Luận văn analysis of some vegetable oils for potential biodiesel production

The production of bio fuel from renewable sources decreases cost of production by 60-90% compared to the energy production from fossil sources Alex et al., 2016.. Biodiesel Among liquid

ANALYSIS OF SOME VEGETABLE OILS FOR POTENTIAL BIODIESEL PRODUCTION

A THESIS

Submitted by

M RAJAKOHILA Reg No 8492

MANONMANIAM SUNDARANAR UNIVERSITY

TIRUNELVELI - 627 012

CERTIFICATE

The research work embodied in the present Thesis entitled “ANALYSIS OF

been carried out in the PG and Research Department of Chemistry, Sri Paramakalyani

College, Alwarkurichi The work reported herein is original and does not form part of any other thesis or dissertation on the basis of which a degree or award was conferred on an earlier occasion or to any other scholar

I understand the University’s policy on plagiarism and declare that the thesis and

publications are my own work, except where specifically acknowledged and has not been

copied from other sources or been previously submitted for award or assessment

M RAJAKOHILA

RESEARCH SCHOLAR

Dr K KALIRAJAN Dr P NAGENDRA PRASAD

JOINT SUPERVISOR SUPERVISOR

Associate Professor Associate Professor & Head (Rtd)

PG and Research Department of Chemistry Department of Biotechnology Sri Paramakalyani College Sri Paramakalyani College

Alwarkurichi - 627 412 Alwarkurichi - 627 412

ACKNOWLEDGEMENT

I am most thankful to God Almighty for sustaining and keeping me in His grace

and providential protection throughout my life

I wish to express my sincere gratitude and indebtedness to my guide

Dr P Nagendra Prasad, Associate Professor & Head (Rtd), Department of

Biotechnology, Sri Paramakalyani College, Alwarkurichi who showed the path and light

to continue my research career and his excellent guidance, constant encouragement and

all other considerations provided me the environment to reach my goal

I express my gratitude to my co-guide, Dr K Kalirajan, Associate Professor, PG

and Research Department of Chemistry, Sri Paramakalyani College, Alwarkurichi for his

guidance and encouragement

I express my heartful thanks to Dr R Venkataraman, Principal and

Dr G Devarajan, Secretary, Sri Paramakalyani College, Alwarkurichi for their advice

and suggestions to carry out my work successfully

I am very much thankful to Dr S Selvaraj, Associate Professor & Head, all

teaching faculties and non-teaching members of PG and Research Department of

Chemistry, Sri Paramakalyani College, Alwarkurichi for their encouragement and

support

I express my sincere thanks to the management of SPKC for all their support in

proving the lab facilities and library facilities to me throughout my studies I also

thankful to the Staff Members, Research Scholars and Non Teaching Staff members of

Sri Paramakalyani College, Alwarkurichi for their encouragement in due course of this

study

My sincere thanks to my family members and all my friends who all behind the

successful completion of this thesis

M RAJAKOHILA

TABLE OF CONTENTS

ABSTRACT

LIST OF TABLES LIST OF FIGURES LIST OF ABBREVIATIONS

3 BIOENERGY CROPS 41

4.4.2.1 Principle and Instrumentation of Ultrasonic Interferometer

4.4.3.6 Average Molecular Weight of Total Free Fatty Acid

79

5.5.1 Variation of mild steel weight loss in acid medium with different concentration of selected bioinhibitors at different duration

5.23 Average Molecular weight of Total Fatty Acid of selected biodiesel

blends

118

5.26 Variation of mild steel weight loss in acid medium with different

concentration of bioinhibitors after 24 hours duration

122

5.27 Variation of mild steel weight loss in acid medium with different

concentration of bioinhibitors after 48 hours duration

122

5.28 Variation of mild steel weight loss in acid medium with different

concentration of bioinhibitors after 72 hours duration

124

5.29 Variation of mild steel weight loss in acid medium with different

concentration of bioinhibitors after 96 hours duration

124

5.30 Variation of mild steel weight loss in acid medium with different

concentration of bioinhibitors after 120 hours duration

125

5.31 Variation of corrosion rate at different concentration of selected

bioinhibitors after 24 hours duration

127

5.32 Variation of corrosion rate at different concentration of selected

bioinhibitors after 48 hours duration

127

5.33 Variation of corrosion rate at different concentration of selected

bioinhibitors after 72 hours duration

128

5.34 Variation of corrosion rate at different concentration of selected

bioinhibitors after 96 hours duration

128

5.35 Variation of corrosion rate at different concentration of selected

bioinhibitors after 120 hours duration

129

5.36 Variation of corrosion inhibition efficiency at different concentration of

selected bioinhibitors after 24 hours duration

131

5.37 Variation of corrosion inhibition efficiency at different concentration of

selected bioinhibitors after 48 hours duration

131

5.38 Variation of corrosion inhibition efficiency at different concentration of

selected bioinhibitors after 72 hours duration

132

5.39 Variation of corrosion inhibition efficiency at different concentration of

selected bioinhibitors after 96 hours duration

132

5.40 Variation of corrosion inhibition efficiency at different concentration of

selected bioinhibitors after 120 hours duration

134

5.1 Scanning electron micrograph of mild steel as received and Mild steel after

120 hours immersion in 1 N HCL without and with Argemone oil

bioinhibitor

136

5.2 Scanning electron micrograph of mild steel after 120 hours immersion in 1

N HCL without and with Cleome oil bioinhibitor

137

5.3 Scanning electron micrograph of mild steel after 120 hours immersion in 1

N HCL without and with Pongamia oil inhibitor

137

5.4 Scanning electron micrograph of mild steel after 120 hours immersion in 1

N HCL without and with Rubber oil bioinhibitor

139

5.5 Scanning electron micrograph of mild steel after 120 hours immersion in 1

N HCL without and with Soapnut oil bioinhibitor

139

LIST OF PLATES

Plate 3.1 Bioenergy crop – Argemone mexicana 45 Plate 3.2 Bioenergy crop – Cleome viscosa 49 Plate 3.3 Bioenergy crop – Pongamia pinnata 54 Plate 3.4 Bioenergy crop – Hevea brasiliensis 58 Plate 3.5 Bioenergy crop – Sapindus trifoliatus 62 Plate 4.1 Seed Powder & Seed oil of selected bioenergy crops 85

