Introduct

ion

CHAPTER-1

Introduction

The use utilization of energy is the basic requirementnecessity for

human survival. Increase in the world’s Day by day increase in
population has demanded claimed more energy for
fulfillmentgratification of their requirements. These energy resources
are limited fFor the growing rate of population, these enegy resources
are insufficient. So there is a need to we have to search alternate
energy resources. The usage use of fossil fuels is increased to such an
extent that this causes the major environmental impacts. Energy
requirements are seen like an insurance policy against different
government insecurity about fossil fuel costs and their security [1].
In recent times, the world has deal with the two twin crises of fossil
fuel, that are decrease and environmental destruction. So people there
is a demand of an alternative fuel to complete their requirements. From
the point of view of protecting the global environment and the concern
for long-term supplies of traditional diesel fuels, we have it becomes
essential to develop alternative fuels comparative to conventional
fuels. Alternative fuels should be, not only sustainable but also
environment friendly [2].
Pakistan, being an energy deficient country tends to import petroleum
fuel from foreign countries in order to keep going. This has lead to
loss of income in order addition to the non-harnessing of native
indigenous resources to meet the energy demands of an ever growing
population, it is going to loss of income. Petroleum fuel is well known

Page 1
 Introduct
ion

to be present in limited to supplies all over the world and have thus
been classified as non-renewable sources of energy. These fuels also
tend to produce destructive emission products of combustion that cause
major damage to the ecological environment [3].
Such alarming effectsimpacts are can also be easily seen easily visible
within the urban environments of Karachi. As a result, a new
alternative is being required sought in order to try and avoid the
damage caused by harmful pollutants into the environment [4].
Due to the shortage of petroleum products and its increasing cost,
efforts are being made to develop alternative fuels are being made,
especially for full or partial replacement of diesel oil. Moreover, the
combustion of petroleum fuels has polluted the air and environment.
Pollutants from internal combustion engines include carbon monoxide
(CO), carbon dioxide (CO2), nitrogen oxide (NOx), sulfur oxide (SOx),
and hydrocarbon (HC)., and particulate matter (PM) [5].

The limited fossil fuel resources along with the need to reduce Green
House Gases emissions were a major impulse to the development of
alternative fuels. As a result, increased attention has been given to
biofuels, such as biodiesel, that can be used as an alternative fuel in
compression–ignition engines are given attention. Biodiesel and
bioethanol have emergedappeared as the most suitable renewable
alternatives to fossil fuel as their quality constituents ingredients
match diesel and petrol respectively. Biodiesel is biodegradable and
non toxic because of iIts production from renewable resources, such as
vegetable oils and animal fats, makes it biodegradable and non-toxic;
also, it contributes to the reduction of CO2 emissions, because it
comprises a closed carbon cycle [6-7].

Page 2
 Introduct
ion

For a decade the duration of the past ten years, much interest has been
paid to these issues in the world and especially in the European Union
Member States. The newly accepted EC biodiesel fuel strategy requires
replacing up to 10% of fossil diesel fuel with biofuel by the year 2020
[8]
.

In diesel engine emissions, using mineral diesel, the presence of

[9-10]
sulphur results in sulphur oxides and sulfates . When these sulfur
chemicals are released into the atmosphere ,they form sulfur dioxide
forms which combines with water to form sulfuric acid. This acid is
carried by winds to neighboring regions, dropping onto the land and its
people inhabitants when it rains, or is hazy misty, or foggy. This
phenomenon is known as acid rain. In the 1930s and 1940s vegetable
oils were used as diesel fuels from time to time, but usually only in
emergency situations. Recently, because of increases in crude oil
prices, limited resources of fossil oil and environmental concerns there
has been a renewed focus on vegetable oils and animal fats to make
biodiesel fuels. Continued and increasing use of petroleum will build
up intensify local air pollution and magnify the global warming
problems caused by CO2 [11].
[12]
The different types of biofuels that already exist in the market are
the following ones:
[12]
Bioethanol : It is produced by fermentation of from sugar, starch
and residual water dust by a fermentation process. It can be used as
replacement or blend for gasoline, and even in high blend percentages
in FFV (Flexible Fuel Vehicles) vehicles.
Bio-ETBE [12]: It is produced from a blend of bioethano (45% volume)
and isobutileno. It can be used in gasoline engines without any
modification on them.

