Doctor of Philosophy: Analysis of some vegetable oils for potential biodiesel production

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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.

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Nội dung Text: Doctor of Philosophy: Analysis of some vegetable oils for potential biodiesel production

ANALYSIS OF SOME VEGETABLE OILS FOR POTENTIAL BIODIESEL PRODUCTION A THESIS Submitted by M. RAJAKOHILA Reg. No. 8492 BIOTECHNOLOGY - BOTANY (Interdisciplinary) in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY MANONMANIAM SUNDARANAR UNIVERSITY TIRUNELVELI 627 012 DECEMBER - 2018
MANONMANIAM SUNDARANAR UNIVERSITY TIRUNELVELI - 627 012 CERTIFICATE The research work embodied in the present Thesis entitled “ANALYSIS OF SOME VEGETABLE OILS FOR POTENTIAL BIODIESEL PRODUCTION” has 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 SL.No Title Page No ABSTRACT LIST OF TABLES LIST OF FIGURES LIST OF ABBREVIATIONS 1 INTRODUCTION 1 1.1. Energy 1 1.2. Types of Energy Sources 1 1.2.1.Non – Renewable Energy 2 1.2.2. Renewable Energy 2 1.3. Fossil Fuel 3 1.4. Need for Alternate fuel 4 1.5. Feasible Alternate energy sources 5 1.5.1.Biofuel 5 1.5.2.Biodiesel 6 1.5.3.Biodiesel Production Method 10 1.5.4.Blending or Dilution 11 1.5.5.Biodiesel Standard 12 1.6. Physico -Chemical Analysis of vegetable oil. 13 1.7. Corrosion 14 1.7.1.Corrosion Inhibitors 14 1.7.2.Green Inhibitors 15 1.8. Objectives 15 2 REVIEW OF LITERATURE 16
3 BIOENERGY CROPS 41 3.1. Introduction 41 3.2. Classification of vegetable oil 41 3.3. Bioenergy crops selected for present study 42 3.3.1.Argemone mexicana 43 3.3.1.1. Scientific classification 43 3.3.1.2. Botanical name 44 3.3.1.3. Common name 44 3.3.1.4. Distribution 44 3.3.1.5. Description 44 3.3.1.6. Ecology 46 3.3.1.7. Chemical Constituents 46 3.3.1.8. Medicinal uses and other 46 3.3.2.Cleome viscosa 47 3.3.2.1.Scientific classification 47 3.3.2.2. Botanical name 47 3.3.2.3. Common name 48 3.3.2.4. Distribution 48 3.3.2.5. Description 48 3.3.2.6. Ecology 50 3.3.2.7. Chemical Constituents 50 3.3.2.8. Medicinal uses and other 50 3.3.3. Pongamia pinnata 51 3.3.3.1.Scientific classification 51 3.3.3.2. Botanical Name 51 3.3.3.3. Common name 51 3.3.3.4. Distribution 52 3.3.3.5. Description 52 3.3.3.6. Ecology 53 3.3.3.7. Chemical Constituents 53 3.3.3.8. Medicinal uses and others 55
3.3.4. Hevea brasiliensis 56 3.3.4.1. Scientific classification 56 3.3.4.2. Botanical Name 56 3.3.4.3. Common name 56 3.3.4.4. Distribution 56 3.3.4.5. Description 57 3.3.4.6. Ecology 57 3.3.4.7. Chemical constituents 59 3.3.4.8. Medicinal Uses and others 59 3.3.5. Sapindus trifoliatus 60 3.3.5.1. Scientific classification 60 3.3.5.2. Botanical name 60 3.3.5.3. Common name 60 3.3.5.4. Distribution 60 3.3.5.5. Description 61 3.3.5.6. Ecology 63 3.3.5.7. Chemical constituents 63 3.3.5.8. Medicinal uses and others 63 4 MATERIALS AND METHODS 65 4.1. Collection of plants 65 4.2. Extraction of oil 65 4.3. Preparation of Blends 66 4.4. Properties of biodiesel blends 66 4.4.1. Analysis of physical properties of biodiesel blends 67 4.4.1.1. Viscosity 67 4.4.1.2. Density 67 4.4.1.3. Specific Gravity 68 4.4.1.4. Conductivity 68 4.4.1.5. Dissolved Oxygen 68 4.4.1.6. Total dissolved solids 69
4.4.1.7.Determination of pH 69 4.4.1.8. Flash Point 69 4.4.1.9.Fire Point 70 4.4.1.10. Cloud Point 70 4.4.1.11. Pour Point 71 4.4.1.12. Smoke Point 71 4.4.1.13.Carbon Residue 71 4.4.2. Ultrasonic Properties Analysis 72 4.4.2.1. Principle and Instrumentation of Ultrasonic 72 Interferometer 4.4.2.2. Ultrasonic Velocity 74 4.4.2.3. Adiabatic compressibility 74 4.4.2.4. Acoustic impedance 75 4.4.2.5. Relaxation time 75 4.4.3. Analysis of chemical properties of biodiesel blends 76 4.4.3.1.Acid value 76 4.4.3.2. Saponification value 77 4.4.3.3. Iodine value 78 4.4.3.4. Cetane number 78 4.4.3.5. Higher Heating value 79 4.4.3.6. Average Molecular Weight of Total Free Fatty 79 Acid 4.4.3.7. Percentage of Free Fatty Acid 80 4.4.4. Statistical Analysis 80 4.4.5. Analysis of Fuel Efficiency of Biodiesel Blends 80 4.4.6. Analysis of Corrosion Parameters 81 4.4.6.1. Preparation of specimen 81 4.4.6.2. Inhibitor 81 4.4.6.3. Gravimetric measurements 82 4.4.6.4. SEM analysis 83
