ABSTRACT
This study presents an empirical analysis of biodiesel production from Jansa seed oil using tranesterification process. Following the quest to achieve improved economic viability and clean production process for biodiesel, lithium ion from lithium carbonate was applied to improve the catalytic properties of calcium oxide and magnesium oxide for biodiesel production. Oil produced from jansa seed was characterized to determine its suitability for biodiesel production. Based on the characterization, an appreciable oil weight or yield of 38.09% was produced. Also, 0.493mgKOH/kg free fatty acid (FFA) content, 205.923 gKOH/kg saponification value and 99.95% ester value which specified its great tendency to be converted into methyl ester (biodiesel) were obtained. Li-CaO and Li-MgO catalysts were prepared in diverse concentrations for use in biodiesel production. Li-CaO-1.50 and Li-MgO-1.50 gave the optimal yield of 76 and 83% volume of biodiesel. These were applied to study the effects of other process parameters (reaction time, reaction temperature, agitation speed, and methanol to oil molal ratio) and optimized using a matrix design. Li-CaO-1.50 gave the optimal yield at other process conditions. A two level, five experimental design matrix was used for transesterification studies for 32 experimental runs using Li-CaO as catalyst. Set of conditions that gave the optimal yield were; catalyst concentration of 1.5 % weight, reaction time of 3 hours, temperature of 600C, methanol and oil molal ratio of 12:1 and agitation speed of 500 rpm respectively. All possible interactions, predicted and actual values, final equation in terms of coded factors and interaction plots were identified. Biodiesel blends from optimal yield of the metallic oxides of the catalysts were formulated and characterized to further determine the physicochemical properties (calorific value, anisidine point, API gravity, diesel index, flash and fire points, cloud and pour points) which were within the ASTM D6751 standard recommendations for use in compression ignition engines. Scanning electron microscopy (SEM) was used to study the active sites of the surface structure of the catalyst in relation to various modifications. The sample indicated increased points of higher porosity as lithium concentration increased (1.5, 2.0 and 2.5%) and less porosity at 0.5 and 1.0% concentration. Gas chromatography (GC) and Fourier transform infrared spectrometry (FTIR) of the jansa seed oil and biodiesel produced were carried out. A total of 7 compounds were identified in the oil of which 4 were FFAs and other 3 were biodiesel esters. For the biodiesel, a total of 12 compounds were identified, of which 9 were methyl esters and 3 non esters, thus, producing 88.35% methyl ester concentration at optimal yield sample. Evidently, the same functional groups identified in the jansa seed oil were present in the optimal biodiesel yield sample which includes; the hydrocarbon group (as a basic characteristics of bio-oil),a halide group and an ester group (as the basic characteristics of biodiesel). Overall, the optimal products developed were found to meet standard properties for biodiesel through free fatty acid methyl ester (FAME) profile test and functional group validation. At such, Li-CaO, Li-MgO, other similar materials should be adopted as catalyst for the production of biodiesel to bridge the energy gaps.
TABLE OF CONTENTS
Cover Page i
Title Page ii
Declaration ii
Dedication iv
Certification v
Acknowledgements vi
Table of Contents vii
List of Tables xi
List of Figures xii
Abstract xv
CHAPTER 1: INTRODUCTION
1.1 Background of the Study 1
1.2 Statement of Problem 2
1.3 Aim and Objectives of Study 3
1.4 Scope of Study 3
1.5 Justification of Study 4
CHAPTER 2: LITERATURE REVIEW
2.1 Catalysts and Compositional Properties 5
2.2 Basic Solid Catalysts 5
2.2.1 MgO as Base Heterogeneous Catalyst 6
2.2.2 CaO as a Base Heterogeneous Catalyst 7
2.2.3 SrO as a Base Heterogeneous Catalyst 8
2.2.4 Biodiesel Production with Mixed Metal Oxide and Derivatives 8
2.2.5 Biodiesel Production with Transition Metal Oxide and Derivatives 9
2.2.6 Waste Material-Base Heterogeneous Catalysts 11
2.3 Acidic Solid Catalysts 12
2.3.1 Acid-Base Solid Catalysts 13
2.4 Adoption of the Catalysts for the Study 15
2.5 Summary of Literature 17
