Production and Characterization of Biodiesel From Avocado Peel Oil

ADDIS ABABA UNIVERSITY
ADDIS ABABA INSTITUTE OF TECHNOLOGY (AAiT)
SCHOOL OF CHEMICAL AND BIO- ENGINEERING
PRODUCTION AND CHARACTERIZATION OF BIODIESEL FROM AVO-

CADO PEEL OIL (APO)
By:
Tafere Aga
A thesis submitted to the school of graduate studies of Addis Ababa University in

partial fulfillment of the requirement for the Masters degree in chemical
engineering (process engineering stream)
Advisor: Dr. Eng. Abubeker Yimam
Addis Ababa
Ethiopia
July, 2018
School of chemical and Bio-Engineering Page i

Production and characterization of biodiesel from avocado peel oil
ADDIS ABABA INSTITUTE OF TECHNOLOGY (AAiT)
SCHOOL OF CHEMICAL AND BIO- ENGINEERING
A Thesis submitted to Addis Ababa Institute of Technology, In Partial

Fulfillment of the requirement of degree of Master Science in
Chemical Engineering (Process Engineering Stream)
By: Tafere Aga
The undersigned have examined the thesis “Production and Characterization of Bi-
odiesel from avocado Peel oil (APO)" presented by Tafere Aga, a candidate for the
degree of Master Science in Chemical Engineering (Process Engineering)), and
hereby certify that it is worthy of acceptance.
Approved By the Examining Board Signatures Date
Dr. Eng. Abubeker Yimam

__________________ _____________ _____________
(Chair, Department Graduate Committee)
Dr. Eng. Abubeker Yimam

_______________________ _____________ _____________
Advisor
Dr. Eng. Zebene Kifile

________________________ _____________ _____________
Internal Examiner
Dr. Anuradha J
_______________________
External Examiner _____________ _____________
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DEDICATION
This thesis work is dedicated to God Almighty for his guidance and protection for the countless
sacrifices made for my sake. This work also dedicated to my parents. I hereby declare that the
thesis is based on my original work except for flotation’s and citations which have been duly
acknowledged .I also declare that it has not been previously or currently submitted for any other
department at Addis Ababa University or other institute.
Tafere Aga
Signature: - ____________
Date: - 17/11/10 E.c
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ABSTRACT
Biodiesel is as alternative energy source and a promising potential that grows rapidly, due to its
great contribution to the environment, renewable, non-toxicity, biodegradability, essentially sul-
fur free and its role as a strategically source of renewable energy in substitution to diesel oil and
contributes a minimal amount of net greenhouse gases.
In this study, biodiesel production from waste avocado peel oil was investigated in laboratory
approach. Experimental results evaluate the major optimum process parameters for base-
catalyzed transesterification on biodiesel yield as well as its properties. The most important var-
iables affecting methyl ester yield during the transesterification reaction are the molar ratio of
alcohol to oil and the reaction temperature.
From this thesis, the optimum operating conditions for the extraction of oil from avocado peel
oil. For this, particle size of 2.6 mm, solvent type N-hexane and extraction time of 3-5 hr were
considered. A general factorial design was applied to investigate the effect of process variables
on oil yield and biodiesel. Maximum oil yield of 40.6% was obtained for particle size of 2.6 mm
at extraction time of 5 hr. A 95.2% FAME conversion was also obtained using a methanol/oil
ratio of 6:1, 1.21g NaOH, reaction time 67.5min and 600C reaction temperature.
The important properties (characterization) of the experimental biodiesel sample of the biodiesel
(pH, specific gravity, API specific gravity, density, kinematic viscosity, cloud point, cetane num-
ber, iodine value, and high heating value) well-matched the relevant international standards for
biodiesel quality, were compared to those of ASTM and EN standards for biodiesel. The compar-
ison shows that the avocado peel oil used as a raw material for biodiesel production as an alter-
native fuel.
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ACKNOWLEDGEMENTS
First and foremost, I would like to thank to God for giving me health and patience to accomplish
this thesis work. I would like to acknowledge my advisor Dr. Eng Abubeker Yimam for his ef-
forts, comments, proper supervision of the thesis and reading the manuscript through my thesis.
His knowledge and hands on experience in chemical engineering discipline has added greatly to
the depth of information provided by this thesis. Next we would like to thankful to all Laboratory
assistances in school of Chemical and Bio Engineering for their support and make the stay so
pleasant. We would like to say ‘thank you’ to all of them.
Finally, I would like to acknowledge my friends at Addis Ababa institute of technology who have
directly or indirectly contributed to my work. And, I am very grateful to my family for their en-
couragement, support and patience.
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Table of Contents
ABSTRACT ..................................................................................................................................... i
ACKNOWLEDGEMENTS ............................................................................................................ ii
List of Figures ........................................................................................................................ viii-ix
List of Tables ..................................................................................................................................x
List of abbreviations and symbols ............................................................................................xi-xii
List of Annexes ........................................................................................................................... xiii
CHAPTER ONE ........................................................................................................................... 1

1. Introduction ................................................................................................................................. 1
1.1. Background .......................................................................................................................... 1
1.2 Status of Biodiesel Production in Ethiopia ........................................................................... 4
1.3. Statement of the problem ..................................................................................................... 5
1.4. Objectives ............................................................................................................................. 6
1.4.1. General objective............................................................................................................... 6
1.4.2. Specific objective .............................................................................................................. 6
1.5. Significance of the thesis...................................................................................................... 7
1.6. Scope of the thesis …............................................................................................................7
1.7. Study outline of the Thesis ................................................................................................... 8

CHAPTER TWO .......................................................................................................................... 9
2. LITERATURE REVIEW ........................................................................................................ 9
2.1 General Overview of Biodiesel Fuel Production .................................................................. 9
2.2. Biodiesel ............................................................................................................................... 9
2.3. History of Biodiesel ........................................................................................................... 12
2.4. Biodiesel as a source of renewable energy......................................................................... 13
2.5. Biodiesel as a Fuel.............................................................................................................. 14
2.6. Properties of Vegetable Oils and Biodiesel........................................................................ 15
2.6.1. Properties of Vegetable Oils ........................................................................................... 15
2.6.2. Properties of biodiesel ..................................................................................................... 15
2.7. General overview of Avocado............................................................................................ 17
2.7.1. Review of avocado production in the world ................................................................... 18
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2.7.2. Review of avocado production in Ethiopia ..................................................................... 19

2.7.3. Avocado Marketing in Ethiopia ...................................................................................... 20
2.7.4. Avocado and Avocado peels ........................................................................................... 21
2.8. Methods for extraction of oil ................................................................................................. 24
2.8.1 Mechanical extraction method ......................................................................................... 24
2.8.2 Solvent extraction method ................................................................................................ 25
2.8.3. Conventional solvent (liquid - solid) extraction.............................................................. 26
2.8.3.1. Soxhlet Extraction method ........................................................................................... 26
2.9. Current Technologies in Biodiesel Production ...................................................................... 28
2.9.1. Pyrolysis (cracking) method of Biodiesel production ..................................................... 29
2.9.2. Micro-Emulsification Method of Biodiesel Production .................................................. 29
2.9.3. Dilution............................................................................................................................ 29
2.9.4. Transesterification Method of Biodiesel Production ...................................................... 30
2.10. Feed material requirement for Biodiesel Production ........................................................... 32
2.11. Catalyst for biodiesel production ......................................................................................... 33
2.11.1. Homogeneous Catalyst .................................................................................................. 34
2.11.2. Heterogeneous Catalyst ................................................................................................. 35
2.11.3. Enzyme Catalyst ............................................................................................................ 35
2.12. Alcohols for biodiesel production ........................................................................................ 36
2.13. Mixing and neutralization .................................................................................................... 37
2.14. Biodiesel Production Process through Transterification reaction ........................................ 37
2.15. Biodiesel compared with other transport fuels .................................................................... 40
2.15.1. Energy comparison ........................................................................................................ 40
2.15.2 Emissions ....................................................................................................................... 40
2.16. Benefits of biodiesel ............................................................................................................ 42
2.16.1. Advantages of biodiesel ................................................................................................ 42
2.16.2. Disadvantages................................................................................................................ 42
2.17. Environmental Impacts of Biodiesels .................................................................................. 43
2.18. Experimental design............................................................................................................. 43
2.18.1. Central composite design .............................................................................................. 43
CHAPTER - 3 .............................................................................................................................. 45
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3.1. Materials and Methods ........................................................................................................ 45

3.1.1 Materials and equipment .................................................................................................. 45
3.1.2. Equipments ...................................................................................................................... 45
3.1.3. Chemicals (Reagent) ....................................................................................................... 45
3.2. Raw material preparation ....................................................................................................... 45
3.3. Drying process ....................................................................................................................... 46
3.4. Determination of moisture content of the Avocado peel ....................................................... 47
3.5. Milling process (Size reduction and sieve analysis) .............................................................. 47
3.6. Oil Extraction process ............................................................................................................ 48
3.6.1. Method for extraction of avocado peel oil by Soxhlet extraction ................................... 48
3.7. Evaporation Process ............................................................................................................... 49
3.8. Degumming process............................................................................................................... 49
3.9. Characterization (Physicochemical) properties of oil ............................................................ 49
3.9.1. Determination of density ................................................................................................. 50
3.9.2. Determination of kinematic viscosity of oil .................................................................... 50
3.9.3. Determination of Saponification Value........................................................................... 50
3.9.4. Determination of acid value ............................................................................................ 51
3.9.5. Determination of iodine value ......................................................................................... 51
3.9.6. Determination of high heating value ............................................................................... 51
3.9.7. Determination of melting point ....................................................................................... 52
3.9.8. Determination of pH........................................................................................................ 52
3.10. Transesterification Reaction ................................................................................................ 52
3.10.1. The Transterification procedure (making biodiesel): .................................................... 52
3.11. Separation process ............................................................................................................... 55
3.12. Washing and Drying ............................................................................................................ 55
3.12.1. Washing (Purification) of crude biodiesel .................................................................... 55
3.12.2. Drying (Evaporation) process ....................................................................................... 56
3.13. Physicochemical Properties of Biodiesel ............................................................................. 57
3.13.1. Determination of Specific Gravity ................................................................................ 57
3.13.2. Determination of density ............................................................................................... 57
3.13.3. Determination of API Gravity of Biodiesel .................................................................. 58
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3.13.4. Kinematic Viscosity ...................................................................................................... 58

3.13.5. Determination of pH Value ........................................................................................... 59
3.13.6. Cloud point (CP) ........................................................................................................... 59
3.13.7. Pour point (PP) .............................................................................................................. 59
3.13.8. Flash point (FP) ............................................................................................................. 59
3.13.9. Determination of Acid Value (Number) ....................................................................... 60
3.13.10. Determination of free fatty acid value......................................................................... 60
3. 13.11. Determination of refractive index .............................................................................. 60
3. 13.12. Cetane Number (Index) .............................................................................................. 61
3. 13.13. Determination of Iodine Value ................................................................................... 61
3.14. Factor affecting on the Extraction of Avocado peel oil by Soxhlet extraction .................... 62
3. 14.1. Effect of Time on the extraction................................................................................... 62
3. 14.2. Effect of Temperature on the extraction of oil ............................................................. 62
3. 14.3. Particle size................................................................................................................... 62
3. 14.4. Solvent Type................................................................................................................. 63
3.15. Factor affecting on the production of biodiesel ................................................................... 63
3. 15.1. Purity of reactants ......................................................................................................... 63
3. 15.2. Water Content............................................................................................................... 63
3. 15.3. The kinetics and mechanism of transesterification reaction ........................................ 64
CHAPTER FOUR ....................................................................................................................... 65
4. RESULTS AND DISCUSSIONS ........................................................................................... 65
4.1.1 Determination of moisture (water) content of the avocado peels .................................... 65
4.1.2. Determination of the percentage of oil yield extracted from avocado peel .................... 65
4.1.3. Physicochemical properties of avocado peel oil ............................................................. 66
4.1.4. Specific gravity ............................................................................................................... 66
4.1.5. Kinematic viscosity ......................................................................................................... 67
4.1.6. Saponification value ........................................................................................................ 67
4.1.7. Acid value ....................................................................................................................... 68
4.1.8. Higher heating value ....................................................................................................... 69
4.1.9. Iodine Value .................................................................................................................... 70
4.1.10. Melting point ................................................................................................................. 70
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4.1.11. Molecular Weight Determination.................................................................................. 71