Plate 4.2 Weight loss measurement of mild steel in 1N HCl

medium with and without selected bioinhibitors 86

LIST OF ABBREVIATIONS

EN European Nationale

INTRODUCTION

1.1 Energy

Energy is the most fundamental requirement for human existence and activities It is our most essential resource without which life would cease In India, the concept of energy as “Shakthi” has been almost at the focus of philosophic, scientific and metaphysical thought from time immemorial According to the science

of Physics, Energy means the ability to do work The laws of thermodynamics describes that energy can be transformed from one form to the other but can neither be created nor destroyed, some energy is always dispersed into unavailable form of heat energy and no spontaneous transformation of energy from one to another form is 100

% efficient

Energy is an integral component of any socio-economic development for raising the standard and quality of life The development of a country depends on the continuous supply of energy for its conservation In the globe the energy requirement

is largely met with fossil fuel for various sector such as industry, transport, agriculture, domestic sector, etc require energy from sources like wood, coal,

petroleum products, nuclear power, solar and wind (Elamathi et al., 2005; Kumar and

Varunchauhan, 2013) In recent years, there has been a growing debate on availability

of energy in the form of petroleum, liquid natural gas and coal Most industrialized countries depend on oil and natural gas for their energy needs (Chopra, 2004)

1.2 Types of Energy Sources

All forms of energy are stored in different forms based on the energy sources that we use every day They are non- renewable and renewable energy Energy sources are the main driver of economic growth and social development of a country

(Obichukwu and Ausaji, 2015) Human energy consumption has grown steadily along

with population and finally reached a stage of extinction (Nayak et al., 2017a)

1.2.1 Non – Renewable Energy

Non- renewable energy is the energy source that we are using up and cannot recreate in a short period Once a non-renewable energy source is depleted, it will not

be replaced with in the span of human time scales Non- renewable energy sources are taken from the ground as liquids, gases and solids in which crude oil is the only natural liquid commercial fossil fuel Coal, petroleum and natural gas are the major non renewable fossil fuel sources because they were formed over a millions and millions of years by the action of heat from the Earth’s core and pressure from rock

and soil on the dead plants and animals (Vijalakshmi et al., 2007)

1.2.2 Renewable Energy

Renewable resources are the resources that can be replenished by the environment over relatively short periods This type of resource is much more desirable to use because it can be compensated by the nature Some examples of renewable energy sources are solar energy, wind energy, hydropower, geothermal

energy and biomass energy (Nayak et al., 2014) Energy generated by using wind,

tides, solar, geothermal heat and biomass including farm and animal waste as well as

human excreta is also known as non-conventional energy (Nayak et al., 2017b)

The use of renewable energy is not new Nearly five generations (125 Years) ago, wood supplied nearly 90% of our energy needs Due to convenience and low prices of fossils fuels, wood use has been fallen Now, the biomass that would

normally present a disposal problem is converted into electricity (Vijayalakshmi et al.,

2007) Combustion of fossil fuels pollutes water, harm plant and animal life, create toxic wastes and contribute to greenhouse gas emissions Global climate changes and

geopolitical factors have forced countries to exploit renewable energy resources

(Colsea and Ciocoiu, 2013) Renewable energy resources can avoid these impacts and

risks, can help in conserving fossil resources for future generations and can lessen our dependence on extraneous sources of oil The production of bio fuel from renewable sources decreases cost of production by 60-90% compared to the energy production

from fossil sources (Alex et al., 2016)

1.3 Fossil Fuel

Petroleum and its different products have a dominant role not only in the overall development of country but also as a source of energy for domestic, industrial, agricultural, transport service and feed stock for fertilizer, chemical and other industries Majority of the world’s energy needs are supplied through petrochemical sources, coal and natural gases but these sources are finite and at current usage rates will be consumed shortly (Srivastava and Prasad, 2000) However, the use of these sources for energy causes climate change leading to various kinds of catastrophes

such as global warming, acid rain, etc (Houghton et al., 2001) In our country the

main source of energy is fossil fuel About 85% of the sources are consumed by the industry, transport and residential sectors India relies heavily on coal for meeting more than half of its total energy requirement India ranks 3rd in coal production and accounts for 100% of the world’s coal reserves The demand of coal is found to increase but the source is not sufficient to meet the demand The single largest source

of energy in India after Coal is Petroleum India imports about 2/3 of its petroleum requirements and 70% of its oil requirements from foreign countries every year

India is sixth in the world in energy demand accounting about 3.5% of world commercial energy consumption The transport sector globally is dependent on liquid fossil fuels As a result, the world’s demand for crude oil has increased by 751 MT

from 2000 to 2014 The last 15 years have seen a drastic increase of 19.6% in

consumption of crude oil (Statistical review of world energy and resources, 2014)

The world is also facing the challenge of gradual degradation of environment due to

the burning of fossil fuels The global surface temperatures are likely to increase by

1.1˚C to 6.4˚C between 1990 and 2100 (IPCC, 2014)

The transport sector worldwide has considerably increased the fuel

consumption reaching 63 % of the total, especially in the last decade (Carlinia et al.,