CHAPTER 3: MATERIALS AND METHODS
3.1 Materials 19
3.1.1 Glass Wares and other Consumables 19
3.1.2 Analytical Grade Reagents 19
3.1.3 Electronic Equipment 19
3.2 Methods 19
3.2.1 Sample Collection and Preparation 19
3.2.2 Oil Extraction (Soxhlet Method) 20
3.2.3 Oil Characterization 21
3.2.4 Catalyst Preparation 26
3.2.5 Effects of Process Parameters on the Biodiesel Production 26
3.3 Design of Experiment for Biodiesel Production 28
3.3.1 Fractional Factorial Design of Experiment for Biodiesel Production 28
3.4 Biodiesel Blends Preparation and Characterization 31
3.5 Gas Chromatography – Mass Spectrometry (GC-MS) Analysis of the Raw Oil and the Biodiesel 33
3.6 Fourier Transform Infra-Red Spectrometry (FTIR) of Raw Oil and Biodiesel 33
3.7 Scanning Electron Microscopy (SEM) of the Catalysts 34
CHAPTER 4: RESULTS AND DISCUSSION
4.1 Characterization Test Result of the Jansa seed Bio-Oil 35
4.2 Gas Chromatography Mass Spectrometry (GC-MS) Analysis
Test Results of the Jansa Seed Oil 36
4.3 Scanning Electronic Microscopy (SEM) of the Lithium-Ions-Doped Metallic Oxides Catalysts for Biodiesel Production 39
4.4 Effects of the Process Parameters on the Biodiesel Production Yield using the Lithium-Doped CaO and MgO Catalysts Variants 42
4.4.1 Effect of Catalyst Concentration Variation on the Biodiesel Yield 43
4.4.2 Effect of Reaction Time Variation on the Biodiesel Yield 44
4.4.3 Effect of Reaction Temperature Variation on the Biodiesel Yield 44
4.4.4 Effect of Agitation Speed Variation on the Biodiesel Yield 45
4.4.5 Effect of Methanol and Sample Molal Ratio Variation on the Biodiesel Yield 45
4.5 Results for Optimization Yield Studies of the Biodiesel Production using the Fractional Factorial Matrix Design 46
4.5.1 Predicted and Actual Values for Biodiesel Production from the Jansa Seed Oil. 46
4.5.2 Analysis of Variance (ANOVA) for Quadratic Model 48
4.5.3 Fit Statistics Results for the Biodiesel Production from the Jansa Seed Oil 50
4.5.4 Results for the Coefficient in Terms of Coded Factors for the Biodiesel Production 50
4.5.5 Matrix Design Final Equation Developed in Terms of Coded Factors for the Effects of the Process Parameters on Biodiesel Produced from the Jansa Seed Oil 51
4.6 Interactions of Significant Variables and Process Factors on the Biodiesel Yield 53
4.6.1 Results of the Predicted and the Actual Interactions of Variables 53
4.6.2 3-Dimensional (3D) Plots Interactions Results of the Process Variables with the Biodiesel Yield. 53
4.7 Characterization of the Developed Biodiesel from the Jansa Seed Oil 59
4.7.1 Physicochemical Characterization Test Result of the Optimal Biodiesel Yield and the Blends from the Jansa Seed Oil. 59
4.7.2 Gas Chromatography of the Optimal Biodiesel Yield from the Jansa Seed Oil 65
4.7.3 Fourier Transfer Infrared Test Results of the Optimal Biodiesel Yield 68
CHAPTER 5: CONCLUSION AND RECOMMENDATIONS
5.1 Conclusion 69
5.1.1 Contributions to Knowledge of this Study 71
5.2 Recommendations 71
References 72
Appendices 81
LIST OF TABLES
3.1 Studied range of each factor in actual and coded form for heterogeneous catalysts 29
3.2 Experimental design matrix for transesterification studies catalyzed by lithium-ions-doped calcium and magnesium oxides 30
4.1 Physicochemical properties of the jansa bio-oil 35
4.2 FFAs profile identified in Cussonia bateri seed oil by GC 38
4.3 Fourier transform infrared spectrometry (FTIR) analysis of raw jansa seed oil 39
4.4 Predicted and actual values for biodiesel production from the jansa seed oil 47
4.5 ANOVA results for quadratic model for the jansa seed oil biodiesel production (Response 1: Biodiesel yield) 49
4.6 Fit Statistics result for the biodiesel production 50
4.7 Results for the coefficients in terms of the coded factors for the biodiesel production 51
4.8 Methyl esters identified in the optimal biodiesel yield by gas chromatography 67
4.9 FTTR analysis of the optimal biodiesel yield from the jansa seed oil 68
LIST OF FIGURES
2.1 Mechanism of SrO catalyst transesterification adapted 8
2.2 Flow chart for biodiesel production from heterogeneous catalyst (Lee et al., 2015) 10
3.1 Soxhlet apparatus set-up for bio-oil extraction from jansa seed 20
4.1 Gas chromatography column over ramping schedule of the jansa seed oil 36
4.2 Gas chromatograph of Cussonia bateri seed oil showing elution peaks of FFAs 37