4.2. Statistical Analysis of the Experimental Results ................................................................... 72
4.3. Main Factor affecting on the Yield of Biodiesel Production ................................................. 81
4.3.1. The effect of molar ratio oil to methanol ........................................................................ 81
4.3.2. The effect of catalyst concentration ................................................................................ 82
4.3.3 Effect of Reaction time .................................................................................................... 83
4.3.4. Reaction temperature....................................................................................................... 84
4.4. Analysis of Fourier transforms infrared (FT-IR) ................................................................... 88
CHAPTER FIVE ........................................................................................................................ 90
5. CONCLUSION AND RECOMMENDATION .................................................................... 90
5.1. Conclusion.......................................................................................................................... 90
5.2. Recommendation ................................................................................................................ 91
Reference ...................................................................................................................................... 92
Appendix ....................................................................................................................................... 94
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List of Figures Page

Figure 1.1: Proposed and outline for biodiesel production process………………………….……8
Figure 2.1: Worldwide fossil, nuclear and renewable energy consumption……………………..13
Fig 2.2: percentage of avocado production in the world……………………………..………….19
Figure 2.3 Yield seeds (liters oil/ha)………………………….…………….…………........……24
Figure 2.4 Solvent extraction……………………………………………….………………...….26
Figure 2.6 Soxhlet extractor set up………………………………………….………………..….28
Figure 2.7 Catalytic transesterification…………………………………….…………...….….…30
Figure 2.8: Flow chart for biodiesel production by homogenous catalyst.............................…....35
Figure 2.9.The production process of biodiesel…………………………………….…….…..….39
Figure 2.10- Potential emissions reductions from biodiesel……………………….…….………41
Fig 3.1: Avocado and avocado peel……………………………………………….….…………46
Figure 3.2: avocado crushed with knife and drying the peel………………………………….…46
Figure 3.3: (a) Milling machine and (b) powder of avocado peel…………………………….…47
Figure 3.4 Extraction of oil by Soxhlet extraction…………………………….………...….……48
Figure 3.5 Degumming process….................................................................................................49
Figure3.6 Mixing of NaOH and methanol and experimental transesterification

reaction process …....................................................................................................................54
Figure 3.7: The production process of the biodiesel by transterification reaction…....................54
Figure 3.8 separation processes………………………………………………………………….55
Figure 4.1 oil yields (%) of oil extraction by Soxhlet extraction at different temperature
and time ………………………………….………………………………………..…… 66
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Figure 4.2 Yield Plot for the actual vs. predicted of FAME yield……….………………………79
Figure 4.3 Normal plots of residuals…………………………………….…………….…………80
Figure 4.4 Residual vs. predicted values……………………………….……………….……… 81
Figure 4.5 The individual effect of ratio methanol to oil………………….……………………..82
Fig.4.6.Effect of catalyst concentration on the biodiesel Production………….……………….. 83
Figure 4.7 Effect of the reaction time on the biodiesel yield…………………………………….84
Figure 4.8.Effect of reaction temperature on biodiesel yield ………………………………….. 85
Figure 4.9 methanol to oil ratio vs. reaction temperature when concentration of catalyst is at 1.21
%...........................................................................……………………...…….………………….86
Figure 4.10 methanol to oil ratio vs. amount of catalyst when the reaction temperature is
600c……………………………………………………………………………………………....87
Figure 4.11 The FT-IR produced biodiesel process……………………………………………...88
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List of Tables Page

Table 2.1: Comparison between biodiesel and petrodiesel properties……….……………………9
Table 2.2: The advantage of biodiesel and disadvantage of fossil Diesel…………………….…10
Table 2.3 Technical properties of biodiesel……………………………………………………...16
Table 2.4: - Availability of modern transportation fuel………………………….………………17
Table 2.5: composition of avocado peel oil……………………………………….……………..18
Table 2.6: Summary of major fruit crops produced in Ethiopia in 2012/2013 cropping sea-
son.............................................................................................................................................19-20
Table 2.7 World production of avocado in 201………………………………………………21-22
Table 2.8 Physicochemical parameters of the different fractions of the avocado ….…………...22
Table 2.9 Liters of oil per ha……………………………………………………….…………….23
Table 2.10 Advantage and disadvantage of Soxhlet extractor……………………..…………….27
Table 2.11 The production process of biodiesel………………………………….…………..38-39
Table 2.12- Energy comparison of biodiesel production from soybean seeds…………….….…40
Table 2.13: Experimental variables and levels…………………………………………….….…44
Table 3-1 Effects of Impurities in biodiesel on diesel engine performance……………….….…56
Table.4.1 show result of Soxhlet extraction with particle size 2.6mm at different temperature and
time ……………………………………………………………………………… 66
Table 4.2: Physico-chemical of Properties of the obtained biodiesel and avocado peel oil and the
standards of biodiesel in the United States and Europe…….……………………………………71
Table 4.3 Result using Experimental design expert 6.8.0 software………………………….72-73
Table 4.4 Design Summary of factorial designs…………………………………………………73
Table 4.5 Actual versus Predicted model of biodiesel yield…………………………………..…74
Table 4.6 Analysis of variance (ANOVA) for the quadratic model of esterification………..75-76
Table 4.7 Model adequacy measures …………………………………………………….……...76
Table 4.8: Regression coefficients and significance of response surface quadratic model for
transterification…………………………………………………………………………………..77
Table 4.9 Sequential model sum of squares and model summary statistics of the response quad-
ratic model for transesterification reaction………………………………………………………78
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List of abbreviations and symbols

AAIT Addis Ababa Institute of Technology
ANOVA Analysis of variance
ASTM American Society for Testing and Materials
API American Petroleum Institute
APOs Avocado peel oil
AV Acid Value
BD Biodiesel
Bxx x% biodiesel and x% petroleum diesel
CARB California Air Resources Board
CCD Central composite design
CIE Compression Ignition engines
CN Cetane number
CSA central statistical agency
CP Cloud point
DOE Dept of Energy
EN European Committee for Standardization
EPA Environmental Protection Agency
EU European Union
FA Fatty Acid
FAAE fatty acid alkyl esters
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FAME Fatty Acid Methyl Esters
FAO Food and agricultural organization
FFA free fatty acid
FT-IR Fourier transforms infrared
g gram
RSM Response surface methodology
HHVs The higher heating values
HPLC High Performance Liquid Chromatography
IV Iodine value
NaOH sodium hydroxide
SV Saponification value
PP Pour point
TG Triglyceride
V Volume
𝞺 Density
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List of Annexes Pages

Table A1: Specification of EN 14214 comparing biodiesel to conventional diesel……....……….93
Table B1: Physico-Chemical Properties of Biodiesel from Different oil raw material………..…94
Table C1: Saponification value of APO………………………………………………………….……..94
Table C2: Infrared Correlations by Wavenumber……………………………………………….…….95
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CHAPTER ONE
1. Introduction
1.1. Background
Biodiesel is the most promising alternative diesel fuel and the challenging of energy problem and
sustainability in our today‟s world increases the number of population and sustainability have
been problems due to the industrial revolution. Since it has received considerable attention due
to it‟s a renewability, reliable, secure, biodegradability, clean, environmental eco-friendly, non-
toxicity, energy efficient, less emission of gaseous and sustainable energy resources substitution
of fuel which can fulfill energy security needs without sacrificing engine‟s operational perfor-
mance thus it provides a feasible solution to the twin crises of fossil fuel depletion and environ-
mental degradation. It meets the currently increasing huge demands of world energy which is
dependent on petroleum based fuel resources. However, energy is often known as the primary
success for a country‟s development. It is often used as an indicator to measure the level of eco-
nomic growth in a country. The occurrence of oil depletion, global warming and the greenhouse
effect has become an alarming condition where it is needed to search for an alternative energy
source (Mazen et al, 2010).
Base catalyzed transesterification is the most commonly used technique as it is the most econom-
ical process base-catalyzed transesterification involves stripping the glycerin from the fatty acids
with a catalyst such as sodium or potassium hydroxide, and replacing it with an anhydrous alco-
hol, usually methanol (van Gerpen, 2005).
Biodiesel is a renewable and biodegradable fuel to ensure the sustainability of energy resources,
and produced from a wide range of naturally occurring fats and oils by a transesterification reac-
tion in which the triglycerides are broken down and fatty acid methyl esters (FAMEs) are
formed. The fatty acid distribution of the original oil is retained in the biodiesel, thus the physical
and chemical properties of the biodiesel have some dependence on the feedstock used.
Biodiesel is a good alternative fuel for internal combustion engines, is defined as a mixture of
monoalkyl esters of long chain fatty acids (FAME) derived from a renewable feedstock, such as
vegetable oil or animal fat, which is one of the most promising energy sources for our country
(Demirbas, 2005).
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Biodiesel is an alternative fuel for diesel engines that is produced by chemically reacting a vege-
table oil or animal fat with an alcohol such as methanol through transterification reaction. The
reaction requires a catalyst, usually a strong base, such as sodium or potassium hydroxide, and
produces new chemical compounds called methyl esters or known as biodiesel. It is a carbon free
fuel because there is no overall increase in CO2 in the atmosphere due to recycling by the grow-
ing plants used to feed the biodiesel industry. Emissions of SO2, SO3, CO, unburnt hydrocarbons
and particulate matter are lower than that of petroleum diesel (Hiwot, 2017).
The most common process used to produce biodiesel is through transesterification, a reaction
between triglycerides and an alcohol with a low molecular weight (ethanol or methanol) in the
presence of a basic catalyst (NaOH or KOH), to obtain esters and glycerol . Any oil from peel,
seed and also animal fat, can be used as a feed stock for the production of biodiesel. Since oils
and biodiesel produced from different oils will likely have different physicochemical composi-
tions and more importantly different properties.
Biodiesel can be used in „„neat” form referred to as B100 or mixed with petroleum-based diesel.
Petroleum and diesel come in the category of non-renewable fuel and will last for a limited peri-
od of time. Biodiesel is the first and only alternative fuel to commercial diesel to have a complete
evaluation of emission results. Biodiesel is a good lubricant (about 66% better than petro diesel)
(Koria &Thangaraj, 2010).
Biodiesel is a renewable fuel which is produced from vegetable oil or animal fat through a chem-
ical process called transterification and can be used as either direct substitute, extender or as an
additive to fossil diesel fuel in compression ignition engines. The most promising feature of bio-
diesel is that it can be utilized in existing design of diesel engine with no or very little modifica-
tions. It has a proven performance for air pollution reduction. Biodiesel is typically produced
through the reaction of vegetable oils or animal fat with methanol or ethanol in the presence of
catalyst to yield glycerol as major by- product and biodiesel chemically called methyl or ethyl
ester. However, the price of biodiesel is presently more as compared to petro diesel, since higher
cost of biodiesel is primarily due to the raw material cost.
There are different types of feed stocks that are used for the production of biodiesel. These in-
cludes linseed oil, palm seed oil ,waste cooked vegetable oil, sunflower seed oil, cotton seed oil,
jatropha seed oil, castor beans oil and animal fats. Avocado peel oil are used for the production

