Onoji's Thesis (PHD) - Final Submission

SYNTHESIS OF BIODIESEL FROM RUBBER SEED OIL FOR
INTERNAL COMPRESSION IGNITION ENGINE
Samuel Erhigare Onoji
A thesis submitted to the Faculty of Engineering and the Built
Environment, University of the Witwatersrand, Johannesburg, in
fulfillment of the requirements for the degree of Doctor of Philosophy.
Johannesburg, South Africa.
2nd December, 2017

DECLARATION
I declare that this thesis is my own, unaided work. It is being submitted for the Degree of Doctor
of Philosophy in the University of the Witwatersrand, Johannesburg. It has not been submitted
before for any degree or examination in any other University.
(Signature of candidate)
2nd.............Day of........December, ..........2017
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ABSTRACT
Biodiesel has been identified as a good complement and plausible replacement of fossil diesel
because of the overwhelming characteristic properties similar to fossil diesel in addition to its
good lubricity, biodegradability, non-toxicity and eco-friendliness when used in diesel engines.
The production of biodiesel from edible vegetable oils competes with food sources, thereby
resulting in high cost of food and biodiesel. Studies have shown that rubber seed contains 35–
45 % oil, which portrays a better competitor to other non-edible oil bearing plants in biodiesel
production. In this study, non-edible vegetable oils from underutilized Nigerian NIG800 clonal
rubber seeds were extracted from 0.5 mm kernel particle size using n-hexane as solvent to
obtain a yield of 43 wt.% over an extraction time of 1 h. The oil was characterized for fatty
acids by using gas chromatography-mass spectrometry (GC-MS), and for structural properties
by Fourier transform-infrared (FT-IR) and nuclear magnetic resonance (NMR) analyses.
The optimization of the process conditions of the vegetable oil extraction was evaluated using
response surface methodology (RSM) and artificial neural network (ANN) techniques both of
which, were based on a statistically designed experimentation via the Box-Behnken design
(BBD). A three-level, three-factor BBD was employed using rubber seed powder (X1), volume
of n-hexane (X2) and extraction time (X3) as process variables. The RSM model predicted
optimal oil yield of 42.98 wt. % at conditions of X1 (60 g), X2 (250 mL) and X3 (45 min) and
experimentally validated as 42.64 wt. %. The ANN model predicted optimal oil yield of 43 wt.
% at conditions of X1 (40 g), X2 (202 mL) and X3 (49.99 min) and validated as 42.96 wt. %.
Both models were effective in describing the parametric effect of the considered operating
variables on the extraction of oil from the rubber seeds. On further examinations of the
potentials of the vegetable oil, the kinetics of thermo-oxidative degradation of the oil was
investigated. The kinetics produced a first-order reaction, with activation energy of 13.07
kJ/mol within the temperature range of 100–250 oC. In a bid to attain enhanced yield of
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biodiesel produced via heterogeneous catalysis, coupled with the carbonaceous potentials of
the pericarp and mesocarp of rubber seed shell casing as a suitable catalytic material, the rubber
seed shells (RSS) were used to develop a heterogeneous catalyst. RSS was washed 3–4 times
with hot distilled water, dried at 110 oC for 5 h, ground to powder, and calcined at 800 oC at a
heating rate of 10 oC/min as a catalyst and analyzed for thermal, structural, and textural
properties using thermogravimetric analyzer, x-ray diffractometer, and nitrogen
adsorption/desorption analyzer, respectively. The catalyst was further analyzed for elemental
compositions and surface morphology by x-ray fluorescence and scanning electron
microscopy, respectively. The catalyst was then applied in biodiesel production from rubber
seed oil. A central composite design (CCD) was employed together with RSM and ANN to
obtain optimal conditions of the process variables consisting of reaction time, methanol/oil
ratio, and catalyst loading on biodiesel yield. The optimum conditions obtained using RSM
were as follows: reaction time (60 min), methanol/oil ratio (0.20 vol/vol), and catalyst loading
(2.5 g) with biodiesel yield of 83.11% which was validated experimentally as 83.06±0.013%.
Whereas, those obtained via ANN were reaction time (56.7 min), methanol/oil ratio (0.21
vol/vol), and catalyst loading (2.2 g) with a biodiesel yield of 85.07%, which was validated
experimentally as 85.03±0.013%. The characterized biodiesel complied with ASTM D 6751
and EN 14214 biodiesel standards and was used in modern diesel test engine without technical
modifications. Though the produced biodiesel has a lower energy content compared with
conventional diesel fuel, in all the cases of blends considered, the optimal engine speed for
higher performance and lower emissions was observed at 2500 rpm. In this study, the B20
blend has best engine performance with a lower emission profile, and was closely followed by
B50 blend.
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DEDICATION
To my lovely wife Mrs. Augustina Onoji, and my children Faith, Emmanuel, Deborah, and
Mishael for their inestimable support, prayers and being my source of strength.
The work is also dedicated to my post-octogenarian Father, Mr. Iboyotete Onoji for his
confidence in me and encouragement throughout my years of study. I will not fail to dedicate
the work also to the memories of my mother, Mrs. Igogoma Onoji who has gone to be with the
Lord.
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ACKNOWLEDGMENTS
First and foremost, I appreciate God Almighty for the strength, knowledge and the grace He
gave me to start and complete the research successfully.
My deep appreciation goes to Professor Sunny E. Iyuke for his thorough supervision,
encouragement, guidance and valuable support he gave me while the project lasted. The three
years under his supervision motivated me to develop a scientific rigour and effectiveness.
My profound gratitude goes to my co-supervisors, Professor Michael O. Daramola of the
University of the Witwatersrand, Johannesburg, South Africa, and Professor Anselm I. Igbafe
of Afe Babalola University, Ado-Ekiti, Nigeria, for their close supervision, expertise and
valuable contributions to this study.
I acknowledged immensely the contributions of Dr. Julius I. Osayi of the Nanotechnology and
Petroleum Research Group of the University of the Witwatersrand for the role he played
throughout the duration of the research. Other members of the Nanotechnology and Petroleum
Research Group are also appreciated for their immense contributions during our weekly
research group meetings, and to Mr. Bruce Mothibeli for his laboratory assistance and materials
provided for the practical work.
I would like to acknowledge the contribution of Dr. Diakanua B. Nkazi and Family for the
hospitality showed to me during my stay in Johannesburg, and to Dr. Tunde F. Adepoju of
Landmark University, Omu-Aran, Nigeria, for his encouragement and laboratory assistance.
I want to warmly appreciate Dr. Kevin I. Idehen and Dr. Reuben M. Umoh, both of the
Petroleum Training Institute, Effurun, Nigeria for their valuable suggestions, insightful advice
and support.
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I sincerely appreciate His lordship, Bishop Dr. & Rev. (Mrs.) Curtis Fianu, Bishop of New
Warri Bishopric Headquarters, Church of God Mission International Inc., Praise Centre,
Effurun, Nigeria for their encouragement and prayers, and to all Pastors, Ordained Ministers,
and Members of the Church for their support and goodwill.
Finally, I truly acknowledge the wonderful support of my beloved wife, Mrs. Augustina Onoji
and my lovely children, Faith, Emmanuel, Deborah, and Mishael for their prayers, patience and
sacrifice that strengthened me throughout the period of my study.
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LIST OF REFERRED PUBLICATIONS
Onoji, S.E., Iyuke, S.E., Igbafe, A.I., & Nkazi, D. B. (2016). Rubber seed oil: A potential
renewable source of biodiesel for sustainable development in sub-Saharan Africa. Energy
Conversion and Management, 110, 125–134.
Onoji, S.E., Iyuke, S.E., & Igbafe, A. I. (2016). Hevea brasiliensis (Rubber seed) oil:
Extraction, characterization, and kinetics of thermo-oxidative degradation using classical
chemical methods. Energy & Fuels, 30 (12), 10555–10567.
Onoji, S.E., Iyuke, S.E., Igbafe, A.I., & Daramola, M. O. (2017). Hevea brasiliensis (Rubber
seed) oil: Modeling and optimization of extraction process parameters using response surface
methodology and artificial neural network techniques. Biofuels, 1–15.
doi:10.1080/17597269.2017.1338122.
Onoji, S.E., Iyuke, S.E., Igbafe, A.I., & Daramola, M. O. (2017). Transesterification of rubber
seed oil to biodiesel over a calcined waste rubber seed shell catalyst: Modeling and
optimization of process variables. Energy & Fuels, 31 (6), 6109–6119.
vii
ORAL PRESENTATIONS AT CONFERENCES
Onoji, S.E., Iyuke, S.E., Igbafe, A.I., & Daramola, M. O. (2017, May). Synthesis of Rubber
Seed (Hevea brasiliensis) Oil Methyl Esters over a Calcined Waste Rubber Seed Shell Catalyst:
Modeling and Optimization of Process Variables. Paper presented at the 13th International
African Scholar Academic Conference on Delving into Issues and Resources for sub-Saharan
Africa Growth in the Millennium Era: A Multi-Disciplinary Approach. Universite de Sciences
et Technologies de Côte d'Ivoire.
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TABLE OF CONTENTS
Contents Page
DECLARATION...................................................................................................................i
ABSTRACT...........................................................................................................................ii
DEDICATION.......................................................................................................................iv
ACKNOWLEDGMENTS......................................................................................................v
LIST OF REFERRED PUBLICATIONS.............................................................................vii
PRESENTATIONS AT CONFERENCES..........................................................................viii
CONTENTS..........................................................................................................................ix
LIST OF FIGURES............................................................................................................xvii
LIST OF TABLES..............................................................................................................xxii
NOMENCLATURE..........................................................................................................xxiv
CHAPTER 1: INTRODUCTION...........................................................................................1
1.1 Research background and motivation................................................................................1
1.2 Hypothesis........................................................................................................................3
1.3 Justification of study.........................................................................................................3
1.4 Research aims and objectives............................................................................................5
1.5 Thesis outline....................................................................................................................7
CHAPTER 2: LITERATURE REVIEW................................................................................9
2.0 Introduction......................................................................................................................,9
2.1 The rubber tree..................................................................................................................9
2.2 Rubber seed capacity in sub-Saharan Africa...................................................................13
2.3 Rubber seed collection and processing............................................................................15
ix
2.4 Biomass valorization processes.......................................................................................15
2.5 Modeling and optimization approach to industrial research............................................18
2.6 Qualitative and quantitative analytical procedures..........................................................21
2.6.1 Thermogravimetric analysis.........................................................................................22
2.6.2 Fourier transform infrared spectroscopy......................................................................22
2.6.3 Scanning electron microscopy......................................................................................23
2.6.4 Brunauer- Emmett-Teller (BET) analysis....................................................................23
2.6.5 Nuclear magnetic resonance.........................................................................................24
2.6.6 Gas chromatography-mass spectroscopy.....................................................................24
2.6.7 X-ray diffraction and X-ray fluorescence.....................................................................25
2.7 Rubber seed analysis.......................................................................................................25
2.8 Rubber seed oil extraction methods.................................................................................29
2.8.1 Conventional extraction methods (mechanical and chemical) .....................................30
2.8.2 Gas-assisted mechanical extraction method.................................................................32
2.8.3 Microwave-assisted extraction (MAE) method............................................................32
2.8.4 Ultrasonic-assisted extraction method..........................................................................32
2.8.5 Aqueous enzymatic extraction method.........................................................................33
2.8.6 Supercritical fluid extraction (SFE) method.................................................................33
2.9 Physico-chemical properties of rubber seed oil...............................................................33
2.10 Thermo-oxidative analysis of rubber seed oil................................................................37
2.11 Industrial applications of rubber seed and oil................................................................39
2.12 Biofuels policies and sustainability in Africa................................................................40
2.12.1 Nigerian biofuel policy (A case study in Africa) ........................................................43
2.13 Catalysis........................................................................................................................45
2.13.1 Catalyst deactivation..................................................................................................47
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2.13.2 Physical adsorption and chemisorption in chemical reaction catalysis......................47
2.14 Gas-solid adsorption systems........................................................................................49
2.14.1 Langmuir model equation (linearized).......................................................................51
2.14.2 BET model equation...................................................................................................51
2.14.3 Freundlich model equation.........................................................................................52
2.14.4 The t-plot....................................................................................................................53
2.14.4.1 Harkins-Jura model.................................................................................................54
2.14.4.2 Halsey equation.......................................................................................................55
2.14.5 Polanyi's potential theory...........................................................................................55
2.14.6 Dubinin-Radushkevich equation................................................................................56
2.14.7 Kelvin equation..........................................................................................................57
2.14.8 Thermodynamics of gas adsorption............................................................................58
2.15 Biodiesel and its origin..................................................................................................59
2.15.1 Biodiesel feedstock....................................................................................................63
2.16 Catalysis in biodiesel production...................................................................................64
2.16.1 Acid-catalyzed esterification reaction........................................................................64
2.16.2 Transesterification of oils using homogeneous catalyst............................................65
2.16.2.1 Alkali-catalyzed transesterification reaction...........................................................66
2.16.2.2 Two-step transesterification reaction......................................................................67
2.16.2.3 Mechanisms for homogeneous catalysis.................................................................67
2.16.3 Transesterification of oils using heterogeneous catalysts..........................................67
2.16.3.1 Heterogeneous acid transesterification reaction......................................................68
2.16.3.2 Heterogeneous base transesterification reaction......................................................69
2.16.4 Enzyme-catalyzed transesterification reaction..........................................................71
2.16.5 Heterogeneous catalyst from natural sources............................................................71
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2.17 Transesterification of rubber seed oil............................................................................72
2.18 Transesterification methods for rubber seed oil.............................................................73
2.18.1 The conventional method...........................................................................................73
2.18.2 The in-situ method......................................................................................................73
2.18.3 The enzymatic method...............................................................................................74
2.18.4 The supercritical method............................................................................................74
2.18.5 The co-solvent assisted method..................................................................................74
2.18.6 The ultrasonic-assisted method..................................................................................74
2.18.7 The microwave-assisted method................................................................................75
2.19 Factors affecting the transesterification of rubber seed oil.............................................75
2.19.1 FFA content of rubber seed oil....................................................................................75
2.19.2 Alcohol/oil molar ratio...............................................................................................76
2.19.3 Catalyst concentration................................................................................................76
2.19.4 Reaction temperature and time...................................................................................77
2.19.5 Agitation speed..........................................................................................................77
2.20 Thermodynamics of internal combustion ignition engines............................................78
2.20.1 Overview of reciprocating engines.............................................................................78
2.20.2 Air-standard assumptions...........................................................................................80
2.20.3 Diesel cycle-The ideal cycle for compression ignition engines..................................81
2.20.4 Mathematical models for internal compression ignition engines...............................84
2.20.5 Models for gas mixture properties..............................................................................87
2.20.6 First and second laws of thermodynamics for internal combustion engines..............88
2.20.7 Second law of thermodynamics analysis (availability).............................................91
2.21 Performance evaluation of diesel engines....................................................................95
2.21.1 Brake mean effective pressure...................................................................................96
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2.21.2 Brake power...............................................................................................................96
2.21.3 Brake specific fuel consumption................................................................................97
2.21.4 Brake thermal efficiency............................................................................................97
2.22 Performance and emissions evaluation of diesel engine using diesel-biodiesel blends of
rubber seed oil.......................................................................................................................97
CHAPTER 3: METHODOLOGY AND EXPERIMENTAL PROCEDURES...................100
3.0 Introduction……………………………………………...............................................100
3.1 Materials and chemicals................................................................................................100
3.2 Experimental procedures for seed oil extraction………………………………………101
3.2.1 Rubber seed preparation……….……………………………………………………101
3.2.2 Extraction of the seed oil……………………………………………………………102
3.3 Characterization of the seed oil……………………………………………………….103
3.4 Spectroscopy analyses of the seed oil…………...…………………………………….104
3.4.1 Fatty acid profile of the seed oil………….….............................................................104
3.4.2 Fourier transform infrared spectroscopy....................................................................105
3.4.3 Nuclear magnetic resonance spectroscopy...………….…………………………….105
3.5 Kinetics of thermal oxidative degradation of the seed oil..............................................106
3.6 Optimization study of the oil extraction process using RSM and ANN techniques.......107
3.6.1 Modeling of seed oil extraction process variables via RSM……...............................108
3.6.2 Modeling of seed oil extraction process variables via ANN………….......................111
3.7 Catalyst preparation and characterization......................................................................113
3.8 Biodiesel production from the extracted seed oil and analysis………….......................115
3.8.1 Acid-catalyzed esterification of rubber seed oil..........................................................115
3.8.2 Biodiesel production from the esterified seed oil........................................................116
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3.9 Characterization of the produced biodiesel…………...................................................118
3.10 Reusability test for the catalyst used in biodiesel production…...................................119
3.11 Statistical analysis of the biodiesel production by RSM..............................................119
3.12 Analysis of variance (ANOVA) study for biodiesel production..................................120
3.13 Modeling of biodiesel production process variables……............................................120
3.14 Data validation for RSM and ANN models.................................................................121
3.15 Combustion of biodiesel-diesel blends in internal compression ignition engine.........121
3.15.1 Biodiesel-diesel blending analysis via ultrasonication technique.............................122
3.15.2 Methodology and experimental setup for combustion study of biodiesel blends......123
CHAPTER 4: RESULTS AND DISCUSSION.................................................................129
4.0 Introduction……………………………………….......................................................129
4.1 Extraction of seed oil and determination of the best seed particle size...........................129
4.2 Physical characterization of the seed and seed oil……………......................................130
4.3 Characterization of the seed oil…….............................................................................131
4.3.1Colour, pH, density and Specific gravity.....................................................................132
4.3.2 Iodine, peroxide, saponification and acid values........................................................132
4.3.3 Kinematic viscosity....................................................................................................133
4.3.4 Cold flow properties...................................................................................................134
4.3.4.1 Pour point................................................................................................................134
4.3.4.2 Cloud point..............................................................................................................134
4.3.4.3 Cold filter plugging point........................................................................................135
4.3.5 Aniline point..............................................................................................................135
4.3.6 Boiling, freezing, flash and fire points........................................................................135
4.3.7 Refractive index.........................................................................................................136
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4.3.8 Other parameters........................................................................................................136
4.3.8.1 Cetane number........................................................................................................136
4.3.8.2 Diesel index.............................................................................................................137
4.3.8.3 Higher heating value...............................................................................................137
4.3.8.4 Average molecular weight of rubber seed oil..........................................................137
4.3.9 Fatty acid profile of the seed oil..................................................................................140
4.3.10 FT-IR and NMR spectroscopy of the seed oil...........................................................142
4.3.10.1 FT-IR analysis of the seed oil................................................................................142
4.3.10.2 1H NMR analysis of the seed oil…………………................................................145
4.3.10.3 13C NMR analysis of the seed oil...........................................................................147
4.4 Kinetic study of thermo-oxidative degradation of rubber seed oil.................................148
4.5 Parametric effects and optimization of oil extraction using RSM………......................154
4.5.1 Full quadratic regression model.................................................................................154
4.5.2 Optimization of oil extraction process variables based on RSM.................................157
4.5.3 Analysis of variance (ANOVA) study for seed oil extraction.....................................158
4.5.4 Parametric effects of interactive factors on the seed oil yield...................................161
4.6 Parametric effects and optimization of oil extraction using ANN model……............164
4.7 Comparison of RSM and ANN models for the seed oil extraction..............................169
4.8 Catalyst preparation and characterization………………………….............................170
4.8.1 Thermo-gravimetric analysis of the rubber seed shell catalyst….............................170
4.8.2 XRF elemental analysis and basic property of the rubber seed shell catalyst….......171
4.8.3 XRD analysis of the rubber seed shell catalyst...........................................................172
4.8.4 SEM analysis of the rubber seed shell catalyst catalyst...............................................174
4.8.5 Surface properties of the rubber seed shell catalyst....................................................175
4.9 Biodiesel production from the extracted seed o………………………….....................180
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4.9.1 Characterization of the rubber seed oil biodiesel......................................................180
4.9.2 Reusability of the catalyst for biodiesel production..................................................182
4.10 Parametric effect and optimization of biodiesel production process variables..........183
4.10.1 Modeling and process variables optimization by RSM…………….......................183
4.10.2 Analysis of variance (ANOVA) for biodiesel production………...........................188
4.10.3 Parametric effects of interactive factors on biodiesel yield using RSM…................191
4.10.4 Optimization and interactive effects of process variables on biodiesel yield by ANN
model..................................................................................................................................193
4.10.5 Comparison of RSM and ANN models for the biodiesel production......................197
4.11 Performance and emissions analysis of test engine using biodiesel-diesel blends.......198
4.11.1 Air/Fuel ratio............................................................................................................198
4.11.2 Brake mean effective pressure..................................................................................199
4.11.3 Brake thermal efficiency..........................................................................................200
4.11.4 Brake specific fuel consumption..............................................................................201
4.11.5 Engine brake power..................................................................................................202
4.11.6 Engine torque...........................................................................................................203
4.11.7 Exhaust gas temperature...........................................................................................204
4.11.8 CO emissions...........................................................................................................205
4.11.9 CO2 emissions..........................................................................................................206
4.11.10 NOx emissions........................................................................................................207
4.11.11 Total hydrocarbons.................................................................................................208
4.11.12 Smoke opacity........................................................................................................209
CHAPTER 5: CONCLUSIONS AND RECOMMENDATIONS.......................................211
5.1 Conclusion....................................................................................................................211
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5.2 Recommendations.........................................................................................................212
5.3 Contributions to knowledge..........................................................................................213
REFERENCES...................................................................................................................214
APPENDIX.........................................................................................................................240
Appendix A.........................................................................................................................240
Appendix B.........................................................................................................................244
Appendix C.........................................................................................................................246
Appendix D.........................................................................................................................248
Appendix E.........................................................................................................................251
Appendix F..........................................................................................................................259
Appendix G.........................................................................................................................262
Appendix H.........................................................................................................................269
Appendix I…………………………………………..........................................................272
LIST OF FIGURES
Figure Page
1.1 Systematic approach employed in this research.................................................................6
2.1 Rubber trees plantation....................................................................................................11
2.2 Rubber seed.....................................................................................................................12
2.3 Top ten leading producers of rubber seeds in 2014..........................................................12
2.4 Overview of main biomass valorizations.........................................................................18
2.5 Multilayer structure of an ANN model............................................................................20
2.6 General flowchart of Genetic Algorithm.........................................................................21
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2.7 Flowchart of rubber seed oil processing..........................................................................30
2.8 Representation of the action of a catalyst.........................................................................47
2.9 Adsorption isotherm classified by Brunauer...................................................................50
2.10 A typical structure of triglyceride molecule...................................................................63
2.11 Scheme for stepwise transesterification of triglyceride to methyl esters........................66
2.12 Schematic diagram for a reciprocating engine cylinder.................................................79
2.13 P–v (a) and T–s (b) diagrams for the ideal Diesel cycle................................................82
3.1 Flowchart of rubber seed powder preparation………………………………………..102
3.2 Schematic of 3-3-1 developed ANN topology..............................................................111
3.3 Levenberg-Marquardt training flowchart for ANN model............................................113
3.4 Experimental setup for biodiesel-diesel blending analysis...........................................123
3.5 Experimental TD202 test engine for performance and combustion analyses located at
Petroleum Training Institute, Effurun, Nigeria....................................................................124
3.6 A schematic layout of TD202 diesel test engine............................................................128
4.1 Effects of kernel particle size on the rubber seed oil yield..............................................130
4.2 Gas chromatogram of the rubber seed oil with identified peaks.....................................141
4.3 FT-IR spectrum of the rubber seed oil...........................................................................143
4.4 1H NMR spectrum of the rubber seed oil.......................................................................147
4.5 13C NMR spectrum of the rubber seed oil......................................................................148
4.6 Overall process of oil degradation.................................................................................150
4.7 Acyclic polymer formations from oleic acid during thermal oxidation of oils...............151
4.8 ln (Ct/Co) vs. time (min) for iodine values at 100, 150, 200 and 250 oC........................152
4.9 Arrhenius plot for kinetics of thermo-oxidative degradation of rubber seed oil..........153
4.10 Correlation of predicted and experimental oil yields of rubber seed oil extraction......155
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4.11 (a) Interactive effects between solvent volume and rubber seed powder weight on oil
yield for RSM response surface (3D) plot...........................................................................162
4.11 (b) Interactive effects between extraction time and rubber seed powder weight on oil
yield for RSM response surface (3D) plot...........................................................................163
4.11 (c) Interactive effects between extraction time and solvent volume on oil yield for RSM
response surface (3D) plot...................................................................................................164
4.12 Correlation of predicted yield and experimental yield of RSO by ANN model...........165
4.13 (a) Interactive effects of rubber seed powder weight and solvent volume on oil yield for
ANN response surface (3D) and contour (2D) plots............................................................166
4.13 (b) Interactive effects of rubber seed powder weight and extraction time on oil yield for
ANN response surface (3D) and contour (2D) plots............................................................167
4.13 (c) Interactive effects of extraction time and solvent volume on oil yield for ANN
response surface (3D) and contour (2D) plots.....................................................................168
4.14 Percentage contribution of process variables to seed oil extraction via ANN model...169
4.15 TGA profile of the rubber seed shell (RSS) catalyst....................................................170
4.16 XRF analysis of the RSS: (a) raw and (b) calcined at 800 oC.......................................172
4.17 XRD diffractograms of the RSS: (a) raw, and (b) calcined at 800 oC...........................174
4.18 SEM images for (a) raw, and (b) calcined RSS catalyst at magnification 2450x..........175
4.19 Nitrogen adsorption/desorption isotherms for the raw and calcined RSS....................176
4.20 Effects of reuse of different catalyst loadings (2, 2.2, 2.5, 3, and 3.5 g) on biodiesel yield
(%) at optimum conditions..................................................................................................182
4.21 Effects of Ca2+ ion leaching from reused catalyst on biodiesel yield (%) at optimum
conditions............................................................................................................................183
4.22 Correlation of predicted vs. actual biodiesel yields (%) for the RSM model................186
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4.23 (a) RSM 3D plot for the interactive effect between reaction time and methanol/oil ratio
on biodiesel (RSOME) yield...............................................................................................191
4.23 (b) RSM 3D plot for the interactive effect between reaction time and catalyst amount
4.23 (c) RSM 3D plot for the interactive effect between methanol/oil ratio and catalyst
amount on biodiesel (RSOME) yield..................................................................................193
4.24 Correlation of predicted vs. actual biodiesel yields for ANN model............................194
4.25 ANN Surface plot for the interactive effect of methanol/oil ratio with reaction time on
biodiesel (RSOME) yield....................................................................................................195
4.26 ANN Surface plot for the interactive effect of catalyst amount with reaction time on
biodiesel (RSOME) yield....................................................................................................196
4.27 ANN Surface plot for the interactive effect of methanol/oil ratio with catalyst amount
4.28 Percentage contribution of process variables to biodiesel production via ANN
model..................................................................................................................................197
4.29 Variation of air/fuel ratio with speed for diesel-biodiesel blends.................................199
4.30 Variation of brake thermal efficiency with speed for diesel-biodiesel blends..............200
4.31 Variation of brake specific fuel consumption with speed for diesel-biodiesel
blends..................................................................................................................................201
4.32 Variation of engine power with speed for diesel-biodiesel blends...............................203
4.33 Variation of engine torque with speed for diesel-biodiesel blends...............................204
4.34 Variation of exhaust gas temperature with speed for diesel-biodiesel blends..............205
4.35 Variation of carbon monoxide emissions with speed for diesel-biodiesel blends........206
4.36 Variation of carbon dioxide emissions with speed for diesel-biodiesel blends............207
4.37 Variation of nitrogen oxides emissions with speed for diesel-biodiesel blends...........208
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4.38 Variation of total hydrocarbons emissions with speed for diesel-biodiesel blends......209
4.39 Variation of smoke opacity with speed for diesel-biodiesel blends.............................210
C.1 Preparation of milled kernel for oil extraction ..............................................................246
C.2 Oil soxhlet extractor used for the study.........................................................................246
C.3 Rotary evaporator used in the study..............................................................................247
C.4 Extracted rubber seed oil: (a) filtered, (b) crude............................................................247
E.1 Calcination of rubber seed shell (RSS) catalyst for biodiesel production.....................259
F.1 Esterified oil separation into two layers.........................................................................260
F.2 Gravity settling of biodiesel, catalyst and glycerol phases….........................................260
F.3 Processed rubber seed oil methyl ester (biodiesel) for analysis.....................................261
F.4 Regression line (−), upper (−), and lower (−) prediction intervals and experimental data
(∎) of oxidation stability determination for biodiesel without additive...............................261
G.1 13C NMR spectra of rubber seed oil (12–28 ppm) ........................................................265
G.2 13C NMR spectra of rubber seed oil (28.4–34.8 ppm) ..................................................266
G.3 13C NMR spectra of rubber seed oil (40–84 ppm) ........................................................266
G.4 13C NMR spectra of rubber seed oil (126.4–132.0 ppm) ..............................................267
G.5 13C NMR spectra of rubber seed oil (165–184 ppm) ....................................................267
13
G.6 Double bond peaks in the C NMR spectrum for pure oleic acid, linoleic acid, and
linolenic acid.......................................................................................................................268
H.1 Nitrogen adsorption/desorption log plot for calcined RSS............................................270
H.2 Nitrogen adsorption/desorption log plot for raw RSS...................................................270
H.3 BJH adsorption pore-size distribution log plot for calcined RSS..................................271
xxi
LIST OF TABLES
Table Page
2.1 Estimated annual rubber seed oil and biodiesel production capacity for sub-Saharan
Africa (SSA) countries in 2013.............................................................................................14
2.2 Typical levels of cellulose, hemicellulose, and lignin in biomass....................................17
2.3 Proximate analysis of rubber seed....................................................................................27
2.4 Amino acid profile of rubber seed...................................................................................28
2.5 Proximate analysis of RSS and RSK...............................................................................28
2.6 Ultimate analysis of RSS and RSK..................................................................................28
2.7 Extractives, holocellulose, hemicelluloses and cellulose contents of RSS and RSK.......29
2.8 Calorific value and oil yield of RSS and RSK..................................................................29
2.9 Physico-chemical properties of rubber seed oil................................................................35
2.10 Fatty acids profile of rubber seed oil..............................................................................36
2.11 Fatty acid compositions of selected non-edible oils (%)................................................37
2.12 Africa countries which import and export energy..........................................................42
2.13 SSA countries and their bioenergy policies....................................................................43
2.14: Comparison between physisorption and chemisorption processes................................49
2.15 Methods of viscosity reduction in vegetable oils for biodiesel production....................62
3.1 Experimental range and levels of independent process variables for seed oil extraction
via Box-Behnken design.....................................................................................................108
3.2 Experimental range and levels of independent process variables for biodiesel production
via central composite design...............................................................................................117
3.3 Technical specifications for TD 202 test diesel engine..................................................124
4.1 Physical characterization of rubber seed and the seed oil...............................................131
4.2 Physico-chemical properties and other characteristics of rubber seed oil......................139
xxii
4.3 Fatty acids profile of rubber seed oil..............................................................................140
4.4 Wavenumbers and their functional groups for FT-IR analysis of rubber seed oil..........144
4.5 1H NMR spectrum analysis of rubber seed oil...............................................................146
4.6 13C NMR analysis of carbon type present in the rubber seed oil.....................................148
4.7 Effect of heating on peroxide, iodine, and refractive index values of rubber seed oil.....149
4.8 Kinetic parameters for degradation of rubber seed oil...................................................153
4.9 Box–Behnken design for the rubber seed oil extraction process optimization by RSM and
ANN....................................................................................................................................156
4.10 Analysis of variance (ANOVA) for response surface quadratic model.......................159
4.11 RSM regression analysis for rubber seed oil extraction...............................................161
4.12 Summary report of N2 adsorption/desorption analysis for raw RSS............................178
4.13 Summary report of N2 adsorption/desorption analysis for calcined RSS (800 oC) ...179
4.14 Fuel properties of biodiesel from rubber seed oil.........................................................181
4.15 Central composite design for optimization of biodiesel production process by RSM and
ANN....................................................................................................................................185
4.16 RSM regression coefficients analysis for the oil biodiesel production.........................187
4.17 Analysis of variance (ANOVA) results for the fitted second-order polynomial
model..................................................................................................................................190
4.18 Properties of the test fuels............................................................................................198
D.1 Variation of oil yield with seed kernel particle size.......................................................249
E.1 Variation of peroxide, iodine, and refractive index values of rubber seed oil with
temperature and time...........................................................................................................258
F.1 Esterification parameters of rubber seed oil..................................................................259
G.1 Infrared group absorption frequencies..........................................................................262
G.2 Assignment of signals of 1H NMR spectra for vegetable oils (hazel nut and walnut)....265
xxiii
H.1 XRF spectroscopic elemental analysis of rubber seed shells catalyst...........................269
H.2 Biodiesel yields for fresh and reused catalyst loadings at optimum conditions.............271
I.1 Variation of engine speed with fuel and air parameters for B00 (diesel).........................273
I.2 Variation of engine speed with fuel and air parameters for B10.....................................273
I.6 Variation of engine speed with fuel and air parameters for B100 (biodiesel).................275
I.7 Variation of brake thermal efficiency with engine speed................................................276
I.8 Variation of brake specific fuel consumption with engine speed....................................276
I.9 Variation of engine brake power with engine speed.......................................................276
I.10 Variation of engine torque with engine speed...............................................................276
I.11 Variation of exhaust gas temperature with engine speed..............................................277
I.12 Variation of carbon monoxide emissions with engine speed........................................277
I.13 Variation of carbon dioxide emissions with engine speed............................................277
I.14 Variation of oxides of nitrogen emissions with engine speed.......................................277
I.15 Variation of total hydrocarbons emissions with engine speed......................................278
I.16 Variation of smoke opacity emissions with engine speed.............................................278
NOMENCLATURE
Description Symbol
Adsorbate molecular area Am
Adsorbed volume Va
Adsorptive energy En
Adsorption enthalpy change ∆Hads
xxiv
Adsorption entropy change ∆Sads
Air-box differential pressure ∆P
Avogadro's number N
Brake thermal efficiency ηth
Brunauer-Emmett-Teller constant C
Carbon dioxide, Carbon monoxide CO2, CO
Clearance volume Vc
Coefficient of discharge Cd
Compression ratio r
Concentration Ct, Co
Conference of the Parties COP
Connecting rod l
Crank angle θ
Crank radius α
Critical pressure, Critical temperature Pc, Tc
Cutoff ratio rc
Engine speed N
Exergy ai
Fuel f
Hectares, Hour ha, h
Internal energy, Velocity U
Irreversibility I
Langmuir constant b
Langmuir specific surface area SL
Mass m
xxv
Mass flowrate of air 𝒎̇𝒂
Minutes min
Molecular mass M
Monolayer volume Vm
Number of moles, variables, and order of reaction n
Orifice diameter d
Oxides of nitrogen NOx
Pressure P
Process actual variable X
Process coded variable x
Quantity of heat Q
Rate constant k
Saturation pressure Po
Specific heat at constant pressure Cp
Specific heat at constant volume Cv
Specific heat ratio (Cp/Cv) γ
Specific volume v
Standard deviation of data σ
Statistical thickness t
Temperature, Torque T
Time t
Universal gas constant R
Volume of biodiesel blends (%) Bxx
Work W
xxvi
CHAPTER 1: INTRODUCTION
1.1 Research background and motivation
Industrial advancement in recent times has accelerated the need for sustained energy
requirement across the globe. The depletion of non-renewable fossil materials (oil, gas, and
coal) that arises from their continued usage, their price instability, energy insecurity, and the
concern for the degraded environment stimulated global research for alternative sources of
energy (Aldhaidhawi et al., 2017; Onoji et al., 2016a). Renewable energies from biomass,
hydropower, solar, tidal waves, wind and geothermal have been proposed and considered as
cheap sources of sustainable energies (Dwivedi et al., 2013; Thanh et al., 2012). The biomass
source option, which appeared the cheapest or easiest to acquire will most certainly result to
fast economic and sustainable growth of most developing countries in Africa (Onoji et al.,
2016a; Thanh et al., 2012). Vegetable oils from biomass are seen as source materials for
renewable energy production. The suitability of vegetable oils as source of biodiesel production
has been reported in the literature by several researchers in recent times. Biodiesel is a mono-
alkyl fatty acid methyl ester (FAME) produced by the transesterification of vegetable oils,
animal fats and other sources of oils/fats with primary alcohols (methanol, in this study) in the
presence of suitable catalysts (homogeneous, heterogeneous, and enzymes, etc) (Roschat et al.,
2012; Guo et al., 2010).
The choice of biodiesel is based on its biodegradability, non-toxic, lower emissions, sulphur-
free, low levels of polycyclic aromatic hydrocarbons (PAHs) and n-PAHs (Mofijur et al., 2014;
Portet-Koltalo & Machour, 2013; Jaya & Ethirajulu, 2011; Kumar & Purushothaman, 2010).
In recent times, most of the biodiesel production routes are from edible oil plants such as palm
oil, soybean, rapeseed, sunflower, and these compete with food/pharmaceutical and cosmetic
uses, resulting to food-fuel crisis and high price of biodiesel generated thereof (Onoji et al.,
1
2016a; Ahmad et al., 2013; Asuquo et al., 2012; Ma & Hanna, 2012). To avert a food-fuel
crisis, non-edible vegetable oils considered as low-grade oils that are not suitable for food uses,
could be an attractive preference to edible oils for industrial applications (Dharma et al., 2016).
One of the few versatile bioenergy crops with non-edible oil that has attracted the attention of
researchers in recent times is the rubber tree (Hevea brasiliensis) (Ng et al., 2013).
Hevea brasiliensis is economically cultivated for the production of latex as a source of natural
rubber for the production of various rubber products in use globally, while the seeds are
underutilized (Takase et al., 2015; Atabani et al., 2013; Ng et al., 2013). However, the oil from
the seed is the second most valuable product after the latex (Banković-Ilić et al., 2012). With
the concept of sustainable development and the Paris Agreement on climate change (UNFCCC,
2015), the production of synthetic rubber would be reduced when the use of fossil materials is
phased out in the dawn of next century. The cultivation of rubber tree to generate latex for
natural rubber production, and the utilization of its seeds to produce non-edible oil for biodiesel
production will boost the economy of most Africa countries that are poverty-ridden.
Homogeneous base catalysts such as NaOH, KOH and methoxides of sodium and potassium
are most suitable for industrial transesterification of edible vegetable oils that are generally low
in free fatty acids (FFAs). However, associated problems such as difficulty in catalyst-products
separation, initial catalyst cost, soap formation, low-grade by-product glycerol, reactor
corrosion and large volume of washing water requirements induced further research for
environmental benign heterogeneous catalyst for biodiesel synthesis from non-edible oils
though high in FFAs (Roschat et al., 2012; Zabeti et al., 2009). In addition, the use of
homogeneous catalysts in transesterification of non-edible oils to biodiesel is hampered by the
high FFAs of the oils that react with the catalyst resulting to low biodiesel yield. Uprety et al.
2
(2016) reported that heterogeneous catalysts are easily separated from reaction mixtures
through simple filtration, and reused severally producing high-grade glycerol. Against this
background, this study investigated the conversion of non-edible rubber seed oil to biodiesel
over a catalyst derived from waste rubber seed shells (RSS). The results obtained from the
study are promising and it is expected that this will further reduce the cost of biodiesel produced
from rubber seed oil and make it more competitive to petro-diesel.
1.2 Hypothesis
 Industrial processes go faster to completion when homogeneous, heterogeneous, or
enzymes catalysts are employed;
 Homogeneous catalysts are not suitable for the transesterification of non-edible rubber
seed oil with high FFAs;
 Heterogeneous catalyst proposed in this research will attempt to solve the problems and
will provide a better product output when employed for the transesterification reaction.
 When reactions take place in solid-liquid-vapour phase, mass transfer limitations are
avoided, and the reaction may be enhanced if solid surface area becomes large;
 The structural and textural properties of the catalyst may offer insight to anticipated
behaviour.
1.3 Justification of the study
During the Climate Change Summit (COP 21) held in Paris, from November 30 to December
12, 2015 to address the threat posed to humanity from climate change, world leaders, Policy
makers, and scientists agreed that man is the major cause of climate change that results to
increased global warming. A universal climate change agreement termed 'Paris Agreement'
was reached and agreed that clean renewable energy sources would replace fossil materials for
3
energy generation in the dawn of next century (UNFCCC, 2015). The agreement will cause a
reduction in the production of synthetic rubber from petrochemicals derived from fossil
materials. The rubber tree (Hevea brasiliensis) from which natural rubber is sourced will play
a significant role in the future energy mix. The underutilized rubber seeds will provide non-
edible oil for biodiesel production to avert food-fuel crisis and enhance poverty-alleviation
programme especially in the third world countries. The rubber seed shells (RSS) generated
during oil extraction posed waste disposal problems to rubber seed oil millers. Synthesis of
solid catalyst from waste RSS for use in biodiesel production in this study will further reduce
the cost of biodiesel and make it more affordable.
Pursuant to government directives in 2005 for the diversification of Nigeria’s economy through
the mainstreaming of an Automotive Biomass Programme, the Nigerian National Petroleum
Corporation (NNPC) was mandated to create a conducive environment for the take-off of a
domestic bioenergy industry. The underlying objectives for government interest in a national
biofuel programme are revenue diversification, reduced dependence on imported refined
petroleum-derived products, improved agricultural productivity, job creation, meeting energy
needs, and environmental benefits (Ishola et al., 2013; Abila, 2012). The Nigeria biofuel policy
did not address the potential food-fuel conflicts that could arise from the use of food crops as
biofuel feedstock (Ohimain, 2013). In Nigeria, about 18 million hectares (ha) of land are
suitable for industrial cultivation of rubber trees in the southern region (Onoji et al., 2016a).
The complete life cycle and environmental benefits of rubber trees in Nigeria is well
investigated and defined compared to Jatropha curcas, a similar non-edible plant (Ishola et al.,
2013), but detailed study on the benefits of rubber tree as a versatile bioenergy crop is limited
as it was not mentioned as a plausible feedstock in the Nigeria's biofuels policy.
The outcomes of this research, as documented in this thesis, will encourage the continued
cultivation of rubber trees for latex production, and harvesting the seed to produce oil for
4
biodiesel synthesis. It will also serve as a pool of information for the relevant Government
Ministries, Departments, and Agencies that will serve as advocates for the implementation of
the National Biofuels Policy across Nigeria's business strata with respect to biodiesel
production from rubber seed oil and other African nations where rubber trees are cultivated.
1.4 Research aims and objectives
The main objectives of this research study were as follows:
 Extract, characterize, and determine the kinetics of thermo-oxidative degradation of
rubber seed oil;
 Develop a mathematical model, and optimize the extraction of rubber seed oil using the
developed model;
 Synthesize and characterize a solid catalyst from waste rubber seed shells for
transesterification of rubber seed oil to biodiesel;
 Develop a mathematical model, and optimize the biodiesel production from rubber seed
Oil using the developed model;
 Characterize the produced biodiesel and compare the properties with biodiesel
Standards (ASTM D 6751 and EN 14214);
 Study the internal combustion of diesel-biodiesel blends using a test engine;
 Analyse the level of pollutants and emissions arising from the use of diesel, biodiesel,
and diesel-biodiesel blends to ascertain their levels of environmental friendliness.
Figure 1.1 depicts the systematic approach employed in this research. The approach involves
catalyst synthesis from waste rubber seed shells (RSS) calcined at 800 oC based on thermo-
gravimetric analysis. The catalyst was characterized for structural and textural properties.
Rubber seed oil (RSO) extracted from rubber seeds was esterified with methanol using 6% v/v
sulphuric acid as catalyst. The esterified oil was then transesterified to biodiesel over a calcined
5
RSS as base catalyst. The biodiesel produced was blended with petro-diesel, and the blends
were analysed in TD202 internal combustion diesel test engine for performance and emissions
evaluation.
rubber seeds
oil extraction
process
rubber seed oil