4.3 Fourier transform infrared spectrometry (FTIR) of oil jansa seed oil 39
4.4 Scanning electron microscopy of lithium doped metal oxides 42
4.5 Variation of biodiesel yield with catalyst variants for the initial biodiesel production 43
4.6 Effect of process conditions variation on biodiesel yield 43
4.7 Effect of reaction time variation on the biodiesel yield 44
4.8 Effect of reaction temperature variation on the biodiesel yield 44
4.9 Effect of agitation speed variation on the biodiesel yield 45
4.10 Effect of methanol and sample molal ratio variation on the biodiesel yield 45
4.11 Predicted versus actual plots for the biodiesel yield 53
4.12 3D plot of Catalyst concentration and reaction temperature with biodiesel yield 54
4.13 3D plot of Catalyst concentration and reaction time with biodiesel yield 54
4.14 3D plot of Catalyst concentration and agitation speed with biodiesel yield 55
4.15 3D plot of Catalyst concentration and molal ratio with biodiesel yield 55
4.16 3D plot of reaction temperature and reaction time with biodiesel yield 56
4.17 3D plot of reaction temperature and agitation speed for the biodiesel yield 57
4.18 3D plot of reaction temperature and molal ratio for the biodiesel yield 57
4.19 3D plot of reaction time and agitation speed with biodiesel yield 58
4.20 3D plot of reaction time and molal ratio with the biodiesel yield 58
4.21 3D plot of agitation speed and molal ratio with the biodiesel yield 59
4.22 Variations of specific gravity with the fuel blends 59
4.23 Variations of kinetic viscosity with the fuel blends 60
4.24 Variations of flash point with the fuel blends 61
4.25 Variations of fire point with the fuel blends 61
4.26 Variation of cloud point with the fuel blends 62
4.27 Variations of pour point with the fuel blends 62
4.28 Variations of free fatty acid with the fuel blends 63
4.29 Variations of API gravity with the fuel blends 63
4.30 Variations of anisidine value with the fuel blends 64
4.31 Variation of diesel index with the fuel blends 64
4.32 Variation of calorific value with the fuel blends 65
4.33 Gas chromatography column-oven ramping schedule of methyl ester (biodiesel) analysis 66
4.34 Chromatogram of the optimal biodiesel yield from the jansa seed oil showing elution peaks of the methyl ester 67
4.35 Fourier transform infrared spectrometry (FTIR) of the optimal biodiesel yield from jansa seed oil 68
CHAPTER 1
INTRODUCTION
1.1 BACKGROUND OF THE STUDY
The environmental benefits of biodiesel fuel has made it more attractive in recent times. Its primary advantages deal with it being one of the renewable fuels currently available and it is also non-toxic and biodegradable. It can also be used directly in most diesel engines without requiring extensive engine modifications.
Van Gerpen (2005) defined biodiesel as a renewable, biodegradable, environmentally benign, energy efficient, substitution fuel which can fulfill energy security needs without sacrificing engine’s operational performance. From the above definition, it can be deduced that biodiesel is a resource that satisfies both vehicular and industrial energy need (fuel for engines without causing damage to them) as well as being environmentally compatible (renewable and biodegradable). In coming years, some crucial factors that will drive research and development in biodiesel production technologies as Van Gerpen (2005) stated are; fluctuation in the pricing of fossil based petrol, necessity for climate stabilization, economic policies and domestication of biodiesel production technologies. To further this cause, 38 nations recently from America, Asia and Europe adopted the biodiesel blend program (B5 to B10) aimed at widening its use for transportation and industrial purpose.
Biodiesel according to Arzamendi et al.(2008) is an alternative to petroleum-based fuels. It has found a very wild application as energy source to drive passenger cars, sport utility vehicles, light trucks, buses, ships, trains, off-road heavy equipment, and mining equipment, as well as for home heating fuel, power generation, and as a mixing agent in two-stroke engines. Thus, in long term prospect, biodiesel usage will radically cover all types of consumer demand in ground transportation, aviation, and maritime fuel markets (Arzamendi et al., 2008).