5 RESULT 84 5.1 Analysis of physical Property 87 5.1.1 Viscosity 87 5.1.2 Density 87 5.1.3 Specific Gravity 87 5.1.4 Conductivity 91 5.1.5 Dissolved Oxygen 91 5.1.6 Total dissolved Solids 94 5.1.7 pH 94 5.1.8. Flash Point 94 5.1.9. Fire Point 98 5.1.10. Pour Point 98 5.1.11. Cloud Point 98 5.1.12. Smoke Point 102 5.1.13. Carbon Residue Analysis 102 5.2. Ultrasonic Study 105 5.2.1. Ultrasonic Velocity 105 5.2.2. Adiabatic Compressibility 105 5.2.3. Acoustic Impedance 105 5.2.4. Relaxation Time 109 5.3. Analysis of Chemical properties 109 5.3.1. Acid Value 109 5.3.2. Saponification Value 112 5.3.3. Iodine Value 112 5.3.4. Cetane Number 112 5.3.5. Higher Heating Value 116 5.3.6. Average Molecular Weight of Total Fatty Acid 116 5.3.7. Percentage of Free Fatty Acid 116 5.4. Fuel Efficiency 120 5.5. Corrosion Study 121
5.5.1. Variation of mild steel weight loss in acid medium with 121 different concentration of selected bioinhibitors at different duration 5.5.2. Variation of Corrosion rate in acid medium with different 126 concentration of selected bioinhibitors at different duration 5.5.3. Variation of Corrosion inhibition efficiency in acid medium 130 with different concentration of selected bioinhibitors at different duration 5.5.4. Morphological study of Mild steel using Scanning Electron 135 Microscope 6 DISCUSSION 140 7 SUMMARY 160 8 CONCLUSION 162 9 REFERENCES 164 10 APPENDICES LIST OF PUBLICATIONS REPRINTS OF JOURNAL PUBLICATION BIO-DATA
LIST OF TABLES TABLE PAGE TITLE NO NO 3.1 List of bioenergy crops screened 42 5.1. Viscosity of selected biodiesel blends 88 5.2. Density of selected biodiesel blends 89 5.3. Specific Gravity of selected biodiesel blends 90 5.4. Conductivity for different biodiesel blends. 92 5.5. Dissolved Oxygen of selected biodiesel blends 93 5.6. Total Dissolved Solids of selected biodiesel blends 95 5.7. pH of selected biodiesel blends 96 5.8. Flash Point of selected biodiesel blends 97 5.9. Fire Point of selected biodiesel blends 99 5.10. Pour Point of selected biodiesel blends 100 5.11. Cloud Point of selected biodiesel blends 101 5.12. Smoke Point of selected biodiesel blends 103 5.13. Carbon Residue of selected biodiesel blends 104 5.14. Ultrasonic Velocity of selected biodiesel blends 106 5.15. Ultrasonic Adiabatic Compressibility of selected biodiesel blends 107 5.16. Acoustic Impedance of selected biodiesel blends 108 5.17. Relaxation Time of selected biodiesel blends 110 5.18. Acid Value of selected biodiesel blends 111 5.19. Saponification Value of selected biodiesel blends 113 5.20. Iodine Value of selected biodiesel blends 114 5.21. Cetane Number of selected biodiesel blends 115 5.22. Higher Heating Value of selected biodiesel blends 117 5.23. Average Molecular weight of Total Fatty Acid of selected biodiesel 118 blends 5.24. Percentage of Free Fatty Acid of selected biodiesel blends 119 5.25. Fuel Efficiency of selected biodiesel Blends. 120
5.26. Variation of mild steel weight loss in acid medium with different 122 concentration of bioinhibitors after 24 hours duration 5.27. Variation of mild steel weight loss in acid medium with different 122 concentration of bioinhibitors after 48 hours duration 5.28. Variation of mild steel weight loss in acid medium with different 124 concentration of bioinhibitors after 72 hours duration 5.29. Variation of mild steel weight loss in acid medium with different 124 concentration of bioinhibitors after 96 hours duration 5.30. Variation of mild steel weight loss in acid medium with different 125 concentration of bioinhibitors after 120 hours duration 5.31. Variation of corrosion rate at different concentration of