(RSO)
esterification
6% v/v H2SO4 process
waste water
rubber seed
shells (RSS)
methanol esterified RSO
catalyst transesterification
synthesis RSS process high grade
furnace Cat. glycerol
operated
@ 800oC
(10 oC/min)
methanol biodiesel
internal
blending process exhaust gases
blend combustion
diesel s
TD 202 (for analysis)
diesel
test engine
Electrical energy
Figure 1.1: Systematic approach employed in this study
6
1.5 Thesis outline
The layout of the thesis is as follows:
This thesis investigated the conversion of non-edible and high free fatty acids rubber seed oil
to biodiesel over a catalyst synthesized from waste rubber seed shells. The following chapters
discuss the issues related to the synthesis and characterization of the catalyst, biodiesel
production and evaluation of the performance and emission profiles of diesel-biodiesel blends
using a diesel test engine.
Chapter 1 is the introductory chapter of the thesis and it provides information on the research
background and motivation, hypothesis, and justification of the study. The chapter further
discusses the aims and objectives, conceptual approach used to achieve the main goal of the
research, and finally the thesis outline.
Chapter 2 presents the literature review and background information on rubber tree (Hevea
brasiliensis). The chapter further highlights the benefits of biodiesel policies in sub-Saharan
Africa (SSA); rubber seed capacity in SSA; industrial applications of rubber seeds; modeling
and optimization in research. Others include oil extraction methods; kinetics of oil degradation;
transesterification methods; catalysis; optimization of oil extraction and biodiesel production;
and finally, the thermodynamics of the internal combustion of diesel-biodiesel blends for the
evaluation of engine performance and emission analysis.
Chapter 3 contains details of the research methodology, experimental methods, and analytical
procedures used in this research. The chapter presents materials and seed preparation; seed oil
extraction; characterization of seed oil; oil degradation kinetics and optimization of oil
extraction process. It also includes catalyst synthesis and characterization; biodiesel production
and characterization; modeling and optimization of biodiesel production process; and engine
performance and emission analysis of biodiesel-diesel blends.
7
Chapter 4 presents the experimental results and discussion on oil extraction, catalyst synthesis,
biodiesel production, and their analyses. The chapter also discusses the performance of the
blends in the internal compression ignition engine, and emission analysis. Results of previous
researchers were compared with the findings of this research.
Chapter 5 concludes this research by providing a summary of the main findings,
recommendations for future work, and contributions to knowledge.
8
CHAPTER 2: LITERATURE REVIEW
2.0 Introduction
The literature review presented in this chapter is a part of a review article, and experimental
work on this research published in Energy Conversion and Management, 2016 (issue 110, pp.
125-134), and Energy & Fuels, 2016 (issue 30, number 12, pp. 10555-10567). The cover and
abstract pages of the published papers are provided in Appendix A.
2.1 The rubber tree
The rubber tree (Hevea brasiliensis) shown in Figure 2.1, also known as the Para rubber
belongs to the plant family Euphorbiaceae and it is the most economically important member
of the genus Hevea that originated from Amazon region of Brazil in South America (Onoji et
al., 2016a; Reshad et al., 2015; Kittigowittana et al., 2013). Hevea exhibits morphological
variability, with ten species (H. brasiliensis, H. benthamiana, H. camorun, H. guianensis, H.
microphylla, H. nitida, H. pauciflora, H. rigidifolia, H. camargoana, and H. spruceana)
identified that range from large forest trees to shrubs with latex in their parts (Venkatachalam
et al., 2013). Hevea brasiliensis produces about 99% of the world's natural rubber (Aravind et
al., 2015; Atabani et al., 2013). It was commercialized for latex production to boost the
economy of Brazil in the 1800s. Several researchers investigated the properties of rubber latex
(natural rubber) as it was an important product during the industrial revolution era. Notable
among them was Charles Mariѐ de La Condamine who brought rubber seeds to Acadèmic
Royale des Sciences of France in 1736 and published the first scientific properties of rubber
(Charles, 2002).
Joseph Priestley, an English scientist discovered in 1770 the erasing nature of rubber on pencil
mark on papers, earning it the name ‘rubber’. Vulcanization of rubber with sulphur to improve
9
its elastic and resistance properties was discovered by Charles Goodyear and Hancock in 1839
(Charles, 2002).
In 1876, Sir Henry Wickham, a British explorer took 70,000-Para rubber tree seeds out of
Brazil to the Kew botanical gardens in London, England for research where different resistant
varieties of the seeds were developed. The developed species were sent to the British colonies
of Southeast Asia countries of Malaysia, Sri Lanka, and Singapore in 1876 for planting (Reshad
et al., 2015). The most successful application of latex rubber was achieved in the 1880s when
rubber was found to be the basic material for pneumatic tyres for automotive industry.
Obviously, the well-organized plantations in the Southeast Asia countries resulted in a
significant increase in productivity. The competition from Southeast Asia brought down the
decades of rubber latex boom to an end for much of northern Brazil in the early 1900s. In the
later part of the 19th century, Indonesia, Thailand, Malaysia, China, India, and Vietnam joined
the league of natural rubber producers. Rubber seed (Figure 2.2) was introduced into Nigeria
in 1895 from the Kews botanical gardens in London, and the first rubber plantation established
at Sapele, Delta State in 1903 (Omo-Ikerodah et al., 2009). Rubber tree has 6-9 years of
gestation period before tapping for latex, though the seeds are available between 4-6 years
(Onoji et al., 2016a; Eka et al., 2010). A recent statistical analysis put the global harvested areas
of rubber trees plantations at 11,096,400 ha (FAOSTAT, 2014), thus eliminating competition
for land space with vegetable crops (Zhu et al., 2014). Rubber trees have been reported to grow
to a height of 34 to 40 m in the wild (Takase et al., 2015; Ashraful et al., 2014; Kumar &
Sharma, 2011). It requires warm humid climate with temperatures ranging from 20 to 35 oC, a
fairly-distributed rainfall of about 1800 to 2000 mm throughout the year (Ashraful et al., 2014;
Omo-Ikerodah et al., 2009) and growth is most rapid at altitudes below 200 m (Reshad et al.,
2015). The analysis depicted in Figure 2.3 identified Southeast Asia countries of Indonesia,
Thailand and Malaysia as major areas where rubber trees are cultivated; Nigeria and Côte
10
d'Ivoire are Africa dominant. Other Africa countries where rubber trees are cultivated include
Democratic Republic of Congo, Cameroon, Republic of Congo, Central African Republic,
Ghana, Liberia, Gabon and Guinea (Onoji et al., 2016a). Seeds from rubber tree considered as
wastes over the years except for seed propagations (Kittigowittana et al., 2013), is the second
most valuable product after the latex as source of non-edible oil (Banković-Ilić et al., 2012).
Researchers in Asia (Zhu et al., 2014) investigated the factors influencing rubber seed yield
through in-situ counting of rubber seeds in Xishuangbanna, China, and reported age, size and
clonal types as dominant. Other factors include powdering mildew disease, abnormal leaf
disease, phytophora disease, and weather (Iyayi et al., 2008). A typical rubber plantation has
about 350-500 trees/ha with each tree yielding about 800 seeds and an average of 70 to 500 kg
seed/ha on annual basis (Abdulkadir et al., 2014; Ebewele et al., 2010a; Eka et al., 2010).
Figure 2.1: Rubber trees plantation (Adapted from Onoji et al., 2016a)
11
Figure 2.2: Rubber seed (Adapted from Onoji et al., 2016a)
Cotê d'Ivoire
Philippines 2%
2%
Burma Others
2% 7%
Nigeria
3%
India
Indonesia
4%
33%
Vietnam
5%
China
6%
Malaysia
10%
Thailand
26%
Figure 2.3: Top ten leading producers of rubber seeds in 2014 (Adapted from FAOSTAT,
2014)
12
2.2 Rubber seed capacity in sub-Saharan Africa
In consideration of the nature of non-edible oil plants such as rubber, jatropha, castor, linseed,
moringa oleifera, cotton, neem, and tobacco for energy production to avert food-fuel crisis,
rubber tree has fewer investigation on its potential in many sub-Saharan Africa (SSA) countries
where it is cultivated for latex production. Onoji et al. (2016a) provided a holistic comparative
data relevant to rubber seed as a significant source route of biodiesel production for the
sustainable development of SSA countries. Using statistical data from Food and Agriculture
Organization (FAO) of the United Nations for 2013, Onoji et al. (2016a) reported the hectares
(ha) of rubber plantations cultivated in SSA as follows: Nigeria (345,000 ha), Côte d'Voire
(135,000 ha), Liberia (76,000 ha), and Cameroon (55,000 ha). Others are Ghana (26,800 ha),
Gabon (15,000 ha), Guinea (10,800 ha), Democratic Republic of Congo (50,500 ha), Republic
of Congo (2,400 ha) and Central African Republic (CAR) (1,250 ha). With a plantation density
of 350 trees/ha, 150 kg/ha and a projected 717,750 ha, the researchers reported that SSA could
produce 17,947 ton (RSO) and 16,691 ton (biodiesel). Table 2.1 presents the details of their
findings. The cultivation of rubber trees will sustain the production of rubber products from
latex. It will also provide seed oils for biodiesel that will create additional financial benefits to
the plantation farmers and reinvigorates the economies of the local communities in sub-Saharan
Africa.
13
Table 2.1: Estimated annual rubber seed oil and biodiesel production capacity for SSA countries in 2013 (Onoji et al., 2016a)
Country Harvested Trees/ha Trees Seed (ton/ha), Seed (ton) RSO (ton) Biodiesel (ton)
area (ha), (million) B A×B = RStotal = RStotal × 0.1667 = RSO× 0.93
A
Nigeria 345,000 350 120.75 0.15 51,750 8,626.725 8,022.854
Côte d'Voire 135,000 350 47.25 0.15 20,250 3,375.675 3,139.378
Liberia 76,000 350 26.6 0.15 11,400 1,900.380 1,767.353
Cameroon 55,000 350 19.25 0.15 8,250 1,375.275 1,279.006
D.R. Congo 50,500 350 17.675 0.15 7,575 1,262.753 1,174.360
Ghana 26,800 350 9.38 0.15 4,020 670.134 623.225
Gabon 15,000 350 5.25 0.15 2,250 375.075 348.820
Guinea 10,800 350 3.78 0.15 1,620 270.054 251.150
Rep. Congo 2,400 350 0.84 0.15 360 60.012 55.811
CAR 1,250 350 0.4375 0.15 187.5 31.256 29.068
Total 717,750 251.2125 107,662.5 17,947.339 16,691.025
14
2.3 Rubber seed collection and processing
The matured rubber seeds dehisce from the trees with a loud sound similar to that of a military
rifle during the short period of dry season between the months of July and October in Nigeria
(Onoji et al., 2016a), although it varies from one geographical region to another (Iyayi et al.,
2008; Igeleke & Omorusi, 2007). Overgrown weeds make seed collection a difficult task as
most seeds hide under the cover of weeds. During the period of rainfall, the seed pods will not
dehisce to release the seeds as they pick up moisture that facilitates its deterioration (Iyayi et
al., 2008). Sunshine is therefore a critical factor required to dehisce the seeds for a good yield.
Igeleke & Omorusi (2007) listed excessive moisture, fungi, and pests such as insects and
rodents as major causes of post-harvest deterioration of rubber seeds, and suggested that the
seeds be dried to a moisture level of 7% or less, before storage. Aniamaka & Uriah (1990)
suggested that the seeds should be collected as soon as they dehisce from the trees, and
collection period repeated at least every fourth day to avoid deterioration. Seed that is not
properly stored after harvesting could be affected by chemical reactions that may increase the
free fatty acids content of the seed and reduce its potency for biofuels production. Drying of
seeds at 70 oC or less will halt biochemical processes and reduce cyanide content; chemical
treatment with 2% primiphos methyl and aluminum phosphide, and storage in polypropylene
bags were suggested methods to extend the shelf life of post-harvested seeds in bulk storage
(Igeleke & Omorusi, 2007). The seeds enclosed in a pod of 3-ellipsoidal capsules are mottled
brown with glossy surfaces. They are oval-shaped, 2–5 cm long and average weight of 2–6 g
(Onoji et al., 2016a).
2.4 Biomass valorization processes
Biomass covers organic matter that are traceable to plant or animal origin, either as raw (wood,
energy crops, and agricultural residues, etc.) or processed (effluents, food processing residues,
15
and green wastes, etc.). Biomass materials are generally composed of cellulose, hemicellulose,
lignin, lipids, proteins, simple sugars, and starches, depending on its origins (Claude et al.,
2016). Among these compounds, cellulose, hemicellulose, and lignin are the three main
constituents as shown in Table 2.2 (Zhang et al., 2010). The renewable aspect that is attributed
to biomass can be explained by the carbon cycle: the carbon dioxide emitted during its use is
compensated for by the carbon stock accumulated during its growing stage. Therefore, the
biomass can only be considered as a clean and renewable energy source if obtained in a
sustainable manner (Kumar et al., 2009). Bioenergy is a term that refers to all the processes
whether industrial or not, that can produce energy from biomass. A general view of the
worldwide energy consumption in 2013 depicts renewable energy accounting for about 19%
(Claude et al., 2016). Biomass can be converted into energy or byproducts via versatile
transformation technologies such as physico-chemical or thermo-chemical as shown in Figure
2.4. It is expected that at the dawn of the 22nd century when the use of fossil fuels would be
limited, biodiesel that currently accounts for 0.15% of the share of renewable energy will
become a major source of energy from biomass.
16
Table 2.2: Typical levels of cellulose, hemicellulose, and lignin in biomass (Zhang et al.,
2010)
Component Dry weight (%) Description
Cellulose 40–60 A high-molecular weight (106 or more) linear chain of

glucose linked by β-glycosidic linkage. This chain is stable
and resistant to chemical attack.
Hemicellulose 20–40 Consists of short, highly branched chains of sugars (five-

carbon sugars such as σ-xylose and ι-galactose, and six-
carbon sugars such as σ-galactose, σ-glucose, and σ-
mannose) and aromic acid. Lower molecular weight than
cellulose. Relatively easy to be hydrolysed into basic sugars.
Lignin 10–25 A biopolymer rich in three-dimensional, highly branched

polyphenolic constituents that provide structural integrity to
plants. Amorphous with no exact structure. More difficult to
be dehydrated than cellulose and hemicelluloses.
17
Thermochemical
processes
Heat
Combustion Combustion
Electricity
Biomass Bio-oils
Pyrolysis Bio-chars
Reforming Bio-fuels
- Energy crops
(biodiesel, bio-
(rubber, jatropha,
cotton ...) Gasification Syngas ethanol)
- Agricultural and Bio-materials

urban wastes Physicochemical
(bio-based
transformations
polymers)
- Food and industrial
processing residues
Oil extraction
Syngas
Fermentation
Heat
Methanization Combustion
Reforming
Electricity
Figure 2.4: Overview of main biomass valorizations (Adapted and modified from Claude
et al., 2016)
2.5 Modeling and optimization approach to industrial research
Modeling and optimization of process variables to increase the efficiency of a process is one
of the most important stages in a biochemical process (Baş & Boyaci, 2007a). The traditional
method of optimization is expensive, complex and time consuming due to large amount of
experiments required. It considers one variable at a time, while other factors are kept constant
and the interactive effects of the variables on the response of the system are neglected (Ma et
al., 2016; Kostić et al., 2013; Baş & Boyaci, 2007a). The disadvantages of the traditional
method prompted researchers to look for alternatives that will describe the entire system
comprehensively. In the present day, industrial research uses response surface methodology
18
(RSM), and artificial intelligence tools such as artificial neural network (ANN) and genetic
algorithm (GA), fuzzy logic (FL), ant algorithm (AA) and particle swarm optimization (PSO)
to effectively optimize a process (Gueguim Kana et al., 2012).
Response surface methodology (RSM) is a collection of statistical and mathematical techniques
useful for developing, improving, and optimizing processes in which responses of interest are
influenced by several process variables and the objective is to optimize these responses (Kostić
et al., 2013; Baş & Boyaci, 2007b). RSM defines the effect of these variables, alone and/or
their interactive effects on the response of the process. RSM offers a large amount of
information from a small number of experiments to explain the behavior of the system (Baş &
Boyaci, 2007b). RSM generates a second-order polynomial predictive model that relates the
response of a process to the independent variables considered. On the other hand, ANN is a
modeling tool inspired by biological neural networks which consists of interconnected group
of artificial neurons (input, hidden and output), and processes information using a connectionist
approach to computation (Kostić et al., 2013). In an ANN, a neuron sums the weighted inputs
from several connections and then applies a transfer function (e.g. sigmoid) to the sum. The
resulting value is propagated through outgoing connections to other neurons. Figure 2.5 depicts
a typical multilayer structure of an ANN model (Gueguim Kana et al., 2012). The ANN model
describes processes that exhibit nonlinearities better than RSM, since it does not require
theoretical knowledge or experience during the training process (Zahedi & Azarpour, 2011). It
has the inherent ability to learn and generalize data by producing reasonable outputs, for inputs
that were not encountered during the training process, and update easily when new set of data
are submitted to it. The limitation in process optimization by ANN model is overcome by
coupling a cost-effective and less time-consuming GA as described in Figure 2.6 (Chuahy &
Kokjohn, 2017). Design of experiments (DOEs) such as central composite design (CCD), Box–
19
Behnken design (BBD), and Taguchi experimental design (TED) employing RSM and ANN–
GA optimization techniques are commercially available for research. Dhawane et al. (2015)
employed CCD approach using RSM to study the influence of process variables (methanol/oil
ratio, catalyst loading, temperature) at a reaction time of 1 h on the yield of biodiesel produced
from Hevea brasiliensis oil. They reported an optimal yield of 89.3% at the following
conditions: methanol/oil ratio (15:1), catalyst loading (3.5 wt.%), and reaction temperature (60
o
C). A BBD-RSM was used by Dwivedi & Sharma (2015) to study the optimization of biodiesel
synthesized from pongamia oil and reported a yield of 98.4% at optimal process conditions of
MeOH/oil ratio (11.06:1), KOH catalyst loading (1.43% w/w), reaction time (81.43 min), and
reaction temperature (56.6 oC). Taguchi optimization method was used to investigate the
influence of process variables (MeOH/oil ratio, reaction temperature, and catalyst amount) at
constant reaction time (3 h) on biodiesel yield from Kapok (Ceiba pentandra) oil (Norazahar
et al., 2012). They reported 98% maximum yield at conditions of 55 oC, 2 wt % KOH catalyst,
and 8:1 methanol/oil ratio.
Hidden layer
Output layer
Input layer
Input variable 1
Input variable 2
Output
Input variable 3
Input variable 4
Figure 2.5: Multilayer structure of an ANN model (Adapted and modified from Gueguim
Kana et al., 2012)
20
Initial DOE
Design-Expert® Software
Factor Coding: Actual
% RSO
Design points above predicted value
Design points below predicted value
43
44.1124
28.64
50
X1 = A: Rubber seed powder weight (g)
X2 = B: Solvent volume (ml) 45
Actual Factor
R S O
C: Extraction time (min) = 50.00 40
35
%
30
25
200.00
40.00
212.50 45.00
225.00 50.00
237.50 55.00
Solvent volume (ml) Rubber seed powder weight (g)
250.00 60.00
1st response surface
Search surface for optimal using GA
Restrict DOE space

based on results
Design-Expert® Software
Factor Coding: Actual
% RSO
Design points above predicted value
Design points below predicted value
43
44.1124
28.64
50
X1 = A: Rubber seed powder weight (g)
X2 = B: Solvent volume (ml) 45
Actual Factor
R S O
C: Extraction time (min) = 50.00 40
35
%
30
25
200.00
40.00
212.50 45.00
225.00 50.00
237.50 55.00
250.00 60.00
Refined response surface
No Yes
Is optimal Search surface with GA and
in DOE within find optimal point
interval?
Figure 2.6: General flowchart of Genetic Algorithm (Adapted and modified from Chuahy
& Kokjohn, 2017)
2.6 Qualitative and quantitative analytical procedures
Various spectroscopy methods of analysis have been developed to quantify and/ or quantify
the relative proportions of different materials present in compounds such as lipids and solids
(Guillèn & Ruiz, 2003). These methods are relatively fast, and provide great deal of
information on the material under consideration. Some of the spectroscopy methods include
Fourier transform infrared and scanning electron microscopy. Others include Brunauer-
Emmett-Teller analysis, nuclear magnetic resonance, gas chromatography-mass spectroscopy,
21
x-ray diffraction, and x-ray fluorescence. These methods of analyses and information
obtainable from them are discussed below.
2.6.1 Thermogravimetric analysis (TGA)
The application of thermal techniques of analysis has gained much attractiveness in recent
years. Thermal techniques of investigation are methods used to characterize a system, an
element of a compound (Coats & Redfern, 1963). Thermogravimetry analysis has received
immense patronage in the understanding of solid fuel substrate degradation to release energy
(Islam et al., 2016). The TGA traces the thermal degradation patterns of fresh biomass, char
and hydro-char under air and inert environment for subsequent kinetic studies (Molintas &
Gupta, 2011). The patterns revealed the response of heating rates, the inherent biomass
properties and severity that define the char combustion profiles in the form of thermographs
(Ceylan & Goldfarb, 2015). The degradation of biomass by pyrolysis occurs over wide
temperature ranges. For instance, holocellulose was reported to decompose between 200 and
380 oC, and lignin component degrades over wide temperatures (180–600 oC) to char
(Slopiecka et al., 2012). A typical TGA studies reveal three stages of differential weight loss
of biomass combustion that include dehydration, devolatilization and char oxidation (Islam et
al., 2016). The two leading methods include; differential thermal analysis and
thermogravimetric analysis, where changes in the system weight are measured as a function of
temperature (Coats & Redfern, 1963).
2.6.2 Fourier transform infrared spectroscopy (FT-IR)
One of the most common spectroscopic techniques applied by organic and inorganic chemists
is the Fourier infrared spectroscopy. FT-IR is used to study surface chemistry of materials
or substance and equipped with the ability of conveying information about the
22
molecules in a specimen with their respective concentrations (Smith, 2011), and where
all infrared frequencies in a specimen are detected simultaneously (Bohre, 2013). FT-
IR as an analytical technique has been widely used to monitor the quality of biodiesel/diesel
blends, including checking for fuel adulteration (Valente et al., 2016). It has been reported for
use in the analysis of free fatty acids (Ismail et al., 1993), anisidine determination (Man &
Setiowaty, 1999), and monitoring of the transesterification of oils with methanol to biodiesel
(Knothe, 1999). Infrared spectroscopic analysis is also used to identify the chemical
functional groups present in a specimen undergoing analysis (Bohre, 2013).
2.6.3 Scanning electron microscopy (SEM)
Scanning electron microscopy is a technique used to investigate morphology of a
designated sample by scanning with a beam of electron (Khan, 2014). Interactions
between electrons and atoms in a sample creates signals that are detected, and convey
information about the sample’s composition, morphology and surface topology. The
sample to be analysed should be conductive (Hosmani, 2014). A non-conductive
material to be analysed is usually coated with a conductive material such as gold,
gold/palladium alloy, or platinum prior to analysis.
2.6.4 Brunauer- Emmett-Teller (BET) Analysis
The Brunauer-Emmett-Teller explains the theory behind the physical adsorption of gas
molecules on a solid surface. It serves as a basis for an analytical technique to measure
the specific area of a solid and other textural properties such as pore size and pore
volume that play important role in its catalytic behaviour (Lowell et al., 2004). Since
the surface area of a solid cannot be calculated directly from particle size information,
23
a method to do this is to determine its surface area at an atomic level. The amount of
gas adsorbed is a function of the total amount of exposed surface. It is also a function
of temperature, gas pressure and the strength of interaction between gas and solid
(Lowell et al., 2004). Nitrogen gas is commonly used for BET analysis because of high
purity, availability, and relatively strong interaction with most solid surfaces.
2.6.5 Nuclear magnetic resonance (NMR)
Proton (1H) and carbon-13 (13C) NMR spectroscopy is a technique that is useful to determine
the proportion of different acyl groups present in oils and fats, and other liquids in a very short
time (Onoji et al., 2016b). The area of the signals of the 1H NMR spectra is proportional to the
number of hydrogen atoms that produce the signals. This method has many advantages in
relation to the classical methods because it does not involve chemical modification of the
sample.
2.6.6 Gas chromatography-mass spectroscopy (GC-MS)
Gas chromatography is a process of separating component (s) from the given sample by using
a gaseous mobile phase. It involves a sample being vapourized and injected onto the head of
the chromatographic column (Karger et al., 1973). The sample is transported through the
column by the flow of inert gas (Helium or nitrogen) or hydrogen gas. The components are
recorded as a sequence of peaks as they leave the column. The peaks can be read and analysed
to determine the exact components of the mixture. The components are recorded as a sequence
of peaks as they leave the column. The peaks can be read and analysed to determine the exact
components of the mixture (Skooge at al., 2007). The number of peaks determines the number
of components in a sample. The amount of a given component in a sample is determined by
the area under the peaks. The identity of components can be determined by the given retention
24
times. Detecting the mass of the individual compound allows for conclusive of the sample
(Willard et al., 1981). This is confirmed by the mass spectrometer coupled to it to obtain the
compound’s molecular weight.
2.6.7 X-ray diffraction and X-ray fluorescence of solid materials
The powder X-ray diffraction is a non-destructive technique used to identify crystalline phases
and orientation of materials. It determines the structural properties and atomic
orientation/arrangement of the material. The diffractometer will create the IRD pattern of the
sample, measure d- spacing and obtain integrated intensities. The data are compared with
known standards in the Joint Committee on Powder Diffraction Standards (JCPDS) site, which
are for random orientations (Cullity, 1978).
XRF is a non-destructive technique used for the determination of elemental compositions of a
material. An X-ray source is used to irradiate the sample and to cause the elements in the sample
to emit (or fluoresce) their characteristics X-rays. A detector system (Wavelength dispersive)
is used to measure the position and intensity of peaks of the emitted X-rays for qualitative and
quantitative measurements of the elements and their amounts.
2.7 Rubber seed analysis
Eka et al. (2010) analysed rubber seed to determine its potential use as proteins, fats,
carbohydrate and amino acids as food supplements for livestock. They reported that well
processed rubber seed could be used as food claiming that good storage and heat treatment can
reduce the levels of poisonous hydrogen cyanide present in the seed. The results of the
proximate analysis and amino acids profile of rubber seed are presented in Table 2.3 and Table
2.4, respectively. The use of rubber seed shell (RSS) and rubber seed kernel (RSK) as source
materials for biofuel has been reported in literature. Hassan et al. (2014) investigated RSS and
25
RSK before oil extraction as raw materials for bio-oil production. They determined their
proximate (Table 2.5) and ultimate (Table 2.6) compositions, extractives, cellulose,
holocellulose and hemicelluloses content (Table 2.7) and, calorific value and oil yield (Table
2.8). The ultimate analysis from their report shows that carbon and oxygen are the major
components of RSS and RSK while other elements are in minority. The proximate analysis
indicates that volatile matters in both samples are a major component. High amount of volatile
matter indicates that the material could liquefy easily. The knowledge of the number of
extractives (Waxes, fats, resins, gum, sugars, starches, sterols, flavonoids, etc.) helps to
estimate exact amount of fermentable sugar present in biomass, and should be extracted before
processing the lignocelluloses material as a biofuel feedstock (Sasmal et al., 2012). The report
also shows that cellulose contents of RSS and RSK are significantly different. Kim et al. (2012)
reported that cellulose content of approximately 40% would be useful for biofuel production.
From the analysis presented by Hassan et al. (2014), RSK is a more suitable material for biofuel
production than RSS. The results presented in Table 2.8 shows that the calorific value of both
samples is in the range 23–28 MJ/kg, and the highest oil yield of 33.1% was obtained from
RSK. The TGA results presented show that major degradation of RSS and RSK was observed
at 300 and 350 oC, respectively. The differential thermo-gravimetric analysis (DTG) showed
two major weight losses for both samples. The first major loss occurred within 250–350 oC and
the second around 400 oC. Weight losses resulting from hemicelluloses and cellulose occurred
at the region between 250–350 oC, while the lignin degradation starts at 500 oC. Sun & Jiang
(2010) investigated the use of RSS as a raw material for the production of activated carbon by
the physical activation with steam. Their results of the proximate analysis (Table 2.5) obtained
for RSS were very close to those reported by Hassan et al. (2014). Other results presented by
Sun & Jiang (2010) show that RSS is a good precursor for activated carbon. The optimal
activation conditions, reported are pyrolyzed temperature (880 oC), steam flowrate (6 kg/h),
26
and residence time (60 min). The characteristics of the activated carbon from RSS with a yield
(30.5%) reported are specific surface area (SBET) 948 m2/g, total volume (0.988 m2/kg), iodine
number of adsorbent (qiodine) 1.326 g/g, amount of methylene blue adsorption of adsorbent (9
mb) 265 mg/g, and hardness 94.7%. The results of TGA show two stages of decomposition as
follows: stage one (273–385 oC) and stage two (385–800 oC). Little weight loss was observed
at temperature below 270 oC because the rubber seed had been dried under 105 oC for 3 h. The
TGA results from both researchers are very similar as presented above. The DSC analysis
presented by Sun & Jiang (2010) shows a little drop at a temperature of 100 oC, because the
sample needs heat to evaporate the remaining water. The reported decomposition temperatures
for hemicelluloses and cellulose are 180 and 240 oC, respectively. When temperature was about
320 oC, DSC arrived at valley, where hemicellulose and cellulose decomposed and produced
abundant organic compounds (wood tar, ketone and methanol) which would vapourized by
adsorbing large heat. At 500 oC, DSC curves climbed up steeply and reached at a peak, because
at this step lignin pyrolyzed and emitted abundant heat. At 800 oC, DSC curve reached a base
line, pyrolysis reaction was over and the residue reported as graphite carbon and ash (Sun &
Jiang, 2010).
Table 2.3: Proximate analysis of rubber seed (Eka et al., 2010)
Parameter Value
Moisture, % 3.99 ± 0.01
Protein, g/100g 17.41 ± 0.01
Fat, g/100g 68.53 ± 0.04
Ash, g/100g 3.08 ± 0.01
Total Carbohydrate, % (by difference) 6.99
27
Table 2.4: Amino acid profile of rubber seed (Eka et al., 2010)
Non-essential amino acids (g/100g protein) Essential amino acids (g/100g protein)
Aspartic acid 11.18 ± 1.57 Threonine 3.72 ± 0.42
Serine 5.89 ± 0.38 Valine 7.08 ± 0.27
Glutamic acid 16.13 ± 0.34 Methionine 1.37 ± 0.31
Glycine 5.14 ± 0.00 Lysine 4.26 ± 0.41
Histidine 2.95 ± 0.25 Isoleucine 3.28 ± 0.04
Arginine 12.45 ± 0.19 Leucine 6.81 ± 0.08
Alanine 4.71 ± 0.15 Phenylalanine 4.88 ± 0.46
Proline 6.77 ± 0.02
Cysteine 0.78 ± 0.79
Tyrosine 2.99 ± 0.25
Table 2.5: Proximate analysis of RSS and RSK (Hassan et al., 2014; a Sung & Jiang, 2010)
Biomass Moisture Ash Volatile mater Fixed carbon
RSS 14.3, 14.37a 0.1, 0.17a 71.7, 71.76a 13.9, 13.97a
RSK 4.3 0.2 89.4 6.1
Table 2.6: Ultimate analysis of RSS and RSK (Hassan et al., 2014)
Biomass C H N S O*
RSS 48.8 5.9 1.5 0.1 43.7
RSK 64.5 8.2 3.6 0.3 23.4
28
Table 2.7: Extractives, holocellulose, hemicelluloses and cellulose contents of RSS and
RSK (Hassan et al., 2014)

*
Biomass Extractives Holocellulose Hemicelluloses Cellulose
RSS 7.8 92.2 66.4 25.8
RSK 3.6 96.4 26.9 69.5
*calculated by difference
Table 2.8: Calorific value and oil yield of RSS and RSK (Hassan et al., 2014)
Calorific value (MJ/kg) Oil yield (%)

Biomass
RSS 23.9 8.7
RSK 27.5 33.1
2.8 Rubber seed oil extraction methods
Industrially, several methods are employed for oil extraction such as mechanical (hydraulic
and screw press), solvent extraction, enzymatic, aqueous, supercritical fluid extraction, and
their combinations (Onoji et al., 2016b). Mechanical type of extraction is widely used and well
adapted to rural communities with moderate initial and operating costs, but oil yield is low
(Subrotoet al., 2015; Willems et al., 2008; Olajide et al., 2007). Modeling and optimizing the
extraction process variables is paramount to obtaining a higher oil yield. Such optimized
parameters could provide vital information to researchers and industrialists. Figure 2.7 depicts
a typical flowchart for rubber seed oil processing with a combination of mechanical and
chemical methods. The seeds are dried, crushed, and milled to reduce particle size. Milled seed
(meal) was conditioned with scorching gas in a heated rotary dryer for 10–20 min at 60–70 oC
(Iyayi et al., 2008). It was then introduced into a mechanical screw press to recover rubber seed
29
oil, cake and foots (wastes). Rubber seed oil was recovered from the foots using a filtration
unit and stored for further use. More rubber seed oil was further extracted from the oily cake
in a solvent extraction unit using n-hexane. The cake was stored in a storage unit, and oil-
hexane mixture vacuum evaporated to recover the oil, while n-hexane solvent recycled.
Seed storage Kernel

Drying unit Crushing storage unit
unit
unit
Solvent Conditioning Milling Seed shell

tank unit unit
Foots
oily oil +
cake foots Filtration Rubber seed oil Rubber seed oil
Cake unit Screw
Solvent unit storage unit
press unit
extraction unit
Rubber seed oil

Rotary
oil + solvent evaporator
Recovered solvent
Figure 2.7: Flowchart of rubber seed oil processing (Adapted from Onoji et al., 2016a)
2.8.1 Conventional extraction method (Mechanical and chemical)
Conventional method uses mechanical and chemical means to extract the oil. The mechanical
type (mainly hydraulic and screw press) is relatively inexpensive after the initial capital costs
(Onoji et al., 2016a; Li et al., 2013). Quality of the oil is high, but it has low yield compared to
other extraction methods (Ebewele et al., 2010a). Mechanical screw press is relatively
inefficient because it leaves 8–14% of the available oil in the de-oiled cake (Ali & Watson,
2014). Singh & Bargale (2000) recommended the use of double-stage compression expellers
to enhance oil recovery. With increased pressure and heated screw press head, oil could easily
be extracted from pre-treated seeds (Ebewele et al., 2010a; Zheng et al., 2003). The chemical
method is widely used in the laboratory using n-hexane or other suitable organic solvents as
30
extractive media. Co-extraction of undesirable components in the oil results to low quality.
Boiling point of solvent, solvent/seed ratio, seed size, moisture content, drying and extraction
time are some of the parameters that affect the yield (Onoji et al., 2016b). Ebewele et al. (2010a)
employed hydraulic press to study the influence of extraction variables-pressure (5–8 MPa),
temperature (40–90 oC), moisture content (7–16%), and particle size (1.16–3.36 mm) on the
oil yield of different rubber species. They reported that optimal yields for the different species
were obtained at 8 MPa, 70 oC, 10%, and 1.16 mm. Sabarish et al. (2016) studied the effects of
drying time, drying temperature, pressing time, and pressure on the yield of rubber seed oil
extracted with hydraulic press using design of experiment and a 24-full factorial design for the
response surface analysis. The analysis of variance (ANOVA) report indicates that the
maximum oil yield was obtained at the following conditions: drying temperature 55 oC, drying
time 1 h, pressure 35 kg/cm2, and pressing time 25 min. Sayyar et al. (2009) in their study on
the extraction of oil from jatropha seed using n-hexane solvent reported variation in oil yields
(46–47.3%) at 8 h extraction time, 0.16 solute/solvent ratio and particle size (0.5–0.75 mm).
Kostić et al. (2013) considered the effect of solvent/seed ratio (3:1, 6.5:1 and 10:1 ml/g),
extraction temperature (20, 45 and 70 oC) and extraction time (5, 10 and 15 min) on hempseed
oil yield using RSM and ANN optimization techniques. They reported optimal yield of 29.56%
based on ANN conditions: solvent/seed ratio (10:1), temperature (70 oC) and extraction time
(10 min). Bokhari et al. (2012) reported similar observations on extraction of rubber seed oil
using RSM. They obtained an optimal yield of 33.56% with n-hexane as solvent at 0.027 g/ml
solute/solvent ratio and 4.5 h extraction time. Reshad et al. (2015) also applied RSM using
central composite design for the extraction of oil from rubber seeds with n-hexane as solvent.
They reported a maximum yield of 49.36% at optimal conditions of 0.08 g/ml solute/solvent
ratio, 1 mm particle size, and 8 h extraction time.
31
2.8.2 Gas-assisted mechanical extraction method
This process involves the dissolution of supercritical CO2 fluid into the milled seed followed
by the screw pressing process (Ebewele et al., 2010a). It allowed for the use of lower pressure,
while maintaining higher yield without compromising quality (Onoji et al., 2016a).
2.8.3 Microwave-assisted extraction (MAE) method
Microwaves are electromagnetic waves; a combination of a vertical magnetic field and an
electrical wave, with wavelengths ranging from 1 mm to 1 m (Ma et al., 2016). Microwave
irradiation follows two mechanisms; viz. dipolar rotation and ionic conduction that generate
electromagnetic field that accelerates the extraction process (Ma et al., 2016; Li et al., 2013).
The process allows shorter time, low solvent consumption, higher yield and much lower energy
requirements compared to the conventional methods (Ali & Watson, 2014). Gimbun et al.
(2012) in their study on rubber seed oil extraction compared the efficacy of MAE with Soxhlet
method. They obtained a higher oil yield of 40% with MAE and 36% with Soxhlet technique.
They further reported a shorter extraction time of 15 min for MAE and 6 h for Soxhlet method.
The efficiency of MAE is due to good interactive effect of microwave with solvent molecules.
2.8.4 Ultrasonic-assisted extraction method
The process involves the formation and collapse of microscopic bubbles that release huge
amount of energy, pressure and mechanical shear. The ultrasound penetrates the seeds' cell
tissues and extracts the oil into the solvent by disrupting the cell walls (Ali & Watson, 2014;
Li et al., 2004). Shorter time and low solvent consumption are some of its advantages (Onoji
et al., 2016a; Ali & Watson, 2014).
32
2.8.5 Aqueous enzymatic extraction method
The high efficiency and specificity of enzymes allow them to be useful extractive media. They
hydrolyze and rupture the cell walls of the seed kernels and release their oil constituent. Since
no solvent is involved, this method is eco-friendly with low initial cost accompanied with the
ease of processing of the de-oiled cake into livestock feeds (Li et al., 2004).
2.8.6 Supercritical fluid extraction (SFE) method
SFE is a separation process where the substances are dissolved in a fluid that is able to modify
its dissolving power under specific condition above their supercritical regions-critical
temperature (Tc) and pressure (Pc) (Rodríguez-Solana et al., 2014). Supercritical fluids have
the ability to penetrate into the micropores of a solid and good transport properties (Raventós
et al., 2002). Among the available supercritical fluid, carbon dioxide is considered the best
because of its inherent advantages of non-toxic, non-flammable, cost-effective, and it has a low
Tc (304.15 K). Efficiency of CO2 can be enhanced by adding a co-solvent such as methanol
that is capable of hydrogen bonding and dipole-dipole interactions with the contents of the seed
(Murga et al., 2000).
2.9 Physico-chemical properties of rubber seed oil (RSO)
The physicochemical properties of rubber seed oil reported by various researchers are available
in literature. The determination of these properties enables the evaluation of the oil as a source
of potential industrial feedstock for biodiesel production and other uses (Onoji et al., 2016a).
The common fatty acids reported for rubber seed oil are palmitic (C16:0), stearic (C18:0), oleic
(C18:1), linoleic (C18:2) and linolenic (C18:3) (Kittigowittana et al., 2013; Widayat & Kiono,
2012; Ramadhas et al., 2005). Other types of acid may be present in smaller proportions
(Ashraful et al., 2014). The reports indicate that rubber seed oil consists mainly of unsaturated
33
fatty acids with polyunsaturated acids in higher proportion. The values reported by researchers
may be different depending on the extraction processes, clonal types, analytical methods used,
and geographical locations of the rubber tree (Onoji et al., 2016a). Tables 2.9 and 2.10 present
the physico-chemical properties and the fatty acid compositions, respectively, of rubber seed
oil found in literature. These properties are comparable to other non-edible vegetable oils found
in literature (Table 2.11).
34
Table 2.9: Physico-chemical properties of rubber seed oil
Parameters Researchers a, b, c This study d

Colour golden yellow, light/dark brown dark brown
Density, g/cm3 @ 25 oC 0.857–0.943 0.886 ± 0.002
Specific gravity @ 15 oC 0.91 0.909 ± 0.002
o
API gravity @ 15 oC NA 24.1 ± 0.282
Ph 6 6 ± 0.141
Oil content (wt.%) 35–60 43 ± 0.141
Iodine value, g I2/100 g oil 113–146 137.02 ± 0.028
Peroxide value, meq. O2/kg oil 1.6–16 10.46 ± 0.098
Saponification value, mg KOH/g oil 183.91–235.28 195.30 ± 0.282
Acid value, mg KOH/g oil 1.68–42.41 18.20 ± 0.141
Free fatty acid (%FFA as oleic acid) 0.84–42.412 9.10 ± 0.07
Kinematic viscosity, mm2/s @ 40 oC 6–66 40.18 ± 0.028
Refractive index @ 20 oC 1.46–1.47 1.4707 ± 0.00028
Pour point, oC –9 to –1.5 –6
Cloud point, oC 3–4 5.5
Cold filter plugging point, oC NA –0.025
Flash point, oC 72–295 240.3
Fire point, oC 298 256
Aniline point, oC (oF) NA 21 (69.8)
Boiling point, oC NA 119
Freezing point, oC NA –18
Cetane number 45–49.73 43.42
Higher heating value (HHV), MJ/kg 36.1–44 39.37
Mean mol. weight of fatty acids (g/mol) NA 286.74
Average mol. weight of RSO (g/mol) NA 898
Diesel index NA 15.71
NA
means not available; values are mean ± standard deviation of duplicate data .
a
Onoji et al. (2016a); b Aravind et al. (2015); c Reshad et al. (2015); d Onoji et al. (2016b)
35
Table 2.10: Fatty acids profile of rubber seed oil
Fatty acid/Systemic name Chemical Composition (%)

formulae
Researchers a This study d
Myristic (C14:0) / Tetradecanoic C14H28O2 2.2 -
Palmitic (C16:0)/ Hexadecanoic C16H32O2 0.23–10.6 13.85
Palmitoleic (C16:1)/ Hexadec-9-enoic C16H30O2 0.23–0.25 -
Stearic (C18:0)/ Octadecanoic C18H36O2 5.69–12 16.82
Oleic (C18:1)/ cis-9-Octadecenoic C18H34O2 12.7–42.08 64.11
Linoleic(C18:2)/ cis-9-cis-12-Octadecadienoic C18H32O2 39.6–52.84 -
α-Linolenic (C18:3)/ cis-9-cis-12-cis-15- C18H30O2 2.38–26 -

Octadecatrienoic
Arachidonic (C20:0)/ Eicosanoic C20H40O2 0.66–0.97 -
Erucic acid (C22:1)/cis-13-Docosenoic C22H42O2 - 5.22
Total saturated 8.78–23.57 30.67
Total monounsaturated 12.93–42.33 69.33
Total polyunsaturated (linoleic, linolenic, etc) 41.98–78.84 Trace
a
Onoji et al. (2016a); d Onoji et al. (2016b)
36
Table 2.11: Fatty acid compositions of selected non-edible oils (%) (Onoji et al., 2016a)
Fatty acid Rubber Jatropha Neem Linseed Tobacco
Myristic acid 2.2 0.3–1.4 0.2–0.26 0.045 0.09–0.17