of biodiesel through the process called transesterification reaction which is a process by which
alcohol reacts with vegetable oil in the presence of catalyst (Refaat, 2010).
Avocado peel is a waste where so many people are throwing away after using the fruit flesh. It is
one of the most popular fruit in Ethiopia as a result there is a significant rise in avocado fruit
consumption and consequently an increase in the avocado peel waste generation. Therefore, al-
ternative routes are needed for this waste management. This waste cannot be used still for any
consumption. The presence of nitrogen allows it to be directly used as fertilizer or as soil im-
prover (or compost) (Hiwot, 2017). On the other hand, waste avocado peels have oil content of
8-40 % which can be used for biodiesel production. Avocado peels are used to evaluate the pos-
sibility of using and transforming waste to something valuable product, namely biodiesel there
by contributing towards alternative energy supply as well as recycles what would be discarded
and resolves energy scarcity.
Currently, about 84% of the world biodiesel production is met by rapeseed oil. The remaining 16
percent is from sun flower oil (13%), palm oil (1%), soybean and others (2%). Since more than
98% of the biodiesel is made from edible oil, there are many claims due to the depletion of edi-
ble oil supply worldwide. Therefore in order to overcome this problem, the feed stock for the bi-
odiesel production must be replaced by non–edible oil, like oil extracted from waste substances.
Therefore, for this study oil extracted from the waste avocado peels was used for the production
of biodiesel because this have two advantage, one is waste management and second the oil is
non-edible as a result it does not compete with food security (Hiwot, 2017).
Biodiesel is a clean-burning diesel fuel produced from vegetable oils, animal fats, or grease. Bi-
odiesel as a fuel gives much lower toxic air emissions than fossil diesel. In addition, it gives
cleaner burning and has less (free) sulfur content, and thus reducing emissions. Commercially,
biodiesel is produced by transesterification of triglycerides which are the main ingredients of
biological origin oils in the presence of an alcohol (e.g. methanol, ethanol) and a catalyst (e.g.
alkali, acid, and enzyme) with glycerin as a major by-product (Hiwot, 2017).

1.2 Status of Biodiesel Production in Ethiopia

Ethiopia is among the developing countries, with over 45% of the population living below the
poverty line. Significant improvements to Ethiopia‟s trade balance are needed to stimulate the
required economic development. One main issue is that around 65% of Ethiopian export earnings
are needed to pay for the import of petroleum products. Despite the availability of huge energy
resources in Ethiopia, the current level of harnessing this energy is very low. This, to a certain
extent, depicts the poor socio-economic situation in the country on the one side, and a low level
of awareness about the potential and value of energy by most stakeholders on the other side.
Ethiopia, being large country of diverse ecology, may harness the potential benefits from eco-
nomic opportunities that may arise from biofuel production and also minimize the escalating
budgetary pressure from a rise in international oil price. From international experiences, it has
been shown that the production of biofuels, particularly at a large scale, may negative impacts on
the society. Of course, positive impacts are also cited including response to price signals by
smaller farmers and alleviating the environmental problems associated to the use of fossil fuels
(Kalay, 2011). The development of biodiesel is a recent and at its initial stage there is no observ-
able market use of biodiesel products in Ethiopia. However, within a short period of time a sig-
nificant number of foreign, local and joint companies have invested in the biodiesel industry.
Currently more than 50 projects are in progress from which 14 companies are involved in the
biodiesel industry and some of them have already started feedstock plantation for biodiesel pro-
duction in five different regions (Benshangual Gumuz, Amhara, Oromia, SNNP and GPNRS),
while others are at the pre-implementation stage (Kinfu, 2008). For example, in Benshangul
Gumuz there is a major ongoing project of large scale jatropha plantation of more than 80,000
hectares. This project can produce more than 100 million liters of biodiesel per year, and if total
production was converted to biodiesel, it would be equivalent to almost 15% of Ethiopia„s cur-
rent diesel consumption. Obviously, this will have a significant positive impact on Ethiopia‟s
trade balance. Additionally, the inward investment that this project brings will create a large
number of jobs in the sectors helping to alleviate rural poverty. The search for feedstock other
than jatropha is still at its ground level.

1.3. Statement of the problem

Due to the increase in population growth, finding an alternative fuel source for producing valua-
ble products are needed more than ever. In our today‟s world the issues of energy shortage re-
sulting from the depletion of world petroleum reserves, increase of petroleum prices and envi-
ronmental concerns has initiate (stimulated) me to look for alternative renewable energy sources
that are technically feasible, economically competitive and environmentally acceptable. A more
convenient way is to use by- products (wastes) as potential sources due not only reduce the cost
of production but also reduced health effect, since lack of proper management of fruit waste and
not properly disposed this waste creates environmental problems in our country. A considerable
amount of waste ends up in open dumps or drainage system, affecting both surface water and
ground water.
Avocado peels waste largely obtained from hotels, restaurants and juice processing houses as a
by-product in our country. Since this wastes can cause environmental problems unless they
change or convert in to some useful products or disposed properly. Our country spends about
birr10 billion annually to import petroleum products for domestic consumption (MOME). A
convenient way to lower the cost of biodiesel is to use the by-product like cheaper feedstock
(waste like, avocado peel oil) as a potential source of energy, rather than treat them as waste.
This can be used to improve the economics of biodiesel which will lower the price of petroleum
diesel.

1.4. Objectives
1.4.1. General objective
The general objective of this thesis is to produce and characterize biodiesel from avocado peels
oil.
1.4.2. Specific objective

 To extract the oil from the avocado peels by Soxhlet extraction method.
 To investigate the effect of particle size, extraction temperature and extraction time on
the quantity of avocado peel oil.
 Characterizing the physicochemical properties of oil that express (specific gravity, free
fatty acid, pH, refractive index, acid value and density).
 To produce biodiesel from avocado peel oil through transesterification process.
 Characterizing the fuel (biodiesel) physicochemical properties such as, acid value, sa-
ponification number, density, kinematic viscosity, iodine value, flash point, cetane num-
ber, heating value and cloud point by and empirical formula.

1.5. Significance of the Thesis

The significance of this thesis is to use non-edible vegetable oil as source of biodiesel production
to maintain important of food consumption oil. The use of non-edible vegetable oils for biodiesel
production as compared to edible oils is very significant in developing countries because of the
tremendous demand for edible oils as food and they are far too expensive to be used as fuel at
present. In this context, recently biodiesel derived from vegetable oil has been shown to be a po-
tential alternative replacing petroleum-derived diesel oil for diesel engine. Although there is con-
tinuous increase in the production of vegetable oil, however the ending stocks of vegetable oils
are continuously decreasing due to increasing production of biodiesel.
Everything we do is connected to energy in one form or other. All energy sources have an impact
on the environment. Concerns about the greenhouse effect and global warming, air pollution, and
energy security have led to increasing interest and more development in renewable energy
sources such as biofuel, solar, wind, geothermal, and hydrogen. But we continue to use the non-
renewable fossil fuels and nuclear energy until now, the clear technologies that should replace
this non- renewable resource are renewable source like, biodiesel which is environmentally
friendly.
Eventually, with the implementation of biodiesel as a substitute fuel for petroleum-derived diesel
oil, this may lead to the depletion of edible-oil supply worldwide. So, avocado peel oil is chosen
as non-edible oil to produce biodiesel. It was chosen for the study because it widely available has
no other commercial uses and would not compete for other uses such as consumption. It grows
very well in Ethiopia.
1.6. Scope of the Thesis

The work presented in this thesis was the production of biodiesel from avocado peels oil based
on the availability of raw material. Utilization of crude avocado peels oil for production of bio-
diesel will prevent further wastage of already existing resources and use of environmentally
friendly fuel will create cleaner environment. The main scope of this thesis was mentioned as the
following:
 Avocado peel collection

 Oil extraction and study of physiochemical characterization of extracted oil.
 Study of methods employed in production of biodiesel, i.e. trans-esterification
 To obtain biodiesel from the extracted oil by transesterification.
 Characterization of the produced biodiesel.
1.7. Study outline of the Thesis

The first chapter of this thesis would present an introduction to biodiesel as a renewable source.
Chapter 2 is the detail literature review with information about biodiesel properties and produc-
tion and techniques of production methods. Chapter 3 describes the methodology and details of
the experimental work. Chapter 4 presents and discusses the obtained results from chapter 3 and
all work concludes in Chapter 5 with suggestions for all future work (recommendation).
Oil extraction and

NaOH Transesterification oil characterization
Methanol
Fatty acid Methyl

esters (Biodiesel)
Purification
Characterization of
biodiesel
Result and discussion
Conclusions And
Recommendation
Figure 1.1: Proposed and outline for biodiesel production process.

CHAPTER TWO
2. LITERATURE REVIEW
2.1 General Overview of Biodiesel Fuel Production
Biodiesel, a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable
(virgin) oils, frying oil, animal fats, and mixtures of this is produced by transesterification reac-
tion, with biodiesel as main product and glycerol being produced as a co-product. Biodiesel with
diesel fuel offers improved lubricity and reduced emissions. Diesel fuel use worldwide is esti-
mated to be 1.14 billion tons (330 billion gallons) per year. The United States uses an estimated
18% of that or 205 million tons (Useia, 2004). Because diesel (compression ignition) engines are
more efficient than gasoline (spark ignition) engines (45% versus 30%), there is the possibility
that the use of diesel engines in vehicles will increase, thereby increasing the demand for diesel
fuel (DOE, 2003).
2.2. Biodiesel
Biodiesel is a renewable fuel, non-toxic and biodegradable. It is a good alternative for conven-
tional fossil diesel fuel since it has similar properties as shown in table 2.1. However, it requires
the use of additives to be suitable for motor fuel in order to overcome oxidation processes limita-
tions (Khurshid, 2014).
Table 2.1: Comparison between biodiesel and petrodiesel properties
Types Density at Viscosity at Cetane LHV Fuel eqv.

20°C 20°C (mm2/s) Number (MJ/Kg)
BD 0.88 7.5 56 37.1 0.91
DIESEL 0.83 5.0 50 43.1 1
Source: (Khurshid, 2014).
The main feedstocks for the biodiesel production process through transesterification process (re-
versible reaction) are vegetable oils, waste cooking oil and animal fats. The reaction uses to be
carried out in batch reactor provided with controlled heating and mixing process system. Bio-
diesel has been produced in EU since 1992. The annual production was up to 6,100,000 tones

with about 120 production plants in the EU. From this, Austria, Germany, Italy, France and
Sweden are the main producers of biodiesel in EU. The use of 1 kg biodiesel leads to a reduction
of about 3 kg of CO2 emissions. Since, the use of biodiesel leads to a significant reduction in
CO2 emission from 65% to 90% less compared with the use of conventional diesel (Khurshid,
2014).
Table 2.2: The advantage of biodiesel and disadvantage of fossil Diesel
Advantage and disadvantage

Nontoxic material, better lubrication.
Renewable and biodegradable.
It free from greenhouse gasses emission.
Due to high flash point it was safe to store.
Increase combustion efficiency due to high cetane
Biodiesel number.
Require anti freezing additive in cold weather due to
its higher density.
Toxic.
Lower lubrication, not renewable.
Greenhouse gasses emission e.g. CO2, NOx, SOx.
Fossil Diesel Low flash point.
Low cetane number.
Require less amount of anti-freezing additive in cold
weather due to its lower density.
Biodiesel is an alternative fuel, which can be produced from renewable sources such as vegetable
oils. It is biodegradable and nontoxic has low emission profiles and environmentally beneficial.
The strongest motivation for increasing of production and consumption of biodiesel is environ-
mental issues. Biodiesel contains no petroleum, but it can be blended at any level with petroleum
diesel to create a biodiesel blend. It can be used in compression-ignition (CI-diesel) engines with
little or no modifications (Akhtar, 2011).