2014) Recent research expects that the amount of petrol in the world can be used

merely for next 46 years Hence, interest in research for an effective substitute for

petroleum diesel is increasing Currently India produces only 30% of the total

petroleum fuels required for its consumption and the remaining 70% is imported,

which costs about Rs 80,0000 million per year It is evident that mixing of 5% of

biodiesel fuel to the present diesel fuel can save Rs.40, 000 million per year (Nantha

Gopal et al., 2014)

1.4 Need for Alternate fuel

Fossil diesel contributes almost 80% of the world’s energy needs

(Ali et al., 2008; Kesari and Rangan, 2010; Huang et al., 2012) Nevertheless the

reservoirs of fossil fuels are depleting rapidly all over the world Therefore, the

renewable fuels are the best alternative source available for the same Now a day, due

to limited resources of fossil fuels, rising crude oil prices and increasing concerns for

environment, there has been renewed focus on vegetable oil and animal fats as an

alternative to petroleum fuels (Anbumani and Singh 2010)

India alone requires around 140 million metric tons of diesels per year, out of

which around 40 million metric tons only produced locally This gap is likely to go up

further as the diesel consumption rate is expected to increase by 14 percent per

annum In order to import diesel, the Government of India spends lot of foreign exchange equivalent to 2 lakh crore rupees per year, a colossal drain of valuable foreign exchange (IEA, 1998; Agarwal, 2000)

The total world energy requirement is met 84% by non-renewable energy

and 16% by renewable energy resources (Moghaddam et al., 2015) In the

non-renewable energy contribution, 80% comes from fossil fuels and 4% from nuclear energy For the renewable energy supply, 6% comes from clean energy and 10% from

bio energy (Conconi and Crnkovic, 2013; Azad et al., 2015) Bio energy is currently

the largest source of renewable energy (IEA 2014) Diesel engines operating on biodiesel have lower emissions of carbon monoxide, unburned hydrocarbons, particulate matter and air toxics than when operated on petroleum-based diesel fuel

(Rodriguez et al., 2014)

1.5 Feasible Alternate energy sources

In this context, fuels of biological origin have drawn a great deal of attention during the last few decades Some alternatives are liquid or gaseous forms of biofuel obtained from different types of biomass Biomass refers to all plant material and animal product when pulp, livestock and human waste Among various biomass

sources, plant oils and fats from bio energy crops have a bright future (Lang et al., 2001; Sajjadi et al., 2016) An energy crop is a plant domesticated for use in

agriculture and is produced as a low cost and low maintenance harvest to be used to produce biofuel or directly exploited for its energy content

1.5.1 Biofuel

Energy is fixed in the universe that cannot be created or destroyed The Sun maintains endless source of energy due to constant nuclear reactions in the solar system Only the green plant has the power to transform Sun’s energy into potential

energy by photosynthesis Mankind has been using energy from time immemorial by raising and harvesting plant materials Plant products like oil, wood, dried leaves and others have been used as energy sources in developing countries (Solmon, 2007) The primary products from the plants could be used as food and fuel Biofuels are renewable liquid fuels derived from biological raw materials like botafuels and zoofuels The biofuel have the potential to improve performance and emission

characteristics of the engine due to more oxygen content (Tomic et al., 2014)

Biofuels are also said to be carbon neutral as the amount of carbon dioxide released

by their combustion is same as absorbed by plants during their growth (Sorate and Bhale, 2014) Biofuels have been used for years as a way to increase energy self-sufficiency, reduce import costs, and strengthen domestic agricultural development

(Kovarik, 2013; Araujo, 2017) At present biofuel are gaining worldwide acceptance

as a solution for problems of environmental degradation, energy security, restricting imports, rural employment and agricultural economy (Planning commission, 2003) Global production of biofuel has been growing rapidly in recent years, rising from about 18 billion liters in 2000 to 110 billion liters in 2013 It is expected to reach to

140 billion liters by 2018 Current consumption of biofuel globally constitutes about 3.5% of transportation fuels by energy content, and this could expand to about 4% by

2018 (IEA, 2014) Biofuels obtained from edible crops are already being in practice in transport industry These biofuel increase the fuel security at the expense of food security (Nonhebel, 2012) This problem can be solved by using non-edible crops to produce biofuel

1.5.2 Biodiesel

Among liquid biofuel, the next possible alternative energy source to fossil fuel

is the vegetable oils, the hydrocarbon class ester which is gaining acceptance in many

countries (Ma and Hanna, 1999) Biodiesel obtained from vegetable oils is considered the most suitable alternative to diesel around the world (Barnwal and Sharma, 2005; Issariyakul and Dalai, 2014) because their properties are similar to diesel fuel and are renewable, easily available and environmental friendly (Agarwal and Das, 2001;

Encinar et al., 2002; Ramadhas et al., 2005a) This alternative diesel fuel is termed as biodiesel The name bio-diesel was introduced in the United States during 1992 by the National Soy Diesel Development Board (presently National Bio-diesel Board) which

has pioneered the commercialization of biodiesel in the US (Ramadhas et al., 2004)

In 1994, the Biodiesel Development Board came into existence in India

Biodiesel has been widely accepted as petro-diesel substitute has the potential

to revolutionize the motor fuel industry because some of its physicochemical properties, such as cetane number, heat content, viscosity, cloud point and pour point

which are very similar to those of diesel No2 (Fillires et al., 1995; Vicente et al.,

2005) Biodiesel has a very high flash point (300°F), almost 3 times higher than diesel making it one of the safest of all alternative fuels, from a combustibility point Biodiesel is a plant derived product hence it contains oxygen in its molecule (up to 10%), that ensures more complete combustion of hydrocarbons and making it a

petro-cleaner burning fuel than petrol and diesel (Sastry et al., 2006)