Page 3
 Introduct
ion

[12]
Biodiesel : It is produced by the vegetal oil and/or animal fat
esteritification process. It is similar in some way to the diesel fuel,
especially in density and cetane number. Furthermore, its flash point is
higher than the diesel one, which means more security on its use.
[12]
Biomethanol : It is produced from methanol, due to the high
hydrogen percentage; it could become an interested option for fuel cell
propelled cars.
[12]
Biogas : It is mainly produced by anaerobic fermentation of wet
biomass produces biogas..
[12]
Biosynthetic fuels : They are produced from biogas derived from
biomass during the Fisher-Tropsch process. Any of these can be
produced from single CO and H2 molecules, so a wide range of fuels of
high quality standards can be produced on this basis; however, it is an
expensive production process.
Bio-MTBE [12]: It is similar to Bio-ETBE produced from biomethanol
(36% volume) and isobutanol. Biodimetileter [12]: It is similar to LPG
(liquid petrol gas) in terms of physical characteristics; therefore it can
be used as a replacement for GLP, as an addictive of gasoline blends or
as a component for other diesel blends.
Vegetable fuels could be used as an emergency energy source in the
event of another petroleum fuel shortage. The use of extracted oil has
high viscosity so these can’t be used directly in diesel engines .is
restricted because of its high viscosity. This physical property of pure
vegetable oils would reduce the fuel atomization, which would be
ultimately responsible for high engine deposits and thickening of
lubricating oil [13].

The problems with substituting triglycerides for diesel fuels are mostly
associated with some problems which are their high viscosities, low
volatilities and polyunsaturated character. These can be changed in at
Page 4
 Introduct
ion

least four ways: Pyrolysis is defined as a chemical change caused by

the application of thermal energy in the presence of nitrogen or
[14-17]
absence of air. Many investigators have reported the pyrolysis of
triglycerides to obtain products suitable for diesel engines.

Microemulsions are isotropic, clear or translucent thermodynamically

stable dispersions of oil, water, surfactant, and often a small
[18, 15]
amphiphilic molecule called co surfactant . Dilution of vegetable
oils can be accomplished with materials such as diesel fuels, a solvent
[19]
or ethanol. Ziejewski et al. (1984) concluded that the blend could
not be recommended for long-term use in the direct injection diesel
engines because of severe injector nozzle coking and sticking, heavy
carbon deposit on the tulips of the intake valves and showed
considerable top ring wear.

Transesterification is the general term used to describe the important

class of organic reactions where an ester is transformed into another
ester through interchange of the alkoxy moiety. When the original ester
is reacted with an alcohol, the Transesterification process is called
[20]
alcoholysis . The Transesterification is an equilibrium reaction, and
the transformation occurs essentially by mixing the reactants.
However, the presence of a catalyst (typically a strong acid or base)
accelerates achievment attainment of equilibrium. Higher molar ratio
results in a greater ester conversion in a shorter time [21].

Vegetable oils are chemically triglycerides molecules, in which three

fatty acids groups are esters attached to one glycerol molecule. The
triglyceride molecules differ by the nature of the alkyl chain bound to
glycerol. Transesterification is the process of reacting triglycerides
such as one of the vegetable oils with alcohol in presence of a catalyst

Page 5
 Introduct
ion

strong acid or base producing a mixture of fatty acids alkyl esters and
[22]
glycerol . In this process, there is the displacement of alcohol by a
monohydric alcohol that yields three alkyl esters from one triglyceride
molecule.