In the most general sense, biodiesel refers to any diesel fuel substitute derived from renewable
biomass. More specifically, biodiesel is defined as an oxygenated, sulfur-free, biodegradable,
non-toxic, and eco-environmentally friendly alternative diesel oil. In chemical sense, biodiesel
can be defined as a fuel composed of triglycerides to mono-alkyl esters of long chain fatty acids
derived from renewable sources, such as vegetable oil, animal fat, and used cooking oil and also
it must meet the special requirements of the ASTM and the European standards.
The characteristics of the vegetable oils are significantly different than those of petroleum de-
rived diesel fuels, mainly as the result of their high viscosities. The conversion of vegetable oils
into biodiesel is an effective way to overcome all the problems associated with the vegetable oils.
Dilution, micro emulsification, pyrolysis, and transesterification are the four main modern pro-
duction technology applied to solve the problems encountered with the high fuel viscosity (El-
Solh, 2011). Transesterification reaction is the most suitable process and popular method and
commonly leads to mono alkyl esters of vegetable oils and fats, now called biodiesel when used
for fuel purposes. The methyl ester produced by transesterification of vegetable oil has a high
cetane number, low viscosity and improved heating value compared to those of pure vegetable
oil which results in shorter ignition delay and longer combustion duration and hence low particu-
late emissions.
As fossil fuels are limited sources of energy, this increasing demand for energy has led to a
search for alternative sources of energy that would be economically efficient, socially equitable,
and environmentally sound. Two of the main contributors of this increase of energy demand
have been the transportation and the basic industry sectors, being the largest energy consumers
(Hill et al, 2006).
Biofuels appear to be a solution to substitute fossil fuels because;
 Resources for biofuels will not run out (as fresh supplies can be
regrown).
 Biofuels are becoming cost wise competitive with fossil fuels.
 Biofuels appear to be more environmental eco-friendly and they

are rather accessible to distribute and

 Biofuels use as applicable infrastructure and technologies exists

and are readily available.
2.3. History of Biodiesel

Dr. Rudolf Diesel, who invented the first diesel engine in 1895, used only biofuel in his engine.
His visionary statement was “The use of vegetable oils for engine fuel may seem insignificant
today, but such oils may become in course of time, as important as petroleum and coal tar prod-
ucts of the present time”. The above prediction is becoming true today as more and more bio-
diesel is being used all over the world. Dr. Rudolf Diesel invented the diesel engine to run on a
host of fuels including coal dust suspended in water, heavy mineral oil, and, vegetable oils. Dr.
Diesel‟s showed his first engine experiments at the world exhibition in Paris in 1900; his engine
was running on 100% peanut oil. In 1911 he stated „„the diesel engine can be fed with vegetable
oils and would help considerably in the development of agriculture of the countries, which use
it‟‟. In 1912, Diesel said,‟ the use of vegetable oils for engine fuels may seem insignificant today.
But such oils may become in course of time as important as petroleum and the coal tar products
of the present time‟‟. Since Dr. Diesel‟s untimely death in 1913, his engine has been modified to
run on the polluting petroleum fuel, now known as „„diesel‟‟. Nevertheless, his ideas on agricul-
ture and his invention provided the foundation for a society fueled with clean, renewable, locally
grown fuel.
In the 1930s and 1940s, vegetable oils were used as diesel substitutes from time to time, but usu-
ally only in emergency situations. Recently, because of increase in crude oil prices, limited re-
sources of fossil oil and environmental concerns, there has been a renewed focus on vegetable
oils and animal fats to make biodiesel. The continuity and increasing use of petroleum will inten-
sify local air pollution and magnify the global warming problems caused by carbon dioxide. In a
particular case, such as the emission of pollutants in the closed environment of underground
mines, biodiesel has the potential to reduce the level of pollutants and the level of potential for
probable carcinogens.
In recent times, due to realization that vegetable oil has been revisited for its scope as a fuel in
compression ignition engines. The high viscosity of vegetable oils compared to petroleum diesel
fuel were reported due to some operational problems, which results in poor atomization of the

fuel in the fuel spray and often leads to deposits and coking of the injectors and valves. The use
of biodiesel was recognized much later and became technically relevant only after the energy
crisis in the year 1973 and afterwards.
2.4. Biodiesel as a source of renewable energy

Biodiesel is a renewable, biodegradable, non-toxic, sulfur-free, and environmentally clean alter-
native diesel fuel. Biodiesel is composed by fatty acid methyl esters, produced from renewable
resources, such as vegetable oils, animal fats, and waste restaurant greases. One of the attractive
characteristics of biodiesel is that its use does not require any significant modifications to the
diesel engine, so the engine does not have to be dedicated for biodiesel. Biodiesel has lower
emissions than petroleum diesel and it does not contribute to a rise of the net concentration of
carbon dioxide in the atmosphere and leads to minimize the intensity of greenhouse effects
(Alimova, 2016).
The most prospective recourse of energy is renewable energy sources and it includes biomass,
hydro, wind, solar (thermal and photovoltaic), geothermal, marine, and hydrogen. Every year the
importance of renewable sources increases and by 2040 according to scientists forecasts almost
half of world‟s energy supply will be from renewable sources, meanwhile, 80% of total world‟s
electricity production will be from renewables. Fig. 2.1 compares global energy consumption in
5 different categories as petroleum, coal, natural gas, nuclear and renewables.
45
40
percent of total energy
35
30
25
20
15
10
5
0
Petroleum Coal Natural gas Nuclear Renewables
Figure 2.1 Worldwide fossil, nuclear and renewable energy consumption.

Biodiesel is the type of biofuel and it can be produced by transesterification process from vege-
table oil or animal fat. Biofuels appear to be more environment friendly in comparison to fossil
fuels considering the emission of greenhouse gasses when consumed. Examples of those gasses
are carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O). Those gasses pose risks as
they tend to warm the earth‟s surface‟ (Randelli, 2007). The energy content of biofuels differs
from conventional fuels. Total energy output per liter of biofuel is determined by the feedstock
used, region where the feedstock is grown and production techniques applied.
Biodiesel production is a very modern and technological area for us as an alternative fuel for die-
sel engines because of the increase in the petroleum price, its renewability and the environmental
advantages. Currently, the cost of biodiesel is high as compared to conventional diesel oil be-
cause most of the biodiesel is produced from pure vegetable oil.
Proper utilization of agricultural waste like fruit peels to produce biodiesel is a promising ap-
proach to ensure environmental protection and energy security in this era of energy crisis. Due to
the depletion of petroleum reserves and the environmental impact of using fossil fuel, it is neces-
sary to look for an alternative source of fuel. Biodiesel, derived from vegetable oil or animal fats,
can be a substitute of petroleum based diesel and considered as renewable energy source. It is
estimated that biodiesel could replace approximately 10% of diesel fuel consumption within Eu-
rope and 5% of Southeast Asia‟s total fuel demand. Since compared to commercial diesel, bio-
diesel is environment friendly because of its sulphur free benefit and non-toxicity, lower green-
house gas emission and higher flash point (Duti et al, 2016).
Biodiesel is a liquid biofuel obtained by chemical processes from vegetable oils or animal fats
and an alcohol that can be used in diesel engines, alone or blended with diesel oil. It is a nontox-
ic, biodegradable, and renewable fuel that can be used in diesel engines with little or no modifi-
cation. The use of biodiesel for transportation applications are a relatively new phenomenon but
is gaining acceptance and growing rapidly.
2.5. Biodiesel as a Fuel

Biodiesel was registered as a fuel and fuel additive with the environmental protection agency
(EPA) and meets clean diesel standards established by the California air resources board
(CARB). Neat (100 percent) biodiesel has been designated as an alternative fuel by the depart-

ment of energy (DOE) and the U.S. department of transportation. In petrodiesel the energy con-
tent can vary up to 15% but in biodiesel it is much less variable. Pure biodiesel contains up to 10-
12% oxygen by weight, while diesel contains almost 0% oxygen. The presence of oxygen allows
more complete combustion, which reduces hydrocarbons, carbon monoxide, and particulate mat-
ter emission. However, higher oxygen content increases nitrogen oxides emissions.
The primary reason, why biodiesel is suitable as an alternative fuel for petrodiesel, lies in the ce-
tane number (CN). The cetane number indicates the ignition quality of a diesel fuel. It measures
a fuel's ignition delay, which is a period between the start of injection and start of combustion
(ignition) of the fuel. Fuels with a higher cetane number have shorter ignition delays, providing
more time for the fuel combustion process to be completed (Akhtar, 2011).
2.6. Properties of Vegetable Oils and Biodiesel
2.6.1. Properties of Vegetable Oils

Vegetable oils mainly contain triglycerides (90 to 98%) can be used as alternative fuels because
they are biodegradable, nontoxic, and clean fuels. Vegetable oils and their derivatives as diesel
engine fuels lead to substantial reductions in sulfur, carbon monoxide, polycyclic aromatic hy-
drocarbons, smoke and particulate emissions. The viscosity of liquid fuels affects the flow prop-
erties as well as vaporization, and air/fuel mixture formation (A K and Davies P, 2010,).
The viscosities of vegetable oils are greatly affected by temperature. It has been reported that the
viscosity of oils and fats decreases almost linearly with temperature. The significant fuel proper-
ties of vegetable oils indicate that the kinematic viscosity of vegetable oils varies in the range
from 27– 67 0C St at 40 0C. The high viscosity of oils is due to their large molecular mass in the
range of 600–900, which is an order of magnitude almost 4 times higher than that of diesel. The
flash point of vegetable oils is very high (above 1800 C) and the heating values are in the range
of 36– 40 MJ/kg, as compared to diesel fuels which is about 42-45 MJ/kg. The cetane numbers
are in the range of 30–45.
2.6.2. Properties of biodiesel
Biodiesel is a clear amber-yellow liquid with a viscosity similar to that of petro diesel. Biodiesel
is non-flammable and, in contrast to petro diesel, is non-explosive, is biodegradable and non-
toxic, and it significantly reduces toxic and other emissions when burned as a fuel. The most im-

portant parameters affecting the ester yield during the transesterification reaction are the molar
ratio of alcohol to oil and reaction temperature. The viscosity values of oil methyl esters decrease
sharply after transesterification. Biodiesels are characterized by their viscosity, density, cloud
and pour points, flash point, pH, sulfur content, free fatty acid, acid value, and higher heating
value (HHV).
Table 2.3 Technical properties of biodiesel
Common name Biodiesel (BD)

Common chemical name Fatty acid methyl ester
Chemical formula range C14–C24 methyl esters or C15-25H28-48O2
Kinematic viscosity range (mm2/s, at 40 0C) 3.3–5.2
Density range (kg/m3, at 15 0C ) 860–894
Boiling point range (0C) > 202
Flash point range (0C) 147–177
Vapor pressure (mm Hg, at 25 0C) <5
Solubility in water Insoluble in water
Physical appearance Light to dark yellow, clear liquid
Odor Light musty/soapy odor
Biodegradability More biodegradable than petroleum diesel
Reactivity Stable.
Source: - (Vazquez, 2014)
The current derivative of our natural products and it is more advantages when compare with oth-
er engines. As demand increases, the production of the required agricultural products can be in-
creased to compensate.