The biodiesel has the power to harmonize sustainable development, energy conservation, management, efficiency and environmental preservation The use of vegetable oils as alternative fuels had been found around for 100 years ago when the inventor of the diesel engine Rudolph Diesel, first tested peanut oil (Bobade and Khyade, 2012a) In 1912, he stated that "the use of vegetable oils for engine fuels may seem insignificant today But such oils may in the course of time become as important

as petroleum and the coal tar products of present time." As per his sayings after 100

years the usage of biodiesel for vegetable oil has come to usage due to the depletion of the fossil fuel and the increase demand

The biodiesel industry chose Rudolf Diesel's birthday to honor him for his foresight in recognizing the valuable role of vegetable oil based fuel Rudolf Diesel's prime model, a single 10 ft (3 m) iron cylinder with a flywheel at its base, ran on its own power for the first time in Augsburg, Germany, on August 10, 1893 In remembrance of this event, August 10 has been declared "International Biodiesel Day" National Biodiesel Day (US) takes place on March 18, the date of Rudolf Diesel's birthday Biodiesel is a proven fuel technology for producing and using biodiesel has been known for more than 50 years They have practically no sulfur content, offer no storage difficulty, carbon dioxide neutral and have excellent lubrication properties which can be used for spark-ignited engines due to their low

volatility and high cetane number (Goering et al., 1982; Bagby et al., 1987; Scholl and Sorenson, 1993; Recep et al., 2001) Furthermore, the biodiesel price is nearly 1.5 times greater than the diesel gasoline petroleum price (Uprety et al., 2016; Ali et al., 2016; Roschat et al., 2016)

World annual petroleum consumption and vegetable oil production is about 4.018 and 0.107 billion tons (Demirbas, 2009) Currently, more than 95% of the world biodiesel comes from edible oil Cost of edible oils is very higher than petroleum diesel and we use edible oils for biodiesel production leads food oil crisis The above

problem can solve by using cheapest, low cost non edible plant oils (Leung et al.,

2010) Non-edible vegetable oils are not suitable for human food due to the presence

of some toxic components in the oils (Ahmad et al., 2011) Production of biodiesel

from non-edible oils feedstock can overcome the problems of food verse fuel,

environmental and economic issues related to edible vegetable (Gui et al., 2008;

Atabani et al., 2013) It is renewable, biodegradable, environmentally friendly, toxic, portable, readily available and eco-friendly fuel (Agarwal and Rajamanoharan, 2007; Lapuerta et al., 2008; Singh and Singh, 2010) The Planning Commission,

non-Government of India, had set up a Committee on Development of Biofuel in 2002 The committee submitted its report Planning Commission’s ‘Vision 2020’ in April

2003 called for plantation of non-edible oil yielding plants on large areas of waste and degraded lands in the country (Gupta, 2002)

Chemically, biodiesel is defined as “the mono alkyl esters” of long chain fatty acids derived from renewable lipid feedstock (Harrington, 1986; Korbitz, 1999; You

et al., 2013; Rahimi et al., 2014; Thliveros et al., 2014; Vijay Kumar et al., 2017)

Vegetable oil can be used directly or mixed with diesel oil to operate a diesel engine

Several researchers (Forson et al., 2004; Misra and Murthy, 2010; Tziourtzioumis and

Stamatelos, 2017) have tested the use of vegetable oil and diesel blends Just like

petroleum diesel fuel biodiesel operates in compression ignition engine (Knothe et al., 1997; Keskin et al., 2008; Lin et al., 2009; Qi et al., 2009; Ghobadian et al., 2009)

Blends up to 20% is normally called as B20 (20% biodiesel with 80% petroleum diesel fuel) can be used in all diesel equipment and are compatible with most storage and distribution equipment, requires no engine modification and enhance the engine

life (Mo et al., 2016) Biodiesel is non- toxic, safe to handle and transport because it

is biodegradable Biodiesel has desirable degradation attributes which degrade more rapidly than diesel fuel In general, biodegradability of biodiesel is 4 times faster than

diesel (Dorado et al., 2003; Ramadhas et al., 2004) and degrades within 21 days (Egle

et al., 2007) It can be stored anywhere like petroleum diesel fuel and is quite stable

during long-term storage (Ryan et al., 1984; Knothe and Dunn, 2003; Shiela et al.,

2004)

Biodiesel is the first and only alternative fuel approved by Environmental Protection Agency (EPA), has passed every Heath-Effects Test of the Clean Air Act and meets the requirements of the California Air Resources Board (CARB) and Fuel Additives Registration program (Chang and Gerpen, 1996)

1.5.3 Biodiesel Production Method

Almost all vegetable oils can be directly mixed with diesel fuel It has been experimentally proved that the use of neat vegetable oils in engines is possible with some minor modifications in the fuel system The main problem related to the use of

vegetable oil as fuel is the high viscosity (Si et al., 2017) The high viscosity of the fuel causes problems for engine operation (Kumar et al., 2010) In order that

vegetable oil to be feasible as fuel, it is necessary to reduce its viscosity close to that

of diesel fuel In addition to transesterification, some methods to reduce the viscosity

of vegetable oils are dilution, microemulsion, pyrolysis and catalytic cracking (Jain and Sharma, 2010)

Pyrolysis refers to a chemical change caused by the application of thermal energy in the absences of air or nitrogen The liquid fractions of the thermally decomposed vegetable oil are likely to be similar to diesel fuels But the pyrolysis product had some negative aspect such as low cetane number, acceptable amount of sulphur, water and sediment and give acceptable copper corrosion values So pyrolysis process is not a feasible method for the biodiesel production Another solution for solving the problem of vegetable oil viscosity is formation of micro-emulsion and is defined as transparent thermodynamically stable colloidal dispersions