Peterson (1986) [23] reported that the molecular weight of typical esters
molecules is roughly one third that of straight vegetable oil molecules
and the viscosity is nearly twice that of diesel fuel instead of 10 − 20
times in case of neat vegetable oil. This process has been widely used
to reduce the high viscosity of triglycerides. The overall process is a
sequence of three consecutive and reversible reactions, in which
[24]
diglycerides and monoglycerides are formed as intermediates . A
molar ratio of 6:1 is normally used in industrial processes to obtain
methyl ester yields higher than 98% on a weight basis [25-26].

Transesterified vegetable oils are known as biodiesel, which are

[27]
generally using as alternative fuel resources . It is biodegradable and
nontoxic, has low emission profiles and so is environmentally
[28]
beneficial . Alcoholysis of vegetable oils is an important reaction
that produces fatty acids alkyl esters like methyl and ethyl esters,
[27,
which are excellent substitutes for conventional fossils diesel fuels
29-33]
.

Biodiesel, defined as the simple monoalkyl esters of fatty acids derived

from vegetable oil, animal fat, or waste oils, is an interesting and
environmentally friendly alternative to conventional diesel fuel (CDF)
for combustion in compression-ignition (diesel) engines. Biodiesel is
produced by transesterification of a triglyceride with methanol in the
presence of catalyst to produce fatty acid methyl esters (FAME) and
glycerol. Transesterification employing alkali catalysis and short-chain
alcohols provides a high level of conversion. The main parameters

Page 6
 Introduct
ion

affecting the transesterification reaction are molar ratio of vegetable oil

to alcohol, catalyst type and amount, reaction time and temperature,
and the contents of free fatty acids (FFAs) and water in substrate oil
[31]
.

Most biodiesel is produced nowadays by the transesterification of

triglycerides of refined/edible type oils by means of methanol and an
alkaline catalyst (NaOH, NaOMe) [27, 34, 35]. The glycerol and FAME are
separated by settling after catalyst neutralization. The crude glycerol
and biodiesel obtained are then purified. The biodiesel production has
several advantages over convectional fuels such as could be cheaper
than the convectional fuels [36].

Some of them can be given as under:

(1) An alternative to petroleum-based fuel, which implies lower

dependence on crude oil foreign imports.
(2) Renewable fuel, helping to achieve the EU renewable energy target
(12% of total energy output to consist of renewable energy by 2010).
(3) A favorable energy balance.
(4) A reduction in greenhouse gas emissions in line with the Kyoto
Protocol agreement.
(5) Lower harmful emissions, which is very advantageous in
environmentally sensitive areas such as large cities and mines.
(6) Biodegradable and non-toxic fuel, being beneficial for reservoirs,
lakes, marine life and other environmentally sensitive places.
(7) The use of agricultural surplus, as agreed in the European
Agricultural Policy regulations, which can also help to improve rural
economies
All of the currently and conventional known methods for biodiesel
production require the use of a catalyst, either alkaline or acid catalyst,