Table 2.4: - Availability of modern transportation fuel
Fuel type Availability

Current Future
Gasoline Excellent Moderate-poor
Biodiesel Moderate Excellent
Compressed natural gas (CNG) Excellent Moderate
Hydrogen fuel cell Poor Excellent
Source: - (Vazquez, 2014)
2.7. General overview of Avocado

The avocado (Persea Americana Mill.) is a polymorphic tree species that originated in a broad
geographical area from the eastern and central highlands of Mexico and Central America belongs
to the Lauraceae family, genus perseal and comprises two subgenres: Persea and Eriodaphne
(Barreira, 2013). Currently, avocado is a fruit that has been cultivated in many parts of the world,
especially tropical countries. Avocado is a fruit from a tree that has a variable growth and devel-
opment, reaching a height of a tree between 5 and 15 m in its natural habitat may grow at differ-
ent altitudes. Such habitat is classified as subtropical-tropical evergreen. The weight of the fruit
is between 120 and 2.5 kg and the harvesting period varies from 5 to 15 months. The tree has 25
to 30 years old that can be axillaries or terminal. Avocados are existed in different shape, size,
and color depending on their variety. Avocado fruit can be consumed directly as a high energy
food source because of content of lipids that significantly higher than in other fruit. Besides, av-
ocado fruit is also a good source of oil. Avocados fruits depending on the variety and the growth
conditions it contain from 8 to 40% amount of oil, the percentage varying with the variety, grow-
ing area and seasonal conditions (Islas et al, 2013). Only ripe olives have higher oil content. The
value of avocado oil is related to its fatty acid composition.
Avocado oil is reported to have the beneficial health properties. Compared to other fruits, avoca-
dos contain very little sugar (Usda, 2011). One-half an avocado contains only about 0.2 g sugar
(e.g., sucrose, glucose, and fructose). Avocado fruit has an energetic fruit with great nutritional
value as a source of carbohydrate, protein, fiber and it contains essential micronutrients for hu-
man consumption such as vitamins and is considered a major tropical fruit, since it is rich in pro-

tein and contains fat soluble vitamins lacking in other fruits, including Vitamins A, and B, and
median levels of vitamins D and E. It contains different oil levels in the pulp, thus it is widely
used in pharmaceutical and cosmetic industries, and for obtaining commercial oils similar to ol-
ive oil, because of their similar fatty acid composition. In addition, the oil of an avocado leaves
has contains significant amounts of minerals that could also be consumed as for its medical
properties and health benefits, especially due to the compounds present in the lipid fraction
(Duarte, 2016).
Table 2.5: composition of avocado peel oil
Minerals Fatty acid fraction (%)

Palmitic 4 – 25
Palmitoleic 6-10
Stearic 0-3
Oleic 45-80
Linoleic 6-20
Linolenic Max.14
Free Fatty Acid Max.6
The differences form and yield of the oils from the local avocado peel could be attributed to the
differences in their drying methods and their fatty acid composition. Avocado peel with oven
drying method able to maintain the oil content compared to that dried with direct sun-drying.
2.7.1. Review of avocado production in the world

The avocado (Persea Americana) is a native of Central America and the West Indies. It was in-
troduced into Florida, California and Hawaii in the early 1800s and is now found worldwide
where growing conditions are suitable. World avocado production grew at an average rate of
nearly seven percent (7%) per year (Faris, 2016).
Mexico is the world‟s leading avocado producer. In 2012, it produced 1,300 metric tons (MT),
equivalent to 30 percent of global production. This is nearly four times that of Indonesia. Produc-
tion in Chile, the second largest producer in 2009, has dropped by 45 percent in the past 3 years
as a result of poor weather and drought. Africa accounted for 16 percent of global production in
2012, a slight increase from 15 percent in 2008. Other major producers include Brazil, Colombia,
Dominican Republic, and Peru.

other
29% mexico
32%
peru
4% chile
USA 8%
Brazil DR 7%
4% Colombia 5%
4% Indonesia
7%
Fig 2.2: percentage of avocado production in the world
2.7.2. Review of avocado production in Ethiopia

The relatively early establishment of the avocado industry in Ethiopia is in its infancy and has
not yet utilized the immense potential of this crop. In the context of increasing the high value
production of agricultural commodities and fruit tree play an important role. Except table bana-
na, tropical fruit trees like mango, avocado and the like were not well known and considered as
diet by most Ethiopians (Yilma, 2009). According to CSA (2013) indicated avocado as one of
the third potential fruit crop produced in Ethiopia.
Table 2.6: Summary of major fruit crops produced in Ethiopia in 2016/2017 cropping season
Crop Area in Ha Production in Quintal Yield (Qt/Ha)

Fruits 107,890.6 7,923,665.02
Avocados 17,834.58 649,821.04 36.44
Bananas 63,212.97 5,383,023.41 85.16
Guavas 3248.59 43,265.32 13.32
Lemons 1426.25 77,814.52 54.56
Mangoes 15,413.76 1,046,461.25 67.85

Oranges 2619.8 206,559.48 78.85

Papayas 3489.47 503,961.70 144.42
Pineapples 645.19 12,758.30 *
Source: CSA, 2016/2017, agricultural sample survey result.
2.7.3. Avocado Marketing in Ethiopia

Consumers are those purchasing the products for consumption. Most of the fruits produced in
Ethiopia are consumed locally and are produced by smallholder (individual) farmers. After har-
vest, they are transported to rural market centers for local consumers or bought at the farm by
neighbors. The Ethiopia avocado marketing in agricultural products consists primarily of moving
products from production sites to points of final consumption. In this regard, the market performs
exchange functions as well as physical and facilitating functions. The exchange function in-
volves buying, selling and pricing. Transportation, product transformation and storage are physi-
cal functions, while financing, risk bearing and marketing information facilitating marketing
(Branson and Norvell, 2002).
Market channel is a business structure of interdependent organizations from the point of product
origin to the consumer with the purpose of moving products to their final consumption destina-
tion (Kotler and Armstong, 2003). Or it is the path one good follow from their source of original
production to ultimate destination for final use. The analysis of marketing channels is intended to
provide a systematic knowledge of the flow of goods and services from their origin (producer) to
their final destination (consumer). This knowledge is acquired by studying the participants in the
process, i.e. those who perform physical marketing functions in order to obtain economic bene-
fits (Faris, 2016).
Avocado is channeled from producers to local collectors, Cafeteria and whole sellers and finally
to Addis Ababa market through these channel middle men buys all avocado fruits from the farm-
ers at a lower price and sells them in the market at higher price (Zekarias, 2010). Fruits for both
fresh and processed have a huge domestic market in Ethiopia which is by far significant than that
of the export volume.

2.7.4. Avocado and Avocado peels

Avocado peel (persea Americana) is a waste where so many people are throwing away after us-
ing the fruit flesh. It is one of the most popular fruit in Ethiopia as a result there is a significant
increase in avocado fruit consumption and consequently an increase in the avocado peel waste
generation. Therefore, alternative routes are needed for this waste management. This waste can
be used for various applications. Avocado contain from 5 to 40% oil, the percentage varying
with the variety, growing area and seasonal conditions. Only ripe olives have higher oil content
(Faris, 2016).
Ethiopia has a potential agro-ecologically diverse and has a total area of 3.5 million km2 with net
irrigation area of about 1.61 million ha, of which currently only 4.6 % is utilized. The substantial
areas in the southern and south-western parts of our country receive sufficient rainfall to support
fruits adapted to the respective climatic conditions. In addition, there are also many rivers and
streams which could be used to grow various fruits. The main fruits produced and exported are
banana, citrus fruits, mango, avocado, papaya and grape fruits (Faris, 2016). As a result avocado
is the second largest fruits produced next to banana. According to FAO the world production is
around 4364.94 thousand tons per year where 76% of the total production is controlled by 10
countries (table 2.7). As it originated from Mexico, this country is the biggest producer with 1.9
million tons (32%) of world producer and Ethiopia is 20th in the world (a world share of 1.2%).
Table 2.7 World production of avocado in 2016
Country Production in 1000 tons

Mexico 1889.35
Dominican Republic 601.35
Peru 455.39
Colombia 309.43
Indonesia 304.94
Brazil 195.49
Kenya 176.05
USA 172.63
Chile 137.37

China 122.94
World 4364.94
Source: - (Vazquez, 2014).
Avocados are one of the few fruit that contain significant quantities of oil. Oil content is a key
part of the sensory quality. Oil quality is very similar to that of olive oil. However, avocado peel
is one of the waste materials removed from avocado fruit. In some causes it is used for animals
consumption and having all properties of avocado. The avocado fruit comprises a dark green
peel, green oily pulp and a large seed which represents 10-22% of the total weight depending on
the species. The peel (skin) is mainly composed of moisture, while the remaining 10% is lipids,
proteins, ashes, fibre and others.
Table 2.8 Physicochemical parameters of the different fractions of the avocado
Parameter Pulp Skin Seeds

Moisture (%) 70.83±3.53 69.13±2.58 54.45±2.33
Ash (%) 1.77±0.16 1.50±0.08 1.29±0.03
Proteins (%) 1.82±0.07 1.91±0.08 2.19±0.16
Fat (%) 43.5±4.62 2.20±1.65 14.7±0.32
Total soluble solids 43.5±4.62 3.01±2.03 3.54±1.97
Acidity 1.07±0.02 2.05±0.24 2.67±0.17
Source: (Vazquez, 2014).
The moisture content is one of the most important indices evaluated, especially in avocado fruits
it contains (65%) of moisture or water and it is a good indicator of their economic value chain
because it reflects solid contents. The results indicate in the above table has avocado skin has the
second water content (69.13%) next to pulp (70.83%), and followed the seed (54.45%). The skin
fat and ash quantified were significantly higher than to those found in the pulp. The yields of
oil/ha in liters of the common crops used as feedstocks for biodiesel production are shown in ta-
ble 2.9 and figure 2.3. Avocado produces 2638 liters of oil per ha and it is one of the third feed-
stocks for biodiesel production next to oil palm and coconut.

Table 2.9 Liters of oil per ha [Johnston, 2007]
Crop liters oil/ha US gal/acre

palm 5950 635
Coconut 2689 287
Avocado 2638 282
Calendula 305 33
castor vean 1413 151
cocoa (cacao) 1026 110
coffee 459 49
corn (maize) 172 18
cotton 325 35
jatropha 1892 202
jojoba 1818 194
macadamia nut 2246 240
mustard seed 572 61
oats 217 23
oil palm 5950 635
olive 1212 129
opium poppy 1163 124
peanut 1059 113
pecan nut 1791 191
pumpkin seed 534 57
rapeseed 1190 127
rice 828 88
sesame 696 74
soybean 446 48
sunflower 952 102

Liters oil/ha
7000
6000
5000
4000
3000
2000
1000
Figure 2.3 Yield of seeds (liters oil/ha)
2.8. Methods for extraction of oil

There are different extraction technique used to obtain high value oil from vegetables, fruits etc.
The production process of oil involves the removal of oil from plant components, typically peels.
This can be done via mechanical extraction using an oil mill or chemical extraction using a sol-
vent. In general there are three different methods for extraction of oil: mechanical extraction,
solvent extraction, and Soxhlet extraction method (Kittiphoom and Sutasinee, 2013).
2.8.1 Mechanical extraction method

Oils can be removed via mechanical extraction, termed "crushing" or "pressing." This method is
typically used to produce the more traditional oils (e.g., olive, coconut etc.), and it is preferred by
most "health-food" customers in the United States and in Europe. There are several different
types of mechanical extraction. Expeller-pressing extraction is common, though the screw press

and powered mortar and pestle are also used. Oil seed presses are commonly used in developing
countries, among people for whom other extraction methods would be prohibitively expensive.
The mechanical extraction method is effective for peels or seeds contain 30-70% oil. This meth-
od has several advantages compared to the other methods, such as simple equipment and low in-
vestment, low operating cost, and the oil does not undergo solvent separation process. However,
the oil produced with this method usually has a low price, since it‟s turbid and contains a signifi-
cant amount of water and metals contents. Due to low oil content of feedstocks it is not advisable
to extract the oil using mechanical extraction.
2.8.2 Solvent extraction method

Solvent extraction is the transfer of solutes from a solid, usually in particulate form, to contigu-
ous liquid, the extract (Henry, 1983). If the solute is uniformly dispersed in the solid, the material
near the surface will be dissolved first, leaving a porous structure in the solid residue. The sol-
vent will then have to penetrate this outer layer before it can reach further solute and the process
will become progressively more difficult and the extraction rate will fall. If the solute forms a
very high proportion of the solid, the porous structure may break down almost immediately to
give a fine deposit of insoluble residue, and access of solvent to the solute will not be impeded
(Richardson et al, 2002). Solvent extraction with peels containing only about (12 - 16) per cent
of oil, solvent extraction is often used because mechanical methods are not very efficient.
The solvent extraction method recovers almost all the oils and leaves behind only 0.5% to 0.7%
residual oil in the raw material. In the case of mechanical pressing the residual oil left in the oil
cake may be anywhere from 6% to 14%. The solvent extraction method can be applied directly
to any low oil content raw materials. Because of the high percentage of recovered oil, solvent
extraction has become the most popular method of extraction of oils and fats.
The advantages of solvent extraction over other methods of oil expression include, higher oil
yield (about 95% of the oil content could be obtained), larger processing capacity, solvent extrac-
tion also gave oil that many considered to be of superior bleaching quality, lower refining losses,
reduced susceptibility to rancidity and better retention of fat - soluble vitamin (Lawson et al,
2010).