(C14:0)
Palmitic acid 0.23–10.6 12.6–16.0 16–33 5.85–6.21 8.46–10.96
(C16:0)
Palmitoleic acid 0.23–0.25 0.57–3.5 0.24 0.3 0.2
(C16:1)
Stearic acid 5.69–12 5.97–7.4 9–24 5.47–5.63 2.64–3.34
(C18:0)
Oleic acid 12.7–42.08 34.3–44.7 25–54 20.17–24.05 11.24–14.54
(C18:1)
Linoleic acid 39.6–52.84 31.4–43.2 6–16 13.29–14.93 69.49–75.58
(C18:2)
α-Linolenic acid 2.38–26 0.8–3.4 0.56 46.10–51.12 0.69–4.20
(C18:3)
Arachidonic acid 0.66–0.97 0.17–0.3 1.04 0.2 0.25
(C20:0)
Behenic acid – 0.5–0.7 0.3 0.3 0.12
(C22:0)
Oil content (%) 35–60 20–60 20–30 35–45 35–49
Cxx: y means number of carbon atoms: number of double bonds
2.10 Thermo-oxidative analysis of rubber seed oil
Generally, seed oils deteriorate when handled defectively with the major decomposition
reaction being oxidation in the presence of atmospheric air (oxygen). The oxidative stability of
oils is an important indicator of performance and shelf life, and it depends on the fatty acid
compositions and conditions to which it is subjected (Onoji et al., 2016b; Guillèn and Cabo,
2002). Poor oxidative stability, unpleasant odor, filter clogging tendency, low temperature
fluidity and other conditions that make them unsuitable for long-term storage before use are
some of the characteristics of vegetable oils (Oderinde et al., 2009). Thermal oxidation of seed
oil on prolonged heating occurs through a free radical mechanism. This is characterized by the
initial emergence of a sweetish and unpleasant odor that becomes progressively worse until it
37
attains a characteristic smell of rancid fat, yielding peroxides and unstable hydroperoxides as
primary products (Gouveia de Souza et al., 2004; Guillèn & Cabo, 2002). The primary products
degrade easily to produce secondary products such as aldehydes, ketones, acids and alcohols
(Gouveia de Souza et al., 2004; Santos et al., 2002). Oxidative stability of vegetable oils can
be improved by use of various antioxidant additives available in markets or more importantly
by increasing the saturated fatty acids and oleic acid contents in oil by genetic modification of
oil bearing plants (Borugadda & Goud, 2013). Such thermal oxidative reactions can be
investigated using thermo-analytical methods such as differential scanning calorimetry (DSC),
thermogravimetry analysis (TGA), derivative thermogravimetry (DTG) and Fourier transform-
infrared (FT-IR) spectroscopy (Onoji et al., 2016b; Borugadda & Goud, 2013; Gouveia de
Souza et al., 2004). A good thermal decomposition profile of oil can be obtained at a heating
rate of 10 oC/min under inert atmosphere (Borugadda & Goud, 2013). Reshad et al., (2015)
estimated the thermal properties of rubber seed oil (RSO), rubber seed kernel (RSK), and cake
by TGA and DSC analyses. They reported single-stage decomposition for RSO, while cake
and kernel occurred in two and three stages, respectively. A negligible weight loss (<0.2%) of
RSO was observed at 90 oC due to the presence of moisture (free water). Sudden decrease in
weight of the oil sample started from 250–470 oC which was reported to be due to
decomposition of heavier hydrocarbon molecules to lower molecular hydrocarbons, and non-
hydrocarbon gases such as CO2 and CO. TGA confirms RSO is thermally stable up to
temperature of 290 oC (onset point) higher than kernel (210 oC) and cake (120 oC). These
reports collaborated with the findings of Aravind et al. (2015) who investigated the thermal
degradation of RSO, coconut oil, sunflower oil and SAE20W40 under oxygen environment in
the temperature range 0–500 oC and reported that RSO is thermally stable up to 250 oC and
that gradual degradation occurs after 300 oC. The TGA curve of RSO is similar to that of
SAE20W40 as the degradation is gradual unlike coconut and sunflower oil. However, simple
38
and low-cost classic chemical analysis such as determination of the concentration of peroxide
value, iodine value, acid value and refractive index has been effectively employed to evaluate
the kinetics of oils degradation under thermal conditions that influence the mechanisms of
degradation process (Onoji et al., 2016b; Oderinde et al., 2009).
2.11 Industrial applications of rubber seed and oil
Recent scientific studies show that rubber seed and seed oil have several potential industrial
applications such as biodiesel (Onoji et al., 2016a; Vipin et al., 2016; Reshad et al., 2015),
semi-drying oil (Eka et al., 2010; Ebewele et al., 2010a), paints and coating (Aigbodion &
Pillai, 2000), printing ink (Iyayi et al., 2008; Igeleke & Omorusi, 2007). Others are livestock
feeds and fertilizer (Iyayi et al., 2008; Igeleke & Omorusi, 2007), lubricants (Aravind et al.,
2015), powdered activated carbon (Sung & Jiang, 2010; Okieimen et al., 2005a), cosmetic
(Kittigowittana et al., 2013), liquid soap and hair shampoo (Igeleke & Omorusi, 2007) and as
a carrier for copper fungicide (Ebewele et al., 2010a). Matured fresh rubber seed contains 40-
50% kernels (Banković-Ilić et al., 2012), 37% shell (Atabani et al., 2013) and 20–25wt. %
moisture (Gimbun et al., 2012). The seed contains protein, essential and non-essential amino
acids (Eka et al., 2010), while the dried kernel contains 40-50% oil (Onoji et al., 2016a;
Widyarani et al., 2014). Rubber seed contains toxic substances such as cyanogenic glycoside
(186 mg) and about 638-749 mg HCN per kg of fresh kernel (Eka et al., 2010; Iyayi et al.,
2008). HCN constituent can be reduced on storage for a period not less than 2 months at room
temperature (Iyayi et al., 2008). With the emergence of biodiesel industry in SSA countries,
rubber plantation farmers will earn extra profit by harvesting rubber seeds for biodiesel
production. This will also encourage the cultivation of new plantations that will reinvigorate
the economy of these local communities, which had abandoned their plantations due to low
demand for rubber latex in the past (Onoji et al., 2016a).
39
2.12 Biofuels policies and sustainability in Africa
The African continent is plagued with poverty and unrests because of lack of good governance
and accountability. Africa has about 9.5% of the world proven reserves of crude oil that are
concentrated in four countries (Nigeria, Algeria, Egypt, and Libya) and contributes about 12%
to global oil production (Onoji et al., 2016a; Yang et al., 2014; Amigun et al., 2011). The rest
African countries are net importers of energy (Table 2.12) and that places a heavy economic
burden and reduces energy security and sovereignty. Thus, there is an urgent need to invest in
domestic energy infrastructure driven by the private sector for quick economic recovery and
growth within the continent (Yang et al., 2014).
Biofuels production in Africa could be commercialized to diversify energy and agricultural
activity in best practices, reduce dependence on crude oil and contribute to economic growth
in a sustainable manner.
The advantages of biofuels such as biodiesel, bioethanol, biohydrogen, biogas, biomethanol,
etc. are renewability, biodegradability, lower Sulphur and aromatic content, higher combustion
efficiency, lower emissions and amongst others. However, biodiesel and bioethanol are the two
alternative fuels promoted with potential to reduce dependence on fossil oil derived products
imports (Demirbaş, 2009). The development of biodiesel industry in most African countries is
still in the infancy stage with Jatropha curcas as the main non-edible oil source (Yang et al.,
2014). Advanced countries of US, Germany, France, Spain, Italy, and emerging economies like
Brazil and India, have well-articulated and sustainable biofuels policies that enhance their
development. Availability of adequate arable land for bioenergy crops cultivation is a major
challenge to these nations (Amigun et al., 2008).
40
Onoji et al. (2016a) suggested that African countries should articulate institutional policies and
regulatory frameworks to guard against deforestation and biodiversity challenges. This is due
to the presence of foreign investors that will invest in bioenergy crops cultivation for biodiesel
production. Most of the bioenergy policies in draft forms in African countries targeted food
crops as biofuels feedstock. These policies are counterproductive as most Africans depend
heavily on these crops for food. Available reports in literature support rubber tree seeds as
plausible source of non-edible oil to complement jatropha seed oil for biodiesel production in
sub-Saharan Africa (Onoji et al., 2016a). However, none of the sub-Saharan African countries
where rubber trees exist in large quantity considers it as a feedstock for biodiesel production in
their bioenergy policies shown in Table 2.13. This is a policy oversight considering the multiple
applications of rubber plant in automotive and biofuel industry. A case study of Nigeria is
presented to show the lapses in biofuel policies in Africa and energy insecurity.
41
Table 2.12: Africa countries which import and export energy (Yang et al., 2014)
Major energy exporters a Net energy exporters Importers b
Algeria Angola Benin
Rep. Congo Cameroon Eritrea
Egypt Congo Ethiopia
Gabon Côte d'Voire Ghana
Libya D.R. Congo Kenya
Nigeria Gabon Morocco
South Africa Sudan Mozambique
Namibia
Senegal
Tanzania
Togo
Zambia
Zimbabwe
a
Major energy exporter are in excess of 0.5 quads.
b
Most of the African countries' imports are very small (less than 0.3 quads).
42
Table 2.13: Sub-Saharan African countries and their bioenergy policies (Onoji et al.,
2016a)
Country Biodiesel feedstock Presence of policies
D.R. Congo rubber*, oil palm, melon, sesame draft energy policy
Cameroon rubber*, oil palm, melon, None
Rep. Congo rubber*, oil palm, melon policy under development
CAR rubber*, melon, sesame None
Nigeria rubber*, jatropha, oil palm, sesame energy policy, biofuels strategy
Ghana rubber*, jatropha, oil palm energy policy, renewable energy
Côte d'Ivoire rubber*, sesame, tobacco policy under development
Liberia rubber*, pongamia pinnata, oil palm draft biofuel policy
Gabon rubber*, oil palm, pongamia pinnata None
Guinea rubber*, oil palm, sesame None
* means available but wasted, and are not listed as feedstock in biofuels policies.
2.12.1 Nigerian biofuel policy (A case study in Africa)
With estimated reserves of 37.2 billion barrels, a daily production output of 2.2 million barrels
of crude oil and gas reserves of about 187 trillion cubic feet, Nigeria is still facing energy
challenges with about 49% of the population lacking access to electricity. Energy output rated
at about 4000 MW is grossly inadequate, and demand is expected to increase over the next 20
years (Ishola et al., 2013). The declining capacity for energy generation in Nigeria has deeply
entrenched the dependence on renewable biomass fuels for cooking (Abila, 2012). The
adoption of biofuel policy in Nigeria in 2007 holds a diversity of opportunities and potentials
to project Nigeria into a bioeconomy and increase her energy generation (Abila, 2012).
Demirbaş et al. (2009) classified the importance of the biofuel industry as economic,
environmental, and energy security. The biofuel industry could attract investment in new
43
technology, boost rural development through industrialization, and create employment leading
to poverty reduction. It could also reduce dependence on revenue from oil, recycle carbon
dioxide, reduce rural-urban drift of unemployed youths (Wohlgemutgh, 1999), and increase
the income of smallholder farmers integrated into the biofuel supply chain (Malik, 2009).
Ohimain (2013) however reviewed the Nigerian biofuel policy and incentives released in 2007
and observed that:
 the policy narrowly classified biofuel to include only bioethanol and biodiesel
neglecting other biofuels and energy carriers obtainable from biomass such as biohydrogen,
biogas, biomethanol, biocrude, biobutanol, dimethyl ether, and other products of Fisher-
Tropsch (FT) synthesis- FT diesel, FT gasoline, and chemicals;
 The policy classified the biofuel enterprise as an agro-allied industry, yet the policy is
driven by the petroleum sector;
 The policy inadvertently refers to food crops as biofuel feedstock and did not address
the potential food-fuel crisis that could arise from the use of food crops as biofuel feedstock;
 The policy did not adequately address issues pertaining to technology transfer, biomass
collection, waste management (environmental impact) and transportation of biofuel feedstock;
 The policy did not encourage expansion of feedstock sources by investing in research
and development on second and third generation biofuel feedstock that do not compete with
food;
 That modern biomass conversion technology issues were not addressed by the policy.
The researcher suggested upgrade of the policy to accommodate the observed lapses. Ishola et
al. (2013) reported similar observations in US$3.86 billion investment in nineteen ethanol bio-
refineries in Nigeria with unsatisfactory results. This could be attributed to limited availability
of food crops as biofuel feedstock. Many of the food crops are staple food in Nigeria and their
44
use as biofuel feedstock is counterproductive. The report however, did not highlight any
expenditure on biodiesel programme. The adoption of rubber seed as a source of non-edible oil
feedstock will drive the Nigerian biofuel policy to fruition. Nigeria has the capacity to produce
over 8,000 ton of biodiesel/annum from rubber seed oil and this figure could increase with
proper management (Onoji et al., 2016a). Despite the potentials and availability of rubber seeds
in Nigeria, there is no trial production of biodiesel from rubber seed oil except on research
scale, which is even limited.
2.13 Catalysis
A catalyst is a substance that affects the rate of a reaction (positive or negative) without been
substantially affected by the process. Catalysts are neither reactants nor product, and have been
used by man for over 2000 years in several industrial applications (Levenspiel, 2005). Catalysis
is the occurrence, study, and use of catalysts and catalytic processes that involve the constant
search for new ways of increasing product yield and selectivity (Fogler, 2008). There are two
broad classes of catalysts: (1) Enzymes - operate at close to ambient temperature with
biochemical systems, (2) Man-made catalysts - operate at high temperature (homogeneous and
heterogeneous). Homogeneous catalysis concerns processes in which a catalyst is in solution
with at least one of the reactants. A heterogeneous catalytic process involves more than one
phase; usually the catalyst is a solid and the reactants and products are in liquid or gaseous
form. A heterogeneous catalytic reaction occurs at or very near the fluid-solid. Because a
catalytic reaction occurs at the fluid -solid interface, a large interfacial area is essential in
attaining significant reaction rate. In many catalysts, this area is providing by an inner porous
structure needed for the high rate of reaction (Fogler, 2008). A typical silica-alumina cracking
catalyst has a pore volume of 0.6 cm3/g, average pore radius of 4mm, and a corresponding
surface area of 300 m2/g (Fogler, 2008). In some cases, a catalyst may contain some minute
45
particles of an active material dispersed over a less active substance called a support. The active
material is frequently a pure metal or a metal alloy. Catalysts can also have small amounts of
active ingredient added called promoters, which increase the activity of the solid catalysts.
Although a catalyst can easily speed up the rate of a reaction in several folds, when varieties of
reactions are encountered, the catalyst selectivity enables it to affect a single reaction, leaving
the rest unaffected. Thus, in the presence of an appropriate catalyst, products containing
predominantly the material(s) desired could be obtained from a given feed. The following are
some general observations made by Levenspiel (2005) on catalyst:
 The selection of a catalyst to promote a reaction is not well understood. In practice,
extensive trial and error may be needed to produce a satisfactory catalyst;
 Duplication of the chemical constitution of a good catalyst is no guarantee that the solid
produced will have any catalytic activity;
 Various theories have been proposed to explain the action of catalyst, and it is thought
that reactant molecules are changed, energized, or affected to form intermediates in the
regions close to the catalyst surface;
 In terms of the transition-state theory, the catalyst reduces the potential energy barrier
over which the reactants must pass to form products (Figure 2.8);
 Though a catalyst may speed up a reaction, it never determines the equilibrium or
endpoint of a reaction. Thus, with or without a catalyst, the equilibrium constant for a
reaction is always the same.
46
Without catalyst, the complex
has high potential energy
Energy of reactants
resulting in low rate of reaction
Different
With catalyst, the lower energy
reaction paths
barrier allows higher rate of
reaction
Initial
State
Final
State
Reactants Complex Products
Reaction Path
Figure 2.8: Representation of the action of a catalyst (Adapted from Levenspiel,
2005)
2.13.1 Catalyst deactivation
Most catalysts do not maintain their activities at the same levels for indefinite periods. They
are subjected to deactivation, which causes a decline in catalyst's activity as time progresses.
Catalyst deactivation may be caused by: (1) Aging -This is a gradual change in surface crystal
structure; (2) Poisoning-This is the irreversible deposition of substances on the active site; or
(3) fouling or coking- This is the deposition of reversible carbonaceous or other material on the
entire surface.
2.13.2 Physical adsorption and chemisorption in chemical reaction catalysis
For a catalytic reaction to occur, at least one, or frequently all of the reactants must be attached
to the surface of the catalyst (Wu, 2004). This attachment known as adsorption, takes place by
two different processes: physical adsorption (physisorption) and chemisorption
(chemisorption) (Mechrafi, 2002). Physical adsorption mainly caused by van der Waals forces
is the result of low energy exchange between the adsorbate and the adsorbent on the solid
47
surface (Desjardins, 1997). The adsorbate is relatively free to move on the surface, as the
attraction is not fixed to a specific site. Physisorption is relatively reversible and capable of
multilayer adsorption (Madani, 2004). The process is similar to condensation, with small
exothermic heat of adsorption (4.2–63 kJ/mol) (Fogler, 2008). In chemisorption, the adsorbed
atoms or molecules are held to the surface by valence forces of the same type as those that
occur between bonded atoms in molecules (Fogler, 2008). In this case, the adsorbed molecules
are not free to move on the solid surface; thus, the adsorption process depends on the functional
groups present on the adsorbent and not on the surface area. As a result, the electronic structure
of the chemisorbed molecule is perturbed significantly, causing it to be extremely reactive. Due
to the stronger molecular electronic structure that results from the formation of chemical bonds
between adsorbate and adsorbent, chemisorption is an irreversible process. It occurs at a higher
temperature that requires more energy. Like physical adsorption, chemisorption is exothermic
process, but the heats of adsorption are generally of the same magnitude as the heat of a
chemical reaction (i.e., 40–400 kJ/mol). Table 2.14 presents the comparisons between
physisorption and chemisorption.
48
Table 2.14: Comparison between physisorption and chemisorption processes
Physisorption Chemisorption
Adsorbates are molecules Adsorbates are atoms or radicals
Multilayer adsorption process Monolayer adsorption process
Attraction is a result of van der Waals forces Attraction is a result of chemical bonds
Reversible process Irreversible process
Molecules are adsorbed on available sites Molecules are adsorbed on active sites only
Adsorption temperature must be below the It occurs at any temperature
boiling point of the Adsorbate
Heat of Adsorption is less than 50 kJ/mol Heat of Adsorption can be more than 100
kJ/mol (Christmann, 2012)
2.14 Gas-solid adsorption systems
The ability of the surface of a solid to adsorb gases and vapour is considered as its most
characteristic property. Surface area and porosity are important properties in the field of
catalyst design and heterogeneous catalysis (Storck et al., 1998). The physisorption method as
routine tool is the most widely used technique for the characterization of micropores (diameter
< 2 nm), mesopores (diameter 2–50 nm) and macropores (diameter> 50 nm) of new materials
for catalysts design. Gas-solid adsorption has been carried out extensively in the past few years
due to the comparative ease of experimental work (Shanavas et al., 2011). The results of
physisorption experiments are usually presented in graphical forms as isotherms. The
Langmuir equation is the simplest equation for the gas-solid adsorption systems upon which
other isotherms were derived. The earliest reports on gas-solid adsorption were classified by
Brunauer-Emmett-Teller (BET) based on their derived models type I, II, III, IV and V
49
isotherms (Figure 2.9), although Freundlich isotherm was reported as the oldest (Iyer & Kunji,
1992).
The Langmuir model and the BET isotherms are used to obtain the monolayer values from
which the specific surface areas are calculated. The monolayer values and the molecular areas
estimated by Langmuir and BET isotherms are inaccurate, resulting to errors in surface areas
estimations. BET admitted that their equation be strictly applied in the range of relative
pressures between 0.05 and 0.35 for adsorption process, since the equation did not fit the
experimental data for all relative pressures (De Boer et al., 1966). The Langmuir equation has
only limited applicability, for it is valid for type I isotherm of Brunauer's classification.
Figure 2.9: Adsorption isotherm classified by Brunauer (Adapted from Storck et al., 1998)
50
2.14.1 Langmuir model equation (linearized)
The linear form of the Langmuir equation is described as:
P P 1
 
V Vm bVm (2.1)
Where: 'b' is the Langmuir constant related to the affinity of binding sites, P, Po, and Vm are
P
as defined earlier. A plot of versus P yields a straight line from Langmuir Vm and b can be
V
evaluated. The quantity Vm obtained from the Langmuir equation is the monolayer value, which
is used to determine the Langmuir specific surface area (SL) of the adsorbent by using Equation
(2.2) (Shanavas et al., 2011).
𝑆𝐿 = 𝑉𝑚 × 𝑁 × 𝐴𝑚 (2.2)
Where: N is the Avogadro's number; and Am is the adsorbate molecular area (0.162 nm2 for
nitrogen).
The Langmuir equation derived from the adsorption on the nonporous surface adsorption, gives
the type I isotherm. In physical adsorption, however, the type I isotherm is obtained from
microporous adsorbents such as active carbons or zeolites. In such microporous adsorbents, the
type I isotherm can be explained by filling of the adsorbate molecules into micropores observed
as initial sharp rise of the isotherm. The flat region of the isotherm appears when the micropores
are completely filled by adsorbate. It is reasonable to conclude that the monolayer volume (Vm)
of microporous adsorbent obtained from the Langmuir plot corresponds to the microspore
volume. The surface area of microporous adsorbent estimated from Vim occasionally gives the
abnormally high value.
2.14.2 BET model equation
The assumptions of the BET equation are:
 Estimates monolayer capacity;
51
 Adsorption occurs layer by layer;
 Molecules in the first layer interact with the solid, and molecules in the following
layers behave as in bulk liquid;
 Heat of adsorption for the first layer is higher than successive layers;
 Heat of adsorption for second and successive layers equals the heat of liquefaction;
 Lateral interactions between adsorbed molecules are ignored.
x  C 1 1
   x 
V 1  x   Vm C  Vm C
(2.3)
where: 'x' is the relative pressure (P/Po); P is the partial pressure; Po is the saturation pressure;
Vm is the maximum amount of gas adsorbed/unit mass of solid at high pressure conditions
required to form a complete monolayer over the entire surface of the solid, and C is the BET
x
constant related to the heat of adsorption. A plot of versus x yields a straight line
V 1  x 
from which Vm and C are calculated. The volume of the monolayer (Vm) is converted to a
specific surface area (SBET) by assuming that each molecule in the monolayer occupies a given
surface (0.162 nm2 for nitrogen).
2.14.3 Freundlich model equation
The Freundlich isotherm represents the isothermal variation of adsorption of a quantity of gas
adsorbed by unit mass of solid adsorbent with pressure. The isotherm is obeyed when the
adsorbate forms a monomolecular layer on the surface of the adsorbent. It was determined
experimentally that the extent of adsorption varies directly with pressure until saturation
pressure Po is reached. Beyond that point, the rate of adsorption saturates even after applying
higher pressure. The Freundlich isotherm indicates that:
x
 At low pressure, the extent of adsorption varies linearly with pressure,  P1 ;
m
52
x
 At high pressure, it becomes independent of pressure,  P0
m
Thus, Freundlich adsorption isotherm fails at higher pressure.
Mathematically, the model equation is expressed as:
1
x
 KF P n (2.4)
m
Equation (2.4) in linearized form becomes:
x 1
log   log K F  log P (2.5)
m n
where, x = mass of adsorbate
m = mass of adsorbent
P = equilibrium pressure of adsorbate
KF and n are constants for a given adsorbate and adsorbent at a particular temperature. The value
of n is always greater than 1; indicating that the amount of gas adsorbed does not increase as
rapidly as the pressure.
2.14.4 The t-plot
Various thickness equations have been developed and reported in literature to relate thickness
of adsorbed film to pressure in gas-solid adsorption. The characteristics of these equations are:
 Compares an isotherm of a mesoporous materials with a standard type II isotherm of a
nonporous adsorbent with BET C constants similar to that of the microporous sample;
 Existence of a direct relation between thickness and specific volume of gas adsorbed;
 Thickness equation predicts V at various pressures for nonporous materials;
 Plotting experimental data against thickness equation data yields a straight line for
nonporous solids, and a deviated line for porous solids.
The t-values are in practice calculated with a thickness equation that describes the particular
standard reference curve

53
Practically, an adsorbate has never been reported to cover an adsorbent with a film of uniform
thickness. In many instances, it is assumed that the film thickness on pore walls is uniform
which then allows for the calculation of statistical thickness (t) from gas adsorption isotherms.
Several model equations have been reported in the literature developed to calculate statistical
thickness. The t-plot method permits the determination of micropore volume, surface area, and
help to obtain in principle information about the average pore size of the adsorbent.
De Boer et al. (1966) in their study of gas-solid adsorption proposed a master t-curve
multimolecular N2-adsorption to overcome limitations of Langmuir and the BET isotherms.
Their reports indicated an identical multilayer adsorption curves for variety of adsorbents
considered; provided no capillary condensation occur and no narrow pores are excluded during
the adsorption process. A master t-curve in terms of an average thickness of the adsorbed layer
for the adsorption of nitrogen at 78 K over the range 0.1–0.75 P/Po was developed. This
developed curve gave the same surface area with a fitted BET isotherm. If the statistical
V 
thickness (t) of one layer is 3.5 Å, then a value of 3.54 (Å) indicates an adsorption of n   
 Vm 
layers where V is the adsorbed volume, and Vm the monolayer capacity both in cm3/g STP
adsorbent.
2.14.4.1 Harkins-Jura model
Harkin-Jura model that was derived from an empirical equation of state for condensed films,
attempts to modify earlier models of Langmuir and BET. The model proposes that the
adsorptive film is of the condensed type (liquid) and hence its surface pressure, the difference
of the surface tension of the bare surface and film-covered surface is a linear function of the
area per molecule (Shanavas et al., 2011). The isotherm does not rely on parameters such as
molecular area and monolayer values, and thus gives reliable results compared to Langmuir
isotherm. The Harkins-Jura model is given as:

54
A
log x  B  (2.6)
Va 2
P
where x  , A and B are constants, Va is the adsorbed volume.
Po
A similar thickness equation was obtained by De Boer et al. (1966), which represents nitrogen
adsorption on solid adsorbents at 77 K:
13.99
log x  0.034  (2.7)
t2
And,
0.5
 
t Å   
13.99
 (2.8)
 0.034  logP / Po 
For carbon-like derived materials, a developed thickness equation is given as:
t (Å)  0.88P/Po   6.45( P / Po )  2.98 (2.9)
2.14.4.2 Halsey equation
The Halsey equation provides another alternative to calculate the statistical thickness. The
equation for nitrogen adsorption at 77 K was described as:
1/ 3
 5 
t Å   3.54  (2.10)
 lnP / Po 
2.14.5 Polanyi's potential theory
The Polanyi's potential theory occupies a unique position in the study of physisorption. For
different number of adsorbents, the theory has been successfully used to correlate data at
different temperatures and for different adsorbates, although it is reported not consistent with
monolayer adsorption on heterogeneous surfaces (Harris, 1969). The theory explained that the
adsorption process is facilitated by the existence of potential fields around the surface of the
55
adsorbent, and the adsorptive potential energy (En) needed to energize the adsorbate from its
equilibrium pressure to the saturation pressure is described by (Polany et al., 1970; Harris,
1969):
RT  P 
dP  RT ln sat 
Psat Psat
En   VdP   (2.11)
Pequil Pequil P P 
 equil 
2.14.6 Dubinin-Radushkevich equation
Dubinin-Radushkevich method, which is based on the Polanyi's potential theory, is widely used
to describe adsorption in microporous solids such as activated carbon and zeolites. The
equation has a semi-empirical origin and is based on the assumptions of a change in the
potential energy between the gas and adsorbed phases and a characteristic energy of a given
solid. This equation yields a macroscopic behaviour of adsorption loading for a given pressure
(Nguyen & Do, 2001). The proposed equation allows the calculation of micropore volume from
the adsorption isotherm.
In its basic form, the Dubinin-Radushkevich can be described as (Nguyen & Do, 2001; Misra,
1969):
V   P  
2

 exp   RT ln  / E 

 (2.12)
Vo    Po   
 
2 P 
2
 RT 
loge V  loge Vo    loge   (2.13)
 E   Po 
where, V = volume adsorbed (cm3/g); Vo = micropore volume (cm3/g). A plot of loge V vs.
loge2 p / po known as a characteristic curve plotted to test the suitability of the equation and/ or
to determine its range of applicability. If the model equations were applicable, the plot would
be a straight line with an intercept loge Vo and a slope  RT / E 2 , from which micropore
volume and characteristic energy (E) can be obtained (Nguyen & Do, 2001).
56
2.14.7 Kelvin equation
The Kelvin equation provides a correlation between pore diameter and pore condensation
pressure. The relative pressure where the pore condensation occurs depends on the pore radius.
Basic assumptions are:
 Pores of cylindrical shapes;
 No fluid-wall interactions;
 Zero (0) contact angle (θ).
The basic form of the Kelvin equation is described by (Siboni & Volpe, 2008; Mitropoulos,
2008; Aylmore, 1974):
P 2Vl Cos  1 
ln    (2.14)
Po RT  rm 
If contact angle θ = 0, then Equation (2.14) becomes:
P 2Vl  1 
ln   
RT  rm 
(2.15)
Po
where θ is the contact angle between solid and the condensed phase, and:
rP  rK  t (2.16)
When fluid-wall interactions are considered, the modified Kelvin equation for nitrogen at a
temperature of 77 K becomes:
4.15
rK (Å)  (2.17)
logPo / P 
where 𝛾 is the surface tension of liquid adsorbate (N/m), Vl is the molar volume of the bulk
liquid adsorbate (vol/mol) and the value is 34.68 cm3/mol for nitrogen at 77 K, rm is the mean
radius of curvature of the liquid/gas interface; rK is the Kelvin radius; rP is the pore radius; R
57
is the universal gas constant; T is the absolute temperature; and t is the statistical thickness of
the adsorbed film (deposited or retained).
For many practical purposes, this model is commonly a cylinder with infinite length and for
many mesoporous materials; the adsorption isotherm is of type IV. Hysteresis in capillaries
open at both ends, results from the fact that in desorption, evaporation takes place from a
hemispherical meniscus while in adsorption, condensation occurs from a cylindrical film. In
both cases, condensation or evaporation occurs at some distance t from the pore walls
(Mitropoulos, 2008). On assumption of zero contact angle, rm for a hemispherical meniscus will
be equal to rm  rK .
where rK is Kelvin radius, rK  rP  t while for a cylindrical interface, rm  2rK .
2.14.8 Thermodynamics of gas adsorption
Adsorption process is exothermic in nature, and the heats released might be the result of
energetic interactions between the adsorbate and adsorbent species. The thermodynamic
relation of gas adsorption is given by Equation (2.18).
Gads  H ads  TS ads (2.18)
where ∆Gads, ∆Hads, and ∆Sads are the Gibbs free energy change of adsorption, the enthalpy
changes of adsorption, and the entropy change of adsorption, respectively. ∆Gads is negative
because gas adsorption proceeds spontaneously. Furthermore, ∆Sads is negative because the
molecules moving at random in gas phase are fixed on the solid surface by adsorption. The
adsorbate amount and the heat released during the adsorption process could be used to
determine the thermodynamic quantities. The isosteric method is used to measure the molar
enthalpy at different temperatures and from which the heat of adsorption is calculated (van
58
Dongen & Broekhoff, 1969). The isosteric adsorption enthalpy and entropy can be determined
P 1
from the gradient and y-intercept of ln versus from the following equation:
Po T
P H ads 1 S ads
ln   (2.19)
Po R T R
The equation above is similar to the Clausius-Clapeyron relation given by:
  P
H ads   RT 2  ln 
T  Po 
(2.20)
2.15 Biodiesel and its origin
Biodiesel is a long chain fatty acid mono-alkyl esters (FAME) produced from acyl glycerol
(triglyceride) in vegetable oils and animal fats via transesterification with short chain alcohols
(in this study, methanol) (Issariyakul & Dalai, 2014). Biodiesel has good properties like
renewability, biodegradability, lower emission profile and excellent lubricity amongst others
(Sajjadi et al.,2016; Guo et al., 2010). Triglyceride (Figure 2.10) is the major component of
vegetable oils composed of three esters of fatty acid chain (acyl group) attached to the glycerol
backbone (glycerol group). Typical fatty acid chains attached to triglycerides found in
vegetable oils are usually from 10 to 24 carbon atoms. The major difference between various
vegetable oils is the type of fatty acids attached to triglyceride molecule. Rudolf Diesel (1858-
1913) invented the diesel engine in 1892 (Marchetti & Errazu, 2008) out of his desire to
improve on the steam engines of the late 1800s that were considered dangerous. In 1900, he
demonstrated the newly designed engine running on peanut oil at Paris World Exhibition
(Marchetti & Errazu, 2008). The diesel engine later became the engine of choice for power,
reliability and high fuel economy. Shortly after death of Rudolf Diesel in 1913, cheap diesel
fuel from petroleum became available. With the availability of cheap petroleum, the diesel
engine design was modified to match the properties of petro-diesel (Ma & Hanna, 1999) and
59
this discourages the use of vegetable oils in that era. Several researchers (Aransiola et al., 2014)
have reviewed the use of vegetable oil as a source of fuel. Their publications show satisfactory
performance of vegetable oils as plausible source material as fuels for use in diesel engines. In
spite of the benefits of vegetable oils as fuel in diesel engines, their high viscosity is a major
drawback when used as fuels in direct-injection diesel engines resulting in poor atomization
and engine deposits (Issariyakul & Dalai, 2014).
The World War II and the oil crises of the 1970s saw a brief interest in the use of vegetable
oils to fuel diesel engines. Unfortunately, the newer diesel engine designs could not run on
traditional vegetable oils, due to high viscosity compared to petro-diesel. In the early 1980s,
concerns over the degradation of the environment, energy security, and agricultural over
production once again brought the use of vegetable oils to the forefront. A renewed effort was
focused on the use of vegetable oils as sources of fuels and was debated at the first International
Conference on plants and vegetable oils as fuel in Fargo, North Dakota in August 1982 (Ma &
Hanna, 1999). Four major technologies adapted to reduce the viscosity of vegetable oils, such
as direct blending with petrol-diesel, micro-emulsification, pyrolysis, and transesterification
have been suggested by Subramaniam et al. (2013), Boro et al. (2012), and Schwab et al. (1987)
for use in biodiesel production. The advantages and disadvantages of these methods as listed
in Table 2.15 show that transesterification is the best choice. Currently, transesterification is
the most commonly employed method for biodiesel production. The biodiesel produced
through this process is burned directly in unmodified diesel engines, with very low deposit
formation. The idea of transesterification dated back to 1938 when it was found that the
glycerin component of the triglyceride has no calorific value and was likely to cause excessive
carbon deposit on the engine. The residue fatty acid of the oil after the removal of the glycerin
part through a catalyzed chemical reaction (transesterification) with a simple short chain
alcohol, is referred to as biodiesel, a term that made its first appearance in a paper published in
60
1988 (Issariyakul & Dalai, 2014). Over 90% biodiesel produced, is currently sourced from
edible vegetable oils that compete with food use (Sajjadi et al., 2016; Ashraful et al., 2014).
Food is a necessity of man after shelter; and the use of edible vegetable oils as biodiesel source
materials is counterproductive. Feedstock accounts for about 60–95% of the total cost of
biodiesel (Banković-Ilić et al., 2012) and the production of biodiesel from low-cost materials
will reduce its price and makes it more competitive with fossil-diesel. Non-edible rubber seed
oil can be exploited as low-cost industrial oil for biodiesel production and this will reduce
biodiesel cost and avoid food-fuel crisis in future (Morshed et al., 2011). Homogeneous base
catalysts such as NaOH, KOH and methoxides of sodium and potassium are most suitable for
industrial transesterification of edible vegetable oils that are generally low in free fatty acids
(FFAs). However, associated problems such as difficulty in catalyst-products separation, initial
catalyst cost, soap formation, low-grade by-product glycerol, reactor corrosion and large
volume washing water requirements induced further research for environmentally benign
heterogeneous catalyst for biodiesel synthesis from non-edible oils (Roschat et al., 2012; Zabeti
et al., 2009). Heterogeneous (solid) catalysts are separated from reaction mixtures by simple
filtration process. They are reused and recycled severally producing high-grade glycerol
(Uprety et al., 2016). In the recent past, successful ventures were reported on the utilization of
calcined wastes such as eggshell (Piker et al., 2016) and animal bones (Nisar et al., 2017) to
generate CaO as low-cost solid base catalysts for transesterification of oil to biodiesels with
yields above 96%. Betiku and Ajala (2014) also used a solid catalyst obtained from waste
plantain peels calcined at 500 oC for 3.5 h as direct basic heterogeneous catalyst to transesterify
pretreated yellow oleander (Thevetia peruviana) oil to biodiesel with a yield > 95% (w/w) at
RSM optimized conditions of methanol/oil ratio (0.3 v/v), reaction time (1.5 h), and calcined
plantain peels catalyst (3.0 w/v).
61
Table 2.15: Methods of viscosity reduction in vegetable oils for biodiesel production
(Adapted from Boro et al., 2012)
Methods Definition Advantages Disadvantages
Pyrolysis or thermal Method of conversion of one 1.Lower processing Energy intensive

cracking substance into another by cost, compatibility
application of heat with the aid with infrastructure,
of the catalyst in the absence of engines and fuel
air or oxygen standards, and feed
stock flexibility
2.The final products
are similar to
diesel fuel in
composition
Micro-emulsions A micro-emulsion is a colloidal 1. Fuel viscosity is Lower cetane

equilibrium dispersion of lowered number and energy
optically isotropic fluid 2. They can improve content
microstructures with spray
dimensions generally in the characteristics by
range of 1–150 and explosive
spontaneously formed from two vaporization of the
normally immiscible liquids and low boiling
one or more ionic or non-ionic constituents in the
amphiphiles. micelles
Direct use and Either use vegetable oil directly Liquid nature and 1. Higher viscosity
blending or is blended with diesel portability. Heat 2. Lower volatility
content ~80% of 3. The reactivity of
diesel fuel) readily unsaturated
available; hydrocarbon
renewability chains
Transesterification Transesterification (also called Renewability; higher Glycerol disposal