Page 7
 Introduct
ion

and results in a more complicated process. The reaction products are

separated in two phases, an ester phase and a glycerol phase. Although
the removal of the excess alcohol from both phases can be easily
achieved by distillation, the removal of catalyst and the by-products
formed from its reaction with the reactants, e.g. soaps when a base
catalyst is used, is more complicated and time consuming. This
conventional method not only makes the process longer, but also
results in lower yield because vegetable oil contains mainly of
triglycerides with free fatty acids in a minor quantity, the latter being
unable to be converted to methyl esters [37].
The three basic methods of ester production from oils/fats are the base-
catalyzed transesterification, the acid-catalyzed transesterification, and
enzymatic transesterification. The most commonly used method of
which is the base catalyzed transesterification technique as it is the
most economical process [38].
Acids used for transesterification include sulfuric, phosphoric,
hydrochloric, and organic sulfonic acids. Transesterification by acid
[27, 31, 39]
catalysis is much slower than that by alkali catalysis . Freedman
[31, 40]
et al. (1984) and Aksoy et al. (1984) reported the acid-catalyzed
transesterification is more suitable for glycerides that have relatively
[40]
high free fatty acid contents and more water. Aksoy et al. (1984)
reported that it was necessary to perform transesterification under an
acidic condition when the oil component was a low-grade material
such as sulphur olive oil. In general, the ethyl esters of
monounsaturated or short-chain fatty acids with 2% sulfuric acid
should make good alternative fuels [41].
The base-catalyzed transesterification of vegetable oils and fats to form
alkyl ester is faster than the acid-catalyzed reaction. The base-
catalyzed reaction proceeds rapidly at ambient temperature, whereas

Page 8
 Introduct
ion

the acid-catalyzed reaction commonly uses temperature above 100°C,

depending on the boiling point of the alcohol. This base-catalyzed
reaction normally works well when the substrates contain low free
fatty acids and are substantially anhydrous; that is. The starting
material should have free fatty acid content less than 0.5% (acid value
less than 1) [42] and water content less than 0.3%. Metal hydroxides and
alkoxides are both employed for base-catalysis and are known to be
effective. Being relatively cheap, they are widely used for commercial
processes. For typical base catalyzed alcoholysis of oils and fats, the
catalyst is first dissolved in the alcoho1 such as methano1 or ethanol
and then mixed with oil.
The solubility of alcohol in oil varies depending on the size of the alkyl
group of the alcohol and the reaction temperature. The solubility of
methanol in oil is fairly low at room temperature, even at moderate
temperature such as 60°C. The glycerol starts to form after the addition
of alcohol and slowly settles at the bottom of the reaction vesse1 by
gravity. The lower glycerol-rich phase containing a small amount of
alcohol and probably some monoglycerides is separated for
purification. The excess alcohol is removed by distillation, and the
ester-rich phase is washed with water to pH=7. Soap is usually a by-
product. This base-catalyzed transesterification is exothermic [25].
To overcome the drawbacks of the conventional method of synthesis of
biodiesel, alternative and more sustainable routes for biodiesel
production are being searched. In this contest, biotechnological routes
as “Enzymatic processes” are very promising because of their high
selectivity and mild operative conditions. Enzymatic transesterification
of triglycerides offers an environmentally more attractive option to the
conventional process. Biological reactions are similar to other
chemical process, except that they are catalyzed by variety of

Page 9
 Introduct
ion

biological catalysts. In contrast to conventional processes, biocatalysts

allow synthesis of specific alkyl esters, easy recovery of glycerol, and
transesterification of glycerides with high free fatty acid content [43].
Lipases are biological catalysts that represent a category of enzymes
[44]
that digest or synthesize lipids and fats . They have been employed
in the modification of fats and oils both to provide novel materials of
improved characteristics and to upgrade inexpensive raw materials to
[45]
valuable products by transesterification . Through the use of these
enzymes in water media, esterification and transesterification reactions
can also be carried out. The main advantage of using lipase as a
catalyst is that the reactions catalyzed by lipases are considered natural
and it gives high yield in relatively shorter times at moderate
temperature and pressure [46]. Since enzymes are not soluble in organic
[47]
solvents, the reactions are heterogeneous and mass transfer limited .
The reusability of enzyme and high specificity (absence of side
[48-49]
reaction) is another advantage. Lipases are of interest to the food
and pharmaceutical industries because they are widely used to catalyze
[50-51]
a number of important reactions . The use of enzymes as catalyst
in solvents other than water is a rapidly developing research area. The
most profound difference between aqueous and nonaqueous
enzymology is that enzymes that catalyze reactions in non-aqueous
media are heterogeneous with respect to solvent. Because of mild
reaction conditions required for activity, unique substrate specificity,
and selectivity, enzymes are potential replacements for conventional
catalysts.