Avocado
Decorticating
Avocado peel
Drying Solvent Recycled solvent
Solvent
Peels crushing Oil extraction

Extract Separation
Solid Avocado peel oil
Figure 2.4 Solvent extraction
A certain gram of dried avocado peel was used in the process. The avocado firstly decorticated to
obtain the peels. Then dried and milled to a certain particle size and then fed to an extractor. Af-
ter waiting to a certain time, the separation process proceeds to separate the solvent from the
product. The recycled solvent was used again by adding certain make up solvent.
2.8.3. Conventional solvent (liquid - solid) extraction

The most conventional solvent extraction methods include Soxhlet extraction (SXE), maceration,
percolation, and sonication, while newer techniques comprise ultrasound and microwave-assisted
extraction, as well as pressurized liquid extraction (PLE).
2.8.3.1. Soxhlet Extraction method

A Soxhlet extractor is a piece of laboratory designed equipment for processing certain kinds of
solids invented in 1879 by Franz von Soxhlet. Soxhlet extraction is a process used for liquid-
solid extractions, especially for compounds with limited solubility in a solvent (Meyer and Terry,
2008). According to the Soxhlet procedure, oil from solid material are extracted by repeated
washing (percolation) with an organic solvent usually n-hexane under reflux in a special glass-
ware. Because an avocado peel has low solubility in the solvent (n-hexane), the Soxhlet was the

most suitable extraction technique. Specifically, the sample is dried and milled into small parti-
cles and placed in a porous thimble. If the desired compound has a significant solubility in a sol-
vent then a simple filtration can be used to separate the compound from the insoluble substance.
Avocado peel powder is placed inside a thimble made from thick filter paper, which is loaded
into the main chamber of the Soxhlet extractor. The Soxhlet extractor is placed onto a flask con-
taining the extraction solvent. The Soxhlet is then equipped with a condenser. The thimble is
placed in an extraction chamber, which is suspended above a flask containing the solvent, and a
condenser is placed on top of the extraction chamber (Chemat et al., 2008). After extraction the
solvent is removed, typically by means of a rotary evaporator, yielding the extracted oil. The
non–soluble portion of the extracted solid remains in the thimble, usually discard.
Table 2.10 Advantage and disadvantage of Soxhlet extractor
Advantage Disadvantage
Long experience of use Long extraction time (hours)
A displacement of transfer equilibrium Considerable solvent consumption.
occurs as the solid is continuously ex-
posed to fresh solvent.
High extraction temperature enables ex- Non selective extraction
haustive recovery of interest.
Simple to operate Risk of thermal decompositions as the ex-
traction is conducted at the boiling point of
the solvent.
Economical Only temperature, extracted time and solvent
type can be Varied.

Figure 2.6 Soxhlet extractor set up
Note: From the three we use the Soxhlet extraction method because of it is simple to operate and
uses. The solvent extraction used below the oil contents of avocado peels, we uses only about (12
- 16) per cent of oil content and the mechanical extraction method is used above the oil contents
avocado peel, since the mechanical extraction used about (30-70) % oil content. Since the avoca-
do peel oil contains (8-30) per cent of oil, therefore we use Soxhlet extractor.
2.9. Current Technologies in Biodiesel Production

There are many investigations on biodiesel production of nonconventional feedstock of oils and
have reached a faster pace in the last few years. Oils used in engine lead to various problems like
fuel filter clogging, poor atomization and incomplete combustion because of high viscosity, high
density and poor non-volatility. The conversion of vegetable oils into biodiesel can be realized
using four modern technologies: These are:-Pyrolysis, micro-emulsification, dilution; and trans-
esterification.

2.9.1. Pyrolysis (cracking) method of Biodiesel production

The pyrolysis refers to a chemical change caused by the application of thermal energy in the ab-
sence of air or nitrogen. Or thermal cracking or pyrolysis is the process that causes the break of
the molecules by heating at high temperatures that is, by heating of the substance in the absence
of air or oxygen in temperature superior to 4500C, forming a mixture of chemical compounds
with properties very similar to those of petro diesel. In some situations that process is supported
by a catalyst for the break of the chemical connections, in order to generate smaller molecules
(Sonntag, 1979b). Typical catalysts to be used in pyrolysis are the silicon oxide SiO 2 and alumi-
num oxide Al2O3.
The equipment for Pyrolysis is expensive. However, the products are chemically similar to diesel
oil. The removal of the oxygen of the process reduces the benefits of an oxygenated fuel, reduc-
ing its environmental benefits and usually producing a fuel closer to gasoline than diesel. Pyroly-
sis has great applicability in places that need smaller production volume and with smaller availa-
bility of qualified work. The liquid fractions of the thermally decomposed vegetable oils are like-
ly to approach diesel fuels. The pyrolyzate has a lower viscosity, flash point, and pour point than
diesel fuel and equivalent calorific values. The cetane number of the pyrolyzate is lower.
2.9.2. Micro-Emulsification Method of Biodiesel Production

The formation of micro emulsion is one of the potential solutions for solving the problem of veg-
etable oil viscosity. To solve the problem of the viscosity of vegetable oils, micro emulsion with
solvents such as methanol, ethanol and 1-butanol have been used. A micro emulsion is defined as
thermodynamically stable, isotropic liquid mixture of oil, water and surfactant (compounds that
lower the surface tension of a liquid, the interfacial tension between two liquids) (Pryde, 1984b).
Micro-emulsions are defined as transparent, thermodynamically stable colloidal dispersion. The
droplet diameters in micro-emulsions range from 100 to 1000 Å. All micro-emulsions with buta-
nol, hexanol and octanol met the maximum viscosity requirement for diesel fuel.
2.9.3. Dilution
The dilution of vegetable oils can be accomplished with such material as diesel fuels, solvent or
methanol. Dilution results in the reduction of viscosity and density of vegetable oils. The addi-
tion of 4% methanol to diesel fuel increases the brake thermal efficiency, brake torque and brake

power, while decreasing the brake specific fuel consumption. Since the boiling point of methanol
is less than that of diesel fuel, it could assist the development of the combustion process through
an unburned blend spray.
2.9.4. Transesterification Method of Biodiesel Production

The most common way and the accepted processes to biodiesel production are by transesterifica-
tion process by which to catalyze chemical reaction involving vegetable oil and an alcohol in the
presence of a catalyst, to produce fatty acid alkyl esters and glycerin. A byproduct of transesteri-
fication reaction is glycerin, also known as glycerol. The most common alcohol, which is used in
biodiesel production is methanol, another name for biodiesel is fatty acid methyl esters (FAME)
(Alimova, 2016).
Avocado Methanol
peel oil
Catalyst
Biodiesel + glycerin
Figure 2.7 Catalytic transesterification
The mixture (NaOH + methanol) is then added to the pre-heated warm oil (normally to about
(50-650C), also with stirring for (45-90min), to undergo the transesterification reaction. The reac-
tion mixture is normally maintained above the boiling point of the alcohol, but in some systems
for safety reasons it is recommended to maintain the temperature range from room temperature
to 550C. To prevent evaporation of the alcohol the reaction should be carried out in a closed con-
tainer, but it is important to avoid a sealed system (because of risk of explosion) (Alimova,
2016). According to stoichiometry, three moles of methanol reacts with one mole triglyceride to
produce three moles of fatty acid methyl ester (FAME) and one mole of glycerine as shown in
the following reaction.

Transesterification reaction significant reduces the viscosity of vegetable oils without affecting
the heating value of the original fuel. Therefore, fuel combustion and emission characteristics
will display better results than pure vegetable oils are used in engines. Alcohols that can be used
in the transesterification reaction are methanol, ethanol, propanol, butanol, and amyl alcohol.
From these methanol is most commonly alcohol used for the transesterification reaction
(Demirbas, 2009). Moreover, the catalyst NaOH quickly reacts with triglycerides and is easily
dissolved in it. In this case, the reaction is referred to as methanolysis. In general the stoichiome-
try of methanolysis reaction requires 3mole of methanol and 1mole of triglyceride to give 3mole
of FAME and 1mole of glycerol (Kiakalaiehn, 2013). This reaction, in turn, consists of three
consecutive reversible reactions with intermediate formation of triglycerides and monoglycer-
ides. After the reaction, the glycerol is separated by settling or density difference.
Transesterification reactions are basically of three types of catalysts used (i.e. alkali, acid and
enzyme based), alkali based catalysts are most widely used in industrial processes because it is
more cost effective and less corrosive to the industrial equipment [Alimova, 2016]. The third one
is expensive and relatively slow than the first two (Marchetti et al, 2007). Sodium hydroxides are
the commonly used alkali catalysts due to rapid reaction rate and produce high yields. By alkali
catalyzed process, biodiesel production from avocado peel waste is challenging due to the pres-
ence of undesirable components such as free fatty acids (FFAs) and water. Water can be origi-
nated from the oils and formed during the saponification reaction and can hydrolyze the triglyc-
erides to diglycerides resulting in the formation of FFA (Komintarachat & Chuepeng, 2010).
Avocado peel waste typically contains 2–6 % FFAs and upon addition of an alkali catalyst to it,

the FFAs react with the catalyst to form soap and water. Biodiesel is a safer alternative to diesel
fuel because it is environmentally safe and has no known side effects on humans.
From all this techniques, transesterification is the most popular (commonly) used for biodiesel
production and the most convenient and the most promising method because, it significantly re-
duces the viscosity of vegetable oils without affecting the heating value of the original (fuel re-
duction of viscosity), high yields and short reaction times, direct conversion process, simple in
operation and environmentally friendly, density, low temperature and pressure and other proper-
ties of the vegetable oils. In transesterification, three consecutive reversible reactions convert tri-
glycerides into a mixture of esters and glycerol, in the presence of a suitable catalyst and alcohol.
The selection of biodiesel production method also depends on the level of free fatty acids (FFA)
present in the feedstock (Abidin, 2012). A pre-treatment stage (transesterification process) is
used to reduce the amount of FFA in the feedstock before base-catalyzed transesterification.
2.10. Feed material requirement for Biodiesel Production

40ml of treated oil was used for the maximum oil to alcohol ratio. The amount of methanol and
catalyst required for the process parameters at central point was calculated as follows. The
amount of methanol required when the molar ratio of oil to methanol ratio is 6:1;
The following data provides the basis for calculation of esters concentrations are:-
Volume of avocado peel oil = 40 mL
Based on above data, amount of methanol, total concentration of methanol is calculated in the
following way.
= 6………………………………………….……. (2.1)
= 6 ……………….……………………. (2.2)
Where,
Molar mass of methanol = 32.04 g/mol