alcoholysis) is the reaction of a cetane number; and waste water
fat or oil with an alcohol to lower emissions; problem
form esters and glycerol higher combustion
efficiency
62
Figure 2.10: A typical structure of a triglyceride molecule
2.15.1 Biodiesel feedstock
Lipids and simple alcohols are the main feedstock required for the production of biodiesel.
There are over 350 oilseed crops identified worldwide as sources of lipids suitable for biofuels
(Ashraful et al., 2014). Lipids can also include animal fats, and more recently, micro-algae and
cyanobacteria (Kings et al., 2017). Over 95% of biodiesel are sourced from edible vegetable
oils that are regionally based: rapeseed and sunflower in European countries and Canada;
soybean oil in United States; palm oil in tropical countries such as Indonesia and Malaysia;
coconut oil in the Philippines (Bankovic-Ilic et al., 2012; Ashraful et al., 2014). Several
researchers have reported that the cost of biodiesel depends on the feedstock that accounts for
about 60-95% (Ashraful et al; 2014; Morshed et al., 2011). The debate over the food versus
fuel crisis on the use of edible oils for biofuel production simulated research into the use of
non-edible and used oils as a veritable source of raw material for biodiesel production (Onoji
et al., 2016a).
Oil seed bearing plants such as rubber tree, jatropha curcas, and karanja just to mention a few
have been described as promising sources of non-edible oil for biodiesel production to avert
food shortage. The rubber tree with a high seed oil yield (35–60%) and with the potential to
generate natural rubber for production of various rubber products placed it at an advantageous
position over other non-edible oilseeds (Onoji et al., 2016a; Atabani et al., 2013). The rubber
63
is the bioenergy crop of the next century considering its versatile use in biofuels and automobile
industry.
The most frequently used alcohols for biodiesel production are short-chain alcohols, such as
methanol (CH3OH), ethanol (C2H5OH) and butanol (C4H9OH). The choice of alcohol depends
on cost, sustainability, and performance characteristics (Encinar et al., 2007). In Brazil, for
example, ethanol is preferred because it is readily available, cheap and sustainable. In
transesterification with ethanol, unreacted ethanol forms an azeotrope that is expensive to
purify during recovery. Methanol is much cheaper than ethanol and the literature on biodiesel
is replete with methyl esters rather than ethyl esters (Yuan et al., 2008). Methanol is more easily
recycled because it does not form an azeotrope. Ethanolysis forms stable emulsions depicting
difficulty in product separation and this is contrary to unstable emulsions resulting from
methanolysis. The reaction rate is relatively slow with ethanol because the formation of
ethoxide anion is more difficult than that of the methoxide (OM Tapanes et al., 2008).
2.16 Catalysis in biodiesel production
Esterification and transesterification reactions are commonly employed in biodiesel synthesis.
Vegetable oils that have high content of FFAs will undergo pretreatment process (esterification
reactions) to reduce the levels of FFAs to an acceptable limit (<1%) prior to transesterification
process with base catalysts.
2.16.1 Acid-catalyzed esterification reaction
This method is suitable for processing biodiesel feedstock with high FFAs and other low-grade
oils that are not suitable for direct base transesterification. The catalysts used include sulphuric,
hydrochloric, sulfonic and phosphoric acids (Aransiola et al., 2014). However, the downstream
processing of huge waste water, high oil/methanol ratio, corrosiveness, catalyst recovery
64
problem, longer reaction time, and modulate temperatures and pressures are some of its
disadvantages. The esterification reaction is a simple reversible reaction as shown in Equation
(2.21) (Guo & Fang, 2011). FFA supplies hydroxide and the methanol supplies proton without
intermediate process and FFA is converted to ester (biodiesel) and water as a byproduct.
(2.21)
2.16.2 Transesterification of oils using homogeneous catalyst
Transesterification has been widely accepted as the most viable method to produce biodiesel.
Transesterification is the chemical reaction of vegetable oils, waste oils, animal fats, or
microalgae oils with excess primary alcohol in the presence of a suitable catalyst. The choice
of catalyst and biodiesel production route depends on the physicochemical properties of the
selected oil. The catalysts used are classified as: homogeneous (acid and base), heterogeneous
(acid and base), and enzymes. The triglyceride is converted stepwise to diglyceride and
monoglyceride intermediates, and finally to glycerol with biodiesel (FAME) formed at each
step (Issariyakul & Dalai, 2014; Thanh et al., 2012; Guo & Fang, 2011) as depicted in Figure
2.11. The breakdown of the triglyceride structure requires three steps:
1. The first step produces an intermediate tetrahedral;
2. The second step involves the breakdown of the unstable intermediate tetrahedral into
diglyceride ion and fatty acid ester (biodiesel), and;
3. The final step that involves the recovery of the catalyst by proton transfer.
The three mechanisms are repeated for cleavage of each fatty acid ester and then finally, three
fatty acid esters (biodiesels) and a glycerol is formed as shown in the overall Equation (2.22)
(Thanh et al., 2012).
65
Figure 2.11: Scheme for stepwise transesterification of triglyceride to methyl esters
(Adapted from Guo & Fang, 2011)
(2.22)
2.16.2.1 Alkali-catalyzed transesterification reaction
Hydroxides and alkoxides of alkaline metals as well as the carbonates of sodium and potassium
metals catalyze these reactions. The process is widely used in the laboratory, pilot and industrial
scale levels. The catalysts show a very high performance when the feedstock have low content
of FFAs such as edible vegetable oils of rapeseed, soybean, sunflower etc. However, the
shortcomings of this method such as energy intensive, glycerol recovery problems,
corrosiveness, and food-fuel crisis, have generated debates about their use in different form in
the past few years.
66
2.16.2.2 Two-step transesterification reaction
The method involves acid-catalyzed esterification followed by alkali-catalyzed
transesterification, and useful for processing high FFAs feedstock to biodiesel. It is a
combination of the process as described in Section (2.16.1), followed by a second step, alkali-
catalyzed transesterification, as described in Section (2.16.2.1) (Betiku & Ajala, 2014).
2.16.2.3 Mechanisms for homogeneous catalysis
Homogeneous catalysts used for oil transesterification are either acid or base, and usually in
liquid form. The protonation of the carbonyl group in the triglyceride molecule and the alcohol
attacking the protonated carbon to create a tetrahedral intermediate form the basis of acid
catalysis (Aransiola et al., 2014). However, in a homogeneous-base catalyzed reaction, the
creation of nucleophilic alkoxides from the alcohol to attack the electrophilic part of the
carbonyl group of the triglycerides forms the basis of the reaction. The mechanisms for acid-
catalyzed and base-catalyzed are well documented in the literature (Thanh et al., 2012). These
reactions demonstrate the conversion of triglyceride into diglyceride. The reaction mechanisms
of diglyceride and monoglyceride, which convert into monoglyceride and glycerol,
respectively, take place in the same way as for triglyceride. The overall reactions were earlier
shown in Equation (2.22).
2.16.3 Transesterification of oils using heterogeneous catalysts
Solid catalysts of acid and base origins are known as heterogeneous catalysts. They were
developed to overcome the limitations of homogeneous catalysts, although they have similar
mechanisms to the homogeneous type. Aransiola et al. (2014) report various types of
heterogeneous catalysts and their preparatory methods in their review paper.
67
2.16.3.1 Heterogeneous acid transesterification reaction
Heterogeneous acid catalysts have ability to catalyze both esterification and transesterification
reactions simultaneously, and are less corrosive, less toxic, and generate fewer environmental
problems (Zhang et al., 2011), and thus produce a low-cost biodiesel that is competitive with
commercial diesel. The acids contain variety of acid sites with different strengths of Brӧnsted
or Lewis acidity as compared to homogeneous acid catalysts despite their lower activity
(Aransiola et al., 2014; Thanh et al., 2012). At low temperature, the activity of acid catalysts
in transesterification is normally quite low, and to obtain a sufficient reaction rate, it is
necessary to increase the reaction temperature (> 170 oC) and this could increase the capital
costs thus the cost of biodiesel (Di Serio et al., 2008). Several solid acid-catalysts such as
Nafion-NR50, acid ion-exchange resins, sulfated zirconia (SZ), tungstated zirconia (WZ),
supported acid catalysts (with metal oxides as supports), zeolite-based catalyst (e.g., zeolite β,
HYzeolite) and heteropoly acids have been reported in the literature for the transesterification
of oil to biodiesel with good yields.
The mechanism of solid acid-catalyzed esterification reaction consists of the following steps:
Firstly, solid catalysts provide protons, and carbonyl carbon is protonated. This is followed by
nucleophilic attack of CH3OH on the carbonium ion to form a tetrahedral intermediate. The
last stage involves the migration and reformation of proton with the breakdown of intermediate
to produce biodiesel (Guo & Fang, 2011). As discussed in Section (2.16.2), three consecutive
reactions are required to complete the transesterification of a triglyceride molecule. The
mechanisms of solid acid-catalyzed transesterification of triglycerides show that triglycerides
are protonated at the carbonyl group on the surface of the catalyst. A nucleophilic attack by the
alcohol forms an unstable tetrahedral intermediate that leads to proton migration, followed by
breakdown of the tetrahedral intermediate with the assistance of solvent. After twice
repetitions, three new esters products are produced and the catalyst regenerated. During the
68
catalytic process, protonation of carbonyl group boosts the catalytic effect of solid-acid
catalysts by increasing the electrophilicity of the adjacent carbonyl carbon atom (Guo & Fang,
2011). Issariyakul & Dalai (2014) presented the mechanisms of solid acid-catalyzed reactions
for both esterification and transesterification in a more compacted form. In the esterification
process, free fatty acid initially adsorbs on the active acid site of the catalyst that leads to
carbonation during their interaction. This is followed by an attack of methanol to produce an
unstable tetrahedral intermediate that finally leads to the removal of water molecule to produce
methyl ester (biodiesel). The reaction mechanism for the transesterification part occurs in a
similar manner to that of esterification. The formation of methyl ester stems from an
elimination of diglyceride, monoglyceride, and glycerol from the tetrahedral intermediate when
triglyceride, diglyceride, and monoglyceride are adsorbed in the acidic site, respectively.
2.16.3.2 Heterogeneous base transesterification reaction
The use of heterogeneous base catalyst has received a wider research attention over the last
decade. Such catalysts are known to transesterify low-quality oils with moderately high FFAs
and water contents. Though low in catalytic activity, their performance could be improved by
simple calcinations process. Heterogeneous base catalysts are available in different forms such
as hydrotalcites, metal oxides, mixed-metal oxides, metallic salts, supported-based catalyst and
base zeolites to mention a few (Guo & Fang, 2011). They can be generated from low-cost waste
materials such as eggshell (Piker et al., 2016), plantain peels (Betiku & Ajala, 2014) and animal
bones (Nisar et al., 2017) with their catalytic activity enhanced by calcinations. Hydrotalcites
(HTs) are a class of anionic and basic clays known as layered double hydroxides (LDHs) with
the formula Mg6Al2(OH)16CO3.4H2O. HTs consist of positively charged brucite-like layers and
interstitial layers formed by CO32 anions and water molecules compensate the positive charge
resulting from the substitution. LDHs have strong alkali sites and high stability with good
69
adjustability of composition and structure (Guo & Fang, 2011). Metal oxides are composed of
cations possessing Lewis acid and anions with Brӧnsted base. They are classified as single
metal oxides (e.g., CaO, MgO and SrO) and mixed metal oxides (e.g., A-B-O type metal
oxides, where A is alkaline-earth metal (Ca, Ba, Mg), alkaline metal (Li) or rare earth metal
(La) and B is a transition metal (Ti, Mn, Fe, Zr, Ce) (Kawashima et al., 2008; Liu et al., 2008).
Reports on the use of inorganic solid bases (metallic salts) are rare in literature, although such
materials are easy-to-use and could be sourced from low-cost materials. Available reports
indicate that sodium silicate, vanadyl phosphate, calcium zincate and calcium methoxide have
been investigated as heterogeneous catalysts for biodiesel synthesis with yield of almost 100%
under certain conditions (Guo & Fang, 2011).
Alkali metals (Li, Na, K) and alkaline-earth metals (Mg, Ca, Ba) are the most common sources
of super basicity, and selected as the active species of supported solid base catalysts for
biodiesel synthesis. They are frequently used in the metallic form or as various ionic forms of
hydroxide, halide, carbonate and nitrate. Alumina, silica, zinc oxide, zirconium oxide and
zeolite have been used as supports for these catalysts (Issariyakul & Dalai, 2014; Guo & Fang,
2011) in their preparation by impregnation followed by calcinations. The reaction mechanism
pathway for solid base-catalyzed transesterification seems to follow a similar mechanism to
that of a homogeneous base catalyst. First, ion exchange proceeded after methanol adsorbed
on the surface of solid base, producing active specie (CH3O-) which is strongly basic and highly
active. Secondly, nucleophilic attack of CH3O- on the carbonyl carbon of triglyceride formed
a tetrahedral intermediate. Thirdly, rearrangement of the intermediate results in the formation
of ester (biodiesel). Finally, protons are converted to diglyceride ion to generate diglyceride.
This sequence is then repeated twice to yield glycerol and biodiesel.
70
2.16.4 Enzyme-catalyzed transesterification reaction
Lipases as enzyme-catalysts for biodiesel synthesis have been classified as environmentally
friendly approach to solving energy problems. This new area of research seems to overcome
the challenges of using conventional catalysts-feedstock pretreatment, high energy
requirements, catalyst removal problems and waste water treatment (Aransiola et al., 2014).
Lipases as biocatalysts can be classified as: extracellular lipases and intracellular lipases, and
are produced by microorganisms, animals and plants (Gog et al., 2012; Antczak et al., 2009).
The main drawbacks of lipase-catalyzed transesterification reaction are the high cost of enzyme
production, higher reaction times as compared to base-catalyzed reaction, potential hazard of
explosion, regeneration and reuse of biocatalyst limited with a long operating time. However,
in order to reduce cost of operation and improve catalyst stability and reusability, lipases can
be immobilized on several materials (Modi et al., 2007; Noureddini et al., 2005), and have been
characterized by high selectivity and efficiency, absence of side reactions, and high yield of
biodiesel (Koh et al., 2011; Dizge & Keskinler, 2008).
2.16.5 Heterogeneous catalyst from natural sources
Sourcing for sustainable heterogeneous catalysts derived from waste biomass materials and
other natural sources as alternative to conventional heterogeneous catalysts of chemical origin
is a promising area of research (Aransiola et al., 2014). The conventional heterogeneous
catalysts (acid or base) require high synthesis cost, and sometimes-expert skills are required
for processing them. Therefore, sourcing for solid base catalysts from biomass could reduce
the cost of biodiesel and serve as a platform for converting waste to wealth. Betiku and Ajala
(2014) obtained 95% yield of yellow oleander oil biodiesel with calcined biomass (waste
plantain peels) as solid base catalyst. In addition, the catalytic activity of CaO obtained from
natural and biological waste materials such as eggshell, limestone calcite, dolomite and animal
71
bones through calcinations has been investigated as solid base catalysts for oil
transesterification (Nisar et al., 2017; Piker et al., 2016).
2.17 Transesterification of rubber seed oil
Transesterification reaction is a process generally employed to produce fatty acid mono-alkyl
ester (FAME) popularly called biodiesel when vegetable oil or animal fats reacts with excess
short-chain alcohol (in this case, methanol) in the presence of a suitable catalyst (acid, base or
enzymes) with glycerol as by-product (Onoji et al., 2016a). The free fatty acids (FFAs) and
moisture contents of the oil/fats determine the choice of the catalyst. The transesterification
processes available in literature for rubber seed oil biodiesel production are conventional
method, in-situ, enzymatic, supercritical, co-solvent, ultrasonic-assisted, and microwave-
assisted. Several factors such reaction time, temperature, FFAs and moisture contents, pressure,
capital cost, catalyst type and reagents determine the applicable method of production. Edible
vegetable oils with low FFA (<1 wt. %), commonly employ homogeneous base catalysts such
as NaOH and KOH. Homogeneous base catalyst will form soap during transesterification of
rubber seed oil with simple alcohols because of its high FFA. In a 2-step process, esterification
reaction of rubber seed oil with excess alcohol in the presence of homogeneous acid catalyst
(H2SO4) will reduce the FFA content. The esterified oil is transesterified with homogeneous
base catalyst to produce a higher yield of rubber seed oil's biodiesel and glycerol as waste.
However, the downstream processing of the biodiesel to recover the catalyst and other waste
products possess challenges to industrialists with the attendant high capital costs.
Heterogeneous catalyst that catalyzes both esterification and transesterification reactions is
seen as a better option for high FFA oils. They are stable, active at low temperature, have high
selectivity, relatively cheap and could be locally sourced (Di Serio et al., 2008).
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2.18 Transesterification methods for rubber seed oil
The transesterification methods available for biodiesel production from RSO are conventional,
in-situ, enzymatic, supercritical, co-solvent, ultrasonic-assisted and microwave-assisted.
2.18.1 The conventional method
The common conventional homogenous base catalysts for RSO transesterification reaction are
NaOH, KOH, carbonates and the alkoxides of Na and K (Ahmad et al., 2014a; Ibrahim & Pillai,
2011) with biodiesel yields ranging from 86.7-97.8 wt.%. Homogeneous acid catalysts such as
H2SO4, HCl, and H3PO4 are used for RSO esterification (pre-treatment) process prior to
transesterification reaction (Ahmad et al., 2014b, Ahmad et al., 2014c; Bokhari et al., 2014).
Heterogeneous catalysts such as cation exchange resin, solid metal oxides and their silicates
are tolerant to high FFAs RSO and can be used several times without much loss to activity
(Omorogbe et al., 2013). Gimbun et al. (2012) used lime-based catalyst derived from cement
clinker to obtain 96.9 wt. % yield of biodiesel from high FFA RSO. Krishnakumar et al. (2013)
synthesized biodiesel from rubber seed oil with solid CaO catalyst calcined at 850 oC for 1.5 h
and reported a yield of 98 wt. %.
2.18.2 The in-situ method
This involves contacting the raw-milled seed directly with the alcohol in the presence of a
catalyst (acid/alkali) instead of the pre-extracted oil. The advantages of the process include
reduced reaction time, higher yield, smaller wastewater formation and lower consumption of
reagents (Ma & Hanna, 1999). Abdulkadir et al. (2014) and Widayat et al. (2013) employed
in-situ method and obtained optimum biodiesel yields of 75 wt. % and 91.05 wt. percentage
respectively during RSO transesterification.
73
2.18.3 The enzymatic method
This method uses enzymes such as lipases as biocatalysts. Though characterized by low
reaction rates, when the enzymes are immobilized, they can be re-used several times (Ma &
Hanna, 1999). The process is FFA friendly and the milder conditions allowed biodiesel yield
of at least 90% (Awolu & Layokun, 2013) and can be used to transesterify rubber seed oil to
biodiesel.
2.18.4 The supercritical method
This process is tolerant to high FFA and moisture content and recommended by researchers for
variety of feeds such as rubber seed oil and waste vegetable oils (Sanjel et al., 2014). Under
the supercritical conditions, the alcohol becomes “super acid” thereby eliminating the use of
catalyst creating a single phase with low reaction time (2-4 min) and low mass transfer
limitations are reduced. The high temperature (300–400 oC), high pressure (80–100 atm) and
high molar alcohol/oil ratio (42:1) are some of its inherent disadvantages (Thanh et al., 2012).
2.18.5 The co-solvent assisted method
This is a new greener biotechnological method because of minimum waste generation and low
energy demand. The co-solvent creates a single phase that gives rise to increased reaction rates
within a short time. Among the researched co-solvents such as tetrahydrofuran (THF), 1-4-
dioxane, acetone and di-ethyl ether, THF was the first reported co-solvent used for biodiesel
production (Thanh et al., 2012).
2.18.6 The ultrasonic-assisted method
The immiscibility of alcohol and vegetable oils hinders mass transfer rates between the phases.
This limits the reaction rates and the yield of biodiesel (Guo & Fang, 2011). Widayat and Kiono
74
(2012) employed ultrasonic-assisted technology in the extraction and transesterification of
rubber seed oil simultaneously to biodiesel at 40 oC and 40 Hz. A developed model equation
for the transesterification step based on response surface methodology shows that ultrasound
could reduce process time and increase biodiesel yield significantly.
2.18.7 The microwave-assisted method
This is an alternative heating method to the conventional method of heating because the
microwave energy selectively energizes the catalyst's interaction with the reactants (Hincapie
et al., 2014; Di Serio et al., 2008). Microwave is non-ionizing radiations with low energy. The
changing electrical field component of microwave radiation interacts with the dipoles of the
reactants molecules increasing their rotations. This reflects an increase in reaction rates and
higher biodiesel yield in shorter time, as compared to conventional systems heating (Hincapie
et al., 2014; Guo & Fang, 2011).
2.19 Factors affecting the transesterification of rubber seed oil
Transesterification of rubber seed oil to synthesize biodiesel is affected by number of factors.
The parameters considered in this thesis are as follows:
2.19.1 FFA content of rubber seed oil
The FFA content of rubber seed oil is reportedly high with the range 23.471–45 wt. % (Ahmad
et al., 2014a; Omorogbe et al., 2013; Ebewele et al., 2010b). The reduction of FFA values of
crude rubber seed oil is significant to avoid soap formation and downstream processing
problems when a homogeneous base catalyst is used in transesterification reaction (Ibrahim &
Pillai, 2011). Homogeneous acid catalyst such as H2SO4 is employed in esterification of the oil
with alcohol to reduce the FFA to less than 1 wt.% prior to transesterification. Catalyst
75
concentration followed by alcohol/oil ratio is the most influential parameters compared to
reaction temperature and time (Ahmad et al., 2014b).
2.19.2 Alcohol/oil molar ratio
Alcohol/oil molar ratio is one important variable that affects the yield of biodiesel. The
stoichiometric ratio for transesterification requires three moles of alcohol and one mole
triglyceride to yield three moles of fatty acid esters and one mole of glycerol (Ma & Hanna,
1999). The molar ratio depends on the catalyst type and may be as high as 30:1 for acid
catalyzed reaction and 6:1 for base reaction for butanol-soybean oil (Freedman et al., 1986).
Various researchers (Bokhari et al., 2014; Ahmad et al., 2014b; Abdulkadir et al., 2014)
reported a 6:1 molar alcohol/oil ratio for maximum biodiesel yield of 75–96.8 wt. % when
homogeneous catalyst such as KOH is employed for rubber seed oil transesterification. Ahmad
et al. (2014b) observed that alcohol/oil molar ratio is the most influencing factor in rubber seed
oil biodiesel production up to certain limit, beyond which the amount of methanol has no effect
on the biodiesel yield while a higher methanol concentration may result to downstream
processing problems.
2.19.3 Catalyst concentration
Different catalyst loadings for the successful transesterification of rubber seed oil to biodiesel
have been reported in the literature. Gimbun et al. (2012) reported an optimum 6 wt. % with a
yield of 92.3% using a limestone-based catalyst for rubber seed oil transesterification. Optimal
conditions such as catalyst loading, calcination temperature and time are usually determined
through optimization process (Ahmad et al., 2014a; Ahmad et al., 2014c). Catalyst loading was
reported the second most influencing factor that determines higher of biodiesel (Ahmad et al.,
2014b; Widayat & Kiono, 2012). The physical appearances of rubber seed oil biodiesel are
76
determined by the concentration of the catalyst with higher concentration giving rise to a darker
colour (Widayat et al., 2013). Dhawane et al. (2015) studied the influence of using flamboyant
pods derived steam activated carbon as catalyst (0.5–5 wt.%) on the transesterification of
rubber seed oil at 60 oC, 15:1 methanol/oil ratio, 750 rpm, and 60 min reaction time. they
reported a maximum FAME yield of 89.3% at catalyst loading of 3.5 wt.%. Further increase in
catalyst concentration decreases the yield due to soap formation during the reaction, viscous
and emulsified reaction mixture at higher catalyst loadings.
2.19.4 Reaction temperature and time
Generally, increase in temperature increases the rate of a chemical reaction and the yield of
rubber seed oil biodiesel (Abdulkadir et al., 2014; Gimbun et al., 2012). Dhawane et al. (2015)
reported 60 oC as most desirable temperature for transesterification reaction when methanol is
used. Gimbun et al. (2012) observed that increasing the temperature above the boiling point of
methanol (65 oC) to about 70 oC reduces the yield from 96.9 to 95.8 wt. % when rubber seed
oil was transesterified with derived CaO as a base catalyst. The decrease yield is explained by
the evaporation of methanol when reaction temperature is above 65 oC. Most work cited in
literature suggests that 1 h reaction time is sufficient for the completion of a transesterification
reaction with base catalyst. Solid catalyst leaching may increase may increase when a higher
reaction time is considered (Dhawane et al., 2015).
2.19.5 Agitation speed
Agitation speed plays significant role in the esterification and transesterification of vegetable
oils to esters because of mass transfer limitations imposed by the immiscibility of the reaction
mixtures. Dhawane et al. (2016) in their study reported the influence of agitation speed on the
optimization of Iron (II) doped carbonaceous catalyst for biodiesel production from rubber seed
77
oil at 12:1 methanol/oil ratio, 55 oC, and 1 h reaction time. They observed that at 500 rpm, the
yield was 94.5%, and subsequently decreases to 85.01% at 750 rpm that was attributed to the
leaching of the adsorbed Iron (II) from the surface into the reaction mixture. Further reduction
in yield to 75.34% was reported when agitation speed increases to 100 rpm.
2.20 Thermodynamics of internal combustion ignition engines
The reaction paths for complex fuel mixtures such as diesel, biodiesel or gasoline are not well
defined compared to the actual path of combustion process for simple fuels such as hydrogen
and methane. However, the first and second laws of thermodynamics can be applied to analyze
the combustion performance of internal combustion ignition engines. First law of
thermodynamics can be used to relate the end states of mixtures undergoing a combustion
process, and its application does not require the details of the process as it fails to give the best
insight into the engine's operation (Abassi et al., 2010). Energy balance on the cylinder is made
with the aim of obtaining power and efficiency using first law. Otto and Diesel cycles are the
common methods applied to analyze the performance of engines using the first law.
2.20.1 Overview of reciprocating engines
A reciprocating engine also called internal combustion ignition engine is a piston cylinder
device (Figure 2.12) that has a wide range of applications in automobiles, truck, light aircraft,
ships, and electric power generators. The piston reciprocates in the cylinder between two fixed
positions, known as the top dead center (TDC) and the bottom dead center (BDC). The TDC is
the position of the piston when it forms the smallest volume in the cylinder, while the BDC is
the position of the piston when it forms the largest volume in the cylinder (Ҫengel & Boles,
1994). The distance between the TDC and BDC is the largest distance that the piston can move
in one direction, and it is called the stroke of the engine. The diameter of the piston is called
78
the bore. The air or air-fuel mixture is drawn into the cylinder through the intake valve, and the
combustion products expelled from the cylinder through the exhaust valve. The minimum
volume formed in the cylinder when the piston is at TDC is the clearance volume, while the
volume displaced by the piston as it moves between TDC and BDC is the displacement volume.
The ratio of the maximum volume formed in the cylinder to the minimum (clearance) volume
is the compression ratio (r ) of the engine (Ҫengel & Boles, 1994):
Vmax V BDC
r  (2.23)
Vmin VTDC
Reciprocating engines are classified as either compression-ignition (CI) engines (e.g., diesel
engine) or spark-ignition (SI) engines (e.g., petrol engine) depending on how the combustion
process is initiated. They operate as either four-stroke or two-stroke internal combustion
engines depending on designs.
intake exhaust
valve valve
TDC
Bore
Stroke
BDC
Figure 2.12: Schematic diagram for a reciprocating engine cylinder (Adapted from
Ҫengel & Boles, 1994)
79
2.20.2 Air-standard assumptions
The working fluid remains a gas throughout the entire cycle in the gas power cycle.
Compression-ignition (diesel), spark-ignition (petrol), and the conventional gas turbine engines
are devices that operate on gas cycle. During the combustion process, the composition of the
working fluid changes from air and fuel to combustion products during the course of the cycle.
The working fluid closely resembles air at all times because air is predominantly nitrogen that
hardly undergoes chemical reactions in the combustion chamber. The working fluid is expelled
as exhaust gases instead of returning to its initial state at a point in the cycle. This tells us that
the working fluid does not undergo a complete thermodynamic cycle, though internal
combustion engines operate on a mechanical cycle (i.e., the piston returns to its starting position
at the end of each revolution). To simplify the analysis of actual gas power cycles, the following
air-standard assumptions are usually applied:
 The working fluid is air. It circulates continuously in a closed loop, and behaves as an
ideal gas,
 All the processes which make up the cycle are internally reversible,
 The combustion process is replaced by a heat addition process from an external source,
 A heat rejection process that restores the working fluid to its initial state replaces the
exhaust process.
The air-standard assumption is called the cold-air standard assumption if the air has constant
specific heats whose values are determined at room temperature (25 oC). This simplified model
enables us to study qualitatively the influence of major parameters on the performance of the
actual engines (Ҫengel & Boles, 1994).
80
2.20.3 Diesel cycle-The ideal cycle for compression ignition engines
The Diesel cycle (Figure 2.13) is the ideal cycle for CI reciprocating engines. The CI engine,
first proposed by Rudolf Diesel in the 1890s is very similar to the SI engine. In SI engines, the
air-fuel mixture is compressed to a temperature below the auto-ignition temperature of the fuel,
and the combustion process is initiated when a spark plug is fired (Ҫengel & Boles, 1994). In
CI engines, only air is compressed to a temperature above the auto-ignition temperature of the
fuel, and combustion starts on contact as the fuel is injected into the hot air. Therefore, a fuel
injector in diesel engines replaces the spark plug and carburetor. In gasoline engines, a mixture
of air and fuel is compressed during the compression stroke, and the compression ratio is
limited by the onset of auto-ignition or engine knock. In diesel engines, only air is compressed
during the compression stroke, thereby eliminating the possibility of auto-ignition. Therefore,
diesel engines can be designed to operate at much higher compression ratios, typically between
12 and 24 (Ҫengel & Boles, 1994).
The fuel injection process in diesel engines starts when the piston approaches TDC and
continues during the first part of the power stroke. Therefore, the combustion process in these
engines takes place over longer intervals and thus, diesel cycle is approximated as a constant-
pressure (process 2 → 3) heat addition process. This is the only process where Diesel cycle
differs from Otto cycle. The remaining three processes are the same for both ideal cycles
(processes 1 → 2, 3 → 4, and 4 → 1). Diesel cycle, like the Otto cycle, is executed in a closed
system (piston-cylinder).
81
(a)
P Qin
2 3
isentropic
isentropic Qout
1
v
T
(b)
Qin
P =constant 3
2
4
Qout
1 v =constant
Figure 2.13: P–v (a) and T–s (b) diagrams for the ideal Diesel cycle (Adapted from Ҫengel
& Boles, 1994)
Under the cold-air standard assumptions, the amount of heat added to the working fluid at
constant pressure and rejected at constant volume can be expressed as:
Qin  Q23  W23  (U ) 23  P2 v3  v2   U 3  U 2  (2.24)
Qin  h3  h2  C p T3  T2  (2.25)
Qout  Q41  W41  (U ) 41  U 4  U1  Cv T4  T1  (2.26)
W41  0 (2.27)
82
The thermal efficiency of the ideal diesel cycle under the cold-air standard assumptions
becomes:
T 
T1  4  1
T T
 4 1  1  1 
Wnet Q T
nth , Diesel   1  out
 T3  T2 
(2.28)
Qin Qin T 
T2  3  1
 T2 
Cp
where   , the specific heat ratio and equal to 1.4 for ideal gas (Azoumah et al., 2009).
Cv
If (r ) is defined as the engine's compression ratio and (rc ) represents the cutoff ratio, expressed
as the ratio of the cylinder after and before the combustion process, then Equation (2.28) can
be expressed as (Azoumah et al., 2009):
1  rc  1 
nth ,Diesel  1    (2.29)
r  1   rc  1
V1 V
where r  , and rc  3 ; V1 is the maximum volume, and V2 represents the clearance volume
V2 V2
as earlier discussed.
The combustion chamber temperature (T3 ) under ideal conditions can be evaluated from the
measured exhaust gas temperature (T4 ) by the relation (Azoumah et al., 2009):
 1
r
T3  T4   (2.30)
 rc 
The compression stroke (process 1 → 2) is assumed an isentropic process, and the following
equations used to determine the pressure and temperature at stage 2.
 1
V 
T2  T1  1  (2.31)
 V2 

V 
P2  P1  1  (2.32)
 V2 
83
Process 2 →3 ( P  constant heat addition to the air-fuel mixture, i.e. P2  P3 ):
P2V2 P3V3
 (2.33)
T2 T3
V 
T3  T2  3  (2.34)
 V2 
Process 3 → 4 (isentropic expansion of the combustion gases):
 1
V 
T4  T3  3  (2.35)
 V4 

V 
P2  P3  3  (2.36)
 V4 
Process 4 →1 (constant-volume heat rejection process with no work interactions is shown in
Equations (2.26) and (2.27), respectively.
The mean effective pressure (MEP) is determined as:
Wnet Wnet
MEP   (2.37)
Vmax  Vmin V1  V2
2.20.4 Mathematical models for internal compression ignition engines
The analysis of the performance of internal compression ignition (diesel) engines based on the
second law of thermodynamics is made possible by first-law mathematical modeling of the
various processes inside the cylinder and its subsystems. Examples of such mathematical
models include zero-dimensional models also referred to as single-zone models, two-zone,
four-zone or multi-zone models (Rakopoulos & Giakoumis, 2006). The single-zone model
assumes the working fluid in the engine to be a thermodynamic system (mixture of gases) that
undergoes energy and mass exchange with the surroundings, and the energy released is
computed using first law of thermodynamics. In the two-zone models, the working fluid in the
engine is split into two zones (burned and unburned gases) that are analyzed separately (Hago
84
& Morin, 2010; Rakopoulos & Giakoumis, 1997). Computer simulations of internal
combustion engine cycles have been of tremendous use in design studies, as diagnostic tools
in analyzing data obtained from experiments, and in understanding the complex processes
occurring in the combustion chamber. Quasi-dimensional model, a double-zone model has
been the most frequently used model because it predicts the performance of the engine better
than the single zone models (Rakopoulos & Giakoumis, 1997).
As discussed above, the Diesel cycle is useful for analyzing diesel engine’s performance. The
compression stroke of Diesel engine can be simulated from the following equations based on
ideal gas behaviour.
PV  nRT (2.38)
dp 1   R  dv R 
  1   P  
d V   Cv  d Cv 
(2.39)
The volume of the cylinder at any crank angle (θ) can be defined as (El-Seesy et al., 2017;
Heywood, 1988):
 2

V  Vc 1  rc  1   1  Cos   2  Sin 2  
 1

0.5 

(2.40)
l
 (2.41)

where Vc  clearance volume as earlier defined, rc  cutoff ratio, l  connecting rod length
(m), and   crank radius (m).
Differentiating Equation (2.40) with respect to the crank angle (θ) gives:
1 
 Vc  rc  1Sin  0.5 2Sin2 
dV
(2.42)
d 2 
The net heat release rate (HRR) in the cylinder during the combustion process using a single-
zone combustion model can be determined from the expression described by (Bayindir et al.,
2017; Ibrahim, 2016):
85
dQ  dV 1 dP
 P  V (2.43)
d   1 d   1 d
The cumulative heat release (CHR) is the integral of HRR over a restricted crank angle ( )
interval that depends on the HRR curve and given as (Guardiola et al., 2017):
   1
 dQ      1  PdV     1VdP (2.44)
Where Q  apparent heat release rate (J), P  cylinder pressure (bar), and V instantaneous
volume of cylinder (m3).
Computer software like MATLAB can be used to simulate Equation (2.38) to Equation (2.44)
and the results obtained can be compared with those from experiments.
To model the performance of a compression ignition (CI) engine according to the first law of
thermodynamics, Rakopoulous & Giakoumis (2006) suggested the following simplifying
assumptions:
(a) Spatial homogeneity of pressure for two-zone models;
(b) Spatial homogeneity of temperature for the whole cylinder or for each zone considered;
(c) Working fluid is considered an ideal gas;
(d) Gas properties (enthalpy, internal energy, etc.) are modeled using polynomial relations with
temperature (and pressure);
(e) Heat released from combustion is distributed evenly throughout the cylinder;
(f) Blow-by losses are neglected;
(g) Enthalpy associated with pressure of injected fuel is negligible;
(h) Spatially averaged, instantaneous (time resolved) heat transfer rates are used to estimate
heat transfer to the cylinder walls;
(i) Dissociation is usually, but not always neglected;
(j) No heat transfer occurs between burned and unburned zones;
(k) Work required to transfer fluid from the unburned zone to the burned zone is negligible.
86
2.20.5 Models for gas mixture properties
One of the processes that control engine power, efficiency, and emission inside the diesel
engine cylinder, is the combustion of fuel-air mixture (Heywood, 1988). The components that
make up the working fluid in the engine cylinder such as oxygen, carbon dioxide, carbon
monoxide, water vapour, fuel vapour, nitrogen, etc. are treated as ideal gases for simplification
in engine performance evaluations.
Thus,
m
PV  RT  nRT (2.45)
M
where P  pressure, V  volume, m  mass of gas, T  temperature, R  universal gas constant,
M  molecular weight, and n  number of moles.
The mixture of diesel and biodiesel properties can be determined from individual properties
using the following relations:
mix  i xi (2.46)

i 1
where mix is the property of the mixture, i is the property of pure diesel or biodiesel, and xi is
the fraction of diesel or biodiesel.
Air-fuel ratio is defined by:
 A i xi
   (2.47)
 F  mix i 1 i xi  A F i
The lower heating value (LHV) of the fuel mixture as given by Bayraktar (2005) is:
 x LHV 
i i i
LHVmix  i 1
(2.48)
 x i 1
i i
The general chemical reactions occurring in the engine cylinder for diesel/biodiesel blend-air
mixture with humid air is approximated by the following reactions (Meisami et al., 2017).
87
aC14 H 25  bC18 H 34O2  cO2  3.76N 2  xH 2O  dCO2  eCO  fO2  gNO  hNO2  iN2  jH 2O
(2.49)
where O2  3.76 N 2  xH 2O is the inlet air entering the combustion chamber.
x  7.655 (2.50)
Pv
  0.622
Pa (2.50-a)
where  represents specific humidity of air, Pv and Pa are the partial pressure of vapour and
dry air, respectively, and combustion reaction based on one mole of the fuel a  b  1 .
Özkan (2015) in a comparative study on energy and exergy analyses of a diesel engine reported
a combustion equation for diesel fuel (No. 2) based on Equation (2.49).
C14 H 25  35.264O2  3.76 N 2   14.929O2  0.017CO  14.04CO2  0.00236C14 H 25  0.4911NO 

0.0161NO2  132.343N 2  12.363H 2 O
(2.51)
2.20.6 First and second laws of thermodynamics for internal combustion engines
Energy analysis of a process is based on the first law of thermodynamics, which embodies the
principle of energy conservation. It is a traditional method used to assess the performance and
efficiency of energy systems and processes. The first law deals with the quantity of energy and
does not fully analyze the performance of internal combustion ignition engine.
According to the first law, the energy balance for steady-state control volume (combustion
chamber volume) of the engine is given as:
Q  W  H (2.52)
where Q represents the heat transfer through the combustion chamber to cooling water and
lubrication systems per mole of fuel, W represents the mechanical useful work done by the
engine in one cycle per unit mole of fuel, and H represents the enthalpy change between the
products  H p  and reactants  H r  .

 
   
88
Thus,
 
H  H p  H r (2.53)
When we substitute Equation (2.53) into Equation (2.52), we obtain an expression:
 
Q  H r  W  H p (2.54)
The enthalpy terms can be evaluated from the following equations:
  0 
H r   ni  h f   h  (2.55)
r  i
  0 
H p   ne  h f   h  (2.56)
p  e
where, ni and ne are the moles number of reactants and products, respectively, per mole of fuel
0
obtained directly from the balanced combustion equation, h f is the standard enthalpy of

formation and  h represents the difference in enthalpy between any given state and the
enthalpy of ideal gas at 25 oC and 1 atm.
Introducing Equation (2.55) and Equation (2.56) into Equation (2.54) yields:
 0   0 
Q   ni  h f   h   W   ne  h f   h  (2.57)
r  i p  e
 
where Q , W , H r , and H p are in kJ/kmol of fuel.
The lower heating value LHV  at constant pressure equals the enthalpy at complete
combustion when water is present as a vapour and based on first law, it is described by the
relation (Caton, 2000):
0 0
LHV  H P0 ,T0   ni h f ,i   ne h f ,e (2.58)
r p
89
where H P ,T represents the enthalpy of the combustion at reference dead state pressure P0 
0 0
and temperature T0  .
The second law of thermodynamics can be used to obtain a model expression for the maximum
useful work an engine can deliver, based on the assumption that an internal combustion engine
is an open system that exchanges heat and work with its surrounding. Exergy (also called
Availability) is defined as the maximum amount of useful work that can be obtained by bringing
a system to a state of thermodynamic equilibrium (thermal, mechanical, and chemical) with the
common components of the environment by means of a reversible process (Peduzzi et al.,
2016). Exergy analysis based on the second law of thermodynamics is a thermodynamic
analysis technique for systems and processes that deal with the quality of energy. It has been
increasingly applied on energy systems over the last few decades because of its advantages
over energy analysis based on first law (Abassi et al., 2010; Rakopoulos & Giakoumis, 1997).
In evaluating exergy, the characteristics of the reference environment (temperature, pressure,
and chemical composition) must be specified. Thus, exergy depends on the properties of the
system or process, and the environment. Exergy is not conserved like energy, but destroyed by
processes such as combustion, friction, mixing and throttling that decrease the ability of the
system to produce useful work (Abassi et al., 2010; Rakpoulos & Giakoumis, 1997). The
destruction of exergy, called irreversibility is the source of non-maximum conversion of fuel
energy into useful mechanical work in a diesel (and Otto) engine. The reduction of
irreversibility can lead to better engine performance through a more efficient exploitation of
fuel (Rakopoulos & Giakoumis, 2006).
From the second law of thermodynamics, the heat transfer (Q) can be expressed as follows:
Q
 S (2.59)
TA
where TA is the temperature of the surrounding and S is the entropy.
90
Combining Equation (2.52) and Equation (2.59) results in:
W  H  TA S  (2.60)
Maximum work is achieved when the pressure and temperature of the products equals that of
the atmosphere.
Under these conditions:
Wmax  G PA ,TA

(2.61)
where G P ,T represents the change in the Gibbs free energy for the conversion of reactants
A A
r  to products  p  at atmospheric temperature and pressure, and will be at its maximum at the
complete combustion of the fuel (Caton, 2000).
The availability (exergy) conversion efficiency   , which measures the effectiveness of any
internal combustion engine is determined from the ratio of the actual work delivered compared
with this maximum work, and expressed as follows:
W W
 
Wmax  G PA ,TA
(2.62)
2.20.7 Second law of thermodynamics analysis (availability)
The second law of thermodynamics analysis applies exergy (availability) equations in the
engine cylinder of internal combustion ignition engine. The different forms of availability that
exist for the analysis of the engine cylinder are chemical availability, flow availability, thermal
availability, mechanical availability and fuel availability (Caton, 2000).
The chemical exergy (fuel availability) associated with the burning of fuel in the cylinder, and
for hydrocarbon liquid fuel of the general type, C x H y on kg basis is given as (Rakopoulos &
Giakoumis, 2006):
91
 y 0.042 
a fch  LHV 1.04224  0.011925  
 x x  (2.63)
For fuel of the form C z H y O p S q (Meisami et al., 2017; Özkan, 2015; Rakopoulos & Giakoumis,
2006; Stepanov, 1995):
 y p q y 
a fch  LHV 1.041  0.1728  0.0432  0.2196 1  2.0628  (2.64)
 z z z z 
Thermo-mechanical availability is another form cited by Rakopoulos & Giakoumis (1997):
a ftm  U  P0V  T0 S  G0
(2.65)
where G0 is the working medium’s Gibbs free enthalpy at ambient pressure P0 , and
temperature T0 , calculated based on dead state compositions, and neglecting kinetic and
potential energy terms.
When the system moves from one state to another, the change in exergy as defined by Lior &
Rudy (1988) for ideal Otto cycle is also applicable for Diesel cycle.
 T   P 
a ftm  CP Tn1  Tn   Tn CP loge  n1   R loge  0 
  Tn   Pi  (2.66)
Pi  x i P (2.67)
where n (0, 1, 2, 3, 4) represents the state of the components, Pi represents the partial pressure
of component i .
If T1 represents the intake temperature, and T0 equals the temperature of the environment, then
T1  T0 for n = 0 (i.e., the environment), and the exergy for the intake process becomes:
P 
a ftm , 01   RT0 loge  0  (2.68)
 Pi 
The exergy of the exhaust gases includes thermo-mechanical exergy and chemical exergy
components described by (Meisam et al., 2017; Özkan, 2015):
92
 P
   
a ftm   yi  hi,T  hi,T0  T0 si,T  si,T0  RT0 loge  (2.69)
i  P0 
 y 
a fch  RT0  yi loge  i 
i  yi , 0  (2.70)
a fexh  a ftm  a fch

(2.71)
where a ftm represents the thermo-mechanical exergy, a fch represents the chemical exergy and
a fexh represents the total exhaust exergy in molar basis.
The availability balance can be made on the inlet manifold and the exhaust manifold for each
fuel composition and the results can be used to estimate the exergy efficiency of the engine for
different fuel composition as follows (Rakopoulos & Giakoumis, 2006):
Availability out in product Loss  destruction

  1
Availability in Input (2.72)
If we consider the cylinder as a closed system and for a four-stroke engine based on second-
law, Meisami et al. (2017), Rakopoulos & Giakoumis (2006), and Heywood (1988) describe
the exergy efficiency per cycle as:

𝑊𝑏
𝜀1 = (2.73)
𝑚̇𝑓1 𝑎𝑓𝑐ℎ
where Wb represents the brake work production, and 𝑚̇𝑓1 , represents the total mass flowrate
of fuel entering the cylinder per cycle.
The efficiency 1  can then be compared to the brake thermal efficiency 𝜂𝑡ℎ as defined by first
law of thermodynamics (Meisami et al., 2017; Rakopoulos & Giakoumis, 2006).

𝑊𝑏
𝜂𝑡ℎ = (2.74)
𝑚̇𝑓1 𝐿𝐻𝑉
Thus,
𝐿𝐻𝑉
𝜀1 = 𝜂𝑡ℎ 𝑎 (2.75)
𝑓𝑐ℎ
93
Another approach to second-law exergy efficiency for the cylinder is as defined by Alkidas
(1988):
Wb Wb
2  
Wmax Wb  I (2.76)
where I represents irreversibilities due to combustion and heat transfer.
For a closed system considered for the cylinder, mass transfer is limited in or out of the cylinder
during a single cycle, and the exergy of the fuel is described by the relation (Lior & Rudy,
1988):
a fch ,closed  a fch  P  Pi v (2.77)
where, v  specific volume (vol/mol), Pi is the partial pressure of the components (diesel and
biodiesel once vapourized) which is determined by using Raoult's law as follows:
Pi  xi P (2.78)
The specific volume v  is calculated from equations of state assuming ideal gas behaviour for
the air-fuel mixture.
RT
v (2.79)
P
where R is the ideal gas constant, T is the temperature, and P is the pressure in the cylinder.
If the assumption of zero work done by the exhaust gases as they return to the environment as
discussed earlier (Equation (2.27)) is applied, then the following changes in exergy for the
process could be written as (Lior & Rudy, 1988):
Exergy added during compression (process 1 → 2)  a2  a1 (2.80)
Exergy lost during combustion (process 2 →3)  a2  a3 (2.81)
Exergy extracted during expansion (process 3 → 4)  a3  a4 (2.82)
Exergy lost from exhaust (process 4 → 1)  a4  a1 (2.83)
94
Therefore, the effectiveness of the closed system (piston-cylinder) on the premise of only one
control mass is given below:
sys,eff 
a3  a4   a2  a1  (2.84)
ain
where:
a3  a4   a2  a1  represents the net exergy extracted for intended use, and
ain represents decrease in input fuel exergy.
2.21 Performance evaluation of diesel engines
The ruggedness, fuel economy, and high-power delivery of diesel engines has attracted its use
as engines of choice in industrial applications. The performance and efficiency of an engine is
determined by evaluating engine parameters such as brake mean effective pressure (BMEP),
brake power (BP), brake specific fuel consumption (BSFC), brake thermal efficiency (BTE %),
engine torque, and observing the exhaust gas temperature. The gaseous emissions from diesel
engines increased in the past few decades due to increase in the number of operating power
plants, vehicles, ships, light aircrafts, and agricultural tractors using diesel as fuel. Due to
increasing stringent environmental regulations to protect the environment, the use of diesel-
biodiesel blends has been encouraged to reduce the levels of exhaust gas emissions such as
carbon monoxide (CO), carbon dioxide (CO2), smoke opacity, particulate matters (PM), and
oxides of nitrogen (NOx), etc into the environment (Aldhaidhawi, et al., 2017). The high
content of oxygen (10–12 %) in biodiesel enables near 100% combustion of diesel-biodiesel
blends in diesel engines. The analyses of these parameters will determine the level of
effectiveness of the engine and compliance to environmental laws.
95
2.21.1 Brake mean effective pressure (BMEP)
BMEP is the average mean pressure in the cylinder that would produce the measured brake
power output. This pressure is calculated as the uniform pressure in cylinder as the piston rises
from top to bottom of each power stroke. The BMEP is that part of the indicated mean effective
pressure IMEP the gives the brake power.
BP
BMEP  IMEP  Losses  (2.85)
Ce  N
where Ce represents the engine capacity, N represents the number of working cycles per
rev / s
second, and for a 4-stroke engine, N  ; for a 2-stroke engine, N  rev / s .
2
2.21.2 Brake power (BP)
The brake power (also called engine shaft power) of an engine is the difference between the
indicated power (IP) and the power lost to mechanical friction (FP). The indicated power is the
actual rate of work done by the working fluid (e.g. diesel oil) on the piston measured in
kilowatts. The mechanical efficiency is the measure of the ability of the engine to overcome
the frictional power loss that includes frictions in the bearings, pistons, and other mechanical
parts of the engine (Dwivedi et al., 2013).
60
BP  IP  FP  2N s (2.86)
Te
IP  IMEP  A  l  N (2.87)
BP
 mech  (2.88)
IP
where,  mech represents the mechanical efficiency, IP is in Watts, N s represents the shaft
speed in rev/s, Te represents the effective Torque (Nm), IMEP is in Pa, A is the area of piston
(m2), l is the length of stroke (m), and N as defined in Section (2.21.1).
96
2.21.3 Brake specific fuel consumption (Bsfc)
Bsfc is defined as the rate of fuel by the engine per brake horsepower developed, and it is a
measure of the efficiency of the engine in converting the fuel supplied to produce useful work.
It is desirable to obtain a lower value of Bsfc because it indicates that the engine is more
efficient.
𝑚̇𝑓
𝐵𝑠𝑓𝑐 = (2.89)
𝐵𝑃
where 𝑚̇𝑓 is the mass flowrate of fuel.
2.21.4 Brake thermal efficiency (BTE %)
This is the ratio of the brake power to the energy generated from the engine by burning the
fuel. The energy in the fuel is usually assumed as the lower heating value LHV  .
𝐵𝑃
𝜂𝑡ℎ = (2.90)
𝑚̇𝑓 (𝐿𝐻𝑉)
2.22 Performance and emissions evaluation of diesel engine using diesel-biodiesel blends
of rubber seed oil
Few studies have examined the utilization of rubber seed oil biodiesel as an alternative engine
fuel. Onoji et al. (2016a) in their review, confirm the appropriateness of such promising fuel
for use in diesel engines to boost the economy of most sub-Saharan African countries that
depend on imported fuel. Ramadhas et al. (2005a) examined the performance of unmodified
diesel engine that run on rubber seed oil, diesel, and rubber seed oil biodiesel-diesel blends at
different loads. In all cases considered, the thermal efficiency increases with load to a certain
limit, and begins to decrease. The lower blends of biodiesel increase the thermal efficiency and
reduce the fuel consumption. The low thermal efficiency for pure biodiesel (B100) is due to
97
the reduction in calorific value of biodiesel that results to increased fuel consumption compared
to B10 (10% biodiesel-90% diesel). Pure rubber seed oil has the lowest thermal efficiency in
all cases considered, and for all loads.
The brake specific fuel consumption (Bsfc) variation with engine loads for all cases considered,
decreases with increase in the load. Lower values of Bsfc were observed for lower blends of
biodiesel/diesel, but the trend reverses for higher blends of B50-B100. This is because biodiesel
is about 14% lower in calorific value than diesel fuel. The Bsfc of rubber seed oil was higher
than those of the blends and diesel because of high viscosity and low atomization.
The carbon monoxide emission increases with load capacity in all the cases considered. This
is typical with all internal combustion engines since the air-fuel ratio decreases with increase
in load, and becomes greater than the stoichiometric value. Biodiesel blends have lower CO
emissions compared to those from diesel, biodiesel and rubber seed oil.
The profile of carbon dioxide emissions in the all cases considered by the researchers increases
with load. The CO2 emissions for the blends are lower than those reported for diesel and
biodiesel. Biodiesel combustion emits more CO2 than diesel fuel because of oxygen content
(10–12 %) of biodiesel that aids higher combustion rate.
In consideration of the variation of smoke opacity of the different fuels considered with loads,
lower values were observed for biodiesel blends compared to diesel and rubber seed oil. The
blend of B20 appears to give the lowest opacity while rubber seed oil and diesel gave similar
results.
The exhaust gas temperature increases with loads for all the cases considered by the researchers
and for all fuels tested. The exhaust gas energy loss is lower for blends up to B20 because of
lower exhaust gas temperature observed. This fact is confirmed by the higher brake thermal
efficiency and lower brake specific fuel consumption obtained for B20 and below. Pure rubber
98
seed oil gave the highest exhaust gas temperature in all loads, indicative of higher energy loss
and higher concentration of NOx in the exhaust gas stream.
The foregoing results of engine performance and emissions analyses for blends of rubber seed
oil biodiesel tested by Ramadhas et al. (2005a) are similar to those reported for biodiesel from
pongamia oil (Prabhahar et al., 2011), jatropha curcas (Elango & Senthilkumar, 2011), other
non-edible oil biodiesels (Ashraful et al., 2014), and rubber seed oil-diesel blends (Ramadhas
et al., 2005b). The NOx emissions for diesel and biodiesel blends follow an increasing trend
with loads for all types of biodiesels. NOx is generally formed at higher combustion
temperatures, and lower values are for diesel fuel compared with the blends. In all cases, pure
biodiesel (B100) generates higher concentration of NOx compared with diesel and the blends
(Elango & Senthilkumar, 2011). Geo et al. (2010) injected diethyl ether (DEE) through the
intake port during suction stroke at different flowrates of 100, 150, and 200 g/h into rubber
seed oil that was injected directly inside the cylinder at the end of compression stroke in order
to study the engine performance. Their results indicate that the brake thermal efficiency
improves from 26.5% with neat rubber seed oil to a maximum of 28.5% with DEE injection
rate of 200 g/h. Smoke opacity also reduce from 6.1 to 4 BSU along with marginal reduction
in hydrocarbons and CO emissions with DEE injection. Other researchers (Senthilkumar &
Purushothaman, 2012) examined the use of high FFA rubber seed oil biodiesel-diesel blend in
a diesel engine with respect to performance and emission analysis. Their report for B00, B5,
and B100 indicated similar trends for Bsfc, BTE, and CO emissions up to 100% load with those
reported by Ramadhas et al. (2005a).
CHAPTER 3: METHODOLOGY AND EXPERIMENTAL PROCEDURES
99
3.0 Introduction
This chapter documents all methods and techniques used to achieve results in this thesis. This
includes, but not limited to the collection of rubber seeds, seed oil extraction, characterisation,
and the determination of the physicochemical properties of the extracted oil. It also discusses
the experimental procedures and methods used in the transesterification process, and the
modelling approach used in this thesis. The oil extraction process was modeled to determine
the optimum extraction process variables. The kinetics of the oil degradation under thermal
conditions was studied. The synthesis and characterisation of catalyst from waste rubber seed
shell for transesterification of the rubber seed oil to biodiesel is reported in this chapter.
Finally, the produced biodiesel was characterised, and tested in an unmodified diesel engine to
determine its performance and emission evaluation in compliance with environmental laws.
3.1 Materials and Chemicals
Matured and fresh rubber seeds (Hevea brasiliensis) used in this work was handpicked from
different clones of NIG800 series at the plantations of Rubber Research Institute of Nigeria
(RRIN), Iyanomo, Benin City.The seeds are usually available in the early months of dry season,
usually July to August each year but could be harvested until October.
Various sizes of Duran beakers, flasks, measuring cylinders and separating funnels were used
in this work. Other glass wares used include density bottles, pipettes, burettes, etc. Muslin cloth
with Whitman filter paper was used to enclose a known weight of milled rubber seed powder
into the extraction thimble during the extraction process.
All chemical reagents used in this study were of analytical grades manufactured by BDH
Chemicals Ltd., Poole England and GFS Chemicals, Inc., 867 McKinley Ave., Columbus, OH
43223, and they include n-hexane, NaOH, KOH, CaCl2, methanol, ethanol, phenolphthalein,
100
starch, KI, CCl4, Na2S2O3, ethanoic potassium hydroxide, HCl, p-anisidine, iso-octane, diethyl
ether, and ethyl alcohol.
3.2 Experimental procedures for seed oil extraction
This work was carried out in the Biochemical Engineering Laboratory at the Department of
Chemical Engineering, Landmark University, Omu-Aran, Kwara State, Nigeria, using the
experimental procedures described in this section.
3.2.1 Rubber seed preparation
Figure 3.1 shows the flowchart for the preparation of rubber seed powder from which oil was
extracted. The rubber seeds were examined for freshness, washed 3–4 times with hot distilled
water to get rid of dust and solid impurities, and dried at room temperature for 48 h (Onoji et
al., 2017a). Separation of the chaffs from the seeds was carried out by winnowing.
Approximately 500 g of seeds were de-shelled manually using laboratory mortar and pestle to
free the kernels from the shells. The seed shells and kernels were weighed separately and their
weights recorded (see Section B.1 of Appendix B for calculations). About 100 g of seed kernel
was dried for 5 h at 105 oC using U CLEAR heating drying oven (Model DHG-9053A) to
constant weight to determine the initial moisture content of the seeds. Moisture content after
conditioning was determined by calculating the weight difference of the sample before and
after oven drying (see Section B.1 of Appendix B for calculations). The remaining seed kernels
were processed to 15% absolute moisture content required for higher oil yields before
extraction (Bhuiya et al., 2015). A portion of the processed kernel was milled and sieved into
five-particle sizes (0.5, 1, 1.5, 2 and 2.5 mm) and were used to determine which particle size
would give the maximum oil yield from the available sizes (Onoji et al., 2017a).
Raw rubber seeds
101
Sun drying
(4 to 5 days)
Manual cracking
(5 days)
Winnowing
Grinding
Rubber seed powder (for oil extraction and optimisation process)
Figure 3.1: Flowchart of rubber seed powder preparation
3.2.2 Extraction of the seed oil
The main industrial process parameters influencing oil extraction are as follows: type of
solvent, kernel particle size, seed/solvent ratio, extraction time and temperature (Elkhaleefa &
Shigidi, 2015). The solvent chosen is usually based on cost, behaviour towards the matrix, and
toxicity. In this study, five-particle sizes of rubber seed kernel (0.5, 1, 1.5, 2 and 2.5 mm) were
considered to determine the particle size that will give the maximum oil yield (Onoji et al.,
2016b). For each particle size considered, the extractor was charged with 50 g of milled rubber
seed kernel packed in a muslin cloth (Figure C.1 of Appendix C), and placed in a thimble of
102
the Soxhlet extractor. A 500-mL round-bottom glass flask was filled with 225 mL n-hexane
solvent and tightly fixed to the end of the extractor (Figure C.2 of Appendix C). Heating was
provided for the setup by a heating mantle regulated at 60 oC for 45 min. Extraction time was
considered to end when the first drop of the extracting solvent recycled back into the thimble.
Each experiment was conducted in three replicates, and the mixture was concentrated at 65 oC
using rotary evaporator (Figure C.3 of Appendix C) under vacuum to recover the extracted oil
(Figure C.4 of Appendix C) (Onoji et al., 2017a, 2016b). The oil yield was gravimetrically
determined using Equation (3.1), and average values recorded in Table D.1 of Appendix D and
presented in Figure 4.1. The particle size that gave the maximum oil yield was employed for
further oil extraction.
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑 𝑜𝑖𝑙 (𝑔)