1.2 STATEMENT OF PROBLEM
One of the earliest forms of fuel for engine combustion is straight vegetable oil of which majority are edible. However, the use of vegetable oil as a direct form of fuel has its challenges following some of the unfavourable physical properties. Lee et al.(2015) identified the undesirable physical properties of straight vegetable oils that made them non excellent choices for biodiesel production. They include; high viscosity which leads to poor fuel atomization, inefficient mixing of oil with air leading to high smoke emission, coking and trumpet formation (carbon deposit) on the injectors which results to clogged orifices, low volatility as a result of high flash point, lubrication oil dilution, thickening or gelling of lubricating oil, high carbon deposits, oil ring sticking, scuffing of the engine liner, injection nozzle failure and high cloud and pour points. To this end, it is important to formulate a product, through modification of straight vegetable oil, with superior physical properties for energy production. Though significant progress have been made in the utilization of biodegradable materials for the production of biodiesel, there still exist some challenges in feed stock sourcing and selection, production pathway, choice of catalyst and other production conditions, product storage and distribution.
Homogeneous alkaline catalysts (sodium hydroxide and potassium hydroxide) have been widely applied as catalysts for the production of biodiesel from various feed stock. Even as high yields are obtained most times, the process is mostly time consuming and could be expensive. The process of biodiesel production through reaction between vegetable oil feed stock and an alcohol in the presence of catalyst is called transesterification. When alkaline catalyst is used, it involves a set of sequential processes which requires neutralization to ensure the free fatty acid (FFA) content is considerably low.
Also, following the use of alkaline catalyst, the process effluent, being alkaline, if passed into farm lands and fresh water bodies could be a major source of environmental concern. In strict adherence to local environmental safety standard, effluent treatment such that it should be neutralized will in no lesser form add to the production cost. These, notwithstanding, the processes are still time consuming even when other competitive processes are adapted to reduce time and cost. Using lithium- doped in magnesium or calcium oxides consequently will ensure that the catalysts are used up before disposal. The doping will increase the transesterification process and make it alkaline, as the waste water is neutralized before disposal to the municipal waste route. Hence, this causes no harm to the environment.
1.3 AIM AND OBJECTIVES OF STUDY
The aim of this study is to determine the optimum conditions for biodiesel production from jansa (Cussonia bateri) seed oil using lithium-doped (Li-doped) catalysts. The specific objectives are to :
i. produce biodiesel by transesterification process from the jansa seed oil using methanol in the presence of the alkaline metal-based catalysts, and make the characterization.
ii. establish the optimal biodiesel yield (by volume) from the metallic oxides of the catalysts.
iii. formulate the biodiesel blends from the optimal yields of the two metallic oxides of the catalysts in the following forms; B100, B90, B80, B70, B60, B50, B40, B30, B20, B10 and D100 ; and characterize the blends.
iv. perform scanning electron microscopy (SEM) of the doped / modified catalysts.
v. carryout gas chromatography (GC) and Fourier transfer infrared spectrometry (FTIR) analyses of the Jansa seed oil and the optimal biodiesel yield from the two metallic oxides of the catalysts to determine the available free fatty acids methyl ester (FAME) profiles and the functional groups respectively.
1.4 SCOPE OF STUDY
The study is limited to :
i. Jansa seed (Cussonia bateri or Ugbaokwe in Igbo) oil production and its characterization.
ii. Transesterification process of the bio-oil with methanol in the presence of alkaline based catalysts (Li-CaO and Li-MgO) and their characterization.
iii. Perform gas chromatography (GC) and Fourier transfer infrared spectrometry (FTIR) analyses of the Jansa seed oil and the optimal biodiesel yield from the two metallic oxides of the catalysts
iv. Evaluation of the results and making comparison of the results with standard conventional diesel to establish the produced biodiesel suitability in diesel engine operations.
1.5 JUSTIFICATION OF THE STUDY
This research is an attempt to add value towards reducing the cost, as well as managing time of biodiesel production. This intention was achieved through the use of lithium-doped heterogeneous (CaO and MgO) catalysts. Though lithium being alkaline was applied, its adoption basically modified the physical properties of the heterogeneous catalysts, thus increasing their catalytic properties. The development in no little way provided significant foundational knowledge that created curiosity into further research opportunities on technological innovation. The development directed towards providing cleaner and safer transportation and industrial energy for power plant and automotive operations, was the hallmark for this research effort.
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