Density of methanol = 0.791 g/mL
Density of oil =0.91g/ml
Molar mass of oil =880 g/mol
Substituting the values in to the formula:
= 6, from this, Solving for VMeOH
VMeOH = 10.2 ml of methanol
The amount of catalyst required when the ratio of catalyst weight to oil is 5 %;
Moil = ρoil Voil
Moil = 40 ml
Moil = 36.4 g oil
From the catalyst to oil ratio (% wt.),
=5%
MNaOH =5% Moil = 1.8 g. Similarly for the minimum molar ratio of oil to methanol (3:1), the
volume of methanol (VMeOH =3.8 ml) and MNaOH=0.68 g, therefore we use between in this gap for
the design experiments run. The amount of methanol and NaOH for all design experiments runs
used in the same manner.
2.11. Catalyst for biodiesel production

Generally catalysts are used to accelerate or speed up the reaction or it is usually used to improve
their action rate and yield. Or a material it initiates and enhances the rate of a chemical reaction
without being consumed by that reaction. While catalyst very much participates in the reaction,
yet it does not itself appear in the overall reaction at the end, or on the other hand, it does not en-

ter into the stoichiometry of the reaction. Since the reaction is reversible, excess alcohol is re-
quired to shift the equilibrium to the product side. Some advantages of catalyst are: changes the
rate of reaction, does not affect the equilibrium, can only speed up a reaction that which is ther-
mo-dynamically possible, Lowers the potential energy barriers i.e., lowering the free energy of
activation (energy required to initiate the reaction) and has ability to alter yields and selectivity
by speeding up some reactions more than others.
Currently there are three types of catalyst that used for the biodiesel production. These catalysts
are: homogenous, heterogeneous and enzymatic. Different factors interact in choosing the cata-
lyst, for instance: catalyst thermal stability, deactivation, speed of reaction and conversion rate.
2.11.1. Homogeneous Catalyst

The significant amounts of work have been carried out on homogeneous acid and base catalysis
transesterification of vegetable oils. Most of the biodiesel produced today is obtained with the
base catalyzed reaction for several reasons: It is a low temperature and low-pressure reaction. It
yields high conversion with minimal side reactions and short reaction time. It is a direct conver-
sion to biodiesel with no intermediate compounds. Biodiesel production from feed stocks with
high FFA is extremely difficult using alkaline catalyzed transesterification. The alkaline catalysts
react with FFAs to form soap that prevents the separation of the glycerine and ester. Sulphuric
acid and hydrochloric acid are normally used as acid catalysts especially when the oil contains
high amount of free fatty acids and water.
The desired products of the reaction are the methyl or ethyl esters of the fatty acids initially con-
tained in the fat or oil. Glycerine and alkali salts (using alkaline transesterification) are also ob-
tained as by-products, which may be used as raw materials in the chemical industry. One of the
major disadvantages of homogeneous catalysts is that they cannot be reused or regenerated, be-
cause the catalyst is consumed in the reaction and separation of catalyst from products is difficult
and requires more equipment which could result in higher production costs (Khurshid, 2014).

Methanol
Water
Reactor Neutralization
Settler Evaporation
(washing)
APO biodiesel
Catalyst
Glycerin
purification Glycerin
Fatty acids
Figure 2.8: Flow chart for biodiesel production by homogenous catalyst.
2.11.2. Heterogeneous Catalyst

Heterogeneous catalysts can be separated from final product by filtration and reused. This causes
less consumption of both chemicals and time of course. Heterogeneous catalysts are noncorro-
sive. They have a high selectivity and can be easily separated from the products. Both basic sol-
ids such as metal oxides (CaO) and zeolites as well acid solid such as sulphate tin oxide are used.
The use of catalyst supports such as alumina, silica and zinc oxide in order to improve the mass
transfer limitation of the three phase reaction will be included. Examples of heterogeneous cata-
lyst are; BaO, KNO3, KF, CaO, CaCO3. Mass transfer limitations in heterogeneous catalyst are
due to two phase zone (solid – liquid) requires well mixing efficiency in order to reduce the ex-
ternal limitations. It uses to be operated at high temperature and high alcohol to oil mole ratio.
Heterogeneous catalyst can be used in batch or continues system. Acid catalysts are more expen-
sive than alkali heterogeneous catalysts. They have also less active site, therefore, they are more
affected by adsorption reactants rate, surface reaction rate, desorption product rate resulting in
limiting biodiesel yield (Khurshid, 2014).
2.11.3. Enzyme Catalyst

In the past years research has been focused on use of an enzymatic catalyst for production of bi-
odiesel. Lipases used in biotechnology are normally of microbial origin and produced by fermen-
tation processes. The use of lipases makes the reaction less sensitive to high free fatty acid (FFA)

content which is a problem with the standard biodiesel process. Enzyme catalysts have high se-
lectivity and have approximately fixed running cost and reliable capital investment. It consumes
low energy since it operates at low temperature and pressure with one or two steps of isolated
enzymes and no side reactions (saponification) compared with alkali transterification. It is insen-
sitive to water content. Enzymatic reaction has low reaction rate and the enzyme has high cost
and less activity which is considered as drawback affecting the economic benefit of the process.
The produced glycerol covers the enzyme and reduces its efficiency, therefore, it is required ad-
ditives to observe and remove the glycerol such as silica gel (Khurshid, 2014).
From the three we use the homogeneous catalysts. Because of homogeneous catalysts are favor-
able due to their capability to produce a high yield of biodiesel under optimum reaction condi-
tions, their simplicity, the process proves faster and the reaction conditions are moderated and
short reaction times. However, Sodium hydroxide is very well accepted and widely used because
of its low cost and high product yield.
2.12. Alcohols for biodiesel production

Alcohol is one of the most important materials for the production of biodiesel. A number of al-
cohols have been explored for biodiesel production, the most widely used alcohol are methanol
and to a slight extent, ethanol. Other alcohols utilized in producing biodiesel are the short-chain
alcohols such as propanol, butanol, isopropanol, tert-butanol, branched alcohols and octanol;
however these alcohols are costly.
The selection of alcohol usually depends on the reaction performance and cost. Methanol is
commonly preferred because of it is considerably easier to recover physical and chemical ad-
vantages, it has a good reactivity with triglycerides, good physico-chemical properties, low cost,
the short-chain alcohols provide better conversions under the same reaction time and is easily
available. Additionally the reaction with triglycerides was quickly and it can be easily dissolved
in NaOH, Ethanol forms an azeotrope with water so it is expensive to purify the ethanol during
recovery. If the water is not removed it will interfere with the reactions. Methanol recycles easier
because it does not form an azeotrope. These crucial factors are the reason that evens though
methanol is more toxic, it is the preferred alcohol for producing biodiesel.

2.13. Mixing and neutralization

The purpose of mixing methanol with the catalyst is to produce methoxide which reacts with the
base oils. Most of the catalysts (NaOH and KOH) are in solid form and do not readily dissolve
into methanol, it is best to start agitating the methanol in a mixer and add the catalyst slowly and
carefully mixed together (Istc, 2006). Once the catalyst completely dissolves in the methanol, the
methoxide is ready to be added to the warm oil. Once the methoxide is added into the oil, a neu-
tralization reaction will immediately start. Some alkali catalysts will react with acids during the
pretreatment step or will react with the free fatty acids from the oil. Therefore, more catalyst
needs to be added to complete the reaction.
2.14. Biodiesel Production Process through Transterification reaction

Transesterification is the process of using an alcohol (e.g. methanol, ethanol or butanol), in the
presence of a catalyst, such as sodium hydroxide or potassium hydroxide, to break the molecule
of the raw renewable oil chemically into methyl or ethyl esters, with glycerol as a byproduct.
Glycerol is the major value-added byproduct produced from oil and fat from trans-esterification
reactions performed during biodiesel manufacturing processes. When the catalyst, alcohol, and
oil are mixed and agitated in a reaction vessel, a transesterification reaction will start. A stirred
reactor is usually used as the reaction vessel for continuous alkali-catalyzed biodiesel production.
The two reactants fluids fed were into the designed experimental setup; the first is the preheated
oil at 50 0c, and the second is the well proper mixture of methanol and sodium hydroxide in the
well proper flask. The proper amount of catalyst (sodium hydroxide) was dissolved completely
in methanol to avoid clogging. The reactants molar ratio was optimized to determine the most
proper mixing ratio. The mixer that includes the process reactants was maintained at specific wa-
ter bath temperature (50-65)0C (Jagadale S.S, 2012). The production processes of biodiesel from
the extracted avocado peel oil are in general consists of the following steps.

Table 2.11 the production process of biodiesel
N0. Operation Description

1 Avocado Avocado peels are removed by hand from avocado fruits. After removing the
peel pre- peels, avocado peels destined for oil production must be firstly inspected for phys-
treatment ical damage and other abnormalities like reducing the size of peels by knife cut-
ting. Then the peels drying in oven at temperature 500c for 18 hours (at constant
mass). Then the dried avocado peels milled. The powder is prepared to extract oil
by Soxhlet extraction method.
The oil feedstock is pre-heated to remove any free fatty acids. Some biodiesel pro-
ducers are etherifying the fatty acids with strong base, and then feeding the mix-
ture to the transesterification process.
2 Catalyst First the catalyst is weight, then the catalyst sodium hydroxide reacting with meth-
Preparation anol. The catalyst sodium hydroxide is dissolved in the methanol using a simple
mixing process. The proportion of sodium hydroxide to methanol is based on the
ratio of transterification reaction.
3. Reaction Excess methanol is normally added to ensure high levels of conversion of the fat
to methyl esters. The catalyst (NaOH) will first react with methanol which can
form emulsions and hamper separation and catalyze the reaction. After the
(NaOH) react with methanol, oil is added to the reactor and mix in the temperature
and time limits.
4. Methanol After the well mixed reaction, the excess methanol is removed (recovered) at this
Recovery stage via a simple vacuum distillation. In other processes, the methanol is removed
after the glycerine and esters have been separated. In either case, the excess meth-
anol is recovered and distilled using a conventional distillation equipment to re-
move any water. Some care must be taken to ensure no water accumulates in the
recovered methanol stream.
5. Product Once the reaction is complete, and the methanol has been removed, two major
Separation products exist: methyl esters and glycerine. Product Separation due to the density
difference between glycerine and methyl esters, it is easy to separate both in a
gravity separator. The crude glycerine is simply drawn off the bottom and the bio-

diesel (methyl esters) at the top layer.

6. Biodiesel Once separated from the glycerol, the biodiesel are gently washed with warm wa-
Washing ter to remove the residual, like catalyst and soaps or any impurities. The esters are
dried by oven and sent to storage. In some cases, the esters are distilled under vac-
uum to achieve even higher purity.
7. Glycerine The co-product, crude glycerine, contains water, residual base catalyst and fatty
Recovery acid base soaps. The fatty acids usually are separated from the crude glycerine by
gravity separation and each phase is sent to storage. Any catalyst remaining in the
glycerine (sodium hydroxide) is neutralized by the acid creating a sodium salt,
which is simply left in the glycerine.
Avocado peels
Drying
Milling
Soxhlet extraction Extraction of oil

of peels
Physico-chemical Washing Drying Biodiesel

analysis of oil
oil Physico-chemical
Transterification Crude Biodiesel analysis of biodiesel
Methanol NaOH
Figure 2.9.The production process of biodiesel.