A micro-emulsion can be made of vegetable oil with an ester and dispersant, an alcohol and a surfactant and a cetane improver, with or without diesel fuels This process had the drawback such as the requirement of surfactant, cetane improver and

also the formation of water during the process Nevertheless, at present transesterification is widely used in the production of biodiesel, which is the process

of exchanging the alkoxy group of an ester compound, by another alcohol often catalyzed by the addition of a base and acid Nevertheless, both the reaction is time consuming and cost effective So from the present study, the dilution or blending process was identified as a reasonable and possible method for the production of biodiesel

1.5.4 Blending or Dilution

Blending or dilution is the process of mixing vegetable oils with materials such as diesel fuels, solvent or ethanol It is generally known as bio-diesel if the viscosity of vegetable oil was reduced by blending it with diesel alone in absences of the surfactants If the viscosity of vegetable oil was reduced by blending it with diesel

or ethanol in the presence of surfactants, it is generally called hybrid fuel (Goering et

al., 1982) Vegetable oil can be directly mixed with diesel fuel and can be used for

running an engine (Ozaktas, 2000) which has been experimentally proved by Rudolf Diesel that the use of neat vegetable oils in engines is possible Biodiesel may be used

in pure form (B100) or blended with petroleum diesel at any concentration A system known as the ‘B’ factor is used to state the amount of biodiesel in any fuel mix

The vegetable oils mixed well with the diesel at both proportions (B10 and B20) had a high miscibility France, a leading country in terms of biodiesel production

in the world uses 50% of biodiesel is mixed with fossil fuel diesel to run different vehicles and Europe uses 20% biodiesel In India, initially 5% of the biodiesel was blended with HSD (High-Speed-Diesel) and later increased to 20% called B20 to run diesel engines B20 is compatible with existing diesel engines and hence there is no need for modification of engines and provides similar horsepower, torque and mileage

as diesel (Narayan, 2002; Viswanathpatil, 2007) It has been proven that biodiesel containing up to B5 will have no table difference in terms of power and fuel economy when it is compared to diesel (Benz, 2014) ASTM D7467 suggests blending of 20% biodiesel with diesel In 2014, the Chevy Cruze Clean Turbo Diesel is directing the engine with rated B20 biodiesel compatibility Now-a-days research is going on to increase the use of biodiesel blending with diesel Consequently, biodiesel blending (biodiesel and diesel) bring a new topic in research area A number of researches have

been undertaken already on biodiesel blending (Sarin et al., 2010; Chen et al., 2010; Beatrice et al., 2011; Gill et al., 2012; Stromberg et al., 2014) Blends of 20%

biodiesel and lower can be utilized in diesel instrumentation with only minor

modifications (Saribiyik et al., 2012; Javidialesaadi and Raeissi, 2013)

1.5.5 Biodiesel Standard

The biodiesel is produced in quite differently scaled plants from vegetable oils

of varying origin and quality Researchers have shown that the properties of biodiesel vary significantly due their diverse fatty acid composition which provides an obvious effect on engine performance Therefore, it is important to characterize biodiesel according to preset standard testing methods American Standard Test Method (ASTM) and European (EN) standard have formulated the specification for biodiesel

(Olutoye and Hameed, 2011; Hoekman et al., 2012) Austria was the first country in

the world to define and approve the standards for rapeseed oil methyl esters as diesel fuel There are various standard followed by different country The most common standard used is the National standards and ASTM standards

In May 2007, the Indian Government has declared a biodiesel purchase policy

to replace fossil fuel through non- conventional means of energy The salient features

of the policy are that the public sector oil marketing companies will purchase

biodiesel meeting the Bureau of Indian Standard specifications through their select purchase centers (Biofuel news, 2007) For India, the use of current BIS (Bureau of Indian Standards Act 1986) specifications has same standards This standard is prepared keeping in view of the end use application, production and feedstock availability Considerable assistance has been drawn from ASTM D 6751-02 and EN

14214 standards, while preparing BIS standard specifications

1.6 Physico-Chemical Analysis of vegetable oil

Biodiesel quality depends on several factors that reflect its chemical and physical characteristics The main criterion of biodiesel quality is the inclusion of its physical and chemical properties into the requirements of the adequate standard The physical and chemical fuel properties of biodiesel fundamentally depend on the fatty acids distribution of the triglyceride obtained from the raw material used for biodiesel

production (Gerhard et al., 2005) Quality standards for biodiesel are continuously

updated, due to the evolution of compression ignition engines, ever-stricter emission standards, reevaluation of the eligibility of feedstock’s used for the production of biodiesel etc The physical and chemical properties of any fuel are significant factors which help to decide whether the oil is suitable for engine or unsuitable The chemical and physical properties of a vegetable oil as fuel are numerous and are mentioned in technical regulations and suggestions Most of the important parameters of the end product biodiesel are a fatty characterization of mono-alkyl esters, fatty acids, glycerol, and derivatives Feature structure, the length of the carbon atom, and the degree of saturation of fatty acids determines the physical properties of biodiesel such

as viscosity, flash point (FP), cetane number, density, high heating values (Cheenkachorn 2006) It takes the alternative technologies that are a simple, non-

invasive and low cost to evaluate and monitor the production process and the quality

of biodiesel

1.7 CORROSION

Corrosion is a natural process for metal that causes them to react with their environment to form more stable compounds (Bradford, 1993) Metals are considered the corner blocks of various industries due to their hard structure, which make them suitable for handling and processing various corrosive fluids and gases Mild steel is commonly used in a wide range of industries due to its cheap cost and availability Corrosion of metals however is considered to be serious problem in industries that has

to be prevented with kind of new invention or technology developed

1.7.1 Corrosion Inhibitors

Several methods are available to prevent or retard corrosion of metallic materials The use of inhibitor is one of the most practical method for protection

against corrosion (Raja et al., 2016) Recently, the inhibition of the corrosion of metal

in acidic aqueous solutions by different organic compounds has been widely studied