𝑅𝑆𝑂 𝑦𝑖𝑒𝑙𝑑 (𝑤𝑡. %) = × 100 (3.1)
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑟𝑢𝑏𝑏𝑒𝑟 𝑠𝑒𝑒𝑑 𝑘𝑒𝑟𝑛𝑒𝑙 𝑢𝑠𝑒𝑑 (𝑔)
3.3 Characterization of the seed oil
The physico-chemical properties of the extracted rubber seed oil were determined to ascertain
its industrial applications. Standard procedures as described by American Society for Testing
and Methods (ASTM) and Association of Official Analytical Chemists (AOAC, 1990) were
used to characterize the oil. The extracted rubber seed oil was analyzed for density, specific
gravity, oAPI, saponification value, acid value, % free fatty acids (FFA), iodine value, peroxide
value, kinematic viscosity, refractive index and pH using standard procedures as described by
ASTM and AOAC (1990).
The acid value was determined by titration method, while the iodine value was obtained by
Wijs' method. The specific gravity measurement was carried out at room temperature using
standard specific gravity bottles. The state and colour of the oil were noted using visual
inspection at room temperature (Onoji et al., 2016b). Other parameters evaluated are aniline
point, diesel index, cetane number (Mofijur et al., 2014), higher heating value (HHV)
103
(Demirbaş, 1998), mean molecular mass of fatty acids (Ajiwe et al., 1995), and average
molecular mass of oil (Fillières et al., 1995). The procedures and calculations of these
parameters are presented in Sections E.1.1 through E.1.12 of Appendix E. ASTM standard
procedures were followed to determine cloud, flash, freezing, boiling, and pour points,
respectively. The cold filter plugging point (CFPP) was estimated using the correlation cited
by Verma et al. (2016).
3.4 Spectroscopy analyses of the seed oil
The extracted oil was characterized by gas chromatography-mass spectroscopy (GC-MS),
Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR)
techniques.
3.4.1 Fatty acid profile of the seed oil
The fatty acid profile was determined qualitatively using GC-MS (QP2010 Plus Shimadzu,
Japan) system equipped with flame ionization detector (FID) with capillary column DB-1
(length 30 m x diameter 0.25 mm x film thickness 0.25 μm). Helium was used as carrier gas
with a linear velocity of 49.2 cm/s and a purge flow of 3 mL/min. The column oven temperature
was programmed at 70 oC and was quickly ramped at 10 oC/min until it reached 280 oC and
held for 5 min. A sample of the oil was mixed with 1 mL HPLC grade n-hexane. A portion of
this mixture (0.5 μL) was injected into the GC at 250 oC at split ratio of 20:1. A column pressure
of 116.9 kPa and column flowrate of 1.80 mL/min was maintained. The mass spectrometer
(MS) was operated in electron ionization mode with the following parameters: ion source
temperature 200 oC, interface temperature 250 oC and solvent cut time 2.5 min. It was scanned
from m/z 30 to 350, and identification of the peaks was performed by comparing retention
times with those of National Institute of Standards and Technology (NIST) library analyzed
104
under the same conditions (Onoji et al., 2016b). The area percentage method was used to
estimate the amount of fatty acid compositions of the oil (Sanjel et al., 2014).
3.4.2 Fourier transform infrared spectroscopy
FT-IR spectroscopy can be employed to identify the various functional groups present in oils
and gives an insight into formation of primary and secondary oxidation products when the oil
is under thermal stress (Ogbu & Ajiwe, 2016). In this study, FT-IR was used to characterize
the oil at room temperature (28 oC) in order to assess the oxidation state of the oil prior to
thermal treatment using FT-IR spectrometer (Model: TENSOR 27, Bruker Optics Inc, USA)
equipped with a detector having a spectral range 4000–500 cm-1. The FT-IR was analyzed using
OPUS spectroscopy software supplied with the instrument.
3.4.3 Nuclear magnetic resonance spectroscopy
The NMR spectroscopy is a useful nondestructive tool that complements GC-MS in the
characterization of lipids and identification of compounds present. In this study, the 1H NMR
spectrum was recorded on Bruker ultra-shield TM 500-MHz NMR spectrophotometer using
deuterated chloroform (CDCl3) as solvent (δ = 7.26 ppm) containing a small amount of
tetramethylsilane (TMS) as an internal standard (δ = 0 ppm) and put in a 5-mm diameter tube.
The 13C NMR experiments were performed using the same equipment, and the carbon atom in
CDCl3 was taken as 77.42 ppm. All other peaks were assigned with respect to it. About 25–30
mg of RSO was dissolved in 1 mL of CDCl3, and the experiments were performed at 25 oC
(Onoji et al., 2016b).
3.5 Kinetics of thermal oxidative degradation of the seed oil
105
Vegetable oils (mainly triglycerides) undergo chemical reactions such as oxidation,
isomerization, polymerization and hydrolysis when subjected to prolonged heating process
(Onoji et al., 2016b). These reactions affect the physico-chemical properties of these oils and
their quality. The thermal study of oils before their industrial applications permits data to be
obtained on the influence of time and temperature on their thermal oxidation (Gouveia de Souza
et al., 2004).
In this study, classical chemical analysis methods were used to determine the change in
peroxide value, iodine value and refractive index of RSO when subjected to heat treatment
(Oderinde et al., 2009). Rubber seed oil has been reported to be thermally stable up to 250 oC
under heat treatment (Aravind et al., 2015). For this reason, the peroxide value, iodine value
and refractive index were determined at 100, 150, 200 and 250 oC at various time intervals
using methods prescribed by ASTM and AOAC (1990). The procedures outlined in Sections
E.1.7, E.1.8, and E.1.9 of Appendix E was followed at the conditions of temperature and time
considered for each case. The iodine value is a measure of the degree of unsaturation to quantify
the amount of double bonds present in the oil. It reflects its susceptibility to oxidation
(Hrušovský et al., 2013), and was used in the present study to generate data for kinetic plots.
The broad reaction rate expression proposed by several researchers for the kinetics of thermo-
oxidative degradation of RSO is expressed in Equation (3.2) (Santos et al., 2002; Van Boekel,
1996; Ramaswamy et al., 1989).
−𝑑𝐶 ⁄𝑑𝑡 = 𝑘𝐶 𝑛 (3.2)
where 'C' is iodine value at any time, 'n' is order of reaction, and 'k' is the reaction rate constant
whose temperature dependence is commonly described by Arrhenius Equation (3.3).
𝑘 = 𝐴𝑜 exp(− 𝐸𝑎 ⁄𝑅𝑇) (3.3)
106
T is the absolute temperature, R is the universal gas constant, Ea is the activation energy, and
Ao is the pre-exponential factor. The thermo-oxidative degradation of vegetable oils generally
follows a first-order reaction as given in Equation (3.4) (Ramaswamy et al., 1989).
𝑙𝑛 𝐶𝑡 ⁄𝐶𝑜 = 𝑘𝑡 (3.4)
where 𝐶𝑡 iodine value at time t is, 𝐶𝑜 is initial iodine value.
3.6 Optimization study of the oil extraction process using RSM and ANN–GA techniques
RSM based on Box–Behnken experimental design, and ANN–GA was used to model and
optimize the extraction process conditions for rubber seed oil production. A three-level, three-
factor design was employed in this study (Table 3.1). The extraction process parameters
investigated were rubber seed powder weight (X1), solvent volume (X2) and extraction time
(X3). The BBD generated 17 experimental runs that were randomized to minimize the
unpredictable variations in the observed responses due to uncontrolled extraneous factors. The
experimental runs included 12 factorial points, and 5 centre points that provide information on
the interior of the experimental regions to evaluate the curvature effect. The experiments were
carried out in series as described in the preliminary assay for the determination of optimum
particle size. An average particle kernel size of 0.5 mm that gave the maximum oil yield was
used to obtain experimental oil yields that were employed in RSM and ANN modeling (Onoji
et al., 2017a)
107
Table 3.1: Experimental range and levels of independent process variables for seed oil
extraction via Box-Behnken design (Onoji et al., 2017a)
Independent process variables Symbols Coded factor levels
(uncoded) –1 0 +1
Rubber seed powder weight (RSPW) (g) X1 40 50 60
Solvent volume (mL) X2 200 225 250
Extraction time (min) X3 40 45 50
3.6.1 Modeling of seed oil extraction process variables via RSM
The experimental oil yields obtained from BBD, and the process parameters were statistically
analyzed using RSM and least-squares method to fit a second-order polynomial model
generated by the Design-Expert software trial version 8.0.3.1 (Stat-Ease Inc., Minneapolis,
MN, USA) for the complete BBD (Onoji et al., 2017a). The relationship between the response
and the input variables is given in Equation (3.5) (Baş & Boyaci, 2007b):
Y  f ( X 1 , X 2 ,.....X n )   (3.5)
where Y is the response, f is the unknown function of the response, X1, X2, …. Xn denote the
actual independent process variables, n is the number of the independent variables and 𝜀 the
statistical error that represents other sources of variability not accounted for by f. It is generally
assumed that ε has a normal distribution with mean zero and variance (Baş & Boyaci, 2007b).
The relationship between independent coded and actual values is defined by Equation (3.6):
𝑋𝑖 −𝑋𝑖
xi = (3.6)
∆𝑋𝑖
where xi is the coded value of the ith factor, Xi is actual (experimental) value of the ith factor in
the uncoded units, 𝑋𝑖 is the average of the low and high values for the ith factor, and ∆𝑋𝑖
represents the step change for the ith factor.
108
The general second-order polynomial regression model shown in Equation (3.7) was used to
develop the empirical model that establishes the correlation between the coded process
parameters (x1, x2 and x3) and the response variable 𝑌 (% yield).
𝑌 = 𝛽𝑜 + ∑𝑘𝑖=1 𝛽𝑖 𝑥𝑖 + ∑𝑘𝑖=𝑖 𝛽𝑖𝑖 𝑥𝑖2 + ∑𝑘𝑖<𝑗 𝛽𝑖𝑗 𝑥𝑖 𝑥𝑗 + 𝜀 (3.7)
where 𝛽o, 𝛽i, 𝛽ii, and 𝛽ij represent the regression coefficients of intercept, linear, quadratic and
interactive terms, respectively, while xi and xj represent the coded process parameters.
The regression coefficients of Equation (3.7) were estimated using the least square estimation
method based on multiple regression technique. In this method, it is assumed that random errors
are identically distributed with a zero mean and a common unknown variance. The residual is
an estimate of the corresponding ε i which is the difference between the actual value (𝑌𝑖 ) and
the predicted value as shown in Equation (3.8).
𝜀𝑖 = 𝑌𝑖,𝑒𝑥𝑝− 𝑌𝑖,𝑝𝑟𝑒𝑑 (3.8)
The objective of the optimization step is to minimize the sum of the squares of the residuals,
often called the sum of squares of the errors (SSE). Thus,
SSE    i2   Yi ,exp  Yi , pred 

n n
2
(3.9)
i 1 i 1
The residuals may be expressed in different as in Equation (3.10), and SSE may be written as
shown in Equation (3.11) (Baş & Boyaci, 2007b).
ε =Y-x𝛽 (3.10)
SSE   T   Y  x  Y  x 
T
(3.11)
Differentiating the SSE with respect to β, yields a vector of partial derivatives (Equation
(3.12)), as follows:

SSE   2 x T Y  x  (3.12)

109
When Equation (3.12) is equated to zero, we have xβ = Y that is solvable directly to
obtain the coefficients β from Equation (3.13).
xT x  xT Y (3.13)
The rearrangement of Equation (3.13) in matrix form is given in Equation (3.14) (Baş &
Boyaci, 2007b):
  Cx T Y (3.14)
where C  x T x  is a squared matrix. After the regression coefficients are obtained from
1
Equation (3.14) using the experimental response Y, the model-predicted response could
be easily calculated using the developed model from Equation (3.7) with all the
regression coefficients incorporated.
The developed second-order regression model that adequately describes the behavior of the
process with respect to the operating variables was used to create contour (2D) and surface
responses (3D) plots. This was used to explore the designed space, and to predict the optimal
conditions for RSO extraction yield. The variability of the response variable was determined
by the adjusted multiple coefficient of determination (R2adj.) which is a measure of the amount
of variation around the mean explained by the model and adjusted for the number of terms in
the model. In addition, the adequate precision (signal-to-noise ratio) was calculated using
Equation (3.15) to verify that the quadratic regression model is adequate (Onoji et al., 2017a;
Cerino Córdova et al., 2011).
Max (𝑌)−𝑀𝑖𝑛 (𝑌)

𝐴𝑑𝑒𝑞𝑢𝑎𝑡𝑒𝑝𝑟𝑒𝑐𝑖𝑠𝑖𝑜𝑛 = 2
(3.15)
√𝜔𝜎
𝑛
where Max (Y) is the maximum predicted oil yield; Min (Y) is the minimum predicted oil yield;
ω is the number of model parameters (including βo); σ2 is residual mean square; and n is the
number of experimental runs.
110
3.6.2 Modeling of seed oil extraction process variables via ANN
A commercial ANN program, Neural Power trial version 2.5 (CPC-X software) was employed
in this study. RSO yield was predicted by using back-propagation multi-layer feed-forward
neural network algorithm. A topology of 3–3–1 network (Figure 3.2) corresponding to the
number of neurons within the input, hidden and output layers, respectively was used for the
training. A sigmoid transfer function was adopted for the study. The input vector consisted of
the rubber seed powder weight (X1), solvent volume (X2), and extraction time (X3) while the
output vector (Y) was the rubber seed oil (RSO) yield (Onoji et al., 2017a). The functional
relationship to be estimated by the ANN model could be expressed as follows:
Y  f X1 , X 2 , X 3  (3.16)
where X1, X2, X3, and Y are as defined earlier. The output of a neuron is computed from Equation
(3.17) (Shokri et al., 2011):
 n 
Oi  f   wij I j  bi  (3.17)
 j 1 
where Oi is output of the ith neuron, f is transfer function, bi is bias of the ith neuron, wij is
synaptic weight corresponding to jth synapse of ith neuron, Ij is jth input signal to the ith neuron
and n is number of input signals to the ith neuron.
bias bias
s
Rubber seed powder weight, X1 (g)
Solvent volume, X2 (mL) Y (%)
Extraction time, X3 (min)
Figure 3.2: Schematic of 3-3-1 developed ANN topology (Onoji et al., 2017a)
111
The experimental oil yields obtained from the 17 experimental runs of BBD was divided into
two sets. Experimental oil yields of 14 set of data was used for ANN training and cross
validation, and the other set of 3 data was used for testing of the trained network. The network
was trained using the back-propagation method implemented by Levenberg-Marquardt
algorithm depicted in Figure 3.3 (Onoji et al., 2017a). The training was carried out by adjusting
the connection weights and biases between neurons with the aim of reducing the mean square
error (𝑀𝑆𝐸) between the predicted and experimental outputs below an acceptable threshold
(Gueguim Kana et al., 2012). A network will memorize results instead of generalizing when it
is over trained. In such a case, the resulted model can perfectly predict the data similar to
training data, but will perform poorly if new set of data are submitted to it. The training was
completed when the network is able to predict the given output. The trained model was
validated by using it to predict RSO yield of the 3 data that were not used during the training
phase. The validated model was subsequently used as evaluation function (Equation 3.18) for
Genetic Algorithm (GA) optimization process to predict the optimal values of RSO extraction
variables (X1, X2, X3 and Y) applied in developing the model (Onoji et al., 2017a; Kostić et al.,
2013; Gueguim Kana et al., 2012).
1
f (X )  (3.18)
1 eX
112
Inputs: X1, X2, X3
Experiments Process Simulation
Actual Output (YA)
ANN model Predicted MSE=YA - YP

Output
(Yp)
Validate
ANN model
Adjust weights and

biases based on MSE
Min (MSE) MSE<Ɛ Save

Save best
best weights
Back-propagation min (MSE) and biases
weiuddudududud
NO YES
ududuights and
Figure 3.3: Levenberg-Marquardt training flowchart for ANN model (Adapted from
Onoji et al., 2017a).
3.7 Catalyst preparation and characterization
The rubber seed shells (RSS) freed from the kernels in Section 3.2.1 were stored in
polyethylene bags for analyses. The RSS was washed 3–4 times with hot distilled water to get
rid of dust and solid impurities. It was then dried in a laboratory oven at 110 oC for about 5 h,
and stored in a desiccator. The cooled dried RSS was ground to powder with a grinder, and
sieved through a 60-mesh size. The powdered raw RSS was analyzed by thermo-gravimetric
analyzer (TGA) in the range of 30–950 oC at 10 oC/min, under nitrogen environment to
determine a suitable calcination temperature of the catalyst (Onoji et al., 2017b). The RSS
powder was calcined from 40–800 oC at heating rate of 10 oC/min in an electric muffle furnace
(Carbolite, Parson Lane, Hope Valley S33 6RB, England, Model: RWF 12/5) for about 3 h to
113
remove organic materials in it and stored in screwed bottles for analyses. Raw and calcined
RSS (Figure E.1 of Appendix E) were dissolved in deionized water to determine the basic
property (pH). Energy dispersive X-ray spectroscopy (EDX 3600B-XRF Skyray Instrument)
analysis was employed to determine the elemental compositions of the raw and the calcined
RSS. Samples were pulverized using Knife Mill GRINDOMIX (model: GM20), and pelletized
with Mini-pellet press kit Asia (model: GS01152). The equipment was calibrated using pure
silver standard sample. The diffraction patterns of raw and calcined RSS samples were
analyzed with a diffractometer (XRD EMPYREAN mini-material analyzer, manufactured by
PANalytical B.V., Holland) to observe their amorphous and crystalline structures. Sample was
pulverized to homogeneous size and loaded into XRD sample holder. The diffractometer
equipped with PIXcel-3D detector employed Cu-Kα1 radiation source (λ =1.54059 Å) at 45
kV and 40 mA. Scanning was recorded in a continuous mode over 2o-Theta range from 4.0131o
to 79.9849o with a step size 0.026o at 13.77 second per step. The size and morphology of
catalyst was examined with scanning electron microscope (SEM-Phenom ProxMVE
016477830, manufactured by Phenom World, Eindhoven, Netherlands). The RSS sample was
dispersed on a stub using a sticky carbon tape before coating with palladium gold. Vacuum
was created before carrying out the analysis by inserting the stub into the equipment (Onoji et
al., 2017b).
Surface area and porosity, pore volume, and pore-size distribution are important parameters in
heterogeneous catalysis and catalyst design (Storck et al., 1998). Prior to analysis, about 335.3
mg of raw sample was weighed and outgassed at 250 oC for 11 h under a stream of nitrogen
gas to remove moisture and impurities. Similar analysis was carried out using 382.7 mg
calcined RSS catalyst at same conditions. These analyses were to evaluate the textural
properties of the raw and calcined RSS in order to determine the influence of calcination
temperature (Onoji et al., 2017b).
114
The accessibility of active sites is determined by the total surface area, and thus related to
catalytic activity. Gold App surface area and porosity analyzer (Model: V-sorb 2800p) was
used to estimate the surface textural properties of the raw and calcined RSS from isotherms
generated by Brunauer-Emmett-Teller (BET) model (Equation 3.19) (Vasudevan et al., 2011)
using nitrogen adsorption/desorption at 77.3 K.
P / Po   C  1  P 
1
(3.19)
V 1  P / Po  VmC Po VmC
where P is the partial pressure, Po is the saturation pressure, Vm is the maximum amount of
nitrogen adsorbed/unit mass of catalyst at high pressure conditions required to form a complete
monolayer over the entire surface of the catalyst, and C is the BET constant related to isosteric
heat of adsorption. Barrett-Joyner-Halenda (BJH) model calculated the pore-size distributions
of the raw and calcined RSS. The total pore volume is defined as the volume of liquid N2
corresponding to the amount adsorbed at a relative pressure of P/Po = 0.997, after which N2
desorption commences.
3.8 Biodiesel production from the extracted seed oil and analysis
The rubber seed oil used for the biodiesel production was earlier extracted as in Section 3.2.2.
The high FFA of the oil allows for two-step production routes: Esterification and
transesterification.
3.8.1 Acid-catalyzed esterification of the seed oil
The rubber seed oil used in the study had an initial acid value of 18.02±0.141 mg KOH/g oil,
and FFA level of 9.01±0.07% (Onoji et al., 2016b). Reduction of FFA to <1% prior to
transesterification reaction is necessary to avoid catalyst consumption in soap formation and a
low yield of biodiesel because of the basic nature of the synthesized catalyst (Betiku & Ajala,
2014). 100 mL rubber seed oil was measured into a 250-mL one-neck glass reactor and
115
preheated to 105 oC on a magnetic stirrer hot plate to remove moisture and volatile impurities.
Then, 1.5 % vol/vol H2SO4 catalyst based on methanol volume was mixed with 45 mL of
analytical grade methanol (>99%) and stirred for 5 min. The mixture was added to the oil
maintained at 60 oC, and the reaction continued for 1 h at a stirring rate of 600 rpm. The
esterified oil was transferred into a separating funnel and allowed to stand for 2 h (Figure F.1
of Appendix F). The pretreated oil was separated from the water formed (Equation (3.20)), and
excess methanol was evaporated in a rotary evaporator prior to acid value determination by
standard titration procedure described by ASTM. Similar experiments were carried out using
3, 4.5, and 6 % vol/vol H2SO4 and their acid values determined were recorded in Table F.1 of
Appendix F. The 6% vol/vol H2SO4 obtained for <1% FFA (90.5% conversion) was employed
to esterify the oil used for transesterification reaction (Onoji et al., 2017b).
H2SO4 (catalyst)
RCOOH + CH3OH ↔ RCOOCH3 + H2O
FFA methanol methyl ester water (3.20)
3.8.2 Biodiesel production from the esterified seed oil
A three-factor, three-level (Table 3.2) central composite design using Design-Expert® dx8
software version 8.0.7.1 (Design Ease Inc., USA) coupled with response surface methodology
was used to statistically analyze the experimental data that consisted of 8 factorial points, 6
axial points, and 6 center points. A transesterification reaction of the esterified seed oil was
performed according to the experimental design set by RSM and designed by employing CCD.
Twenty experimental runs were carried out for the optimization process under different
combination of process variables. In each run, and for the reaction time (X1), 180 mL of oil
specified by methanol/oil ratio (X2), and RSS catalyst (X3) as depicted in Table 3.2 were reacted
in a 500 mL three-necked round bottom reactor equipped with a reflux condenser, and magnetic
116
stirrer maintained at 400 rpm throughout the experiment (Onoji et al., 2017b). Heat was
supplied by magnetic hot plate at 60 oC for a reaction time set by the CCD. At the end of the
reaction time, the reaction was quenched in an ice-bath and the content of the reactor was
transferred into a separating funnel for 2 h to separate glycerol and other impurities from the
biodiesel (rubber seed oil methyl ester) phase (Figure F.2 of Appendix F). The biodiesel was
poured into a rotary evaporator to remove excess methanol, and washed thrice with deionized
water at 50 oC to remove entrained glycerol and residual catalyst. Washed biodiesel was dried
over anhydrous sodium sulphate at 50 oC (Dhawane et al., 2016). Dried biodiesel (Figure F.3
of Appendix F) was decanted and filtered to remove sodium sulphate, and the yield was
estimated using Equation (3.21).
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 × 𝐹𝐴𝑀𝐸%

𝐵𝑖𝑜𝑑𝑖𝑒𝑠𝑒𝑙 𝑦𝑖𝑒𝑙𝑑 (%) = × 100 (3.21)
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑟𝑒𝑓𝑖𝑛𝑒𝑑 𝑟𝑢𝑏𝑏𝑒𝑟 𝑠𝑒𝑒𝑑 𝑜𝑖𝑙
where FAME% is the concentration of fatty acid methyl esters (FAME) analyzed by gas
chromatography-mass spectrometry (GC-MS).
Table 3.2: Experimental range and levels of independent process variables for biodiesel
production via central composite design
Independent process variables Symbols (uncoded) Coded factor levels
–1 0 +1
Reaction time (min) X1 60 65 70
Methanol/oil ratio (v/v) X2 0.20 0.25 0.30
RSS catalyst (g) X3 2.5 3.0 3.5
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3.9 Characterization of the produced biodiesel
The physico-chemical properties such as density, color, moisture content, oAPI gravity,
kinematic viscosity, acid value, saponification value, iodine value, and calorific value were
determined. These properties including oxidation stability at 110 oC, cetane number, diesel
index, pour point, cloud point, flash point, fire point and cold filter plugging point of the methyl
ester (biodiesel) produced at optimum conditions were determined following the procedures
prescribed by ASTM standards and other methods (Onoji et al., 2017a). The oxidation stability
was determined by using PetroOXY automatic oxidation stability tester (Protest® Instruments
GmbH & Co. KG, Dahlewitz, Germany). Figure F.4 of Appendix F and Equation (3.22)
developed by Botella et al. (2014) with adjusted R2 of 0.915 at 95% confidence interval was
used to estimate the Rancimat value of the oxidation stability of the produced biodiesel without
additive.
𝑅𝑎𝑛𝑐𝑖𝑚𝑎𝑡 (𝑚𝑖𝑛) = [(31.89 − 20.63𝑓)(𝑃𝑒𝑡𝑟𝑜𝑂𝑋𝑌(𝑚𝑖𝑛)) + (−214.65 + 319.68𝑓)]
(3.22)
where f = 0 if no additive is used, and 1 if an additive has been mixed with biodiesel while
PetroOXY (min) is the value obtained from the Tester.
The fatty acid methyl ester (FAME) content of the biodiesel was determined by GC Agilent©
7890B and MS Pegasus 4D GCXGC (LECO) located in Wits University Johannesburg, and
the value obtained was compared with the correlation of Equation (3.23) developed by
Felizardo et al. (2006).
FAME (%) = – 45.055ln𝜇 + 162.85 (3.23)
whereµ is the kinematic viscosity (mm2/s) at 40 oC.
118
3.10 Reusability test for the catalyst used in biodiesel production
Different loadings (2, 2.2, 2.5, 3, and 3.5 g) of the prepared catalyst at optimum reaction
conditions of RSM, and at 60 oC were used to produce biodiesel in order to determine the level
of loss in activity in the reusability test. After the completion of each reaction, the biodiesel
yield was determined. The catalyst was separated from the reaction mixture by filtration,
centrifuged, washed with acetone to remove impurities blocking the active sites, and oven dried
at 110 oC for 3 h before each successive reuse. Leaching of active sites into the reaction mixture
was determined by atomic absorption spectroscopy (AAS) (Onoji et al., 2017b).
3.11 Statistical analysis of the biodiesel production by RSM
The general second-order polynomial regression model described by Equation (3.24) was used
to develop the empirical model that describes the correlation between the transesterification
uncoded process parameters (X1, X2, and X3), and the predicted response variable, RSOME
yield (%) (Onoji et al., 2017b).
𝑅𝑆𝑂𝑀𝐸 (%) = 𝛽𝑜 + ∑𝛼𝑖=1 𝛽𝑖 𝑥𝑖 + ∑𝛼𝑖=𝑖 𝛽𝑖𝑖 𝑥𝑖2 + ∑𝛼𝑖<𝑗 𝛽𝑖𝑗 𝑥𝑖 𝑥𝑗 + 𝑒 (3.24)
where βo, βi, βii, and βij represent the regression coefficients of intercept, linear, quadratic, and
interactive terms, respectively, while xi and xj, represent the coded independent process
parameters as defined in Equation (3.25), and 'e' the experimental error of analysis.
𝑋𝑖 −𝑋𝑖
xi = (3.25)
∆𝑋𝑖
Xi is actual (experimental) value of the ith factor in the uncoded units, 𝑋𝑖 is the average of the
low and high values for the ith factor, and ∆𝑋𝑖 represents the step change for the ith factor.
119
The adequate precision ratio (signal-to-noise ratio) which verifies the adequacy of the
developed model was estimated by Equation (3.26) (Cerino Córdova et al., 2011).
Max (𝑌)−𝑀𝑖𝑛 (𝑌)

𝐴𝑑𝑒𝑞𝑢𝑎𝑡𝑒 𝑝𝑟𝑒𝑐𝑖𝑠𝑖𝑜𝑛 = 2
(3.26)
√𝜔𝜎
𝑛
where Max (Y) is the maximum predicted RSOME yield (%), Min (Y) is the minimum predicted
RSOME yield (%), ω is the number of model parameters (including 𝛽𝑜 ), σ2 is residual mean
square, and n is the number of experimental runs. The derived model was used to create surface
(3-D) plots to explore the designed space, and predict the optimal conditions for RSOME.
3.12 Analysis of variance (ANOVA) study for biodiesel production
One-way analysis of variance (ANOVA) was used for evaluating statistical significance of the
experimental polynomial model, coefficients, process factors, and the quality of the model fit.
Optimal process conditions for maximizing the yield of RSOME were determined by solving
the model equation using the Design-Expert® dx8 software version 8.0.7.1. The coefficient of
variance (% C.V.), a ratio of standard deviation to mean value was determined to check the
capability of the model to accurately predict yields, and a low value is desirable.
3.13 Modeling of biodiesel production process variables by ANN
ANN Neural Power trial version 2.5 (cpc-x software) was employed in the study. RSOME
yield (%) was predicted using the supervised back-propagation multilayer feed-forward
algorithm. The network consists of an input layer (three neurons), hidden layer (three neurons),
and output layer (one neuron). The same process parameters and experimental data used for
the RSM modeling were deployed in the ANN architectural design. Training of the network,
cross validation and testing were carried out, and the ANN-Genetic Algorithm model was
successfully used as an evaluation function for the optimization of its input space to predict the
120
optimal values (Onoji et al., 2017a) of RSOME yield (%) and process parameters (X1, X2, and
X3) applied in developing the model.
3.14 Data validation for RSM and ANN models
The predicted optimized responses obtained from RSM and ANN models were compared with
the average experimental values from triplicate runs obtained using the optimum conditions in
order to evaluate the efficiencies of these optimization techniques. The percent relative error
(PRE) (Zahedi & Azarpour, 2011) and absolute average deviation (AAD) (Betiku & Ajala,
2014) were determined and these were used to identify the best model by comparing evaluated
values. The PRE and AAD values were calculated using Equations (3.27) and (3.28),
respectively.
𝑜𝑝𝑡𝑖𝑚𝑎𝑙 𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑−𝑜𝑝𝑡𝑖𝑚𝑎𝑙 𝑝𝑟𝑒𝑑𝑖𝑐𝑡𝑒𝑑 𝑦𝑖𝑒𝑙𝑑

𝑃𝑅𝐸 (%) = × 100 (3.27)
𝑜𝑝𝑡𝑖𝑚𝑎𝑙 𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
𝑅𝑆𝑂𝑀𝐸𝑖,𝑎𝑐𝑡𝑢𝑎𝑙 −𝑅𝑆𝑂𝑀𝐸𝑖,𝑝𝑟𝑒𝑑 1
𝐴𝐴𝐷 (%) = {[∑𝑛𝑖= ( )] 𝑛} × 100 (3.28)
𝑅𝑆𝑂𝑀𝐸𝑖,𝑎𝑐𝑡𝑢𝑎𝑙
Where n is the number of experimental runs, while RSOMEi, actual is the actual yield (%), and
RSOMEi, pred is the predicted yield (%).
3.15 Combustion of biodiesel-diesel blends in internal compression ignition engine
Five litres of commercial diesel was purchased from Nigerian National Petroleum Corporation
(NNPC) fuel station located at Refinery road, Effurun, Delta State, Nigeria. The diesel and the
rubber seed oil biodiesel were characterized to ascertain its uniformity with ASTM (American
Society for Testing and Materials) standards for biodiesel and diesel fuels. The biodiesel-diesel
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blends were prepared and tested for performance, and combustion characteristics using internal
compression ignition engine.
3.15.1 Biodiesel-diesel blending analysis via ultrasonication technique
Figure 3.4 depicts the experimental setup for the blending of biodiesel mixtures using the
ultrasonication blending technique. Four different blends of B10, B20, B30, and B50 were
prepared on volumetric basis for test in internal compression ignition engine. Pure diesel (B00)
and biodiesel (B100) fuels were also tested to determine their levels of environmental
friendliness with those of their blends. For each blend (Bxx), where B stands for biodiesel
blend, and xx for the % volume of biodiesel in the blend (e.g. B10 means 10% vol biodiesel,
and 90% vol diesel), the measured volume of biodiesel was poured into a batch blender. The
ultrasonicator horn was lowered to a depth of 2 cm within the biodiesel and then switched on.
Then, an appropriate measured volume of diesel was added to the biodiesel at a constant rate
and allowed to blend for 5 min under standard atmospheric conditions. The ultrasonicator is
then switched off and the mixture emptied into a measuring cylinder for combustion analysis
in an internal compression ignition engine.
122
Ultrasonic
transducer
Ultrasonic processor
Thermometer
Ultrasonic horn
biodiesel – diesel blends
Figure 3.4: Experimental setup for biodiesel-diesel blending analysis
3.15.2 Methodology and experimental setup for combustion study of biodiesel blends
The experimental research was performed on a naturally aspirated single-cylinder, four-stroke,
direct-injection, air-cooled, TecQuipment TD202 (Model: 1B20) Hatz diesel test engine that
was coupled to TecQuipment TD200 small engine test bed shown in Figure 3.5, and connected
to a separate Versatile Data Acquisition System (VDAS) to accurately monitor and record all
measured data on a computer system. The test engine is located in the Biofuels Laboratory at
Petroleum Training Institute, Effurun, Nigeria. The detailed technical specifications of the test
engine are listed in Table 3.3.
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Figure 3.5: Experimental TD202 diesel test engine for performance and combustion
analyses located at Petroleum Training Institute, Effurun, Nigeria
Table 3.3: Technical specifications for TD 202 diesel test engine
Engine make/model Hatz/1B20
Engine type Single cylinder, direct injection and air-cooled
Displacement (Capacity) 232 cm3
Number of strokes 4
Aspiration/starting system Natural/Recoil starter
Cylinder bore/connecting rod length 69 mm/104 mm
Stroke/crank radius 62 mm/31 mm
Compression ratio 22:1
Absolute maximum power 3.5 kW at 3600 rpm
Continuous rated power 3.1 kW at 3000 rpm
Orifice diameter/Coefficient of discharge 0.0185 m/0.6
124
The test engine set included a robust cost effective and efficient hydraulic dynamometer to
control the engine load as shown schematically in Figure 3.6. There are no load resistors needed
because the engine power is dissipated into the water that passes through the dynamometer.
The engine was allowed to warm up before the experiments were conducted to ensure
parameters were being analyzed at steady state (Özener et al., 2014). The performance and
operating parameters, such as the engine torque (Nm), engine power (Watts), exhaust gas
temperature (oC), ambient air temperature, TA (oC), air-box differential pressure, ∆P (Pa), and
ambient pressure, PA (mbar) were measured at the engine speeds of 1500, 2000, 2500, 3000,
and 3500 rpm at fixed 100% engine loading and were digitally displayed on instrument
modules. They were recorded after the conditions of the engine stabilized. The parameters
considered for the engine performance and emission analysis that indicate the applicability of
the produced biodiesel in the engine are air/fuel ratio, brake mean effective pressure (BMEP),
brake thermal efficiency (BTE %), break power (BP), engine torque, brake specific fuel
consumption (BSFC), and exhaust gas temperature for performance evaluation consideration.
The CO, CO2, NOx, total hydrocarbons (THCs), and smoke opacity were considered for the
emission analysis with respect to the test engine. The engine power (Watts) was displayed
digitally on the instrument module (Figure 3.5) and could be calculated using the module
displayed speed (rpm) and the torque (Nm) based on Equation (3.29) used by Ude et al. (2017).
TN
BP  (3.29)
9549.3
where:
BP represents the engine brake power (kW); T represents the developed torque (Nm), and N is
the engine speed (rpm).
125
The air velocity (m/s), air flowrate (kg/s), air/fuel ratio, and the brake mean effective pressure
(bar) are described by Equations (3.30), (3.31), (3.32), and (3.33), respectively (TecQuipment
Ltd, 2011).
2∆𝑃
𝑈 = √𝜌 (3.30)
𝑎𝑖𝑟
𝐶𝑜 𝜋𝑑2 2𝑃 ∆𝑃
𝑚̇𝑎 =
4
√ 𝑅 𝐴𝑇 (3.31)
𝑎 𝐴
𝐴𝑖𝑟 𝑚̇𝑎
𝑟𝑎𝑡𝑖𝑜 = (3.32)
𝐹𝑢𝑒𝑙 𝑚̇𝑓
60 × 𝐵𝑃 × (𝑆𝑡𝑟𝑜𝑘𝑒/2)
𝐵𝑀𝐸𝑃 = (3.33)
0.1 ×𝑆𝑝𝑒𝑒𝑑 ×𝐸𝑛𝑔𝑖𝑛𝑒 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦
where:
U = velocity of air (m/s);
∆P = air-box differential pressure (Pa);
ρair = density of air (1.2754 kg/m3);
d = diameter of the orifice plate (= 0.0185 m for the test engine used);
Co = coefficient of discharge (= 0.6 for the test engine used);
𝑚̇𝑎 = mass flowrate of air (kg/s);
𝑚̇𝑓 = mass flowrate of fuel (kg/s)
PA = ambient pressure (Pa); TA = ambient air temperature (K);
Ra = Gas constant for air (287 J/kg K)
BMEP = brake mean effective pressure (bar);
BP = brake power (Watts);
126
Engine capacity = 232 cm3 for the test engine used, and speed expressed in rpm.
Stroke = 4, for the test engine.
The engine speed was measured using an optical sensor, while the torque was measured using
a load cell. The volumetric flowrate of fuel at each engine speed, for each blend was calculated
using the time (measured by a stopwatch) the engine takes to consume 8 mL of fuel using the
8-mL pipette fitted gauge (AVF1 option). The inlet air flowrate was measured using an orifice
plate of diameter 18.5 mm. A k-type thermocouple and a differential pressure transducer were
fitted near the orifice plate in order to measure the air temperature and pressure, respectively,
needed for the inlet air flowrate calculation. An engine cycle analyzer (ECA 100) received the
signals of both the pressure transducer and shaft encoder.
A Quintox flue gas analyzer (Model: KM 9106) manufactured by KANE International Ltd.,
Swallow fields, Welwyn Garden City, Herts, AL 1JG, UK, and supplied with combustion
analysis display unit was employed to measure the exhaust gas emissions (CO, CO2, NOx, and
THC) at the above stipulated engine speeds, while the smoke opacity was measured with AVL
DiSmoke 4000 opacity smoke meter.
127
Fuel tank
Computer
Data Acquisition System
8 mL
Torque input
Speed input
Air box
pressure 16mL
input Exhaust Temperature
Thermocouple input
To exhaust Optical
Engine gas sensor
cycle analyzer
Signal
Differential
analyzer pressure
Cylinder pressure Air temperature Signal
transducer
Signal Orifice
Shaft encoder
Plate
& rpm sensor
Load cell
Air box
Fuel
Hydraulic flow
dynamometer Test Engine
Fuel flow
Figure 3.6: A schematic layout of experimental TD202 diesel test engine
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CHAPTER 4: RESULTS AND DISCUSSION
4.0 Introduction
This chapter documents and discusses all the results obtained in this study. The results were
compared with the literature, and discrepancies if any were explained.
4.1 Extraction of seed oil and determination of the best seed particle size
The results depicted in Figure 4.1 showed that a seed particle size of 0.5 mm gave the maximum
oil yield of 40.3 wt. % among the available sizes during the oil extraction (Onoji et al., 2017a).
The data for the plots are shown in Table D.1 of Appendix D. The findings of this study concur
with those of Menkiti et al. (2015) who extracted Terminalia catappa L seed oil using n-hexane
solvent, and obtained a yield of 60.45 wt. % from the smallest kernel particle size 0.5 mm
compared to the other sizes (1, 1.5, 2, and 2.5 mm) considered. A similar trend in the reported
work of Reshad et al. (2015) where the smaller particle size of 1 mm gave a rubber seed oil
yield of 49.36 wt. % for 8 h extraction time was also observed. The smaller particle size creates
a larger surface area that enhances oil yield by facilitating solvent diffusivity in the seed
powder. In the present study, particle size of 0.5 mm was considered for oil extraction for the
modeling and optimization processes, and chemical analyses. However, for industrial
application, 1 mm particle size with a yield of 40.1 wt. % is preferred to 0.5 mm size as less
energy is required to process the 1 mm kernel size (Onoji et al., 2017a).
129
45
40
Oil yield (%)
35
30
25
0.5 1 1.5 2 2.5
kernel size (mm)
Figure 4.1: Effects of kernel particle size on the rubber seed oil yield
4.2 Physical characterization of the seed and seed oil
Table 4.1 presents the analysis of rubber seed and the extracted seed oil (Onoji et al., 2016b).
The computations are presented in Section B.1 of Appendix B. The kernels moisture content
(9.7 wt.%) of rubber seed evaluated was higher than the reported value of 6.5 wt.% for yellow
horn seed kernels (Li et al., 2013). The determined rubber seed oil moisture content is low
(1.73 wt.%) compared to castor oil (8 wt.%) and shea nut oil (10 wt.%) (Asuquo et al., 2012),
Afzelia africana oil (2.10 wt.%) and Hura crepitans oil (1.90 wt.%) (Ogbu & Ajiwe, 2016).
High moisture content initiates oxidation process that reduces the oil's shelf life. The low value
for this oil is an indication that it could be stored for a long period without appreciable
deterioration in value. The ash content of the rubber seed oil (0.001 wt.%) is lower than the
prescribed ASTM ash limit (0.01 wt.% max) and those of Afzelia africana oil (0.006 wt.%) and
Hura crepitans oil (0.004 wt.%) (Ogbu & Ajiwe, 2016). The low ash value is an indication that
the oil lacks trace metals that catalyze oxidation reactions that cause rancidity, high acidity and
130
other unpleasant characteristics during storage. The carbon residue (0.4 wt.%) is close to the
ASTM standard limit of 0.35 wt.% max for diesel fuels (Demirbaş, 1998), but higher than other
vegetable oils such as sunflower (0.03 wt.%), rapeseed (0.05 wt.%) and olive (0.09 wt.%)
(Anastopoulos et al., 2009). The high volatile content of the oil suggests that it could be a
plausible source material for biodiesel synthesis for use in internal compression ignition
engines.
Table 4.1: Physical characterization of rubber seed and the seed oil
Parameter Composition (wt.%)
Rubber seed
Kernel 40.47 ± 0.07
Kernel moisture 9.7 ± 0.07
Shell 49.83± 0.14
100
Rubber seed oil
Conradson carbon residue 0.4 ± 0.028
Moisture content 1.73 ± 0.028
Ash content 0.001 ± 0.0001
Volatile matter 97.869± 0.056
100
values are mean ± standard deviation of duplicate data.
4.3 Characterization of the seed oil
The extracted rubber seed oil was subjected to physico-chemical analysis following the
procedures prescribed in AOAC (1990) and ASTM methods. A comparison of the properties
of the oil with values in the literature (Onoji et al., 2016a; Aravind et al., 2015; Reshad et al.,
131
2015) for rubber seed oil is presented in Table 4.2. The results of the analyses indicate the
potentials of rubber seed oil as an alternative feedstock to edible oils for commercial production
of biodiesel, and other industrial applications of oils where non-edible oil is preferable (Onoji
et al., 2017a).
4.3.1 Colour, pH, density and Specific gravity
The colour of the rubber seed oil was dark brown after clarification, and it remained liquid at
room temperature (Onoji et al., 2016b). The pH value of 6.0 obtained for the oil compares
favorably with those reported for castor oil (6.8) and luffa cylindrica seed oil (3.93) (Asuquo
et al., 2012). This value is an indication of the presence of reasonable amount of free fatty acid
and the advantageous utilization of the oil in soap making (Hosamani & Katagi, 2008). The
density at 25 oC was determined using a pycnometer and was found to be 0.886 g/cm3, which
implies that the oil is less than water with the absence of heavy elements. The specific gravity
at 15 oC was determined as 0.909 using standard specific gravity bottles and the oAPI gravity
of 24.1 was calculated for the oil (Onoji et al., 2016b). Specific gravity is an indication of the
energy content of a fuel. A fuel with a high specific gravity (low oAPI) has a higher heating
value than a fuel with a low specific gravity (high oAPI). The physical characteristics seem to
be similar to other common vegetable oils, and the oil was validated as environmentally
friendly.
4.3.2 Iodine, peroxide, saponification and acid values
Iodine value (IV) measures the degree of unsaturation in a fat or vegetable oil and determines
its oxidative stability. The iodine value of rubber seed oil (137.02 g I2/100 g oil) was estimated
by Wijs' method and falls within the range specified for semi-drying oils (100–150 g I2/100 g)
(Asuquo et al., 2012). The higher iodine value may be due to high-unsaturated fatty acid
132
content, as observed in GC-MS analysis of oil. The peroxide value (PV) determines the extent
to which the oil has undergone rancidity when stored, heated, or in contact with air and could
be used to assess the quality and stability of oils. Oils become rancid when the PV range from
20–40 mequiv O2/kg oil (Bora et al., 2014). Standard Organization of Nigeria (SON, 2000) and
the Nigerian Industrial Standards (NIS, 1992) specify a peroxide value of 10 mequiv O2/kg oil
for edible oils. The PV obtained for rubber seed oil in this study was 10.46 mequiv O 2/kg oil,
and it is within the range reported in literature for RSO (1.6–16 mequiv O2/kg oil) (Onoji et al.,
2016a), and close to Nigerian standards for edible oils. This indicates that the rubber seed oil
can be stored for a long period without deterioration. The saponification value (SV) indicates
the amount of alkali required to convert the oil into soap and is an index of average molecular
mass of fatty acid in the oil sample (Toscano et al., 2012; Anastopoulos et al., 2009). As oil is
mainly triglycerides, it allows for comparison of the average fatty acid chain length. The SV
of 195.3 mg KOH/g RSO obtained in this study (Onoji et al., 2016b) lies between those of
sunflower (186) and coconut oils (265) (Aravind et al., 2015), and within the range of 195–205
mg KOH/g oil for edible palm oils as specified by SON (2000) and NIS (1992). This shows
that rubber seed oil has lesser tendency to saponify at elevated temperatures than coconut oil.
The acid value (AV) of rubber seed oil was 18.20 mg KOH/g oil, which indicates high levels
of free fatty acids (9.10 wt.%), a limiting factor in its use as a source of food. The acceptable
limit for edible oils is ≤ 10 mg KOH/g oil. Therefore, chemical re-esterification or physical
refining would be required to de-acidify the oil (Ebewele et al., 2010b). However; this value
is low enough and is within the limits for industrially useful oils (Oyedeji & Oderinde, 2006).
4.3.3 Kinematic viscosity
Kinematic viscosity (KV) is a measure of the resistance of oil to shear. The dynamic (absolute)
viscosity for the rubber seed oil was digitally determined at 40 oC using Brookfield DV - I +
133
Viscometer (Model LVDV - |+) manufactured by Brookfield Engineering Laboratories Inc.,
Middleboro, MA 02346 USA. It was operated at 100 rpm with spindle No. 61 and a Torque of
59.2%. The average KV of the RSO was calculated as 35.6 cP and converted to 40.18 mm2/s
based on Equation (4.1). This is a low value compared to jatropha curcas L. oil (77.4 mm2/s)
but higher than that of conventional diesel (<5 mm2/s) (Reshad et al., 2015).
𝐴𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 (𝑐𝑃)