selected 127 bioinhibitors after 24 hours duration 5.32. Variation of corrosion rate at different concentration of selected 127 bioinhibitors after 48 hours duration 5.33. Variation of corrosion rate at different concentration of selected 128 bioinhibitors after 72 hours duration 5.34. Variation of corrosion rate at different concentration of selected 128 bioinhibitors after 96 hours duration 5.35. Variation of corrosion rate at different concentration of selected 129 bioinhibitors after 120 hours duration 5.36. Variation of corrosion inhibition efficiency at different concentration of 131 selected bioinhibitors after 24 hours duration 5.37. Variation of corrosion inhibition efficiency at different concentration of 131 selected bioinhibitors after 48 hours duration 5.38. Variation of corrosion inhibition efficiency at different concentration of 132 selected bioinhibitors after 72 hours duration 5.39. Variation of corrosion inhibition efficiency at different concentration of 132 selected bioinhibitors after 96 hours duration 5.40. Variation of corrosion inhibition efficiency at different concentration of 134 selected bioinhibitors after 120 hours duration
LIST OF FIGURES FIGURE PAGE TITLE NO NO. 5.1 Scanning electron micrograph of mild steel as received and Mild steel after 136 120 hours immersion in 1 N HCL without and with Argemone oil bioinhibitor 5.2 Scanning electron micrograph of mild steel after 120 hours immersion in 1 137 N HCL without and with Cleome oil bioinhibitor 5.3 Scanning electron micrograph of mild steel after 120 hours immersion in 1 137 N HCL without and with Pongamia oil inhibitor 5.4 Scanning electron micrograph of mild steel after 120 hours immersion in 1 139 N HCL without and with Rubber oil bioinhibitor 5.5 Scanning electron micrograph of mild steel after 120 hours immersion in 1 139 N HCL without and with Soapnut oil bioinhibitor
LIST OF PLATES PLATE NO TITLE PAGE NO. 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 Weight loss measurement of mild steel in 1N HCl Plate 4.2. 86 medium with and without selected bioinhibitors.
LIST OF ABBREVIATIONS ANOVA Analysis Of Variance AOCS American Oil Chemists’ Society ASTM American Standard Test Method AV Acid Value B Blends of Biodiesel B0 Petro diesel B5 5 percent Blend of Biodiesel B10 10 percent Blend of Biodiesel B20 20 percent Blend of Biodiesel B100 Biodiesel in pure form BIS Bureau of Indian Standards BSFC Break Specific Fuel Consumption BTE Break Thermal Efficiency CARB California Air Resources Board CI Engine Compression Ignition Engine CKO Crude Karanja Oil CN Cetane Number CO Carbon Monoxide CO2 Carbon Dioxide DI Engine Direct Injection Engine DO Dissolved Oxygen EC Electrical Conductivity
EN European Nationale EPA Environmental Protection Agency FA Fatty Acid FAME Fatty Acid Methyl Ester FFA Free Fatty Acid FP Flash Point GC Gas Chromatography GOI Government Of India HC Hydro Carbon HCl Hydrochloric Acid H3PO 4 Phosphoric Acid HHV Higher Heating Value HSD High Speed Diesel IE Inhibition Efficiency IEA International Energy Agency IPCC Intergovernmental Panel On Climate Change IR Infra Red ISI Indian Standard Institution IV Iodine Value KCl Potassium Chloride KI Potassium Iodide KOH Potassium Hydroxide M Molar
MHz Mega Hertz Mmpy Millimetre per year MT Million Tons N Normality N Nitrogen NaCl Sodium Chloride NaOH Sodium Hydroxide NFTS Nitrogen Fixing Trees NOx Generic term for Nitric Oxide and Nitrogen Dioxide NMR Nuclear Magnetic Resonance O Oxygen P Phosphorus ppm Parts per million P value Probability Value RT Relaxation Time S Sulphur SEM Scanning Electron Microscope SV Saponification Value TDS Total Dissolved Solids US The United Nation V/V Volume/Volume WEO Waste Edible oil
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 1
(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 2
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 3
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 4