(Obot and Obi-Egbedi, 2010; Shaker et al., 2011) Corrosion inhibitors are those

compounds that when added in suitable amounts cause lowering in the corrosion rate

of metal without significantly changing the concentration of any other corrosive agent

(Abdel Hameed and Al-shafey, 2012; Abboud et al., 2006) Many of the inhibitors are

organic molecules containing nitrogen, oxygen, sulphur and phosphorous heteroatoms

in their structures, which can adsorb into active sites of the metal surface through

conjugated bonds (Prabakaran et al., 2016; Mourya et al., 2014) Corrosion inhibitors

help the metal or the alloy to maintain its resistance against corrosion via various inhibition mechanisms The process of corrosion inhibition is based on the adsorption

of the inhibitor molecules on the active sites and or deposition of the corrosion products on the alloy surface (Bereket and Yurt 2001)

1.7.2 Green Inhibitors

Plant extracts have become important as an environmentally acceptable, biodegradable, readily available and renewable source of materials for wide range of corrosion prevention Due to increasing awareness of toxic risks to environment and human plant extract have been used as a naturally occurring non-toxic corrosion

inhibitor which are generally denominated as green inhibitor (Saufi et al., 2015; Ji et

al., 2016) Therefore the natural products such as plant extract, vegetable oils and its

derivatives have attracted much more interest for their environmental friendless

(Chevalier et al., 2014)

1.8 OBJECTIVES

The present study was undertaken with the following objectives

· To identify different oil seeds which are feasible for the production of biodiesel

· To collect different oil seeds based on different agro climatic conditions

· Extract the oil for further analysis

· To obtain the biodiesel from different bio energy crops by blending process

· To determine the Physicochemical properties of different biodiesel at different proportions from the identified resources

· To screen the biodiesel property by the novel Ultrasonic method

· To find out the corrosion inhibition rate of neat oil by Mass loss method

· SEM analysis were carried out to evaluate the efficacy of neat oil as a green inhibitor

· To find out the most potential biodiesel resource for future use

as fuel, biodiesel preparation methods, optimization of biodiesel production and use

of biodiesel and its diesel blends as fuel in an unmodified diesel engine

Pryde et al., (1984) reviewed the reported successes and shortcomings for

alternative fuel research The outcome showed the vegetable oils must either be chemically altered or blended with diesel fuel to prevent premature engine failure due

to deposit formation, carbon build up and lubricating oil contamination Peterson et

al., (1983) reiterated that the two major problems associated with the use of vegetable

oils as fuels were oil deterioration and incomplete combustion Bagby (1987) reported that the high viscosity of vegetable oils leads to poor fuel atomization and inefficient mixing with air, which in turn contribute to incomplete combustion Markley (1960) presented empirical models and data for predicting the viscosity of individual fatty acids and vegetable oils Bhatt (1990) used some non-edible vegetable oils as alternative to petrodiesel in a diesel engine and observed that the performance characteristics of the diesel engine They observed that methyl ester of non-edible vegetable oils are almost comparable to the diesel engine performance

Nag and Paul (1994) were analyzed the fuel efficiency in mixtures of

non-edible oil and run a diesel engine using 50% ester fed non-non-edible vegetable oil The

findings were closer to performance of the diesel engine Nag et al., (1995)

investigated the utilization of non-edible vegetable oil as an alternative fuel of diesel engine Comparative study was made which is closer to fossil fuel Graboski and McCormick (1998) provided a recent extensive review of the utilisation of biodiesel fuels in compression ignition engines The general conclusion from the literature is that, in terms of power, wear, efficiency and emissions, biodiesel fuels are a viable alternative Ma and Hanna (1999) reported that the viscosity of vegetable oils can be reduced by several methods which include blending of oils, microemulsification, pyrolysis and transesterification Gubitzet al., (1999) reported that the biodiesel made from virgin or used vegetable oils and animal fats through transesterification is a diesel substitute and requires very little or no engine modifications up to 20% blend

and minor modification for higher percentage blends Allen et al., (1999) predicted

the viscosities of biodiesel fuels from the knowledge of their fatty acid composition The fatty acid compositions of six typical oils were simulated by mixing fatty acid methyl ester (FAME) standards in appropriate amounts

Augustus et al., (2003) screened twenty-two taxa of Western Ghats as

potential alternative crops for renewable energy, oil, hydrocarbon and phytochemicals In this, phytochemicals of the Argemone species was analysed and showed 5.0% oil content Verma and Patel (2004) concluded that in India it is possible to use the edible oils for biodiesel and non-edible oils to make the desirable feedstock for biodiesel The Planning Commission has deliberately recognized this fact The B10 blending non-edible oils can meet potential of properties with diesel

fuel Garba et al., (2006) were examined the precedence of biofuel as a fuel and

highlight the advances made in the production, use and quality assessment at the global level Research reports have showed that biodiesel and bioethanol has the same

calorific value as fossil-based diesel and gasoline and, its combustion products have lesser health hazards and are particulate matter concentrations

