol is obtained by distillation. The main producers are Brazil and the

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USA. Ethanol can be blended with petrol or burned in nearly pure form in slightly
modified spark-ignition engines. A litre of ethanol contains approximately two thirds of
the energy provided by a litre of petrol. However, when mixed with petrol, it improves
the combustion performance and lowers the emissions of carbon monoxide and sulphur
oxide.
2. Biodiesel is produced, mainly in the European Union, by combining vegetable oil or
animal fat with an alcohol. Biodiesel can be blended with traditional diesel fuel or burned
in its pure form in compression ignition engines. Its energy content is somewhat less
than that of diesel (88 to 95%). Biodiesel can be derived from a wide range of oils,
including rapeseed, soybean, palm, coconut or jatropha oils and therefore the resulting
fuels can display a greater variety of physical properties than ethanol.

Generations of Biofuels
1. First-generation biofuels include ethanol produced from crops containing sugar
and starch and biodiesel from oilseeds. These fuels only use a portion of the energy
potentially available in the biomass. First generation biofuels are produced through
conventional technology with sugar, starch, vegetable oil, or animal fats as sources.
Because their feedstocks are also sources of food, the “food vs. fuel” debate is the
major issue with first generation biofuels. Production of first generation biofuels has a
limitation because it might threaten food supply and biodiversity.

2. Second-generation biofuel is composed of cellulose, hemicellulose and lignin, Once

commercially viable, these could significantly expand the volume and variety of sources
that could be used for biofuel production. Potential cellulosic sources include municipal
waste and waste products from agriculture, forestry, processing industry as well as new
energy crops such as fast growing trees and grasses. As a result second
generation biofuel production could present major advantages in terms of
environmental sustainability and reduced competition for land with food and feed
production. To address the increasing biofuel demand, the second generation biofuels
were developed. These second generation biofuels are produced from non-food crops or
portions of food crops that are not edible and considered as wastes, e.g. stems, husks,
wood chips, and fruit skins and peeling.

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3. Third generation biofuels are those that are produced from algae. Production of
oilgae or algae fuel involves fermentation of the algae carbohydrate.

Second and third generation biofuels are also called advanced biofuels. An example of an
advanced fuel that is still under development is the hydrogenation-derived renewable diesel.
HDRD is produced from animal fats or vegetable oils that have been refined in oil refineries.
This fuel can be blended with petroleum.

General Overview of Biofuel Conversion

The feedstock chosen depends on the conversion process in question. For example, they select
it based on quality, composition, and size. The biochemical processes often include grasses and
agricultural and woody residues. The general procedures for conversion include deconstruction
to break the biomass down into its chemical components. There are different deconstruction
processes. The required temperatures differentiate the types that will yield proper results.
Thermochemical deconstruction ranges from 300 to 1,000°C.

High-temperature deconstruction

1. Pyrolysis, which is the thermal/chemical decomposition of feedstock without oxygen.

The outcome is a bio-oil with hydrocarbons. There are more oxygenated compounds per
unit than in petroleum crude oils. Before it can be made into a fuel or processed in a
refinery, it must upgrade the intermediate.
2. Hydrothermal liquefaction produces a bio-oil by adding heat and pressure to a wet
feedstock slurry. After you treat it with water, it is further processed in a reactor.
3. Thermal deconstruction is also accomplished with gasification, which occurs at
temperatures above 700°C. You can add oxygen carrier or steam before you clean and
condition the gas.

Low-temperature deconstruction

To facilitate the conversion process, you can use enzymes and other catalysts, such as heat.
The carbohydrate material converts into an intermediate sugar compound. They can then
ferment the building blocks. It’s also possible to chemically catalyze them. The process involves
pretreatment, where you prepare the feedstock for hydrolysis using mechanical or chemical

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processing methods. They break down this material into soluble and insoluble components. This
exposes the sugar polymers. Hydrolysis further breaks down the polymers. This forms
molecules that are used as fuels or building blocks.

Production Stages

Manufacturing biofuel occurs in a few basic stages; considering the use of waste vegetable oil
from a standard kitchen, these include:

1. Filtration: They filter the oil, which eliminates all food particles. It is easier to filter

warmer liquids. You can do this with a coffee filter.

2. Water Removal: The reactions are faster when you remove water. You can accomplish

this by boiling the mixture at about 100°C.

3. Titration: A method of chemical analysis to determine the concentration of the analyte

present. It helps determine how much lye is needed.

4. Sodium methoxide preparation: You mix methanol, at a quantity of around 20

percent of the vegetable oil used, with sodium hydroxide.

5. Heating/mixing: The results mixture is heated and mixed with care.

6. Settling/separation: As the mixture cools, the biofuel will float on top. You drain the

leftover glycerin and use the pure biofuel.

Biofuels as a Source of Renewable Energy

Bioenergy is one of many diverse resources available to help meet our demand for energy. It is
a form of renewable energy that is derived from recently living organic materials known as
biomass, which can be used to produce transportation fuels, heat, electricity, and products.

Solid, liquid, or gaseous fuels that are produced from biomass are called biofuels. They are
renewable and are good substitutes to fossil fuels. Most biofuels available in the market today
are made from plants. They are often used as transportation fuels.

Certain plants are being cultivated specifically for biofuel production. In the U.S., switchgrass,
soybeans, and corn are the major sources of biofuel. Brazil uses sugar cane while Europe
processes sugar beet and wheat. Other agricultural products being processed into biofuels are
cassava and sorghum in China, miscanthus and palm oil in Southeast Asia, and jatropha in
India.

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Examples of biofuels are biodiesel, bio-alcohols (bio-ethanol, biomethanol, biobutanol), biogas,

syngas, and solid biofuels like wood, charcoal, and sawdust. Countries that have strongly
promoted biofuel development and use include Brazil, the U.S., France, Sweden, and Germany.

 It reduce vehicle emission which makes it eco-friendly.

 It is made from renewable sources and can be prepared locally.
 Increases engine performance because it has higher cetane numbers as compared to
petro diesel.
 It has excellent lubricity.
 Increased safety in storage and transport because the fuel is nontoxic and bio
degradable (Storage, high flash pt)
 Production of bio diesel in India will reduce dependence on foreign suppliers, thus
helpful in price stability.
 Reduction of greenhouse gases at least by 3.3 kg CO2 equivalent per kg of biodiesel.

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