𝐾𝑖𝑛𝑒𝑚𝑎𝑡𝑖𝑐 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 (𝑚𝑚2 ⁄𝑠) = (4.1)
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 (𝑔⁄𝑐𝑚3 )
4.3.4 Cold flow properties
The flow properties of RSO were observed under low temperatures, and the parameters
considered are pour point (PP), cloud point (CP) and cold filter plugging point (CFPP),
respectively.
4.3.4.1 Pour point (PP)
The PP is the lowest temperature at which the oil suffers from gel formation and attains semi-
solid state and become deprived of its flow ability (Verma et al., 2016). The value of –6 oC
observed for this rubber seed oil is lower than that of Jatropha oil (4 oC) (Reshad et al., 2015;
Mazumdar et al., 2012) and castor oil (–2 oC), comparable to waste cooking oil (–7 oC), but
higher compared to canola (–18 oC) (Reshad et al., 2015). The value obtained is close to
reported value of –9 oC for RSO (Aravind et al., 2015). This suggests that it can be employed
under cold climatic conditions as a source material for lubricating oil formulation.
4.3.4.2 Cloud point (CP)
CP is the temperature at which a cloud or haze first appears in a liquid when cooled under
carefully controlled conditions. The observed CP for rubber seed oil was 5.5 oC. This value is
lower than 10–11 oC reported for Jatropha oil (Mazumdar et al., 2012). This suggests that RSO
134
is mainly unsaturated and a good source material for biodiesel synthesis for use in cold regions
compared to Jatropha oil (Onoji et al., 2016b).
4.3.4.3 Cold filter plugging point (CFPP)
The CFPP measures the lowest temperature at which a fuel gives trouble-free flow in a fuel
system. The CFPP value of –0.025 oC was estimated from Equation (4.2) cited by Verma et al.
(2016).
CFPP  0.8537  CP  4.72 (4.2)
The low CFPP confirms that the rubber seed oil is mainly unsaturated fatty acids and its use is
favourable in cold climatic regions.
4.3.5 Aniline point
The aniline point (AP) of oil is defined as the minimum temperature at which equal volumes
of aniline and oil are miscible. It is a measure of the aromatic content of oil and an evaluating
factor for diesel index determination and cetane number. At room temperature (28 oC),
complete miscibility of rubber seed oil with an equal volume of aniline was observed. The oil
was cooled to 10 oC in an ice-bath and mixed with equal volume of aniline to form a 2-phase
mixture. The mixture was heated gradually until complete miscibility was observed at 21 oC
(69.8 oF) as the aniline point (Onoji et al., 2016b).
4.3.6 Boiling, freezing, flash and fire points
The boiling point was determined as 119 oC using Stanhope-Setastill apparatus (Model: 11860-
3U). This suggests that moisture present could be removed at 105 oC without affecting its
properties prior to industrial applications such as biodiesel and lubricant synthesis. The freezing
point was observed at –18 oC using Stanhope-Seta Cloud and Pour Point Refrigerator Surrey,
135
England (Test Bath No. 4) calibrated to –51 oC. The fire and flash points were determined by
using Stanhope-Seta Pensky-Martens (A and B closed Cup-Model 34100-2/34000-0U) multi-
flash equipment. The flash and fire points were observed as 240.3 and 256 oC, respectively.
This shows that the oil can be stored safely at room temperature.
4.3.7 Refractive index (RI)
The refractive index (RI) is the ratio of the velocity of light in vacuum to the velocity of light
in a medium (in this case, RSO) and an indication of the level of saturation of the oil. RI was
determined at 20 oC using Abbe Refractometer (Model: 60/ED) and calibrated chart. The value
of 1.4707 calculated for RSO falls within the range reported in the literature for vegetable oils
(Rashad et al., 2015).
4.3.8 Other parameters
Other parameters determined for RSO are cetane number, diesel index, higher heating value,
and average molecular weight.
4.3.8.1 Cetane number (CN)
Cetane number is a measure of the tendency a fuel to knock in a diesel engine. It is an indication
of the ignition quality of a fuel. CN for RSO was calculated as 43.42 using the correlation
developed by Mofijur et al. (2014) as expressed in Equation (4.3).
𝐶𝑁 = 46.3 + (5458⁄𝑆𝑉) − (0.225 × 𝐼𝑉) (4.3)
This value compares favourably with those reported in the literature (45–49.73) for RSO
(Omorogbe et al., 2013; Kumar et al., 2010). However, with the recent price instability of crude
oil in the world markets, there is renewed interest in the use of vegetable oils such as RSO to
produce biodiesel for use in diesel engines.
136
4.3.8.2 Diesel index (DI)
The diesel index of RSO is computed using Equation (4.4) as follows:
𝐴𝑛𝑖𝑙𝑖𝑛𝑒 𝑝𝑜𝑖𝑛𝑡 (℉)× 𝐴𝑃𝐼 𝑔𝑟𝑎𝑣𝑖𝑡𝑦 (60 ℉)

𝐷𝑖𝑒𝑠𝑒𝑙 𝑖𝑛𝑑𝑒𝑥(𝐷𝐼) = (4.4)
100
The value 15.71 obtained is below minimum standard of 50 specified for diesel fuel. Therefore,
this oil cannot be used directly on diesel engines without chemical conversion because of its
high viscosity that will result to poor atomization in engine during operation.
4.3.8.3 Higher heating value (HHV)
The HHV of vegetable oils can be calculated by using SV and IV obtained from simple
chemical analyses using common laboratory equipment. In this study, a simple correlation (R2
= 0.9999) developed by Demirbaş (1998) as expressed in Equation (4.5) was used to estimate
HHV for RSO.
𝐻𝐻𝑉 (𝑀𝐽⁄𝑘𝑔) = 49.43 − [0.041(𝑆𝑉) + 0.015(𝐼𝑉)] (4.5)
The value obtained (39.37 MJ/kg) is within the range reported in literature for RSO (36.1–44
MJ/kg) (Onoji et al., 2016a; Reshad et al., 2015) and comparable to those reported by Rahman
et al. (2014) for jatropha curcas L. oil (38.66).
4.3.8.4 Average molecular weight of rubber seed oil
Vegetable oils are mainly triglycerides of three fatty acid chains with a glycerol backbone. The
average molecular weight of vegetable oils can be estimated using simple analytical processes
in laboratories. Higher molecular mass indicates higher heating values for the oil. The
determination of the molecular weight of vegetable oil is important for biodiesel production
reactions because the quantity of reagents used is based on molecular weight of the vegetable
137
oil. The average molecular weight of the RSO was calculated using Equation (4.6) reported by
Fillières et al. (1995).
𝐴𝑣𝑔. 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑜𝑖𝑙 (𝑔⁄𝑚𝑜𝑙. ) = 3𝑀𝑤𝐹𝐴 + 𝑀𝑤𝑔𝑙𝑦 − 3𝑀𝑤𝑤𝑎𝑡𝑒𝑟 (4.6)
where 𝑀𝑤𝐹𝐴 is the mean molecular weight of fatty acids present, 𝑀𝑤𝑔𝑙𝑦 is the molecular weight
of glycerol (92.09), and 𝑀𝑤𝑤𝑎𝑡𝑒𝑟 is the molecular weight of water (18.01).
The mean molecular weight of fatty acids of RSO was estimated from Equation (4.7) reported
by Ajiwe et al. (1995) and calculated as 286.74.
𝑀𝑒𝑎𝑛 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑓𝑎𝑡𝑡𝑦 𝑎𝑐𝑖𝑑𝑠 = (56⁄𝑆𝑉) × 1000 (4.7)
The average molecular weight of the RSO estimated from Equation (10) is 898 g/mol. The
value obtained compares favourably with those reported by Anastopoulos et al. (2009) for
sunflower oil (876), rapeseed oil (992), olive oil (857), and used frying oil (882).
138
Table 4.2: Physico-chemical properties and other characteristics of rubber seed oil.
Parameters Refs.a, b, c This study

Colour Golden yellow, light/dark brown Dark brown
Density, g/cm3 @ 25 oC 0.857–0.943 0.886± 0.002
Specific gravity @ 15 oC 0.91 0.909± 0.002
o
API gravity @ 15 oC NA 24.1± 0.282
Ph 6 6± 0.141
Oil content (wt.%) 40–50 43± 0.141
Iodine value, g I2/100 g oil 113–146 137.02± 0.028
Peroxide value, meq. O2/kg oil 1.6–16 10.46± 0.098
Saponification value, mg KOH/g oil 183.91–235.28 195.30± 0.282
Acid value, mg KOH/g oil 1.68–42.41 18.20± 0.141
Free fatty acid (%FFA as oleic acid) 0.84–42.412 9.10± 0.07
Kinematic viscosity, mm2/s @ 40 oC 6–66 40.18± 0.028
Refractive index @ 20 oC 1.46–1.47 1.4707±
0.0003
Pour point, oC –9 to –1.5 –6
Cloud point, oC 3–4 5.5
Cold filter plugging point, oC NA –0.025
Flash point, oC 72–295 240.3
Fire point, oC 298 256
Aniline point, oC (oF) NA 21 (69.8)
Boiling point, oC NA 119
Freezing point, oC NA –18
Cetane number 45–49.73 43.42
Higher heating value (HHV), MJ/kg 36.1–44 39.37
Mean mol. weight of fatty acids, (g/mol) NA 286.74
Average molecular weight of RSO, (g/mol) NA 898
Diesel index NA 15.71
a
Onoji et al., 2016a; bAravind et al., 2015; c Reshad et al., 2015.
NA: means not available; values are mean ± standard deviation of duplicate data.
139
4.3.9 Fatty acid profile of the seed oil
Gas chromatography-mass spectrometry (GC-MS) analysis was employed to characterize the
oil to determine its fatty acid profile. The identification of compounds and their structures was
based on data from NIST library. The results presented in Table 4.3 and Figure 4.2 indicates
that the oil is mainly unsaturated. The fatty acids present are palmitic (13.85%), stearic
(16.82%), oleic (64.11%), and cis-erucic (5.22%). The total unsaturated fatty acid composition
of the rubber seed oil was 69.33% with a saturated content of 30.67% (Onoji et al., 2016b).
Table 4.3: Fatty acids profile of rubber seed oil
Fatty acid/systemic name Chemical formulae Compositions (wt. %)

Ref.q This study
Myristic (C14:0) / C14H28O2 2.2 –
Tetradecanoic
Palmitic (C16:0)/ C16H32O2 0.23–10.6 13.85
Hexadecanoic
Palmitoleic (C16:1)/ C16H30O2 0.23–0.25 –
Hexadec-9-enoic
Stearic (C18:0)/ C18H36O2 5.69–12 16.82
Octadecanoic
Oleic (C18:1)/ cis-9- C18H34O2 12.7–42.08 64.11
Octadecenoic
Linoleic(C18:2)/ cis-9-cis- C18H32O2 39.6–52.84 –
12-Octadecadienoic
α-Linolenic (C18:3)/ cis-9- C18H30O2 2.38–26 –
cis-12-cis-15-
Octadecatrienoic
Arachidonic (C20:0)/ C20H40O2 0.66–0.97 –
Eicosanoic
Erucic acid (C22:1)/cis-13- C22H42O2 – 5.22
Docosenoic
Total saturated 8.78–23.57 30.67
Total monounsaturated 12.93–42.33 69.33
Total polyunsaturated 41.98–78.84 Trace
(linoleic, linolenic, etc)
q
Onoji et al., 2016a
Although the composition of this oil did not follow the trend of some of the reported fatty acid
profile for rubber seed oil in the literature (Onoji et al., 2016a), genetic variations could be
140
responsible for the disparity observed in the fatty acid profile of seed oil from NIG 800 clonal
series of Nigerian rubber seeds. The high content of oleic acid and the presence of cis-erucic
acid indicate the potential use of seed oils from the NIG800 series as a source of oleo chemicals.
This could replace the oleo chemicals from petroleum currently used for the oleo chemical and
steel industries. The mean molecular weight of fatty acids present in the rubber seed oil was
computed as 280.81 using Equation (4.8). This value compares favourably with 286.74
obtained using chemical analysis method earlier shown in Equation (4.7) with 2.06 %
deviation.
f i
Mean molecular weight of fatty acids = f (4.8)
M i
wi
where f I = % composition of fatty acids from GC-MS analysis and M wi = molecular weight
of a fatty acid.
Figure 4.2: Gas chromatogram of the rubber seed oil with identified peaks: peak 4
(palmitic acid), peak 5 (oleic acid), peak 6 (stearic acid), peak 10 (cis-erucic acid) (Onoji
et al., 2016b)
141
4.3.10 FT-IR and NMR spectroscopy of the seed oil
The structural characterizations of rubber seed oil were further performed by FT-IR, 1H NMR,
and 13C NMR analyses to confirm results from GC-MS analysis. These analyses are essential
for industrial applications of the oil.
4.3.10.1 FT-IR analysis of the seed oil
Further insight into the chemical compositions of the rubber seed oil was provided by the FT-
IR spectrum at room temperature (28 oC) based on Table G.1 of Appendix G. It has been
reported that very low proportions of compounds present in a mixture exhibit very weak band
which are not detectable in the IR spectrum (Guillèn & Cabo, 2002). The absorption bands of
vegetable oils at intervals of 3200 and 3600 cm-1 are usually due to O–H stretching vibration
of alcohols, carboxylic acids, and hydroperoxides (Ogbu & Ajiwe, 2016). These bands range
is conspicuously absent at room temperature for the oil under study. This indicates the absence
of a free hydroxyl functional group (O–H) for alcohols, phenols, primary and secondary
oxidation products for the extracted oil, as shown in the FT-IR spectrum (Figure 4.3). Data
showed that triglyceride (TG) was the main component in this rubber seed oil. The strong
absorption band of the ester carbonyl functional group of TG, i.e. C=O was observed around
1742 cm-1. The stretch vibration of C–O at 1160 cm-1 is attributed to the presence of ester
groups. The FT-IR spectrum presents a fingerprint region (1461–585 cm-1) that can be used as
an analytical tool to detect rubber seed oil adulteration. Table 4.4 shows the functional groups
and modes of vibration present in this rubber seed oil at room temperature (Onoji et al., 2016b).
The results compared favourably and within the ranges reported for rubber seed oils by other
researchers (Reshad et al., 2015; Bakare et al., 2006).
142
400 900 1400 1900 2400 2900 3400 3900
wavelength (cm-1)
Figure 4.3: FT-IR spectrum of the rubber seed oil
143
Table 4.4: Wavenumbers and their functional groups for FT-IR analysis of the rubber seed oil
Wavenumber (cm-1) Functional group Description of vibration
3009 Alkenes This is due to =C–H stretching of non-conjugated unsaturation (methylene group)
2921–2853 Alkanes These strong peaks are attributed to the stretching of C–H (methyl group)
1742 Carbonyl This strong and sharp peak is attributed to –C=O stretching of esters
1710 Carboxylic acids This assigned peak is due to stretching vibration of C=O
Fingerprint region (1461–585 cm-1)
1461 Alkenes The medium signal can be attributed to bending frequency of C–H
1377 Alkenes The assigned peak is due to C–H bending vibrations of alkenes (CH2 group)
1238 Carboxylic acids, Esters The assigned peak is attributed to stretching vibration of C–O
1160 Esters C–O stretching vibration attributed to ester groups
1118–1033 Esters =C–O–C stretching vibration of ester groups
721 Aromatics Assigned to out-of-plane bending vibration of saturated carbon atom (C–H )
585 Alkanes The weak signal is due to C–H vibration
144
4.3.10.2 1H NMR analysis of the seed oil
The assignments of the signals of the rubber seed oil spectrum to the different kinds of
hydrogen atoms of the acyl chains based on the literature provided by Guillén & Ruiz (2003)
as in Table G.2 of Appendix G are presented in Table 4.5. The 1H NMR spectrum of the rubber
seed oil shown in Figure 4.4, with ten different signals of variably significant intensity
depending on the proportions of the different acyl groups, is comparable with those of most
vegetable oils reported in the literature (Guillén & Ruiz, 2003) and that of rubber seed oil
presented by other researchers (Reshad et al., 2015; Bakare et al., 2006; Okieimen et al.,
2005b).
The signals are due to the protons of the triacylglycerols and are proportional to the number of
hydrogen atoms of each kind that are present in the oil sample. Signal 1 (Figure 4.4 and Table
4.5) is produced by overlapping of doublet signals of methyl group protons of the saturated and
omega-9 (i.e. oleic acid) acyl groups, and it appears at 0.80 and 0.81 ppm, respectively. Signal
2 is a singlet due to methyl protons of erucyl group (i.e. cis-erucic acid) and appears at 0.89
ppm. Signal 3 is due to the protons of the saturated methylene group of all acyl chains and
appears at 1.19 and 1.23 ppm. Signals 4 and 6 are due to methylene protons in the β and α
position and appear at 1.53 and 2.22 ppm, respectively. Signal 5, between 1.94 and 1.98, are
due to α-methylene protons in relation to a single double bond (allylic protons). Signal 7, an
overlapping signal between 2.68 and 2.72 ppm, is due to signals from α-methylene protons in
relation to double bonds (bi-allylic protons). Signal 8, which appears between 4.05 and 4.23
ppm, is due to the protons on carbon atoms 1 and 3 of the glyceryl group. Signal 9, which
appears at 5.25, is due to the proton on carbon atom 2 of the glyceryl group that overlaps with
signal 10 (olefinic protons of different acyl groups) at 5.26 ppm.
145
Table 4.5: 1H NMR spectrum analysis of the rubber seed oil
Signal Chemical shift Functional group Assignments
(ppm)
1 0.80 and 0.81 –CH3 (terminal methyl protons (saturated and oleic acids) all acyl chains
except linolenyl
2 0.89 –CH3 (terminal methyl protons (cis-erucic acid) acyl chains
3 1.19 and 1.23 –(CH2)n - (saturated methylene proton) all acyl chains
4 1.53 –OCO–CH2–CH2– (β-methylene protons (carbonyl) acyl chains
5 1.94-1.98 –CH2–CH=CH (allylic methylene protons) all acyl chains
6 2.22 –OCO–CH2– (α-methylene protons) acyl chains
7 2.68 and 2.72 =HC–CH2–CH= (bis-allylic methylene protons) acyl chains
8 4.05-4.23 –CH2OCOR (methylene protons on carbons 1, 3) glyceryl group
9 5.25 >CHOCOR (proton on carbon atom 2). It overlaps with glyceryl group
signal 10
10 5.26 –CH=CH– (olefinic protons) acyl chains

1
H NMR chemical shift (2.8 ppm) (Sadowska et al., 2008) usually attributed to the presence of linolenic and
linoleic chains (CH=CHCH2CH=CH), is not present in rubber seed oil used in this study. This is in satisfactory
agreement with the GC-MS and 13C NMR analyses of the oil.
146
Figure 4.4: 1H NMR spectrum of the rubber seed oil
4.3.10.3 13C NMR analysis of the seed oil

13
The C NMR spectrum for the oil under study is depicted in Figure 4.5 and presented in
Figures G.1 through G.5 of Appendix G. The spectrum could be grouped into four distinct
spectra regions (A, B, C, and D) as presented in Table 4.6 (Onoji et al., 2016b). The results are
similar to previous studies by other researchers on rubber seed oil (Okieimen et al., 2005b).
When the 13C NMR is compared with spectra in Figure G.6 of Appendix G (Sadowska et al.,
2008), it shows the possible absence of linolenic and linoleic acids as confirmed by the data
from GC-MS analysis (Table 4.3).
147
Figure 4.5: 13C NMR spectrum of the rubber seed oil
Table 4.6: 13C NMR analysis of carbon type present in the rubber seed oil
Group Carbon environment Chemical shift, δ (ppm) Functional group
A Aliphatic 13.91–33.97 CH3
B Glyceryl 61.93–77.16 CH2–OCOR
C unsaturated alkenes 126.99–131.99 CH=CH
D carbonyl 172.41–172.82 C=O
carboxylic acid 178.64 COOH
4.4 Kinetic study of thermo-oxidative degradation of the seed oil
When vegetable oils are heated under extreme conditions experienced in frying or in industrial
applications, they undergo thermal oxidative reactions that are reflected in remarkable changes
148
in peroxide, iodine, and refractive index values, respectively (Oderinde et al., 2009). The
average values of the peroxide, iodine, and refractive index of the Hevea brasiliensis seed oil
used in this study with respect to temperature and time on heating obtained from Table E.1 of
Appendix E are summarized in Table 4.7 (Onoji et al., 2016b).
Table 4.7: Effect of heating on peroxide, iodine, and refractive index values of rubber
seed oil
Temp (oC) Time (min) Peroxide value Iodine value Refractive index
(mequiv O2/kg oil) (g I2/100 g oil) @ 20 oC
100 30 4.02 ± 0.25 117.72 ± 1.10 1.4651 ± 0.013
60 4.50 ± 0.12 117.43 ± 0.16 1.4322 ± 0.048
120 4.81 ± 0.01 117.24 ± 0.05 1.4147 ± 0.018
180 5.00 ± 0.22 117.02 ± 0.02 1.3514 ± 0.043
240 5.40 ± 0.28 116.98 ± 0.66 1.3011 ± 0.001
300 5.61 ± 0.15 116.84 ± 0.05 1.2430 ± 0.011
150 30 4.38 ± 0.04 117.56 ± 0.36 1.4630 ± 0.004
60 4.66 ± 0.08 117.32 ± 0.16 1.4290 ± 0.001
120 4.98 ± 0.12 117.12 ± 0.24 1.4130 ± 0.019
180 5.24 ± 0.05 116.84 ± 0.32 1.3850 ± 0.005
240 5.56 ± 0.35 116.60 ± 0.87 1.3651 ± 0.006
300 5.82 ± 0.16 115.40 ± 0.84 1.3436 ± 0.002
200 30 4.62 ± 0.12 117.38 ± 0.09 1.3647 ± 0.002
60 4.88 ± 0.08 117.02 ± 0.02 1.3230 ± 0.001
120 5.00 ± 0.12 116.61 ± 0.38 1.2991 ± 0.002
180 5.34 ± 0.05 116.32 ± 0.31 1.2911 ± 0.001
240 5.76 ± 0.08 115.68 ± 0.98 1.2834 ± 0.002
300 5.94 ± 0.04 115.24 ± 0.05 1.2433 ± 0.001
250 30 4.74 ± 0.02 117.21 ± 0.50 1.3020 ± 0.002
60 4.90 ± 0.07 116.60 ± 0.28 1.2750 ± 0.001
120 4.98 ± 0.11 116.20 ± 0.28 1.2331 ± 0.001
180 5.20 ± 0.07 115.40 ± 0.28 1.2311 ±0.001
240 5.50 ± 0.07 114.82 ± 1.32 1.2212 ± 0.005
300 5.70 ± 0.14 114.48 ± 0.22 1.2011 ± 0.010
values are mean ± standard deviation of duplicate data
This shows that rubber seed oil undergoes thermal degradation that results to oxidative
rancidity and formation of unstable hydroperoxides. Moisture present in rubber seed oil hastens
its oxidation process (hydrolysis) that generates free fatty acids (FFAs) and their oxidized
compounds as depicted in Figure 4.6.

149
triacylglycerol-oil free fatty acids glycerol acrolein
O
O CH2OC-R R COOH CH2OH CH2
heat heat
R`-COCH O (H2O) R`COOH + CHOH (O2) CH
CH2OC-R`` R`` COOH CH2OH HC=O
(toxic)
heat
free radicals Na, K, Ca, etc.
heat oxidation heat oxidation
dimers and polymers, soap formation oxidation products

increased viscosity (foaming) lactones,
methyl ketones,
aldehydes, etc.
browning (flavor and aroma)
browning
Figure 4.6: Overall process of oil degradation (Adapted from Onoji et al, 2016b)
During thermal hydrolysis, the oil decomposed to produce di- and mono-acylglycerol, glycerol,
and FFAs that accelerate further the hydrolysis of the oil. The major thermal degraded
byproducts of rubber seed oil are low molecular volatile compounds, such as aldehydes,
ketones, carboxylic acids, and short chain alkanes and alkenes (Tables 4.4, 4.5, and 4.6) and
non-volatile dimers and polymers. The rubber seed oil used in this study is rich in
monounsaturated oleic acids (64.11 wt.%) and could form dehydroxydimer, ketohydrodimer,
monohydrodimer, and dehydrodimer of oleic acid if defectively stored. Dimers and polymers
are large molecules with molecular weight range of 692-1600 Da. These compounds are formed
during thermal oxidation by a combination of –C–C–, –C–O–C–, and –C–O–O–C–bonds and
have hydroperoxy, epoxy, hydroxyl, carbonyl groups, and –C–O–C–C–, and –C–O–O–C–
linkages (Choe & Min, 2007). The aforementioned groups and linkages were present in the oil
150
used for this study as deduced from FT-IR and NMR results (Tables 4.4, 4.5, and 4.6). This
establishes the possibility of generating dimers and polymers from rubber seed oil at elevated
temperatures considered in the kinetic study. The mechanism for the formation of acyclic
polymers generated from oleic acid component of the rubber seed oil during thermal
degradation is shown in Figure 4.7. The degradation process also results in loss of unsaturation
(iodine value) in the fatty acids as shown in Table 4.7.
Figure 4.7: Acyclic polymer formations from oleic acid during thermal oxidation of oils
(Adapted from Onoji et al., 2016b)
The iodine data in Table 4.7 were used to generate the kinetic data for the thermo-oxidative
behaviour of the oil under heat treatment. The reaction follows a first order mechanism as
depicted in Figure 4.8. The double bonds in vegetable oils increase the refractive index and the
151
progressive decrease in refractive index on heating as seen in Table 4.7 confirms loss of
unsaturation.
Time (min)
0
0 100 200 300 400 ln (Ct/Co) at 100
deg.C
-0.005 ln (Ct/Co)150 deg. C
R² = 0.914
-0.01 ln (Ct/Co) 200 deg. C

ln (Ct / Co)
ln (Ct/Co) 250 deg. C

R² = 0.866
-0.015
R² = 0.990
-0.02
-0.025 R² = 0.981
-0.03
Figure 4.8: ln (Ct/Co) vs. time for iodine values at 100, 150, 200 and 250 oC (Adapted from
Onoji et al., 2016b)
The kinetic parameters for degradation of rubber seed oil at 100, 150, 200, and 250 oC are given
in Table 4.8. The Arrhenius plot (lnk vs. 1/T) for the degradation kinetics in the temperature
range 100-250 oC is shown in Figure 4.9 with coefficient of determination R2 equals 0.893.
The activation energy (Ea) and the pre-exponential factor determined are 13.07 kJ/mol and
161x10-3 s-1, respectively (Onoji et al., 2016b). The high activation energy suggests that the oil
is less susceptible to thermal deterioration than other vegetable oils, such as Hura crepitans
seed oil (Ea = 1.989 kJ/mol) (Oderinde et al., 2009). The proposed Arrhenius equation for the
kinetics of degradation of rubber seed oil in the temperature range 100-250 oC is given in
Equation (4.9).
152
k (s-1) = 161 x 10-3 exp (-13.07/RT) (4.9)
Table 4.8: Kinetic parameters for degradation of rubber seed oil
Parameters/Temperature 373 K 423 K 473 K 523 K
k (s-1) 2.0 x 10-3 5.0 x 10-3 6.0 x 10-3 7.0 x 10-3
Ea = 13.07 kJ/mol
Ao = 161 x 10-3 s-1
1/T (K-1)
-4.5
0.0017 0.0019 0.0021 0.0023 0.0025 0.0027 0.0029
-4.7
-4.9
-5.1
ln k
-5.3
y = –1572x –1.826
-5.5
R² = 0.893
-5.7
-5.9
-6.1
-6.3
-6.5
Figure 4.9: Arrhenius plot for kinetics of thermo-oxidative degradation of rubber seed oil
153
4.5 Parametric effects and optimization oil extraction using RSM
4.5.1 Full quadratic regression model
The RSM full quadratic regression model for the extraction of rubber seed oil using BBD based
on Equation (3.7) is given in coded extraction process parameters as (Onoji et al., 2017a):
Y (wt. %) = 36.66 + 1.71x1 + 0.77x2 + 3.69x3 – 4.48x1x2 – 3.28x1x3 – 2.88x2x3 + 0.11x12 –

1.24x22 + 0.96x32 (4.10)
The mathematical model generated by Design-Expert software trial version 8.0.3.1 (Stat-Ease
Inc., Minneapolis, MN, USA) was used for the analysis. The correlation between the predicted
and experimental yields data is depicted in Figure 4.10, and data obtained from Table 4.9.
154
44
42
Predicted oil yield (wt.%)
40
y = 0.9996x + 0.0152
38
R2 = 0.9996
36
34
32
30
28
28 30 32 34 36 38 40 42
Experimental oil yield (wt.%)
Figure 4.10: Correlation of predicted and experimental oil yields of rubber seed oil
extraction
155
Table 4.9: Box–Behnken design for the rubber seed oil extraction process optimization by RSM and ANN (Onoji et al., 2017a)
Std. x1 x2 x3 Oil yield (wt. %) Predicted yield (wt. %) Residual value

run RSM ANN RSM ANN
1 –1 –1 0 28.64 28.56 28.641 0.080 0.001195
2 1 –1 0 41.00 40.94 41.531 0.062 0.535070
3 0 0 0 36.44 36.66 36.656 –0.22 0.216070
4 0 0 0 36.64 36.66 36.656 –0.016 0.016071
5 –1 0 –1 29.00 29.04 29.000 –0.042 0.000305
6 1 0 –1 39.00 39.02 39.000 –0.024 0.000257
7 –1 0 1 43.00 42.98 43.000 0.024 0.000470
8 0 0 0 36.76 36.66 36.656 0.01 0.103930
9 0 –1 –1 29.00 29.04 29.000 –0.038 0.000497
10 0 1 –1 36.44 36.34 36.440 0.10 0.000012
11 0 –1 1 42.06 42.16 41.529 –0.10 0.530890
12 0 1 1 38.00 37.96 38.000 0.038 0.000005
13 –1 1 0 39.00 39.06 39.000 –0.062 0.000093
14 1 1 0 33.45 33.53 33.450 –0.080 0.000063
15 1 0 1 39.88 39.84 39.883 0.042 0.000197
16 0 0 0 36.68 36.66 36.656 0.024 0.023929
17 0 0 0 36.76 36.66 36.656 0.10 0.10393
X1: rubber seed powder weight (g), X2: solvent volume (mL), X3: extraction time (min)
156
The analysis of the regression coefficients showed that the linear terms of x1, x2 and x3 were
positive, whereas the quadratic term of x2 was negative. This means that the oil yield was
enhanced by X1, X2 and X3. However, at a certain level of solvent and with more seed powder
weight, the oil yield decreases as the solvent becomes saturated. The curvature of the surface
response was significantly determined by x22. The coefficient of determination (R2) of the
model in predicting the yield was 0.9996. The residual values (Table 4.9) for the RSM in each
case were found to be less than unity and confirm that the R2 value for the model is close to 1.
4.5.2 Optimization of oil extraction process variables based on RSM
The BBD within the experimental range of data for the independent process parameters,
predicted optimal rubber seed oil yield of 42.98 wt. % at the following conditions: rubber seed
powder weight (RSPW) 60 g, solvent volume 250 mL, and extraction time 45 min. Using these
predicted values, the experiment was validated in triplicate and the average optimum rubber
seed oil yield was 42.64 wt. % (Section D.2 of Appendix D). This is close to the model
predicted value (within ± 0.797 % relative error) at same optimum conditions based on
Equation (4.11) (Zahedi & Azarpour, 2011). The absolute average deviation (AAD) obtained
from Table 4.9 and based on Equation (4.12) (Betiku & Ajala, 2014) was ±0.385 %. Evaluation
of R2 and AAD values together was used to check the accuracy of the model (Baş & Boyaci,
2007b). The low value of AAD and R2 = 0.9996 (close to unity) confirms the validity of the
model in predicting the oil. Hence, the regression model gave a good estimate of the response
of the process for low values obtained.
𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑣𝑎𝑙𝑢𝑒−𝑝𝑟𝑒𝑑𝑖𝑐𝑡𝑒𝑑 𝑣𝑎𝑙𝑢𝑒

𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑒𝑟𝑟𝑜𝑟 = × 100 (4.11)
𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑣𝑎𝑙𝑢𝑒
𝑌𝑖,𝑒𝑥𝑝 −𝑌𝑖,𝑝𝑟𝑒𝑑 1
𝐴𝐴𝐷 = {[∑𝑛𝑖=1 ( )] 𝑛} × 100 (4.12)
𝑌𝑖,𝑒𝑥𝑝
157
Where n is the number of experimental runs, while Yi, exp is the experimental oil yield
and Yi, pred is the predicted oil yield.
4.5.3 Analysis of variance (ANOVA) study for seed oil extraction

The statistical significance of the quadratic regression model equation, the individual factors,
their interactions and the goodness of the fit by analysis of variance (ANOVA) are shown in
Table 4.10. The quality of the model fit was evaluated by the Fisher's test (F-value), the
probability value (p-value), the 'lack of fit', the coefficient of determination (R2) and adjusted
coefficient of determination (R2adj). The p-value should be less than 0.05 for the variables to
have a significant effect on the response value - in this case, RSO yield (Onoji et al., 2017a).
158
Table 4.10: Analysis of variance (ANOVA) for response surface quadratic model
Source of variance Sum of squares Degrees of freedom Mean square F-value p-value
Model 303.18 9 33.69 1980.33 <0.0001
RSPW, x1 23.44 1 23.44 1377.89 <0.0001
Solvent, x2 4.79 1 4.79 281.56 <0.0001
Extraction time, x3 108.81 1 108.81 6396.43 <0.0001
x1x2 80.19 1 80.19 4714.29 <0.0001
x1x3 43.01 1 43.01 2528.56 <0.0001
x2x3 33.06 1 33.06 1943.66 <0.0001
x12 0.047 1 0.047 2.79 0.1388
x22 6.47 1 6.47 380.39 <0.0001
x32 3.87 1 3.87 227.49 <0.0001
Residual 0.12 7 0.017
Lack of fit 0.05 3 0.017 0.96 0.4917
Pure error 0.069 4 0.017
Corrected total 303.29 16
RSM: R2 = 0.9996, R2adj. = 0.9991, Root mean square error (RMSE) = 0.088,
Mean = 36.57, Standard deviation = 0.13, Adequate precision = 144.2,
Absolute average deviation (AAD) = ± 0.385 %, % Coefficient of variation = 0.355,
F- Fisher; p- probability.
The quadratic regression model has an F-value of 1980.33 and a p-value <0.0001, which
indicates that the derived model is statistically significant at the 95% confidence level. The
higher the F-value for the specific independent process parameter, the higher will be the effect
of that variable. The main effects, i.e. x1, x2 and x3 are significant terms based on their calculated
p-values (<0.0001). The quadratic effect terms of x22 and x32 are significant, but x12 term is not
significant (p>0.05), with a small F-value of 2.79. The cross-product terms of x1x2, x1x3 and
x2x3, are all significant. In Table 4.11, 95% confidence levels (low and high) represent the range
159
that the true coefficients are found in 95% of the time. If one limit is positive and the other is
negative, then the coefficient zero could be true, which indicates that the factor has no effect.
In this study, x12 has no significant effect on RSO yield having both negative and positive
values as shown in Table 4.11. However, even though x12 has a p-value >0.05 (Table 4.10),
indicating that it has no significant effect on the RSO yield, the magnitude of the change caused
is insignificant; hence, it was retained in the regression model Equation (4.10). In general, if
there is large number of insignificant model terms, model reduction by reducing the ranges of
parameters may improve the model (Dharma et al., 2016). If a model displays a 'lack of fit', it
means that several important terms were excluded from the model, or the presence of unusually
large residuals arising from fitting the model (Dharma et al., 2016). In that case, the model
does not sufficiently describe the relationship between the independent process variables and
the response variable. In this study, the 'lack of fit' of low F-value of 0.96 and high p-value of
0.4917 implied that the model was not significant relative to pure error (0.069). The p-value of
the 'lack of fit' parameter is greater than 0.05, indicating that there is good fit between the
quadratic regression model and the experimental oil yield obtained (Dharma et al., 2016). The
R2 reflects the variability of the dependent variable, which is explained by its relationship with
the independent process variables. In this study, the R2 value is 0.9996, which indicates that
99.96% of the variability in the rubber seed oil yield is attributed to the independent factors
considered (rubber seed powder weight, solvent volume and extraction time), and only 0.04%
was not explained by the model (Onoji et al., 2017a). The R2adj value is 0.9991 and the root
mean squared error (RMSE) is 0.088. These indicate that the estimated model fits the
experimental data satisfactorily, as suggested by Lee et al. (2010). The low values of standard
error observed in the intercept and all the model terms (Table 4.11) confirm that the regression
model equation fits the data well, with acceptable prediction. The variance inflation factor
(VIF) values shown in Table 4.11 indicate that the center points are orthogonal to all other
160
factors in the model. The signal-to-noise ratio is measured by the statistical parameter called
'adequate precision'. In general, an adequate precision >4 is desirable for a good model
(Dharma et al., 2016). In this study, the calculated adequate precision is 144.2 (Table 4.10),
indicating that the signal is adequate and the quadratic model can be used to navigate the
designed space. In addition, the 'coefficient of variation' is low (0.355%), which indicates that
the experimental data are accurate and reliable.
Table 4.11: RSM regression analysis for rubber seed oil extraction
Factor Regression Degrees of Standard error 95% Cnf. level 95% Cnf. level VIF
coefficient freedom (low) (high)
Intercept 36.66 1 0.058 36.52 36.79 1.00
x1 1.71 1 0.046 1.60 1.82 1.00
x2 0.77 1 0.046 0.66 0.88 1.00
x3 3.69 1 0.046 3.58 3.80 1.00
x1x2 -4.48 1 0.065 -4.63 -4.32 1.00
x1x3 -3.28 1 0.065 -3.43 -3.12 1.00
x2x3 -2.88 1 0.065 -3.03 -2.72 1.00
x12 0.11 1 0.046 -0.044 0.26 1.01
x22 -1.24 1 0.046 -1.39 -1.09 1.01
x32 0.96 1 0.046 0.81 1.11 1.01
Cnf: confidence; VIF: variance inflation factor
4.5.4 Parametric effects of interactive factors on the seed oil yield