Toscano and Maldini (2007) studied the possibility to develop systems for the use of vegetable oils, as a source of fuel, is to improve the understanding of the physical and chemical properties of vegetable oils and to define the possible relationships between them Sharma and Singh, (2010) recorded the latest aspects of development of biodiesel It was reported that the yield of biodiesel affected by molar ratio, moisture and water content, reaction temperature, stirring and specific gravity The authors felt that the edible oils are used extensively in developed nations but developing nations are not self-sufficient in the production of edible oils It was concluded that the seeds of many plant species remain unutilized for the production of biodiesel

Chhetri et al., (2008) showed that both edible and non-edible oils have great

potential to use as feedstock for biodiesel production, due to their high oil content Based on Gas chromatography (GC) analysis, eleven types of fatty acid were identified and quantified in soapnut biodiesel Approximately 85% of the fatty acid was found to be unsaturated and six major FA were identified and quantified in jatropha oil biodiesel Moser (2009) reviewed the biodiesel preparation process, the types of catalysts used for the production of biodiesel, the influence of free fatty acids, biodiesel composition on fuel properties, blending of biodiesel with other fuels on fuel properties on biodiesel production

Jaichandar and Annamalai (2011) reviewed the history of biodiesel

development and production practices Fuel properties and the effect of use of biodiesel fuel on engine power, fuel consumption and thermal efficiency are compared with those of conventional diesel fuel The output indicated that biodiesel

as an alternative fuel for diesel engine Hansen et al., (2011) assessed that the

suitability of different materials as sources for food or fuel Fatty acid composition has been shown to have impacts on the properties of oils and fats and thus on both food and fuel quality which highlight the different requirements in the properties of

vegetable oils and animal fats for health and for fuel Mathiyazhagan et al., (2011)

were analysed the non-edible oils as feed stocks for biodiesel production to reduce the cost of biodiesel Normally alkali catalyzed method was followed for biodiesel production process Shikha and Rita (2012) reviewed biodiesel production from non edible-oils This review paper assesses and integrates about the different tree borne oilseeds, extraction of oil, biodiesel processing and effect of different parameters on

production of biodiesel The cost of biodiesel and demand of vegetable oils can be

reduced by non-edible oils instead of vegetable oils Biodiesel can be derived from non-edible vegetable oil and has good potential as an alternative diesel fuel Non-edible plant oils have been found to be promising crude oils for the production of biodiesel Non-edible oils are very important for developing and petroleum-poor countries

Monisha et al., (2013) reviewed about biofuel from various energy sources

and production methodology of biodiesel through different types of transesterification

process Ramadhas et al 2004 described various methods by which vegetable oils can

be used in CI engines It was reported that enzymes, alkali or acids can catalyze process Alkalis result in fast process Barnwal and Sharma (2004) give theoretical knowledge of catalyzed and supercritical method of transesterification process to produce biodiesel It was mentioned that catalyzed process is easy but supercritical method gives better result Gashaw and Lakachew (2014) described the fuel properties of biodiesel, production process and the most important variables that

influence the transesterification reaction The production of biodiesel using edible oils but the use of non-edible oil for biodiesel production has contributed immensely to its cost reduction There are different methods of producing biodiesel but transesterification of vegetable oil and fats are predominantly used method these days and concluded that the biodiesel is a better alternative renewable fuel for the diesel

Demirbas et al., (2016) reviewed numerous options of non-edible oils as the

substantial feedstocks, biodiesel processing and effect of different parameters on production of biodiesel They discussed production of biodiesel from edible oil and extensive use of edible oils for biodiesel production may lead to food crisis These problems can be solved by using low cost feedstocks such as non-edible oils and waste cooking oils for biodiesel production

Takeda (1982) investigated the seed oil of Jatropha as a diesel fuel substitute during the World War II Engine tests with Jatropha oil were done in Thailand,

showing satisfactory engine performance Foidl and Eder (1997) stated that the

economic evaluation has shown the biodiesel production from Jatropha is very

profitable provided the by-products of the biodiesel production can be sold as

valuable products Cardone et al., (2003) studied the agronomic evaluation, fuel

production by transesterification and characterization of Brassica carrinata as an

alternate oil crop for biodiesel production A comparison of the performance of

Brassica carrinata oil derived biodiesel with a commercial biodiesel and petroleum

diesel fuel was conducted as regards engine performance, regulated and unregulated exhaust emissions

Rauf et al., (2004) analysed the distribution pattern of triacylglycerols of

Argemone mexicana seed oil The investigation reveals that the argemone oil contains

a greater percentage of unsaturated acids and used as a potential source of biodiesel

Knothe and Steidley (2005) evaluated the kinematic viscosity of biodiesel fuel components and related compounds with influence of compound structure and

comparison to petrodiesel fuel components Azam et al., (2005) examined fatty acid

profiles of 75 oil bearing plant species having 30% or more fixed oil Saponification value, iodine value and cetane number of fatty acid methyl esters of oil were empirically determined and the data was used to predict the quality for respective vegetable oil methyl ester for use as a biodiesel and described the physical parameters

of Argemone mexicana oil closed to standard values Ramadhas et al., (2005b)

explored high FFA rubber seed oil for biodiesel production The important properties

of biodiesel, such as specific gravity, flash point, cloud point and pour point were compared with conventional diesel and found to be suitable feedstock for biodiesel

Usta et al., (2005) produced a methyl ester bio-diesel from a hazelnut soap-stock and

waste sunflower oil mixture using methanol, sulphuric acid and sodium hydroxide in

a two-stage process and found satisfactory results Ghosh and Nag (2006) examined

the de-gumming of non-edible vegetable oil such as Karanja, Jatropha and Debdaru The finding showed 20% of the non-edible vegetable oil blended with diesel could

yield the satisfactory results Veljkovic et al., (2006) investigated the biodiesel

production from Nicotiana tobacum seed oil The maximum yield of fatty acid methyl

ester was about 91% in 30 min The tobacco biodiesel had the fuel properties within the limits of ASTM and DIN EN 14214 standards, except acid value Thus, tobacco seeds as agricultural waste might be valuable renewable raw material for biodiesel