Canola is one of two cultivars of rapeseed or Brassica campestris

[52]
(Brassica napus L. and B. campestris L.) . Their seeds are used to
produce edible oil that is fit for human consumption because it has
lower levels of erucic acid than traditional rapeseed oils and to produce
Page 10
 Introduct
ion

livestock feed because it has reduced levels of the toxin glucosinolates.

Canola was originally naturally bred from rapeseed in Canada by Keith
Downey and Baldur R. Stefansson in the early 1970s, Richard Keith
[53-54]
Downey, 2007; Storgaard, AK (2008) . But it has a very different
nutritional profile in addition to much less erucic acid. The name
"canola" was derived from "Canadian oil, low acid" in 1978. A product
known as LEAR (for low erucic acid rapeseed) derived from cross-
breeding of multiple lines of Brassica juncea is also referred to as
canola oil and is considered safe for consumption.

Rapeseed (Brassica napus) is widely cultivated throughout the world

for the production of animal feed, vegetable oil and biodiesel. The
seeds contain about 40% oil and after extraction of oil, a meal with
about 38–43% protein is obtained. Rapeseed oil is the preferred oil
stock for biodiesel production because rapeseed produces more oil per
unit of land area as compared to other oil sources. It belongs to the
Brassicaceae family. Rapeseed is one of the most important oilseeds in
the world, ranking fourth with respect to production after soybean,
palm and cottonseed [55].
Food and Agriculture Organization (FAO) reported that world
production of rapeseed oil is growing rapidly with 46 million tons
during the year 2004–05. In Pakistan, its cultivation was noted to be on
257 thousand hectors during the year 2004–05. As an agricultural
product rapeseed is important for its oil and protein contents [56].
Pakistan is one of the largest countries in Asia in terms of land area
and population. The country covers a large variety of agro-ecological
zones ranging from coastal areas in the south to the Himalayan
Mountains in the north; hence it has great capacity for producing a
wide range of food commodities. Most of Pakistan is classified as arid
or semi-arid, so the agricultural sector is highly dependent on water
Page 11
 Introduct
ion

supply through either irrigation or water harvesting. In 2005, the

agricultural sector accounted for 22 percent of gross domestic product
(GDP) and employed 45 percent of the labor force, while agro-
industries accounted for about two-thirds of total industrial output [57].
Canola oil, used for cooking and in margarine, is free from cholesterol
[58]
and reduces cholesterol level in human blood . Pakistan is deficient
in edible oil. Local production stood at 0.606 million tons during
previous crop year, which was sufficient to meet 29% of the demand
and rest of the demand (71%) was met through import [59].
The cultivations of biofuels species have several positive as well as
negative socioeconomic implications. Some of the plant species
appropriate for production of biofuels are capable of growing in arid,
water stressed lands. Their cultivations also is less fertilizer and
chemical intensive, which means that the farmers needs to invest lesser
finances in their farms and they can make use of land that are not
suitable for other crops including food crops. Since biofuels / biodiesel
production cannot be a house hold endeavor, appropriate institutional
arrangements have to be developed. A serious implication of the
biofuels cultivation is the likelihood of good land suitable for other
crops getting diverted to farm biofuels species. In the country that
consumes the largest quantity of petroleum product and is responsible
for the released of largest quantity of green house gas, the USA, food
crops such as sugar cane, corn and wheat are diverted to produce
biofuels. Biofuels based on food crops is disastrous to food availability
world over. Food Appropriate regulations needs to ensure that that type
of diversions are not happening [60].
The present study was conducted to optimize the reaction parameters
for biodiesel production using rapeseed oil as a feed stock and
optimization of catalyst concentration (%), Reaction temperature (oC),

Page 12
 Introduct
ion

oil to alcohol Molar ratio, Reaction time (min) was carried out using
central composite response surface methodology.

Page 13