Figure 4.11 (a) shows the response surface plot that indicates the influence of solvent volume
and rubber seed powder weight on the extraction yield when extraction time was held constant
at 45 min. It was observed that a higher seed powder weight significantly increases the oil yield
at low solvent volume. However, a slight reduction in oil yield was observed when a higher
solvent volume and low seed powder weight was used.
161
are
e predicted value
w predicted value
44.1124
50
owder weight (g)
(ml) 45
R S O
) = 50.00 40
35
%
30
25
200.00
40.00
212.50 45.00
225.00 50.00
237.50 55.00
250.00 60.00
Figure 4.11 (a): Interactive effects between solvent volume and rubber seed powder
weight on oil yield for RSM response surface (3D) plot
Figure 4.11 (b) depicts the response surface plot on the mutual interaction between extraction
time and rubber seed powder weight at constant solvent volume (225 mL). It was observed that
oil yield increased significantly with extraction time at low rubber seed powder weight. This
may be the result of more interaction between rubber seed weight and solvent (Onoji et al.,
2017a). This agrees with the findings of Reshad et al. (2015). Nevertheless, a reduction in oil
yield was observed at higher rubber seed weight and low extraction time.
162
are
44.1124
owder weight (g) 50
(min)
45
= 250.00
R S O
40
35
%
30
25
40.00 40.00
42.00
45.00
44.00
50.00
46.00
Extraction time (min) 48.00 55.00
Rubber seed powder weight (g)
50.00 60.00
Figure 4.11 (b): Interactive effects between extraction time and rubber seed powder
weight on oil yield for RSM response surface (3D) plot
Figure 4.11 (c) describes surface plot for the relationship between extraction time and solvent
volume when the rubber seed powder weight was held constant at 50 g. A significant increase
in oil yield was observed at low solvent volume and high extraction time. However, a marginal
reduction (9.6%) in oil yield was observed when solvent volume and extraction time are both
at high levels.
163
re
e predicted value 44.1124

w predicted value
50
(ml)
(min) 43
R S O
r weight (g) = 40.00 36
29
%
22
15
250.00
50.00
48.00 237.50
46.00 225.00
44.00
42.00 212.50 Solvent volume (ml)
Extraction time (min) 40.00 200.00
Figure 4.11 (c): Interactive effects between extraction time and solvent volume on oil yield
for RSM response surface (3D) plot
4.6 Parametric effects and optimization of oil extraction using ANN model
The optimum number of neurons in the hidden layer that gave good prediction of the outputs
of both training and cross validation sets in this study was iteratively obtained as three. The
genetic algorithm (GA) of the model predicted rubber seed oil yield of 43 wt. % at the following
conditions: rubber seed powder weight 40 g, solvent volume 202 mL, and extraction time 49.99
min. Using these values, the experiment was validated in triplicate, and average optimum
rubber seed oil yield was 42.96 wt. % (Section D.3 of Appendix D). This is close to the model
predicted value (within ±0.093 % relative error) at same extraction conditions. The model was
found to have an R2 value of 0.9982, R2adj value of 0.9964, RMSE of 0.2054, and AAD of
±0.064%. Figure 4.12 compares the predicted and experimental values of the rubber seed oil
164
yield, and the R2 obtained (0.997) shows a good correlation between the data obtained. This
confirms that the model proved suitable for adequate representation of the actual relationship
among the selected factors.
0.044
0.042
Predictrd yield (wt. %)
0.04 y = 0.9979x + 0.0762

0.038
R2 = 0.9979
0.036
0.034
0.032
0.03
0.028
28 30 32 34 36 38 40 42
Experimental yield (wt. %)
Figure 4.12: Correlation of predicted and experimental rubber seed oil yields by ANN
model
Figures 4.13 (a–c) depicts the interactive effects on oil yield between two extraction
independent variables while maintaining the third variable at constant level. The curvature
nature of the 3D surfaces suggests significant interactions of solvent volume with rubber seed
powder weight, extraction time with rubber seed powder weight, and solvent volume with
extraction time. It was also observed that the contour plots obtained by the ANN model were
very similar to those obtained by the RSM model.
165
Figure 4.13 (a): Interactive effects of rubber seed powder weight and solvent volume on
oil yield for ANN response surface (3D) and contour (2D) plots
166
Figure 4.13 (b): Interactive effects of rubber seed powder weight and extraction time on
oil yield for ANN response surface (3D) and contour (2D) plots.
167
Figure 4.13 (c): Interactive effects of extraction time and solvent volume on oil yield for
ANN response surface (3D) and contour (2D) plots
168
The level of importance of the process variables considered for the rubber seed oil extraction
is shown in Figure 4.14, and it is apparent that solvent volume of 50.06% is the most significant
variable on rubber seed oil yield, followed by rubber seed powder weight of 42.47% and lastly,
extraction time of 7.471%.
Figure 4.14: Percentage contribution of process variables to seed oil extraction via ANN
model (solvent volume 50.06%; RSPW 42.47%; extraction time 7.471%)
4.7 Comparison of RSM and ANN models for the seed oil extraction
The accuracies of both RSM and ANN models were evaluated based on the values obtained
for R2, AAD and % relative error. The results show that both optimization techniques gave good
predictions, due to the values of R2 that are relatively close to unity (i.e. 0.9996 and 0.9982 for
RSM and ANN, respectively). However, ANN proved to be a superior model, with lower
values of % relative error (±0.093 %) and AAD (±0.064 %) compared to the RSM model with
relative error ±0.797 % and AAD ±0.385 % (Onoji et al., 2017a).
169
4.8 Catalyst preparation and characterization
This section discusses the preparation of the catalyst derived from rubber seed shells, and the
characterization of the catalyst for biodiesel production.
4.8.1 Thermo-gravimetric analysis of the rubber seed shell catalyst

To study the influence of calcination temperature on weight loss (%), the powdered RSS was
subjected to thermal analysis (30–950 oC) in a nitrogen atmosphere at 10 oC/min heating rate.
The thermogram of RSS in Figure 4.15 shows that less water was evaporated from the surface
of the catalyst in the temperature range 30–348 oC. This indicates that less water moisture from
air was adsorbed on the surface of the catalyst than for the common heterogeneous catalysts
and it confirms its superior hydrophobicity (Onoji et al., 2017b)
120
100
Mass loss (%)
80
60
40
20
0
0 100 200 300 400 500 600 700 800 900
Temperature (oC)
Figure 4.15 TGA profile for the rubber seed shell (RSS) catalyst
The result also shows that the decomposition temperature of RSS catalyst was about 348 oC.
This confirms the stability of the catalyst for the transesterification reaction. The TGA result
from this study is similar to the TGA curve for RSS by other researchers (Sun & Jiang, 2010).
170
Major mass loss (about 90%) was observed between 348 and 465 oC, which resulted from
decomposition of macromolecules and removal of organic compounds such as cellulose and
hemicelluloses (348–400 oC), and lignin (220–465 oC). At temperature range 465-800 oC, an
additional small and steady mass loss was also observed. This may be attributed to the
formation of gaseous components because of decomposition process. Figure 4.15 also shows
that the RSS calcined at 800 oC or above did not indicate any further mass loss, which means
that the composition of the calcined RSS was mainly CaO and SiO2 as observed from XRD
results. It also confirms the high thermal stability of the calcined RSS at 800 oC and above.
Based on TGA results, 800 oC was chosen as the calcination temperature of RSS to produce
the catalyst (Onoji et al., 2017b).
4.8.2 XRF elemental analysis and basic property of rubber seed shell catalyst
XRF spectra of raw and calcined RSS are depicted in Figure 4.16 (a & b). The elemental
compositions are presented in Table H.1 of Appendix H. The pH for raw and calcined (800 oC)
RSS was found to be 7 and 12.5, respectively. This confirms the basic nature of the derived
catalyst. Background adjustment of peaks for trace metals such as niobium, molybdenum, tin,
and antimony brought them within the range. The results show that the major elements present
are calcium, silicon, potassium, aluminum, and iron. Trace metals such as zinc, tungsten,
cobalt, manganese chromium, tin and antimony are present in minute quantities after
calcination. The absence of heavy metals such as cadmium, arsenic, titanium, and lead confirms
that the catalyst synthesized is non-toxic and environmentally friendly.
171
Figure 4.16: XRF analysis of RSS: (a) raw and (b) calcined at 800 oC (Adapted from Onoji
et al., 2017b)
4.8.3 XRD analysis of the rubber seed shell (RSS) catalyst
The XRD diffractograms of the raw and calcined (800 oC) RSS are depicted in Figure 4.17 (a
& b). As shown in Figure 4.17 (a), a wide diffraction peak centered at 2θ = 23o was observed
in the XRD pattern of the raw RSS that suggests its amorphous structure (D'Cruz et al., 2007).
The diffractograms of the calcined RSS show that the catalytic property was improved by the
presence of lime (CaO) and quartz (SiO2), which enhances its thermal stability. The analysis
172
of the crystal using XRD illustrates that the raw RSS is made of CaCO3 and quartz. During
calcination, CaCO3 present in the raw RSS decomposes to CaO, and quartz to SiO2. The
diffractogram patterns of the calcined RSS are similar to the diffractograms CaO nano-particles
reported in the literature (Tang et al., 2008). The CaO generated from RSS during calcination
acts as a solid base catalyst for transesterification of rubber seed oil to biodiesel. CaO has been
utilized as a base catalyst for soybean oil transesterification to biodiesel (Liu et al., 2008). The
mechanisms of CaO as a base catalyst for oil transesterification are well described in the
literature (Issariyakul & Dalai, 2014; Guo & Fang, 2011; Liu et al., 2008). In the presence of a
little water, CaO generates methoxide anions that act as the real catalyst in transesterification
reactions (Liu et al., 2008).
173
Figure 4.17: XRD diffractograms of RSS: (a) raw, and (b) calcined at 800 oC (Adapted
from Onoji et al., 2017b)
4.8.4 SEM analysis of the rubber seed shell catalyst
Scanning electron micrographs (SEM) of the raw and calcined rubber seed shell (RSS) are
presented in Figure 4.18 (a & b). The morphology of the raw RSS looks like a mass aggregate
that has less surface area as compared to the RSS calcined at 800 oC, that shows major alteration
in its morphology. There is an observed maximum particle size reduction in the calcined RSS,
thereby exhibiting a higher surface area, an important characteristic of heterogeneous catalysts.
The SEM image of calcined RSS clearly shows regular particle shapes with clusters of well-
developed cubic crystals with obvious reduction in particle sizes, indicating higher surface area
useful for transesterification reaction (Onoji et al., 2017b).
174
a b
Figure 4.18: SEM images for (a) raw, and (b) calcined RSS catalyst at magnification
2450x
4.8.5 Surface properties of the rubber seed shell catalyst
The physical properties of the raw and calcined catalyst at 800 oC, such as specific surface area,
pore volume, and pore-size distribution, were obtained by N2 adsorption/desorption at 77.3 K
using Gold App surface area and porosity analyzer (Model: V-sorb 2800p). All samples were
outgassed prior to the measurement at 250 oC and 10-4 mbar for 11 h. The adsorption-desorption
isotherms for the raw and calcined RSS are depicted in Figure 4.19 (Onoji et al., 2017b). The
adsorption isotherm at low P/Po for the calcined RSS is similar to type I isotherms that are
characteristic of microporous adsorbent. At higher P/Po, there was increase in the volume
adsorbed caused by adsorption in mesopores as well as a hysteresis loop (0.5–0.9 P/Po)
developed that is typical of type IV isotherms caused by a weak capillary condensation below
the expected condensation pressure of nitrogen (Storck et al., 1998).
175
140
Quantity adsorbed (cm3/g, STP)
120
100
80 Adsorption (calcined)
Desorption (calcined)
60
Adsorption (raw)
40 Desorption (raw)
20
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
P/Po
Figure 4.19: Nitrogen adsorption/desorption isotherms for raw and calcined RSS
The nitrogen adsorption/desorption isotherm log plot (Figure H.1 of Appendix H) presents an
"S" shaped isotherm in the low P/Po region, reaffirming the presence of micropores and
mesopores in the calcined RSS. The nitrogen adsorption/desorption isotherm log plot for the
raw RSS displayed a type III isotherm which is typical of multilayer adsorption in non-porous
solids as shown in Figure H.2 of Appendix H. Brunauer-Emmett-Teller (BET) estimated the
surface area of the raw and the calcined RSS as 21.83 and 352.51 m2/g, respectively. The high
surface area for the calcined RSS clearly shows its superiority over the raw RSS in catalyst
formulation. The pore size for the raw and calcined RSS is 3.61 and 2.29 nm, respectively. The
pore volume for the calcined RSS was estimated at 0.1208 cm3/g, while the raw RSS was a
non-porous material (Onoji et al., 2017b). The increase in BET surface area and pore volume
correlate with the mass loss steps in the TGA curve and probably due to a modification of the
176
sample composition during calcination and crystal growth of calcium oxide (Syazwani et al.,
2015). The derived catalyst has an estimated micropore and external surface areas of 250.71
and 101.8 m2/g, respectively. The surface area of the calcined RSS catalyst, which depends on
the calcination temperature, relates to its catalytic activity. The mesopore-size distribution
analyzed by the Barrett-Joyner-Halenda (BJH) model is depicted in Figure H.3 of Appendix
H. The summary of the nitrogen adsorption/desorption results for the raw and calcined RSS are
shown in Tables 4.12 and 4.13, respectively (Onoji et al., 2017b). The single point surface area
at P/Po = 0.3139 was estimated at 334.23 m2/g for the calcined catalyst, and 8.53 m2/g for raw
RSS at P/Po = 0.2589. The results of the N2 adsorption-desorption listed in Table 4.13 indicate
that RSS catalyst provided a relatively large contact area with reactants that enhances the yield
of the biodiesel produced.
177
Table 4.12: Summary report of N2 adsorption/desorption analysis for raw RSS
S/N Items Description Results
Surface area
1 Single point surface area P/Po = 0.258 8.525 m2/g
2 BET surface area Point range: 0.053–0.206 21.838 m2/g
3 Langmuir surface area Monolayer adsorption model calculations 62.401 m2/g
4 t-plot micropore area A: Harkins-Jura adsorbed thickness (nm): 0.000 m2/g
0.351–0.540
5 t-plot external surface area SBET - Smicro 21.837 m2/g
6 BJH adsorption cumulative Pore width (nm): 2.092–587.658 18.965 m2/g
surface area
7 BJH desorption cumulative Pore width (nm): 2.053–587.658 24.832 m2/g
surface area
Pore volume
1 Single point adsorption P/Po = 0.996, total pore volume of the critical pore 0.019 cm3/g
total pore volume width less than 587.658 nm
2 t-plot micropore volume - 0.000 cm3/g
3 SF micropore volume P/Po = 0.080, total pore volume of the critical pore 0.001 cm3/g
width less than 1.914 nm
4 BJH adsorption cumulative Pore width range (nm): 2.092–587.658 0.024 cm3/g
volume
5 BJH desorption cumulative Pore width range (nm): 2.053–587.658 0.026 cm3/g
volume
Pore size
1 Total adsorption average pore By 4V/A, A: adsorption BET specific surface area 3.607 nm
width value
2 BJH adsorption average pore By 4V/A, A: adsorption cumulative pore surface 5.070 nm
width area
3 BJH desorption average pore By 4V/A, A: desorption cumulative pore surface 3.872 nm
width area
4 BJH median pore width Pore width range (nm): 2.226–587.658 2.500 nm
5 SF median pore width Pore width range (nm): 1.119–1.914 1.510 nm
178
Table 4.13: Summary report of N2 adsorption/desorption analysis for calcined (800 oC)
rubber seed shell catalyst
S/N Items Description Results
Surface area
1 Single point surface area P/Po = 0.313 334.229 m2/g
2 BET surface area Point range: 0.061–0.242 352.518 m2/g
3 Langmuir surface area Monolayer adsorption model calculations 489.503 m2/g
4 t-plot micropore area A: Harkins-Jura adsorbed thickness (nm): 250.713 m2/g
0.382–0.549
5 t-plot external surface area SBET - Smicro 101.804 m2/g
6 BJH adsorption cumulative Pore width (nm): 1.959–675.818 62.630 m2/g
surface area
7 BJH desorption cumulative Pore width (nm): 2.104–587.658 60.893 m2/g
surface area
Pore volume
1 Single point adsorption P/Po = 0.997, total pore volume of the critical pore 0.201 cm3/g
total pore volume width less than 675.818 nm
2 t-plot micropore volume - 0.120 cm3/g
3 SF micropore volume P/Po = 0.096, total pore volume of the critical pore 0.156 cm3/g
width less than 3.053 nm
4 BJH adsorption cumulative Pore width range (nm): 1.959–675.818 0.060 cm3/g
volume
5 BJH desorption cumulative Pore width range (nm): 2.104–675.818 0.058 cm3/g
volume
Pore size
1 Total adsorption average pore By 4V/A, A: adsorption BET specific surface area 2.290 nm
width value
2 BJH adsorption average pore By 4V/A, A: adsorption cumulative pore surface 3.855 nm
width area
3 BJH desorption average pore By 4V/A, A: desorption cumulative pore surface 3.965 nm
width area
4 BJH median pore width Pore width range (nm): 2.226–587.658 2.115 nm
5 SF median pore width Pore width range (nm): 1.119–1.914 0.654 nm
179
4.9 Biodiesel production from the extracted seed oil and analysis
This section discusses the characterization of the produced biodiesel, optimization of the
biodiesel process variables and testing of the biodiesel in an internal compression ignition
engine.
4.9.1 Characterization of the rubber seed oil biodiesel
The biodiesel was characterized by following the procedures outlined by ASTM, AOAC
(1990), and the results are presented in Table 4.14. The properties compared favourably with
similar reports on biodiesel synthesized from Hevea brasiliensis oil (rubber seed) (Dhawane et
al., 2015), and they were in agreement with the ASTM D 6751 and EN 14214 biodiesel
standards. From the results, the methyl ester content of the biodiesel determined by GC-MS
was 96.7%, while the calculated value using the correlation developed by Felizardo et al.
(2006) was 96.9%. The results show that biodiesel produced from rubber seed oil using waste
rubber seed shell as catalyst could be used in modern diesel engines without technical
modifications.
180
Table 4.14: Fuel properties of biodiesel produced from rubber seed oil
Properties Methods ASTM D 6751 standards EN 14214 standards Literature values This study
Density @ 15 oC (kg/m3) ASTM D 1298 870–900 860–900 885a, 842b, 880c 876
Water and sediment (vol %) ASTM D 2709 < 0.05 < 0.05 0.042a 0.0062
Acid value (mg KOH/g) ASTM D 664 < 0.8 < 0.5 0.42a, 0.12b, 0.06c 0.56
Iodine value (g I2/100 g) Wijs' 120 maximum 85.34
Saponification value (mg KOH/g) 182.53
Kinematic viscosity @ 40 oC (mm2/s) ASTM D 445 1.9–6.0 3.5–5.0 3.89a, 5.642b, 4.91c 4.32
Flash point (oC) ASTM D 93 93 minimum 120 minimum 152a, 183b, 151c 158
Fire point (oC) 189b 172
Cloud point (oC) ASTM D 2500 –3 to 12 3.2a, 3b, –7c 4.8
Pour point (oC) ASTM D 97 –15 to 10 0 –2a, –6b, –10c –8
Cold filter plugging point (oC) ASTM D 6371 –2a –0.62
Calorific value (MJ/kg) ASTM D 240 39.70a, 42.372b 40.67
Oxidation stability: @ 110 oC (h) Rancimatd ≥3 ≥6 8.54a 7.8
@ 140 oC (min) PetroOXYe ≥ 17 21.55
Cetane number ASTM D 613 47 minimum 51 minimum 54a, 53b 57
Metals: Group II (Ca-ppm) EN 14538 5 3.26
Ester content (%) EN 14103 ≥ 96.5 96.8a 96.7
aAhmad et al. (2014b); b Dhawane et al. (2015); c Dhawane et al. (2016); d EN 14112; e ASTM D 7545-1
181
4.9.2 Reusability of the catalyst for biodiesel production
As shown in Figure 4.20 and Table H.2 of Appendix H, the biodiesel yield (%) at optimum
catalyst loading of 2.2 g was higher than 80% when the catalyst was used in the fourth cycle
and the value decreased to 77.3% in the fifth cycle of usage. The possible reason for the loss
of catalytic activity was the blockage of active sites by the deposition of organic matter on the
catalyst surface, and the leaching of the active metals from the catalyst into the reaction medium
(Dhawane et al., 2016). This was facilitated by the breakage of bonds and the creation of CH3O-
and Ca2+ ions. The AAS analysis of the biodiesel shows that the concentration of Ca2+ ion was
3.26 ppm (mg/kg). This value is within the limits of 5 mg/kg set by ASTM D 6751 and EN
14214 biodiesel standards. The effects of leaching of Ca2+ ions from the catalyst on the
biodiesel are elucidated in Figure 4.21.
100
2 2.2 2.5 3 3.5
90
80
70
Biodiesel yield (%)
60
50
40
30
20
10
0
Fresh 1st cycle 2nd cycle 3rd cycle 4th cycle 5th cycle
Catalyst cycle
Figure 4.20: Effects of reuse of different catalyst loadings (2, 2.2, 2.5, 3, and 3.5 g)
on biodiesel yield (%) at optimum conditions
182
86 400
85 350
Ca2+ content of catalyst (ppm)

84
300
Biodiesel yield (%)
83
82 250
81 200
80 150
79
100
78 Biodiesel yield (%)
Ca content (ppm)
77 50
76 0
0 1 2 3 4 5 6
Catalyst cycle
Figure 4.21: Effects of Ca2+ ion leaching from reused catalyst on biodiesel yield (%) at
optimum conditions
4.10 Parametric effects and optimization of biodiesel production process variables
The optimization of the process variables for the biodiesel production, and the parametric
effects of these variables on the yield of biodiesel as described by RSM and ANN models are
discussed in this section.
4.10.1 Modeling and optimization of biodiesel production by RSM
The results of the transesterification step based on CCD as depicted in Table 4.15 were
statistically analyzed by RSM. Design-Expert® dx8 software version 8.0.7.1(Design Ease Inc.,
USA) generated the quadratic mathematical model. The full quadratic regression model for
rubber seed oil methyl ester (RSOME) production in coded process variables is given in
Equation (4.13).
183
Biodiesel yield (%) = 83.46 + 0.008629x1 + 0.21x2 – 0.34x3 + 0.26x1x2+ 0.21x1x3 +
0.16x2x3 – 0.11x12 – 0.34x22 – 0.30x32 (4.13)
A good correlation exists between the predicted yields and the experimental yields as shown
in Figure 4.22. The coefficient of determination (R2) given as 0.918 indicates a well-fitted and
reliable model.
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Table 4.15: Central composite design for optimization of biodiesel production process by RSM and ANN
Std. x1 x2 x3 biodiesel Predicted biodiesel yield (%) Residual

run yield (%) RSM ANN RSM ANN
1 –1 –1 –1 83.50 83.50 83.50 0.033 0.00000046
2 1 1 –1 82.50 82.50 82.50 –0.044 0.00000005
3 –1 1 –1 83.00 83.04 83.00 –0.044 0.00000001
4 1 1 –1 83.20 83.16 83.20 0.039 0.00000012
5 –1 –1 1 82.00 82.04 82.00 –0.044 0.00000004
6 1 –1 1 82.00 81.96 82.00 0.039 0.00000001
7 –1 1 1 82.30 82.26 82.30 0.039 0.00000033
8 1 1 1 83.18 83.22 83.18 –0.039 0.00000055
9 –2 0 0 83.00 83.00 83.00 0.0023 0.00000021
10 –2 0 0 83.00 83.00 83.00 0.0023 0.00000021
11 0 –2 0 82.00 81.70 81.70 0.30 0.30000000
12 0 –2 0 81.40 81.70 81.70 –0.30 –0.30000000
13 0 0 –2 82.90 82.95 82.95 –0.047 –0.05000000
14 0 0 –2 83.00 82.95 82.95 0.053 0.05000000
15 0 0 0 83.19 83.46 83.458 –0.27 –0.26833000
16 0 0 0 83.56 83.46 83.458 0.10 0.10167000
17 0 0 0 83.70 83.46 83.458 0.24 0.24167000
18 0 0 0 83.20 83.46 83.458 –0.26 –0.25833000
19 0 0 0 83.20 83.46 83.458 –0.26 –0.25833000
20 0 0 0 83.90 83.46 83.458 0.44 0.44167000
Coded values x1: reaction time (min), x2: methanol/oil ratio (v/v), x3: RSS catalyst (g)
185
84.0
83.5
83.0
Predicted (%)
82.5
y = 0.923x + 6.355
82.0 R2 = 0.918
81.5
81.0
81.0 81.5 82.0 82.5 83.0 83.5 84.0 84.5
Actual yield (%)
Figure 4.22: Correlation of predicted vs. actual biodiesel yields (%) for the RSM model
The residual values for RSM indicated in Table 4.15 were in each case, less than unity, and this
confirms the closeness of R2 to unity. The analysis of regression coefficients (Table 4.16) shows
that the linear terms of x1 and x2 are positive, while x3 is negative. The yield of RSOME (biodiesel)
is enhanced by increase in X1 and X2 and reduction in X3. The negativity of the coefficients of
quadratic terms x12, x22, and x32 suggests that the curvature effect of the surface response is
determined by these terms.
The derived model predicted an optimal rubber seed oil methyl ester yield of 83.11% at optimum
conditions of 60 min reaction time (X1), 0.20 vol/vol methanol/oil ratio (X2), and 2.50 g catalyst
(X3). The experiment was validated in triplicate using the optimum conditions to obtain an average
RSOME yield of 83.06±0.013%. This value is close to the model predicted value, and within
±0.06% relative error based on Equation (3.27). The absolute average deviation (AAD) calculated
from Table 4.15 and based on Equation (3.28) was ±0.022%. Hence, the developed model gave a
good estimate of the response of the process to the process variables for low values obtained.
186
Table 4.16: RSM regression coefficients analysis for the biodiesel
Factor Coefficient of Degree of freedom standard error 95%confidence 95%confidence Variance inflation
Estimate level (low) level (high) factor
Intercept 83.46 1 0.10 83.23 83.69 –
x1 0.008629 1 0.087 –0.18 0.20 1.72
x2 0.21 1 0.087 0.015 0.40 1.72
x3 –0.34 1 0.087 –0.53 –0.15 1.72
x1x2 0.26 1 0.091 0.057 0.46 1.00
x1x3 0.21 1 0.091 0.007 0.41 1.00
x2x3 0.16 1 0.091 –0.043 0.36 1.00
x12 –0.11 1 0.066 –0.26 0.035 1.75
x22 –0.34 1 0.066 –0.48 –0.19 1.75
x32 –0.30 1 0.066 –0.44 –0.15 1.75
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4.10.2 Analysis of variance (ANOVA) for biodiesel production
The statistical significance and the goodness of fit of the developed second-order quadratic
model, as well as the effect of individual terms and their interactions were analyzed by
ANOVA, and the results are summarized in Table 4.17. The quality of the model fit was
evaluated by the Fisher's test (F-value), the probability value (p-value), the "lack of fit", the
coefficient of determination (R2), adjusted R2 (R2adj), and predicted R2 (R2pred). The p-value
should be less than 0.05 for the variables to have significant effect on the response (RSOME
yield). The polynomial model has an F-value of 12.38 and p-value <0.0003, which indicates
that the developed model is statistically significant at the 95% confidence level. The higher the
F-value for the specific independent process variable, the higher will be the effect of that
variable. Two main effects, i.e. x2 and x3 are significant based on their estimated p-values
(<0.05). This shows that biodiesel produced from rubber seed oil could be effectively catalyzed
using indigenously prepared RSS catalyst. From the ANOVA analysis, the interactive effects
of x1x2 and x2x3 on the biodiesel yield are significant (p<0.05) even though x1 appears
insignificant. The effects of individual process variable as shown in Table 4.16 indicate that
the contribution of reaction time is low compared to other variables. However, there is a strong
interaction between reaction time and other variables as presented in Tables 4.16 and 4.17.
In the present study, the "lack of fit" of low F-value of 0.079 and high p-value of 0.9246 implied
that the model was not significant relative to pure error (0.65). The p-value of the "lack of fit"
parameter is greater than 0.05, indicating that there is good fit between the second-order
quadratic model and the experimental esters yield obtained (Dharma et al., 2016).
The coefficient of determination (R2) reflects the variability of the dependent response variable,
which is explained by its relationship with the independent process variables (Dharma et al.,
2016).
188
In the present study, the R2 value is 0.9187, which indicates that 91.87% of the variability in
the biodiesel yield is attributed to the independent factors considered (reaction time,
methanol/oil ratio, and catalyst amount), and only 8.13% was not explained by the model. The
R2 value is close to unity and signifies that the experimental data obtained linearly fits in the
chosen model equation. The adjusted and predicted R2 for the present study was obtained as
0.8436 and 0.7887, respectively. The difference between the adjusted R2 and predicted R2
values, which is 0.0549, is below the maximum allowable difference of 0.2 (Dhawane et al.,
2016). This explains that the model is capable of predicting the response in a reasonable
acceptable range. The adequate precision value measures the signal-to-noise ratio, and the
present study gave adequate precision of 9.83, which was higher than the critical value of 4,
thereby indicating that the model has strong signal to navigate the design space for the
optimization purpose (Kostićet al., 2016; Betiku & Ajala, 2014; Cerino Córdovaet al., 2011).
The coefficient of variance (C.V.) obtained for the present study was found to be low (0.313%),
which indicates that the experimental data are accurate and reliable to suggest that the quadratic
model is capable of optimizing the process.
189
Table 4.17 Analysis of variance (ANOVA) for the biodiesel production using RSM model
Source of variance Sum of squares degree of freedom Mean square F-value p-value
Model 7.44 9 0.83 12.38 0.0003a
x1 0.0006595 1 0.0006595 0.009884 0.9228
x2 0.39 1 0.39 5.78 0.0371a
x3 1.03 1 1.03 15.47 0.0028a
x1x2 0.54 1 0.54 8.11 0.0173a
x1x3 0.35 1 0.35 5.29 0.0443a
x2x3 0.20 1 0.20 3.07 0.1103
x12 0.19 1 0.19 2.85 0.1224
x22 1.75 1 1.75 26.18 0.0005a
x32 1.38 1 1.38 20.66 0.0011a
Residual 0.67 10 0.067
Lack of fit 0.013 2 0.006478 0.079 0.9246
Pure error 0.65 8 0.082
Corrected total 8.10 19
Statistical parameters:
Standard deviation: 0.26 R2: 0.9187
Mean of response: 82.89 Adjusted R2: 0.8436
Coefficient of variance (%): 0.313 Predicted R2: 0.7887
Adequate precision: 9.83
x1: reaction time (min), x2: methanol/oil ratio (vol/vol), x3: catalyst amount (g)
a
statistically significant at the confidence level of 95%
190
4.10.3 Parametric effects of interactive factors on biodiesel yield by RSM
In design of experiments (DOEs), the 3D model equation facilitates examination of the effects
of process variables on the response variable. The surface plot depicted in Figure 4.23 (a) shows
the interaction between reaction time (min) and methanol/oil ratio (vol/vol), with the catalyst
amount constant at the center point. Rubber seed oil methyl ester yield, marginally (0.4%)
increased with increase in reaction time from 60 to 70 min as shown in Figure 4.23 (a). At this
condition, 0.6 vol/vol (coded) that translates to 0.28 vol/vol (actual) methanol/oil ratio was
found to be the optimum for attaining 83.4% of yield when methanol/oil ratio varies from 0.20
to 0.30 vol/vol (actual). This shows that the interactive effect is not significant enough at these
conditions of low range of reaction time (Onoji et al., 2017b).
Figure 4.23 (a): RSM 3D plot for the interactive effect between reaction time and
methanol/oil ratio on biodiesel (RSOME) yield
191
Figure 4.23 (b) depicts the interaction effect between reaction time and catalyst amount on
rubber seed oil methyl ester yield, with methanol/oil ratio constant at the center point. It was
evident that the reaction time's effect had the same trend as in Figure 4.23 (a). The effect of the
reaction time alone on the yield as shown in Tables 4.16 and 4.17 is not significant, although
it has significant interactions with methanol/oil ratio and catalyst amount as previously
observed.
Figure 4.23 (b): RSM 3D plot for the interactive effect between reaction time and catalyst
amount on biodiesel (RSOME) yield
Similar observations, but with slight reduction in yield (83%), were noticed for the plot of
Figure 4.23 (c) that represents the interaction between methanol/oil ratio and catalyst amount,
when the reaction time is constant at the center point. Marginal reduction in yield was observed
when methanol/oil ratio varies from 0.20 to 0.30 vol/vol, with catalyst optimum value of 2.5 g.
It is worthy to note that each of the interactions in the surface plots exhibited a curvature that
indicates good interactive effects between the process factors involved.
192
Figure 4.23 (c): RSM 3D plot for the interactive effect between methanol/oil ratio and
catalyst amount on biodiesel (RSOME) yield
4.10.4 Optimization and interactive effects of process variables on biodiesel yield by ANN
model
Iteratively, three neurons were obtained in the hidden layer that gave a good prediction of the
outputs of training and validation sets in the present study. A network of 3-3-1 topology was
developed, and the genetic algorithm of the model predicted optimal biodiesel (RSOME) yield
of 85.07% at the following conditions: reaction time (X1=56.70 min), methanol/oil ratio
(X2=0.21 vol/vol), and catalyst amount (X3=2.20 g). The experiment was validated in triplicates
using the optimum conditions, and the average optimal biodiesel yield was 85.03±0.0012%.
This value is close to the model predicted value, and within ±0.051% relative error based on
Equation (3.27). The % absolute average deviation (AAD) calculated from Table 4.15, and
based on Equation (3.28) was ±0.000473%. Hence, the developed model gave a good estimate
of the response of the process for the low values obtained. The model has a coefficient of
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determination (R2) value of 0.9198, R2adj value of 0.9182, and R2pred value of 0.9168. These
values indicate a good and reliable model as was obtained for RSM.
Figure 4.24 compares the predicted and experimental values of the biodiesel yield, and the
coefficient of determination (R2 = 0.9198) shows a good correlation between the data obtained.
This confirms that the model is suitable for adequate representation of the actual relationship
among the selected factors.
84.0
83.5
R² = 0.919
83.0
Predicted
82.5
82.0
81.5
81.0
81.0 81.5 82.0 82.5 83.0 83.5 84.0 84.5
Actual
Figure 4.24: Correlation of predicted vs. actual biodiesel yields for ANN model
Figures 4.25, 4.26, and 4.27 depict the interactive effects on biodiesel (RSOME) yield between
two process variables while maintaining the third variable constant at center point. The
curvatures nature of the 3D surfaces suggested significant interactions of methanol/oil ratio
with reaction time, catalyst amount with reaction time, and methanol/oil ratio with catalyst
amount. Figure 4.26 shows steep decrease in the biodiesel yield as catalyst loading increases.
This could be observed as excess catalyst negates the mixing of methanol, oil and catalyst,
which led to phase separation and subsequent reduction in biodiesel yield. The observation is
similar to the reports of other researcher that as catalyst loading increases, biodiesel yield
194
increases until optimum catalyst loading is attained (Syazwani et al., 2015). The level of
importance of the process variables considered for the RSOME synthesis is depicted in Figure
4.28. It is apparent that catalyst amount (45.62%) is the most significant variable, followed by
methanol/oil ratio (36.87%) and lastly, reaction time (17.51%).
Figure 4.25: ANN Surface plot for the interactive effect of methanol/oil ratio with reaction
time on (biodiesel) RSOME yield
195
Figure 4.26: ANN Surface plot for the interactive effect of catalyst amount with
reaction time on (biodiesel) RSOME yield
Figure 4.27: ANN Surface plot for the interactive effect of methanol/oil ratio with
catalyst amount on biodiesel (RSOME) yield

196
Figure 4.28: Percentage contribution of process variables to biodiesel production via
ANN model (catalyst amount 45.62%, methanol/oil ratio 36.87%, and reaction time
17.51%)
4.10.5 Comparison of RSM and ANN models for the biodiesel production
The accuracies of both RSM and ANN models were evaluated based on the values obtained
for R2, % AAD, % relative error and the yields obtained at optimum conditions for the models.
The RSM model equation at its optimum conditions (X1 = 60 min, X2 = 0.20 vol/vol and X3 =
2.5 g) gave a yield of 83.11%. The ANN model at its optimum conditions (X1 = 56.7 min, X2 =
0.21 vol/vol and X3 = 2.2 g) gave a higher biodiesel yield of 85.07%. The supremacy of the
ANN model over RSM was further attested to by the lower values of relative error (±0.051%)
and AAD (±0.000473%) compared to the values of RSM relative error (±0.06%) and AAD
(±0.022%).
However, both optimization techniques gave good prediction due to the values of R2 that are
relatively close to unity (i.e. 0.9187 and 0.9198 for RSM and ANN, respectively). The non-
linearity of the ANN may contribute to its superiority over RSM (Ma et al., 2016).
197
4.11 Performance and emissions analysis of test engine using biodiesel-diesel blends
The experimental analyses of the data for engine performance and emission characteristics
obtained from the tested fuels (B00, B10, B20, B30, B50, and B100) used in this study are
presented in this section. The properties of the tested fuels needed for the computation of
combustion parameters are listed in Table 4.18.
Table 4.18: Properties of the test fuels
Fuel type B00 B10 B20 B30 B50 B100
Density (kg/m3) 850 853 855 858 863 876
LHV (kJ/kg) 42,900 42,400 41,900 41,500 40,500 38,200
Kinematic viscosity (mm2/s) 3.21 3.32 3.43 3.54 3.76 4.32
Cetane number 52 52.5 53 53.5 54.5 57
4.11.1 Air/Fuel ratio (AFR)
The air-fuel mixture formation in the combustion chamber affects the combustion performance
and emission characteristics of diesel engines (Li et al., 2016). The air-box differential pressure
(∆P) and the ambient air pressure (PA) are important parameters for the computation of the
flowrate of air. The flowrate of air and the air/fuel ratio were calculated using Equations (3.31)
and (3.32), respectively. Figure 4.29 depicts the variation of air/fuel ratio with engine speed for
the fuels tested (B00, B10, B20, B30, B50, and B100). The plots data were obtained from
Tables I.1 through I.6 of Appendix I. The Figure depicts that B20 has the best air/fuel ratio,
and biodiesel the least. A higher air/fuel ratio means lower amount of fuel was consumed for
the given air flowrate. The lower value for biodiesel is attributed to its high density and
198
viscosity compared to other blends, and higher fuel consumption rate for biodiesel for same
power output.
45
40 B00
35
B10
Air/Fuel ratio
30
B20
25
20 B30
15 B50
10
B100
5
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.29: Variation of air/fuel ratio with speed for diesel and biodiesel blends
4.11.2 Brake mean effective pressure (BMEP)
The calculated BMEPs for the tested fuels are presented in Tables I.1 through I.6 of Appendix
I, and were computed using Equation (3.33). The BMEP is a useful tool for comparing and
evaluating similar types of engines. The maximum BMEP developed by the engine for all fuels
tested was 4.75 bar for pure diesel (B00) at 2500 rpm and it was within the range of values
reported for this engine using diesel fuel (TecQuipment Ltd, 2011). It was also observed that
for all fuels tested, their maximum BMEP was obtained at 2500 rpm, which appears to be the
ideal speed to operate the test engine for maximum efficiency.
199
4.11.3 Brake thermal efficiency (BTE%)
Brake thermal efficiency is the ratio between the effective power developed and the rate of
energy introduced by fuel injection (Aldhaidhawi et al., 2017). The variation of BTE% of the
engine with speeds for the biodiesel blends used in this study in relation to diesel fuel is
depicted in Figure 4.30 with plot data obtained from Table I.7 of Appendix I. It was observed
that BTE% decreases as the percentage of biodiesel in the blends increases at all speeds due to
poor atomization of the blends coupled with high viscosity. Among the blends, B50 was found
to have the maximum thermal efficiency of 42.8% at a brake power of 1.88 kW, while for
diesel oil, it was 56% and biodiesel 28.2% at 2500 rpm. It can be shown that beyond the speed
limit of 2500 rpm, the brake thermal efficiency trend is reverted and started decreasing. The
lower BTE% obtained for B100 could be due to the low calorific value of biodiesel and increase
in fuel consumption as compared to B50. Ramadhas et al. (2005a) reported this trend for a
diesel engine fueled with rubber seed oil methyl esters (biodiesel).
60 B00 (diesel)
55
Brake thermal efficiency (%)
B10
50
45 B20
40
35 B30
30 B50
25
20 B100 (pure
biodiesel)
15
10
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.30: Variation of brake thermal efficiency with speed for diesel and biodiesel
blends
200
4.11.4 Brake specific fuel consumption (BSFC)
The term brake specific fuel consumption (BSFC) refers to fuel consumption quantities which
have been normalized by the engine power representing actual fuel consumed to produce 1 kW
of power output (Aldhaidhawi et al., 2017). Figure 4.31 depicted below, and obtained from
data presented in Table I.8 of Appendix I shows the variation of BSFC of diesel and biodiesel
blends at full load conditions with engine speeds. It was found that the BSFC for the blend B20
was close to that of diesel. For higher blends, the BSFC was found to be much higher than
diesel at all speeds. This is the result of the combined effects of lower heating value and the
high fuel flow rate due to high viscosity of the blends as reported by other researchers (Celikten
et al., 2012). The finding of this study is consistent with findings of past studies (Labeckas &
Slavinskas, 2006; Raheman & Ghadge, 2008).
0.6
Brake specific fuel consumption (kg/kWh)
B00 (diesel)
0.5
B10
0.4
B20
0.3 B30
B50
0.2
B100 (pure
0.1 biodiesel)
0
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.31: Variation of brake specific fuel consumption with speed for diesel and
biodiesel blends
201
4.11.5 Engine brake power
Figure 4.32 obtained from data presented at Table I.9 of Appendix I shows that the brake power
(BP) increases progressively for all types of fuels tested (B00, B10, B20, B30, B50 and B100)
all speeds at full load conditions. The value of BP recorded followed similar trends for all fuels
blends. The BP value increment was related to the increase in engine speed, since at high speeds
the combustion inside the cylinder was close to completion, which produced increasing brake
power. The lower value of engine power for biodiesel and its blends is related to its lower
calorific value compared to fossil diesel, and it is a natural phenomenon (Mohsin, et al., 2014).
However, since the difference for biodiesel in each fuel blend was 10–20%, the data showed
similar results, but B20 and B50 showed characteristics that are similar to pure diesel with
respect to brake power. It may be argued that the higher brake specific fuel consumption of
rubber seed biodiesel and its blends will compensate this power loss and maintain the fuel
quantity, finally yielding the same engine output. Mohsin et al. (2014) reported a similar trend
at full load conditions using biodiesel blends in a test engine.
202
2.5
2
Engine power (kW)
1.5 B00 (diesel)
B10
B20
1
B30
B50
0.5
B100 (pure
biodiesel)
0
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.32: Variation of engine power with speed for diesel and biodiesel blends
4.11.6 Engine torque
As shown in Figure 4.33 below, there was reduction in the engine torque for each type of fuels
blends used in the present study beyond 2500 rpm. The data for the plots are recorded in Table
I.10 of Appendix I. The value of torque decreased as the engine speed increased beyond 2500
rpm, because of less force needed to push the engine piston at high speed. This decreasing
value of torque for high speed is considered normal for every type of engine (Mohsin et al.,
2014). Lower torque value at a higher engine speed is one of the criteria that ensure positive
reaction of the fuel inside the cylinder.
For all fuels tested, maximum torque was achieved at 2500 rpm, but biodiesel fuel gave the
lowest torque value at all speeds. A similar trend was reported by Mohsin et al. (2014), which
203
showed maximum torque for all blends at 2400 rpm but tended to decrease with further increase
in speed.
10
9 B00 (diesel)
8 B10
Engine torque (Nm)
7
B20
6
5 B30
4 B50
3
B100 (pure
2 biodiesel)
1
0
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.33: Variation of engine torque with speed for diesel and biodiesel blends
4.11.7 Exhaust gas temperature (EGT)
Figure 4.34 shows the plots of exhaust gas temperature (EGT) with engine speeds for biodiesel
blends and diesel obtained from Table I.11 of Appendix I. The results show that the EGT
increases with increase in engine speed for all fuels tested. At all speeds, fossil diesel was found
to have the lowest temperature and the temperature for various blends show an upward trend
with increasing volume of biodiesel in the blends. The ester molecule in the biodiesel contains
oxygen atoms that enhance the combustion process, which results to higher EGTs. In addition,
air-coded engines run hotter resulting to higher EGTs. The high EGT for biodiesel resulted to
higher concentration of NOx in the exhaust gas emission. These findings are consistent with
those reported by other researchers (Ramadhas et al., 2005a; Elango & Senthilkumar, 2011).
204
350
B00 (diesel)
Exhaust gas temperature (o C)
B10
300
B20
B30
250
B50
B100 (pure
biodiesel)
200
150
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.34: Variation of exhaust gas temperature with speed for diesel and biodiesel
blends
4.11.8 CO emissions
Carbon monoxide (CO) is the result of incomplete combustion of fuel such as fossil diesel that
lacks oxygen molecule in its molecular structure. Several factors such as air-fuel ratio, engine
speed, injection timing, injection pressure, and type of fuels affect CO emissions. The different
CO emission values of diesel and biodiesel blends with their trend lines at various engine
speeds are depicted in Figure 4.35 with data obtainable from Table I.12 of Appendix I. In all
causes considered, CO emission at 2500 rpm recorded the lowest values and it could be
considered as the ideal speed for the engine operation. It is interesting to note that the engine
emits more CO using diesel as compared to that of biodiesel and blends at all speeds. This
result can be attributed to the higher oxygen content and cetane number of the biodiesel fuel
than diesel fuel. As the percentage of biodiesel increased in the blend, the higher oxygen
205
content to biodiesel allows more carbon molecules to burn and facilitates the completion of
combustion process (Mofijur et al., 2014).
170
160
B00
(diesel)
150 B10
140 B20
CO (ppm)
B30
130
B50
120
B100 (pure
biodiesel)
110
100
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.35: Variation of carbon monoxide emissions with speed for diesel and biodiesel
blends
4.11.9 CO2 emissions
Figure 4.36 compares the CO2 emissions of various fuel blends tested in the diesel engine at
different speeds. Naturally, emission of CO2 from the engine is due to complete combustion of
the fuel in the combustion chamber. The release of more CO2 indicates the closeness to
complete combustion of fuel. In the present study as shown in Figure 4.36, and data obtained
from Table I.13 of Appendix I, and the blend of B20, gave the highest amount of CO2 emission
starting from 1500 through 3500 rpm. This supports the higher values of exhaust gas
temperature. In all the cases considered, diesel (B00) produces the lowest amount of CO2 due
to incomplete combustion. Although, CO2 is considered a greenhouse gas that causes increased
206
global warming, from the engine performance point of view, it achieved complete combustion
and that the CO2 emitted are readily absorbed by plants for food production process
(photosynthesis) that keeps the level of CO2 in the atmosphere balance (Mohsin et al., 2014).
310
290 B00 (diesel)