Holser and Kuru (2006) transesterified milkweed seed oil as a biodiesel fuel Methyl

and ethyl esters of milkweed seed oil were prepared and properties like pour point, oxidative stability, viscosity, and lubricity were analysed and compared with soybean esters

Sarin et al., (2007) have been examined the blends of Jatropha and Palm

biodiesel for their physico-chemical properties and to get optimum mix of them to achieve better low temperature and improved oxidation stability needed for South Asian and South East-Asian countries Berchmans and Hirata (2008) have been developed a technique to produce biodiesel from Jatropha with high free fatty acids contents (15% FFA), in which two-stage transesterification process was selected to improve methyl ester yield Nabi and Hoque (2008) optimized different parameters for biodiesel production and the performance study of a diesel engine with diesel biodiesel blends The results showed that about 88% biodiesel production was

experienced with 20% methanol, 0.5% NaOH catalyst and at 55°C Dos Santos et al.,

(2008) investigated the fruits of Terminalia catappa for selected fuel properties and

chemical composition of the oil, as well as potential application in biodiesel production The kernel of Terminalia catappa fruit yields around 49% oil The physico-chemical properties of prepared biodiesel were found in acceptable range for

use as biodiesel in diesel engines Predojevic (2008) studied the use of waste frying

oils for biodiesel preparation The biodiesel was prepared by two-step alkali transesterification of waste sunflower oils, using methanol and KOH as catalyst The produced biodiesel met the criteria required to be a diesel substitute

Oliveira et al., (2008) studied the preliminary evaluation of the feasibility of

healthy and defective coffee beans as biodiesel feedstock Type of alcohol employed and reaction time were studied After evaluation, coffee oil from healthy and defective

coffee beans was demonstrated to be a potential feedstock for biodiesel Rashid et al., (2008) investigated Moringa oleifera oil as an alternative to petroleum based

conventional diesel fuel IR and NMR spectrum of prepared methyl ester of moringa oil were reported Overall, moringa oil appears to be an acceptable feedstock for

biodiesel Akubugwo et al., (2008) investigated the oil extracted from seeds of five Nigerian plants using n-hexane and their physicochemical properties compared with oils from other sources Specific gravity of the seed oils ranged from 0.81-0.90 while peroxide value for all the oil seed was less than 6.00 Saponification values were as low as 106.60 in P gratesima and as high as 246.00 in C nucifera seed oils Iodine values were between 9.60 and 52.40 in the extracts These results suggest that oil seeds examined may be viable source of oil going by their oil yield Rachimoellah et

al., (2009) investigated that production of biodiesel from avocado seed oil as an

alternative source of fuel Avocado seed oil contains free fatty acid less than 2%, so that transesterification process can be carried out with no addition step to convert free fatty acid content become esters It can be concluded that the characteristic of biodiesel from avocado seed oil is acceptable for alternative fuel

Singh and Singh (2010) reviewed the production process and characterization

of vegetable oils and their methyl ester as the substitute of the petroleum fuel and future possibilities of biodiesel production Amongst the various vegetable oils

studied as biodiesel resources, Argemone mexicana is an unexploited crop species of

great economic potential and does not have the pitfalls like limited supply and high oil

costs Shokib et al., (2010) investigated the effect of reaction temperature, reaction

time and molar ratio between methanol and oil on the yield of biodiesel product Rubber seeds with 45.63 wt% oil content and contained 17 wt% Free Fatty Acid was used as the main feedstock It was found that yield of biodiesel product increased with

the increase of reaction temperature Antony Raja et al., (2011) analyzed the

utilization of liquid fuels such as biodiesel produced from Jatropha oil by transesterification process represents one of the most promising options for the use of conventional fossil fuels The physical properties such as density, flash point,

kinematic viscosity, Cloud point and Pour point were found out for Jatropha oil and Jatropha methyl ester The values obtained from the Jatropha methyl ester was closely matched with the values of conventional diesel and can be used in the existing diesel

engine without any modification Meena Devi et al., (2012) analyzed the

physico-chemical properties of rubber seed oil for the potentiality for the production of biodiesel and it was found to be efficient biodiesel resources which meets the ASTM standard for biodiesel The rubber oil cake was analyzed and it was found to control the weeds, diseases and it is an efficient biofertilizer

Bobade and Khyade (2012a) investigated the fuel properties of karanja oil methyl ester The experimental results indicate that the karanja oil methyl ester can be used as a source of triglycerides in the manufacture of biodiesel by transesterification reaction and best suited as per ASTM norms for using as biodiesel in pure as well as

in blending form Kumari et al., (2012) investigated the production of biodiesel from seed oil of Cleome viscosa and reported that the fatty acid composition of Cleome to

be similar to the non-edible oil of Jatropha, Rubber and Pongamia Uma

Krishnakumar et al., (2013) confirmed that the biodiesel derived from the rubber seed

oil is suited for use in diesel engines and given that its kinematic viscosity, flash point, cloud point, and calorific value conform to the recommended international

standards Chen et al., (2013) investigated the blends of biodiesels produced from

Soapnut oil and high-oleic free fatty acids (FFAs), which are potential non-edible oil feedstocks with respect to their fuel properties The soapnut oil methyl esters had satisfactory fuel properties with the exception of its high cold filter plugging point The biodiesel blend at a weight ratio of 70:30 can successfully meet all the biodiesel specifications, except the marginal oxidation stability