270
B10
250
CO2 (ppm)
230 B20
210
B30
190
170 B50
150 B100 (pure

130 biodiesel)
110
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.36: Variation of carbon dioxide emissions with speed for diesel and biodiesel
blends
4.11.10 NOx emissions
The variation of NOx emissions of biodiesel-diesel blends with speeds obtained from Table
I.14 of Appendix I is depicted in Figure 4.37. The NOx emission for biodiesel and the blends
followed are increasing trend with respect to engine speed. In all the fuels tested, NOx emission
was higher than the neat diesel (B00) with biodiesel and B50 exhibiting higher values than
other blends. NOx emission is directly related to the engine combustion chamber temperatures
which in turn indicated by the prevailing exhaust gas temperature. With increase in the value
of exhaust gas temperature, NOx emission also increases (Ramadhas et al., 2005a). The results
207
of the present study are in agreement with the reports of researchers cited in the literature
(Özener et al., 2014). Most researchers proposed that oxygen content of biodiesel, unexpected
advance in the fuel injection timing, extended combustion timing, and higher combustion
temperature trigger higher formation of NOx (Ozsezen & Canakci, 2011; Murillo et al., 2007).
60
B00 (diesel)
50
B10
40
B20
NOx (ppm)
30
B30
20 B50
10 B100 (pure
biodiesel)
0
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.37: Variation of nitrogen oxides emissions with speed for diesel and biodiesel
blends
4.11.11 Total hydrocarbons (THCs)
Figure 4.38 with plot data obtained from Table I.15 of Appendix I shows that the amount of
THCs decreased with the increasing amount of biodiesel in the blends. This indicates that most
of the total hydrocarbons emissions present in the combustion chamber were generated from
the pure diesel used since the amount of fuel injected was constant for each type of blend tested.
In all cases considered, engine speed at 3000 rpm produces the lowest amount of THCs, after
which there was sudden increase in the content of THCs emitted at higher speeds.
208
130
B00 (diesel)
120
B10
110
B20
THC (ppm)
100 B30
90 B50
80 B100 (pure
biodiesel)
70
60
50
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.38: Variation of total hydrocarbons emissions with speed for diesel and biodiesel
blends
4.11.12 Smoke opacity
The variation of smoke density with respect to different fuels considered is depicted in Figure
4.39, with plot data presented in Table I.16 of Appendix I. The smoke density for biodiesel and
blends is generally lowered than that of diesel. B20 blend gave the lowest smoke intensity
compared to other blends. Higher cetane number and lower compressibility of the biodiesel
resulted in a lower ignition delay compared to that of diesel. A lower ignition delay reduces the
accumulation of fuel in the combustion chamber and reduces smoke emissions (Geo et al.,
2009). The formation of smoke primarily results from the unburnt molecules of fuels because
of partial reaction of carbon in the liquid fuel (Özener et al., 2014). As shown in Figure 4.39,
the smoke opacity decreases as the content of biodiesel in the blends increases. The reduction
209
in the smoke opacity with increase in biodiesel content can also be attributed to the decrease in
the carbon content, and increase in the concentration of oxygen in biodiesel fuel.
7
B00 (diesel)
6
Smoke opacity (BSU)
B10
5
B20
4
B30
3
B50
2
B100 (pure
1 biodiesel)
0
1000 1500 2000 2500 3000 3500 4000
Engine speed (rpm)
Figure 4.39: Variation of smoke opacity with speed for diesel and biodiesel blends
210
CHAPTER 5: CONCLUSION AND RECOMMENDATIONS
5.1 Conclusion
Energy security has been the major hindrance to the development of African countries. Biomass
in the form of charcoal and fuelwood continues to be the main fuel source in these countries.
Biodiesel, a sustainable energy whose properties are similar to petro-diesel could reduce the
dependency on fossil diesel. Over 90% of biodiesel produced is sourced from edible oils that
compete with food uses. Food is a necessity of man after shelter; and the use of edible vegetable
oils as biodiesel source materials is counterproductive. Non-edible low-cost rubber seed oil
obtained from abundant waste rubber seeds in Nigeria was exploited for biodiesel production
in this study. The oil was chemically extracted from the Nigerian NIG800 clonal seeds using
n-hexane solvent in a soxhlet extractor, and the physicochemical properties determined were
in the range previously reported by researchers for rubber seed oil.
The oil extraction process variables were optimized using the response surface methodology
and artificial neural network techniques via Box-Behnken experimental design. The developed
models were effective in describing the parametric effect of the considered operating variables
on the extraction of oil from rubber seeds. The high oleic acid content and the presence of cis-
erucic acid indicate the potential use of the oil as a source material for oleo chemical and steel
industries in the future. The kinetics of thermo-oxidative degradation of the oil follows first-
order kinetics with activation energy of 13.07 kJ/mol and thermally stable up to 250 oC.
The applicability of the waste rubber seed shell obtained during oil extraction was investigated
as a base catalyst for the oil transesterification to biodiesel.
The lower energy content of the produced rubber seed oil biodiesel affects the brake specific
fuel consumption, but it was compensated by the improved combustion efficiency and lower
environmental pollution as observed for total hydrocarbon, carbon monoxide, and smoke
opacity emissions compared to fossil diesel. Optimal performance of the fuel was observed
211
with the B20 blend followed by B50 and the engine operated at 2500 rpm. To ensure timely
dissemination of the findings in this study, results have been communicated to colleagues and
researchers in the field via four published journal articles and one communication in an
international conference.
5.2 Recommendations
It is recommended that further studies should be undertaken on such as:
1. The developed basic heterogeneous rubber seed shell catalyst doped with sulphuric acid via
wet impregnation method be investigated for biodiesel production. This will ensure that both
esterification and transesterification reactions are carried out in a single stage expected to
generate a higher yield of biodiesel at a lower processing time;
2. The mechanisms of the developed catalyst used in this thesis should be investigated further
to offer insight into its anticipated behaviour during biodiesel production;
3. A zero-dimensional simulation model should be employed to predict performance
characteristics of the engine using biodiesel produced from rubber seed oil catalyzed by rubber
seed shell catalyst;
4. Development of a differential thermodynamic equation system to obtain the pressure inside
the cylinder as a function of the crank angle (θ) for differential engine conditions is
recommended as future work;
5 Effects of the biodiesel on the engine components such as plunger, injectors, cylinder head,
valves, piston and rings should be investigated in an endurance test to determine the level of
components wear.
212
5.3 Contributions to knowledge
1. The outcomes of this research will serve as a pool of information for the relevant
Government Ministries, Parastatals, Departments, Research Institutes, Industries, and
Agencies that will serve as advocates for the implementation of the National Biofuels Policy
across Nigeria's business strata with respect to biodiesel production from rubber seed oil and
other African nations where rubber trees are cultivated;
2. This research provides valuable information to the global community that the genetic
engineered rubber seed obtained from Nigerian NIG800 series contains high content of oleic
acid and cis-erucic acid as a source material for oleo chemicals currently sourced from non-
renewable fossil materials;
3. The performance and emission analyses of diesel engine show that the biodiesel produced
from rubber seed oil via calcined waste rubber seed shell as catalyst could be used in the modern
diesel engines without technical modifications.
213
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239
APPENDIX
Appendix A
240
241
242
243
Appendix B
Section B.1
Rubber seed analysis:
1st Experiment:
Amount of rubber seed used = 500 g
Amount of shell present = 249.65 g
∴ Amount of kernel (solid + moisture) = 250.35 g
2nd Experiment:
Amount of rubber seed used = 500 g
Amount of shell present = 248.65 g
Amount of kernel (solid + moisture) = 251.35 g
249.65
Mass % shell (1st reading) =  100  49.93%
500
248.65
Mass % shell (2nd reading) =  100  49.73%
500
Average mass % shell =

1
49.93  49.73  49.83%
2
Standard deviation,  

 X X 2
n 1 (B.1)
Where X = mean of the data (49.93, 49.73)
n = number of data
 Standard deviation for shell = ± 0.14
Mass % of kernel and moisture calculations:
Average mass of kernel and moisture =

1
250.35  251.35  250.85g
2
250.85
Mass % (kernel + moisture) =  100  50.17%
500
244
Determination of moisture content of the kernel:
1st Experiment:
Amount of kernel used = 100 g
Amount of kernel after drying to constant mass at 105 oC for 5 h = 90.35 g
Mass of moisture = (100 – 90.35) g = 9.65 g
9.65
 Mass % moisture =  100  9.65%
100
2nd Experiment:
Amount of kernel used = 100 g
Amount of kernel after drying to constant mass at 105 oC for 5 h = 90.25 g
Mass of moisture = (100 – 90.25) g = 9.75 g
9.75
 Mass % moisture =  100  9.75%
100
 Average mass % moisture =

1
9.65  9.75  9.7 ± 0.07%
2
Therefore, average mass % kernel in the seed = 50.17 – 9.7 = 40.47± 0.07%
245
Appendix C
Section C.1
This section shows the experimental setup for rubber seed oil extraction using the n-hexane–
soxhlet extractor.
Weighing of milled kernel Milled kernel in muslin cloth
Figure C.1: Preparation of milled kernel for oil extraction
Figure C.2: Oil soxhlet extractor used for the study

246
Figure C.3: Rotary evaporator used in the study
(a) (b)
Figure C.4: Extracted rubber seed oil: (a) filtered, (b) crude
247
Appendix D
Section D.1
This section deals with the determination of the oil yield (%) using the experimental setup in
Appendix C. The oil yield was calculated based on Equation (3.1) for each particle size (0.5,
1, 1.5, 2 and 2.5 mm) considered. The experimental procedures are described in Section 3.2.2.
Calculation of oil yield for 0.5 mm particle size:
1st Experiment:
Mass of kernel charged into extractor = 50 g
Volume of n-Hexane used = 225 mL
Mass of extracted oil = 20.12 g
20.12
Oil yield = 100  40.24%
50
2nd Experiment:
Mass of kernel charged into extractor = 50 g
Volume of n-Hexane used = 225 mL
20.18
Oil yield = 100  40.36%
50
 Average oil yield for 0.5 mm kernel size =

1
40.24  40.36  40.3 ± 0.085%
2
Similar experiments were conducted in duplicates, and the oil yields obtained for 1, 1.5, 2, and
2.5 mm particle size are 39.95, 40.25; 37.8, 37.4; 32.7, 32.3; and 29.5, 29.1%, respectively.
The average results are tabulated in Table D.1, and plotted in Figure 4.1.
248
Table D.1: Variation of oil yield with kernel particle size
Particle size (mm) 0.5 1 1.5 2 2.5
Oil yield (%) 40.3±0.085 40.1±0.212 37.6±0.283 32.5±0.283 29.3±0.283
Section D.2: Validation of optimal oil yield for RSM model
The RSM model predicted an optimum oil yield of 42.98% at the following conditions:
Rubber seed milled kernel = 60 g
Solvent volume = 250 mL
Extraction time = 45 min
60 g of milled kernel of 0.5 mm particle size was charged into the n-hexane extractor with 250
mL hexane. The experiment was conducted for a period of 45 min and repeated in triplicates.
The procedures in Section D.1 were followed and the average oil yield calculated is shown
below.
1st Experiment:
Mass of milled kernel used = 60 g
25.572
Oil yield =  100  42.62%
60
2nd Experiment:
25.59
Oil yield =  100  42.65%
60
249
3rd Experiment:
25.59
Oil yield =  100  42.65%
60
Average oil yield =

1
42.62  42.65  42.65  42.64  0.017%
2
The experimental validated oil yield value of 42.64% is close to the model predicted optimum
value of 42.98% within an error of 0.8%.
Section D.3: validation of optimal oil yield for ANN model
The ANN model predicted on optimum oil yield of 43% at the following conditions:
Rubber seed milled kernel = 40 g
Solvent volume = 202 mL
Extraction time = 49.99 min
Using these optimum conditions, the experiment was conducted in triplicates as described in
Section D.1.
1st Experiment:
17.148
Oil yield = 100  42.87%
40
2nd Experiment:
17.16
Oil yield =  100  42.9%
40
250
3rd Experiment:
17.244
Oil yield =  100  43.11%
40
Average oil yield =

1
42.87  42.9  43.11  42.96  0.131%
2
The experimental validated oil yield value of 42.96% is close to the model predicted optimum
value of 43% within an error of 0.09%.
Appendix E
Section E.1
This section deals with the procedures and calculations of the physicochemical properties of
the extracted rubber seed oil based on the procedures described in ASTM and AOAC methods.
Section E.1.1 Determination of the density (ρ) and specific gravity (SG) of the oil
This was determined using 25 mL capacity density bottles at 15 oC. The SG was calculated as
the ratio of the density of the oil to that of water at 15 oC.
mass
 (E.1)
volume
o
SG  (E.2)
w
Section E.1.2 Determination of the oAPI gravity
Equation (E.3) determined the oAPI of the oil as shown below.
141.5
o
API   131.5 (E.3)
SG @15o C
251
Section E.1.3 Conradson carbon residue of the seed oil
The conradson carbon residue was determined following the procedures described in ASTM
D189-IP 13. The determination of carbon residue left after evaporation and pyrolysis of oil is
intended to provide some indication of its relative coke-forming propensity when used as
source material for fuel. In this study, 3 ± 0.1 g of oil was weighed and placed in a porcelain
crucible containing 0.3149 g of glass bead to maintain uniform heating (Onoji et al., 2016b).
The crucible was placed in the center of the skidmore iron crucible (Stanhope-Seta apparatus)
with a lid. Heat was applied and pre-ignition period observed was 30 ± 5 min when smoke
appeared above the chimney. The experiment lasted for 60 ± 5 min in an air-free environment.
At the end of the specified heating period, the test crucible containing the carbonaceous residue
was cooled in a desiccator and weighed again. The residue remaining was calculated as a
percentage of the original sample, and reported as non-combustible carbon residue. The
experiment was carried out in duplicate and average value computed as shown below.
1st Experiment:
Amount of oil and glass bead placed in a porcelain crucible = 3.3149 g
Mass of oil = 3.0 g
Mass of carbon residue and bead after evaporation and pyrolysis of the oil = 0.3263 g
 Mass of carbon residue = (0.3263 – 0.3149) g = 0.0114 g
0.0114
% mass carbon residue =  100  0.38%
3
2nd Experiment:
Amount of oil and glass bead placed in a porcelain crucible = 3.3149 g
Mass of oil = 3.0 g
Mass of carbon residue and bead after evaporation and pyrolysis of the oil = 0.3275 g
 Mass of carbon residue = (0.3275 – 0.3149) g = 0.0126 g

252
0.0126
% mass carbon residue = 100  0.42%
3
 Average mass % carbon residue =

1
0.38  0.42  0.4%
2
Section E.1.4 Moisture content analysis of the seed oil
The moisture content was determined using a standard laboratory U CLEAR oven (Model:
DHG-9053A) operated at 105 oC. About 20 g of the sample was placed in a clean porcelain
crucible, and weighed. The process of heating and cooling was repeated every 10 min after
weighing until constant weight was obtained. All analyses were done in duplicates, and
moisture content was determined by calculating the weight difference of the sample before and
after oven drying as documented below.
1st Experiment:
Amount of oil used = 20 g
Amount of oil after drying to constant mass at 105 oC = 19.658 g
Amount of moisture removed = (20 – 19.658) g = 0.342 g
0.342
% moisture content =  100  1.71%
20
2nd Experiment:
Amount of oil used = 20 g
Amount of oil after drying to constant mass at 105 oC = 19.65 g
Amount of moisture removed = (20 – 19.65) g = 0.35 g
0.35
% moisture content =  100  1.75%
20
 Average mass % moisture =

1
1.711.75  1.73%
2
253
Section E.1.5 Ash content analysis of the seed oil
The ash content was determined by burning 20 g of oven-dried sample in a porcelain crucible
placed in an electric muffle furnace (Carbolite, Parson Lane, Hope Valley S33 6RB, England,
Model: RWF 12/5) maintained at 550 ± 25 oC for an initial 20 min, cooled in a desiccator and
weighed again. The heating and cooling process was repeated every 10-min interval until the
carbonaceous residue was reduced to an ash. The results were expressed on a dry weight basis
according to procedures prescribed in ASTM D 482-IP 4, and documented as shown below.
1st Experiment:
Amount of oven-dried oil placed in a porcelain crucible = 20 g
Amount of cooled ash content after combustion at 550 ± 25 oC = 0.00018 g
0.00018
% Ash content of oil = 100  0.0009%
20
2nd Experiment:
Amount of oven-dried oil placed in a porcelain crucible = 20 g
Amount of cooled ash content after combustion at 550 ± 25 oC = 0.00022 g
0.00022
% Ash content of oil = 100  0.0011%
20
 Average mass % ash =

1
0.0009  0.0011  0.001%
2
Section E.1.6 Determination of the seed oil volatile matter
The percentage of volatile matter in the oil was obtained by using Equation (E.4).
𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑚𝑎𝑡𝑡𝑒𝑟 (%) = 100 − (𝑐𝑎𝑟𝑏𝑜𝑛 𝑟𝑒𝑠𝑖𝑑𝑢𝑒 + 𝑚𝑜𝑖𝑠𝑡𝑢𝑟𝑒 + 𝑎𝑠ℎ) (E.4)
Therefore, % volatile matter = 100 – (0.4 + 1.73 + 0.001) = 97.869%
254
Section E.1.7 Determination of the peroxide value (PV) of the oil
About 2 g of oil sample was weighed into a 250-mL pyrex flask and 40 mL of solvent mixture
(2:1 glacial acetic acid/chloroform) was added. The content was swirled until it was dissolved
completely and 2 g of KI powder was then added. The mixture was boiled briskly in a water
bath maintained at 70 oC for 1 min. The boiled mixture was added to a flask containing 40 mL
of 5% KI and the resultant mixture was then washed with 50 mL of distilled water. The content
of the flask was titrated with 0.004M Na2S2O3 solution using 1 mL of 0.5% starch solution as
indicator. The experiment was repeated and peroxide value (mequiv O2/kg oil) was calculated
as indicated in Equation (E.5).
V×M
Peroxide value = (E.5)
w
where:
V = volume of Na2S2O3 used for titration
M = molarity of Na2S2O3
w = weight of oil sample
Section E.1.8 Determination of the iodine value (IV) of the oil (Wijs' method)
About 0.26 g of oil was dissolved in 10 mL of carbon tetrachloride and agitated in a stopper
flask. 20 mL of Wijs solution was added and allowed to stand for 30 min in the dark at room
temperature. 20 mL of 10% potassium iodide solution and 100 mL distilled water was added
to the mixture in the flask and titrated with 0.1M Na2S2O3 (sodium thiosulphate) standard
solution using 1 mL of 0.5% starch solution as indicator. The iodine value was calculated using
Equation (E.6).
12.69  M  B  S 
IV  (E.6)
w
where:
255
B = volume of Na2S2O3 titrated in blank
S = volume of Na2S2O3 titrated in test
M = molarity of standard Na2S2O3
w = mass of oil used
Section E.1.9 Determination of the refractive index (RI) of the oil
A digital Abbe Refractometer (Model: 60/ED) was used to determine the refractive index of
the oil that was maintained at 20 oC in a water bath to keep the temperature of the glass slide
uniform. Then, few drop of oil sample was dropped into the glass slide of the refractometer by
means of syringe and needle. This was repeated twice and the values were converted using a
calibrated chart, and average value was recorded.
Section E.1.10 Determination of the saponification value (SV) of the oil
About 4 g of oil was weighed into a 250-mL pyrex flask and 50 mL of 0.5M ethanolic KOH
was added. The setup was connected to a reflux condenser and heated gently for 30 min. The
mixture formed (soap solution) was cooled and titrated with 0.5M HCl solution using 2 drops
of phenolphthalein indicator. The endpoint is reached when the pink colour of the indicator
disappeared. The experiment was conducted for the blank titration and repeated. The
saponification value was calculated according to Equation (E.7).
56.1  M  B  S 
SV  (E.7)
w
where:
B = volume of HCl used during blank titration
S = volume of HCl used for test
M = molarity of standard HCl
w = mass of oil used in gram; Molecular mass of KOH = 56.1

256
Section E.1.11 Determination of acid value (AV) of the oil
The acid value was determined by dissolving 5 g of oil sample in a hot mixture of 25 mL (95%
vol/vol) diethyl ether and 25 mL ethanol in a 250-mL flask. The hot solution was titrated with
0.1M KOH solution using 3 drops of phenolphthalein indicator. The acid value was calculated
using Equation (E.8). It is important to note that %FFA is half the acid value.
56.1  M  V
AV  (E.8)
w
where:
M = molarity of standard KOH
V = volume of titrant (KOH) in cm3
w = mass of oil sample
56.1 = molecular mass of KOH
Section E.1.12 Determination of the pH value of the oil
About 2 g of the oil sample was poured into a clean dry 100 mL beaker and 12.5 mL of hot
distilled water was added to the sample in the beaker and stirred gradually. The resulting
solution was cooled in a water bath at temperature of 28 oC. A standardized pH meter with
buffer solution and the electrode immersed into the sample was used to read up the pH value
of the oil sample. The experiment was repeated and the average value recorded.
Section E.2
This section deals with the effects of temperature and time parameters on the peroxide, iodine,
and refractive index values of the oil during heat treatment. At each temperature and time
indicated, the values are determined as described in Section E.1, and they are recorded in Table
E.1. The average values and their standard deviations are presented in Table 4.7.
257
Table E.1: Variation of peroxide, iodine, and refractive index values of rubber seed oil
with temperature and time
Temp Time Peroxide (mequiv O2/kg Iodine (I2/100 g oil) Refractive index @ 20 oC
(oC) (min) oil)
1st 2nd 1st 2nd 1st 2nd
Reading Reading Reading Reading Reading Reading
100 30 3.84 4.20 118.50 116.94 1.4555 1.4747
60 4.41 4.59 117.31 117.55 1.3982 1.4662
120 4.80 4.82 117.20 117.28 1.4018 1.4276
180 4.84 5.16 117.00 117.04 1.3820 1.3208
240 5.20 5.60 116.51 117.45 1.3001 1.3021
300 5.50 5.72 116.80 116.88 1.2580 1.2352
150 30 4.35 4.41 117.30 117.82 1.4601 1.4659
60 4.60 4.72 117.20 117.44 1.4281 1.4299
120 4.89 5.07 116.95 117.29 1.3991 1.4269
180 5.20 5.28 116.61 117.07 1.3811 1.3889
240 5.31 5.81 115.98 117.22 1.3700 1.3602
300 5.70 5.94 114.80 116.00 1.3420 1.3452
200 30 4.53 4.71 117.31 117.45 1.3628 1.3666
60 4.82 4.94 117.00 117.04 1.3225 1.3235
120 4.91 5.09 116.34 116.88 1.2970 1.3012
180 5.30 5.38 116.10 116.54 1.2900 1.2922
240 5.70 5.82 114.98 116.38 1.2815 1.2853
300 5.91 5.97 115.20 115.28 1.2431 1.2435
250 30 4.72 4.76 116.85 117.57 1.3001 1.3039
60 4.85 4.95 116.40 116.80 1.2745 1.2755
120 4.90 5.06 116.00 116.40 1.2326 1.2343
180 5.15 5.25 115.20 115.60 1.2319 1.2303
240 5.45 5.55 113.88 115.76 1.2254 1.2170
300 5.60 5.80 114.32 114.64 1.2085 1.1937
258
RAW RSS RSS CATALYST
o
Calcined @ 800 C
Figure E.1: Calcination of rubber seed shell (RSS) catalyst for biodiesel production
Appendix F
Section F.1
Esterification of rubber seed oil:
Prior to transesterification reaction, the acid value of the oil is reduced to ≤ 1% FFA to avoid
the consumption of the base catalyst during biodiesel production through saponification
reaction (soap formation). The initial value of the rubber seed oil was 18.02 mg KOH/g oil. For
each concentration of H2SO4 catalyst (1.5, 3, 4.5, and 6 % vol/vol) used, the experiment was
carried out in duplicates as described in Section 3.8.1. The acid value in each case was
determined as discussed in Section E.1.11 of Appendix E, and the values recorded in Table
F.1.
Table F.1: Esterification parameters of the rubber seed oil (Onoji et al., 2017b)
Std run H2SO4 (% vol/vol) Acid value (mg KOH/g oil) FFA (%)
0 0 18.20±0.141 9.10±0.07
1 1.5 12.50±0.125 6.25±0.0625
2 3 4.82±0.021 2.41±0.01
3 4.5 3.98±0.01 1.96±0.005
4 6 1.78±0.005 0.86±0.0025
259
Figure F.1: Esterified oil separation into two layers
Figure F.2: Gravity settling of biodiesel, catalyst and glycerol phases
260
Figure F.3: Processed rubber seed oil methyl ester (biodiesel) for analysis
Figure F.4: Regression line (−), upper (−), and lower (−) prediction intervals and
experimental data (∎) of oxidation stability determination for biodiesel without additive
(Adapted from Botella et al., 2014)
261
Appendix G
Table G.1: Infrared group absorption frequencies (Onoji et al., 2016b)
Type of bond Functional group Type of vibration Wavenumber (cm-1) Wavelength (μ) Intensity (I)
C–H Alkanes stretch 3000-2850 3.33-3.51 s
–CH3 bend 1450 and 1375 6.90-7.27 m
–CH2– bend 1465 6.83 m
Alkenes stretch 3100-3000 3.23-3.33 m
bend 1700-1000 5.88-10.0 s
Aromatics stretch 3150-3050 3.17-3.28 s
out-of-plane bend 1000-700 10.0-14.3 s
Alkynes stretch ca. 3300 ca. 3.03 s
Aldehydes 2900-2800 3.45-3.57 w
2800-2700 3.57-3.70 w
C–C Alkanes not usually useful
C=C Alkenes 1680-1600 5.95-6.25 m-w
262
Aromatics 1600-1400 6.25-7.14 m-w
C≡C Alkyne 2250-2100 4.44-4.76 m-w
C=O Aldehyde 1740-1720 5.75-5.81 s
Ketone 1725-1705 5.80-5.87 s
Carboxylic acids 1725-1700 5.80-5.88 s
Esters 1750-1730 5.71-5.78 s
Amide 1700-1640 5.88-6.10 s
Anhydride ca. 1810 ca. 5.52 s
ca. 1760 ca. 5.68 s
Acyl chloride 1800 5.55 s
C–O Alcohols, Ethers, Esters, Carboxylic acids 1300-1000 7.69-10.0 S
O–H Alcohols, Phenols:
Free 3650-3600 2.74-2.78 m
H-bonded 3400-3200 2.94-3.12 m
Carboxylic acids (2) 3300-2500 3.03-4.00 m
263
N–H Primary and secondary amines ca. 3500 ca. 2.86 M
C≡N Nitriles 2260-2240 4.42-4.46 M
N=O Nitro (R–NO2) 1600-1500 6.25-6.67 s
1400-1300 7.14-7.69 s
C-X Fluoride 1400-1000 7.14-10.0 s
Chloride 800-600 12.5-16.7 s
Bromide, Iodide <600 >16.7 s
(I): s = strong, m = medium and w = weak
264
Table G.2: Assignment of signals of 1H NMR spectra for vegetable oils (hazel nut and
walnut) (Guillèn & Ruiz, 2003)
Signal Chemical shift (ppm) Functional group
1 0.83–0.93 –CH3(saturated, oleic and linoleic acyl chains)
2 0.93–1.03 –CH3 (linolenic acyl chains)
3 1.22–1.42 – (CH2)n -(acyl chains)
4 1.52–1.70 –OCO–CH2–CH2– (acyl chains)
5 1.94–2.14 –CH2–CH=CH (acyl chains)
6 2.23–2.36 –OCO–CH2– (acyl chains)
7 2.70–2.84 =HC–CH2–CH= (acyl chains)
8 4.10–4.32 –CH2OCOR (glyceryl group)
9 5.20–5.26 >CHOCOR (glyceryl group)
10 5.26–5.40 –CH=CH– (acyl chains)
Figure G.1: 13C NMR spectra of rubber seed oil (12–28 ppm)
265
Figure G.2: 13C NMR spectra of rubber seed oil (28.4–34.8 ppm)
266
Figure G.4: 13C NMR spectra of rubber seed oil (126.4–132.0 ppm)
267
Figure G.6: Double bond peaks in the 13C NMR spectrum for pure oleic acid, linoleic acid,
and linolenic acid. Peaks for each characteristic double bond carbon are assigned the
letters A for the peak found in all acids, B for the peak found in both linoleic and linolenic
acid, and C and C’ for the peaks found only in linolenic acid (Adapted from Sadowska et
al., 2008)
268
Appendix H
Table H.1: XRF spectroscopic elemental analysis of rubber seed shells catalyst (Onoji et
al., 2017b)
Elements Raw (uncalcined) RSS Calcined RSS at 800 oC for 3 h

pH=7.0 pH=12.5
Intensity Concentration wt.% Intensity Concentration wt.%
(mg/mL) (mg/mL)
Magnesium, Mg 0.0000 0.0267 0.5801 0.0001 0.1349 1.9423
Aluminum, Al 0.0003 0.0817 1.7749 0.0007 0.2048 2.9487
Silicon, Si 0.0015 0.0533 1.1579 0.0043 0.3392 4.8838
Phosphorus, P 0.0026 0.1202 2.6113 0.0037 0.1746 2.5132
Sulfur, S 0.0055 0.3847 8.3576 0.0059 0.4225 6.0832
Potassium, K 0.0020 0.1566 3.4021 0.0081 0.6516 9.3817
Calcium, Ca 0.0071 0.1195 2.5961 0.0243 0.7247 10.434
Vanadium, V 0.0002 0.0082 0.1781 0.0002 0.0093 0.1339
Chromium, Cr 0.0003 0.0111 0.2411 0.0002 0.0066 0.0950
Manganese, Mn 0.0003 0.0160 0.3476 0.0005 0.0284 0.4089
Cobalt, Co 0.0002 0.0017 0.0369 0.0001 0.0013 0.0187
Iron, Fe 0.0021 0.2766 6.0091 0.0076 0.8000 11.518
Nickel, Ni 0.0018 0.1079 2.3441 0.0015 0.0931 1.3405
Copper, Cu 0.0034 0.0630 1.3687 0.0037 0.1334 1.9207
Zinc, Zn 0.0050 0.1707 3.7085 0.0056 0.1947 2.8033
Tungsten, W 0.0006 0.1971 4.2820 0.0007 0.2528 3.6398
Rubidium, Rb 0.0000 0.0000 0.0000 0.0005 0.0018 0.0259
Niobium, Nb 0.0058 0.0675 1.4664 0.0054 0.0633 0.9114
Molybdenum 0.0035 0.1890 4.1060 0.0045 0.1592 2.2922
Tin, Sn 0.0074 1.3830 30.0456 0.0077 1.4414 20.753
Antimony, Sb 0.0093 1.1685 25.3856 0.0089 1.1078 15.950
269
Figure H.1: Nitrogen adsorption/desorption log plot for calcined RSS (Adapted from
Onoji et al., 2017b)
Figure H.2: Nitrogen adsorption/desorption log plot for raw RSS (Adapted from Onoji et
al., 2017b)
270
Figure H.3: BJH adsorption pore-size distribution log plot for calcined RSS (Adapted
from Onoji et al., 2017b)
Table H.2: Biodiesel yields for fresh and reused catalyst loadings at optimum conditions
Catalyst Yield with fresh Yield with reused catalyst (%)
loading (g) catalyst (%)
1st cycle 2nd cycle 3rd cycle 4th cycle 5th cycle
2.0 75.15 ± 1.25 72.4 ± 1.31 69.31 ± 1.12 67.52 ± 1.3 64.3 ± 1.18 60.4 ± 1.11
2.2 85.03 ± 1.13 84.8 ± 1.09 84.4 ± 1.11 83.5 ± 1.16 80.8 ± 0.04 77.3 ± 0.12
2.5 82.08 ± 1.27 82.01 ± 1.17 81.8 ± 1.32 81.0 ± 1.4 78.1 ± 1.39 74.2 ± 0.94
3.0 81.36 ± 1.18 79.5 ± 1.09 77.6 ± 1.31 75.3 ± 2.04 72.3 ± 1.99 70.4 ± 1.16
3.5 79.01 ± 2.01 76.1 ± 1.23 73.2 ± 1.35 70.4 ± 1.88 67.8 ± 2.04 64.2 ± 1.67
value ± standard deviation of duplicate data.
271
Appendix I
Section I.1
The combustion efficiency of diesel engines has resulted to increase in its usage in the
transportation sector in the last few decades. Thus, the environmental concerns are growing
and the fuels used in road transportation are subject to increasing stringent regulations
(Aldhaidhawi et al., 2017). Biodiesel sourced from non-edible rubber seed oil is considered as
a solution to the existing emission problems arising from the use of fossil diesel.
The experimental data for the analyses of the engine performance and emissions arising from
the use of the rubber seed oil biodiesel-diesel blends used in the study are presented in this
section. This includes air/fuel ratio, brake mean effective pressure, brake thermal efficiency,
brake specific fuel consumption, engine brake power, engine torque, exhaust gas temperature,
and emissions of CO, CO2, NOx, total hydrocarbons, and smoke opacity.
272
Table I.1: Variation of engine speed with fuel and air parameters for B00 (diesel)
Engine Fuel Fuel drain Fuel density Fuel Ambient Air Ambient air Air Air Air/Fuel BMEP
speed volume time (s) (ρ), (gcm-3) flowrate, air temp., differential pressure, PA velocity flowrate, ratio, (bar)
(rpm) (cm3) 𝑚̇𝑓 (kgh-1) TA (oC) pressure, ∆P (Pa) (ms-1) 𝑚̇𝑎 (kgh-1) 𝑚̇𝑎
(Pa) 𝑚̇𝑓
1500 8 94 0.85 0.26 28.6 -136 100,900 14.6 10.32 39.6 3.48
2000 8 79 0.85 0.31 29.0 -140 100,900 14.8 10.46 33.7 4.06
2500 8 72 0.85 0.34 29.3 -153 100,800 15.5 10.93 32.1 4.75
3000 8 44 0.85 0.56 30.1 -184 100,800 17 11.97 21.4 3.89
3500 8 29 0.85 0.83 31.1 -225 100,800 18.75 13.21 15.9 3.14
Table I.2: Variation of engine speed with fuel and air parameters for B10
(Pa) 𝑚̇𝑓
1500 8 91 0.853 0.27 30.1 -138 100,500 14.7 10.35 38.3 1.79
2000 8 79 0.853 0.31 30.2 -140 100,500 14.8 10.42 33.6 2.39
2500 8 66 0.853 0.37 30.5 -156 100,500 15.6 10.99 29.7 2.71
3000 8 38 0.853 0.64 30.7 -171 100,400 16.3 11.5 18 2.22
3500 8 27 0.853 0.90 30.8 -188 100,400 17.1 12.06 13.4 2.11
273
(Pa) 𝑚̇𝑓
1500 8 72 0.855 0.34 31.7 -178 100,400 16.7 11.72 34.5 2.76
2000 8 77 0.855 0.32 31.6 -182 100,400 16.9 11.85 37 2.81
2500 8 77 0.855 0.32 31.7 -220 100,400 18.5 13.03 40.7 3.46
3000 8 70 0.855 0.35 31.6 -240 100,500 19.4 13.6 38.9 2.71
3500 8 66 0.855 0.37 31.6 -247 100,500 19.6 13.8 37.3 2.6
(Pa) 𝑚̇𝑓
1500 8 67 0.858 0.36 30.5 -230 101,000 19 13.39 37.2 1.89
2000 8 71 0.858 0.35 31.0 -244 101,000 19.5 13.78 39.4 2.71
2500 8 71 0.858 0.35 29.5 -253 100,900 19.9 14.06 40.2 3.14
3000 8 55 0.858 0.45 29.5 -259 100,900 20.1 14.22 31.6 2.76
3500 8 51 0.858 0.48 30.9 -272 100,900 20.6 14.54 30.3 2.27
274
(Pa) 𝑚̇𝑓
1500 8 67 0.863 0.37 31.6 -186 100,700 17 12 32.4 2.89
2000 8 71 0.863 0.35 31.6 -243 100,700 19.5 13.71 39.2 3.47
2500 8 65 0.863 0.38 31.5 -282 100,700 21 14.78 38.9 3.88
3000 8 51 0.863 0.49 32.2 -282 100,700 21 14.76 30.1 3.39
3500 8 47 0.863 0.53 32.4 -298 100,600 21.6 15.16 28.6 3.13
Table I.6: Variation of engine speed with fuel and air parameters for B100 (biodiesel)
(Pa) 𝑚̇𝑓
1500 8 87 0.876 0.29 31.1 -125 100,400 14 9.83 33.9 1.89
2000 8 76 0.876 0.33 31.1 -150 100,400 15.3 10.76 32.6 2.26
2500 8 62 0.876 0.41 31.5 -154 100,400 15.5 10.90 26.6 2.60
3000 8 33 0.876 0.77 31.6 -160 100,400 15.8 11.11 14.4 2.38
3500 8 21 0.876 1.19 31.8 -171 100,400 16.3 11.48 9.6 2.17
275
Table I.7: Variation of brake thermal efficiency (BTE %) with engine speed
Engine speed (rpm) BTE (%)

B00 B10 B20 B30 B50 B100
1500 33 15.8 28.4 17 26.7 18.1
2000 42 25.2 30 28.4 36.8 25.1
2500 56 35.9 41.1 34.6 42.8 28.2
3000 33 17.1 22.1 20.4 24 16.7
3500 21 13.5 18 14.1 24 11.5
Table I.8: Variation of brake specific fuel consumption (BSFC) with engine speed
Engine speed (rpm) BSFC ((kg/kWh)

B00 B10 B20 B30 B50 B100
1500 0.26 0.53 0.42 0.65 0.44 0.52
2000 0.20 0.34 0.29 0.33 0.26 0.38
2500 0.15 0.28 0.19 0.23 0.20 0.33
3000 0.25 0.50 0.22 0.28 0.25 0.56
3500 0.39 0.63 0.21 0.31 0.25 0.81
Table I.9: Variation of engine brake power (BP) with engine speed
Engine speed (rpm) BP (kW)

B00 B10 B20 B30 B50 B100
1500 1.01 0.518 0.803 0.55 0.84 0.55
2000 1.57 0.921 1.089 1.047 1.34 0.88
2500 2.30 1.31 1.675 1.518 1.88 1.257
3000 2.26 1.29 1.57 1.602 1.97 1.382
3500 2.13 1.43 1.759 1.539 2.12 1.466
Table I.10: Variation of engine torque with engine speed
Engine speed (rpm) Torque (Nm)

B00 B10 B20 B30 B50 B100
1500 6.4 3.3 5.1 3.5 5.4 3.5
2000 7.5 4.4 5.2 5.0 6.4 4.2
2500 8.8 5.0 6.4 5.8 7.8 4.8
3000 7.2 4.1 5.0 5.1 6.0 4.4
3500 5.8 3.9 4.8 4.2 5.4 4.0
276
Table I.11: Variation of exhaust gas temperature (EGT) with engine speed
Engine speed (rpm) EGT (oC)

B00 B10 B20 B30 B50 B100
1500 175 180 187 192 215 233
2000 185 190 200 215 238 259
2500 217 220 230 240 250 274
3000 240 242 250 260 270 286
3500 300 305 315 320 328 340
Table I.12: Variation of carbon monoxide emissions with engine speed
Engine speed (rpm) CO (ppm)

B00 B10 B20 B30 B50 B100
1500 165 160 157 154 150 145
2000 140 138 136 132 128 120
2500 125 123 120 117 114 110
3000 135 132 130 128 125 119
3500 138 136 134 133 130 124
Table I.13: Variation of carbon dioxide emissions with engine speed
Engine speed (rpm) CO2 (ppm)

B00 B10 B20 B30 B50 B100
1500 130 145 170 152 160 175
2000 135 150 180 165 170 190
2500 150 168 220 180 200 228
3000 170 200 250 225 230 265
3500 215 235 292 260 270 300
Table I.14: Variation of oxides of nitrogen emissions with engine speed
Engine speed (rpm) NOx (ppm)

B00 B10 B20 B30 B50 B100
1500 5 8 10 13 15 15
2000 12 15 17 20 23 25
2500 20 22 25 27 30 33
3000 23 26 30 35 38 42
3500 30 35 44 49 52 55
277
Table I.15: Variation of total hydrocarbons emissions with engine speed
Engine speed (rpm) THCs (ppm)

B00 B10 B20 B30 B50 B100
1500 120 115 110 100 90 80
2000 115 110 100 94 88 75
2500 99 89 85 82 79 70
3000 85 80 76 74 70 65
3500 100 98 90 88 83 73
Table I.16: Variation of smoke opacity emissions with engine speed
Engine speed (rpm) Smoke (BSU)

B00 B10 B20 B30 B50 B100
1500 1.41 1.3 1.01 1.1 1.06 0.89
2000 2.48 2.21 1.12 1.6 1.18 0.92
2500 3.69 3.2 1.98 2.6 2.2 1.89
3000 4.91 4.5 3 3.8 3.3 2.88
3500 6.01 5.6 3.88 5.1 4.3 3.6
BSU: Bosch smoke unit
278

Onoji's Thesis (PHD) - Final Submission

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SYNTHESIS OF BIODIESEL FROM RUBBER SEED OIL FOR

INTERNAL COMPRESSION IGNITION ENGINE

Samuel Erhigare Onoji

A thesis submitted to the Faculty of Engineering and the Built

Environment, University of the Witwatersrand, Johannesburg, in

fulfillment of the requirements for the degree of Doctor of Philosophy.

Johannesburg, South Africa.

2nd December, 2017

before for any degree or examination in any other University.

2nd.............Day of........December, ..........2017

by Fourier transform-infrared (FT-IR) and nuclear magnetic resonance (NMR) analyses.

properties using thermogravimetric analyzer, x-ray diffractometer, and nitrogen

compositions and surface morphology by x-ray fluorescence and scanning electron

experimentally as 85.03±0.013%. The characterized biodiesel complied with ASTM D 6751

gave me to start and complete the research successfully.

My profound gratitude goes to my co-supervisors, Professor Michael O. Daramola of the

valuable contributions to this study.

provided for the practical work.

hospitality showed to me during my stay in Johannesburg, and to Dr. Tunde F. Adepoju of

and Members of the Church for their support and goodwill.

sacrifice that strengthened me throughout the period of my study.

renewable source of biodiesel for sustainable development in sub-Saharan Africa. Energy

Conversion and Management, 110, 125–134.

Extraction, characterization, and kinetics of thermo-oxidative degradation using classical

chemical methods. Energy & Fuels, 30 (12), 10555–10567.

methodology and artificial neural network techniques. Biofuels, 1–15.

optimization of process variables. Energy & Fuels, 31 (6), 6109–6119.

Africa Growth in the Millennium Era: A Multi-Disciplinary Approach. Universite de Sciences

et Technologies de Côte d'Ivoire.

LIST OF REFERRED PUBLICATIONS.............................................................................vii

1.1 Research background and motivation................................................................................1

1.3 Justification of study.........................................................................................................3

1.4 Research aims and objectives............................................................................................5

1.5 Thesis outline....................................................................................................................7

CHAPTER 2: LITERATURE REVIEW................................................................................9

2.1 The rubber tree..................................................................................................................9

2.2 Rubber seed capacity in sub-Saharan Africa...................................................................13

2.3 Rubber seed collection and processing............................................................................15

2.5 Modeling and optimization approach to industrial research............................................18

2.6 Qualitative and quantitative analytical procedures..........................................................21

2.6.1 Thermogravimetric analysis.........................................................................................22

2.6.2 Fourier transform infrared spectroscopy......................................................................22

2.6.3 Scanning electron microscopy......................................................................................23

2.6.4 Brunauer- Emmett-Teller (BET) analysis....................................................................23

2.6.5 Nuclear magnetic resonance.........................................................................................24

2.6.6 Gas chromatography-mass spectroscopy.....................................................................24

2.6.7 X-ray diffraction and X-ray fluorescence.....................................................................25

2.7 Rubber seed analysis.......................................................................................................25

2.8 Rubber seed oil extraction methods.................................................................................29

2.8.1 Conventional extraction methods (mechanical and chemical) .....................................30

2.8.2 Gas-assisted mechanical extraction method.................................................................32

2.8.3 Microwave-assisted extraction (MAE) method............................................................32

2.8.4 Ultrasonic-assisted extraction method..........................................................................32

2.8.5 Aqueous enzymatic extraction method.........................................................................33

2.8.6 Supercritical fluid extraction (SFE) method.................................................................33

2.9 Physico-chemical properties of rubber seed oil...............................................................33

2.10 Thermo-oxidative analysis of rubber seed oil................................................................37

2.11 Industrial applications of rubber seed and oil................................................................39

2.12 Biofuels policies and sustainability in Africa................................................................40

2.12.1 Nigerian biofuel policy (A case study in Africa) ........................................................43

2.13.1 Catalyst deactivation..................................................................................................47

2.14 Gas-solid adsorption systems........................................................................................49

2.14.1 Langmuir model equation (linearized).......................................................................51