2.15. Biodiesel compared with other transport fuels

In this section, the comparison of biodiesel with other transport fuels, especially with diesel, in
terms of energy, properties and emissions are discussed below:-
2.15.1. Energy comparison

There are different ways in which a comparison between conventional road fuels and bio-road
fuels can be made. One valuable way is set on the basis of an energy balance, which is the differ-
ence between how much energy is created when producing the fuel, and how much is obtained
when using the fuel. The approximation considers the energy used to make the plant grow, to
produce biodiesel and to distribute it. According to figures of the US dept. of energy (DOE), the
quantity of energy yield by biodiesel is higher than that used on its production. Biodiesel is much
higher energy output than the other energy use. On the table below, the energy balance of bio-
diesel production by transesterification process is much different when we compare each other.
Table 2.12- Energy comparison of biodiesel production from soybean seeds
Fuel Energy in Energy out %

Biodiesel 1 3.2 320
Ethanol 1 1.34 134
Petro-diesel 1 0.84 84
Gasoline 1 0.81 81
Source U.S. Dept of energy (DOE).
The energy efficiency on the above table shows different studies show different values depend-
ing on the type of raw material used, and the process carried out, thus it is widely accepted that
this will be about 220% higher than other fuel used (Méndez, 2006).
2.15.2 Emissions
According to the environmental protection agencies, using biodiesel are a great contribution in-
stead of petroleum diesel, to nearly 80 per cent reduce greenhouse gas emissions can be made:
Biodiesel also substantially reduces particle emissions which are hazardous to human
health.

The use and the production of biodiesel exhibit a closed-loop carbon cycle. Greenhouse
gases releases to the earth, the emissions released by using biodiesel is equivalent to the
amount absorbed by the plant while growing.
Although emissions vary with engine design with the exception of NOx, vehicle condition, and
fuel quality the US EPA found the potential emissions reductions from biodiesel blends are con-
siderable relative to conventional diesel, and they increase nearly linearly with increasing blend
levels. Toxic emissions reductions are focused in similarly potential emissions reductions (Nerl,
2000), next figure will show it.
Figure 2.10- Potential emissions reductions from biodiesel. Source: EPA (2002b).
In the above figure as show, by using biodiesel B20, carbon monoxide can be decreased on 13%,
hydrocarbons on 11%, particles on 18%. By using biodiesel B100 according to the figure, carbon
monoxide can be reduced on 43%, hydrocarbons on 56%, particles on 55%. In general it was
considered that total air toxics can be reduced 1.5% by using B100 or 0.3% by using B20.

2.16. Benefits of biodiesel

Biodiesel is a renewable source or an ecological fuel which has the following characteristics has
many major advantages, and some minor disadvantages:
2.16.1. Advantages of biodiesel

Important properties of the biodiesel are:
Biodiesel is renewable. As biodiesel is produced from renewable sources, biodiesel fuel

is a renewable energy source.
It can be used in the diesel engine without little or any modifications.

It improves combustion process. The biodiesel contains at least 11% oxygen. Biodiesel
burns better (more completely with few fuel unburned emissions) than petroleum diesel.
Less smoke is produced. The use of biodiesel can reduce the emissions of unburned hy-
drocarbons.
It does not contain sulfur. No sulfur emissions are emitted during the combustion
Biodiesel reduces the health risks associated with petroleum diesel. The use of biodiesel
decreases emission and it is non-toxic.
Greenhouse gas benefit. Moreover, the use of biodiesel can reduced the CO2 emissions
up to 50% in comparison to the use of petroleum diesel.
Biodiesel is biodegradable. The absence of a chemical and synthetic compound makes it
innocuous with our environment.
2.16.2. Disadvantages
There are few disadvantages of using biodiesel as a replacement for diesel fuel that must be tak-
en into consideration:
Slightly higher fuel consumption due to the lower calorific value of biodiesel.
Production costs still can be higher than the cost of diesel itself. It all basically depends
on the oil source which has been used.
The biodiesel needs more additives, mainly in cold countries, due to its high cloud point.

The biodiesel produces more NOx emissions than petrodiesel. It can cause acid rain
2.17. Environmental Impacts of Biodiesels

Biodiesel is the only alternative fuel to have fully completed the health effects testing require-
ments of the clean air act. Biodiesel is safer fuel as it has high flash point. It is regarded as clean
fuel since it does not contain carcinogenic substances and its sulphur content level is also lower
than its content in petrodiesel (Akhtar, 2011). It has many environmental benefits, such as it is
biodegradable, non-toxic, is less pollutant to both water and soil and has low emission profile
(including potential carcinogens). Moreover since the primary feedstock for biodiesel is a bio-
logically-based material that can be grown season after season, it is renewable.
In contrast to diesel engine, biodiesel creates significant reduction in emission of unburned hy-
drocarbons, carbon monoxide and particulate matter compared to emissions from diesel fuel. In
addition, the exhaust emissions of sulfur oxides and sulfates (major components of acid rain)
from biodiesel are essentially eliminated compared to diesel.
2.18. Experimental design

Experiment can be defined as a test or series of tests in which purposeful changes are made to the
input variables of a process or system so that we may observe and identify the reasons for chang-
es that may be observed in the output response.
2.18.1. Central composite design

RSM is a collection of mathematical and statistical techniques that are useful for analysis in ap-
plications where a response of interest is influenced by several variables. These independent
variables for production of biodiesel from avocado peel oil are; the molar ratio of oil to alcohol,
reaction temperature, reaction time, and amount of catalyst concentration that used during the
reaction mixture at different molar ratio.
A central composite design (CCD) of experiments, originally developed by Box and Wilson
(1951), is one the most efficient class of designs capable of generating a response surface. Sever-
al factors at several levels can generate a response surface. Systematic errors were avoided by
randomized order of experimental runs. For each categorical variable, a 26 factorial CCD for the
four variables, consisting of 16 factorial points, 8 axial points and 2 center points are used to re-

duce the experimental error and the reproducibility of the data, indicating that altogether 26 ex-
periments were required, as calculated from the following equation:
𝑁=24+2𝑛+𝑐 …………………………………………………….2.3
Where, N= the total number of experiments run
n= the number of factors
c=center points
 𝑁=24+2*4+2=26
The experimental plan was made using the CCD and the responses measured were the methanol-
to-oil molar ratio, amount of catalyst concentration, reaction time and reaction temperature were
the independent variables selected to optimize the conditions for production of the biodiesel pro-
duction from waste avocado peel oil. The experiments were carried out in randomized order and
data was statistically analyzed by the design expert software version 6.8.0.Portable (Stat-Ease
Inc., USA).
Table 2.13 below shows the specification of, the reaction temperature, reaction time, molar ratio
oil to methanol and amount of catalyst (Hiwot, 2017). The independent variables are coded to the
(−1, 1) interval where the low and high levels are coded as −1 and +1, respectively.
Table 2.13: Experimental variables and levels
Factor Variable Low Level High Level

Code ( –1) (+1)
A Molar ratio of oil to methanol 3:1 8:1
(ml)
B Reaction temperature (0C) 50 65
C Reaction time (min) 45 90
D Amount of catalyst (g) 0.6 1.82

CHAPTER - 3
3.1. Materials and Methods
The experimental work has been done in laboratory of Addis Ababa institute of technology
school of chemical and bio Chemical Engineering and Science faculty Center of food science
and nutrition of Addis Ababa University.
3.1.1 Materials and equipment
Materials that were used in the production of the biodiesel during the experiment work are as fol-
lows: avocado peel oil, filter paper ,heater mantle, knife, pipette, measuring cylinder, hydrome-
ter, conical flask, plastic bags, hot plate, condenser, pH meter, measuring cylinder and Piece of
cloth.
3.1.2. Equipments
The equipment‟s used during this experimental work are: Soxhlet extractor, vacuum pump,
chiller, water bath, oven was used for drying avocado peel and used to evaporate the excess al-
cohol from oil, vibro viscometer, conical flasks, three neck flasks, sample bottles, weighing bal-
ance, magnetic stirrer, test tubes, milling machine, FT-IR, sieve, beaker, density bottle, measur-
ing cylinder, extraction glass column, heating device, refractometer, thermometer and separation
funnel.
3.1.3. Chemicals (Reagent)
The most commonly (primary) used alcohol in production of biodiesel are methanol, ethanol,
propanol, butanol, and amyl alcohol. Methanol was the most commonly used alcohol. N-hexane
(99%) was used as a solvent for oil extraction from avocado peel powdered. The most commonly
used catalyst was alcoholic sodium hydroxide (NaOH) (97%), hydrochloric acid (HCl), distilled
water and phenolphthalein indicator.
All the chemicals and reagents were purchased and obtain from Wise team PLC, school of chem-
ical and bio Chemical Engineering of Addis Ababa institute of technology, center of food sci-
ence and nutrition of science faculty of Addis Ababa University.
3.2. Raw material preparation
The avocado was cut into two pieces and the peels were removed from avocado fruits by hand.
The waste avocado peels collected from hotels, cafeteria and juice processing house. The raw

material (sample) preparation process include: - manual size reduction (Knife cutting), drying
and grinding. Waste peel of avocado 10 kg was used for the sample preparation.
Fig 3.1: Avocado and avocado peel.

3.3. Drying process
Drying process is important in removing water contents from avocado peel. Lipids are impervi-
ous to water; therefore any water in the sample will hinder the isolation of triglycerides, which
are the precursors needed to generate biodiesel. To determine the most appropriate moisture con-
tent of avocado peels, avocado peels were manually crushed with a knife and drying the peel un-
til all of its moisture content was removed. The peel was dried by sun for five days.
Figure 3.2: avocado crushed with knife and drying the peel.

3.4. Determination of moisture content of the Avocado peel

10 kg sample of the avocado peel were weighed and dried by sun for five days and the weight
was measured every two hours. The procedure was repeated until a constant weight was obtained
and the percentage moisture content of the peel was determined. After a constant weight the
moisture content of the sample was obtained by calculating for the water lost upon the drying
process.
Moisture content (%): W = …………………………. (3.1)
Where: M = the final weight of the dried sample (peel).

Mo = initial weight of the fresh sample (peel).
3.5. Milling process (Size reduction and sieve analysis)
After the moisture was removed by placing in sun for five days the dried avocado peel was
milled in centrifugal miller. The purpose of milling is to size reduction by cutting action is car-
ried out by feeding dried avocado peels against the rotating cutter. Thus, the spindle, speed, the
table feed, the depth of cut, and the rotating direction of the cutter become the main parameter of
the process. The particle size was standardized with 2.6 mm sieve. This particular size was se-
lected because literature reveled that to have a higher yield of oil the particle size should be less
than 5mm and higher than 0.2mm (Henry, 1983), we use the mean of the two. Finally, the pow-
der was stored in a dark bottle until we use.
(a) (b)
Figure 3.3: (a) Milling machine and (b) powder of avocado peel.
3.6. Oil Extraction process
3.6.1. Method for extraction of avocado peel oil by Soxhlet extraction

A Soxhlet extraction was one of the most used for extraction of the oil. A ratio of crushed avoca-
do peels (powder) to solvent of 1:5 (m/v) was used.100 g of avocado peel powder with the aver-
age size of 2.6 mm sieve was placed into the thimble and placed in the Soxhlet chamber. The
solvent used for oil extraction was n-hexane.
The extraction was carried out using 500 ml with n-hexane at 690C (below the boiling tempera-
ture) of hexane with purity 99.0 % for 3-5 hr were placed in a round bottom in1000 ml flask and
assembled for Soxhlet extractor. Then solvent evaporates and moves up into the condenser,
where it is converted into a liquid that trickles into the extraction chamber containing the sample.
Eventually, the solvent builds up in the extraction chamber and completely surrounds the sample.
The extraction chamber is designed so that when the solvent surrounding the sample exceeds a
certain level, it overflows and trickles back down into the boiling flask (Chemat et al., 2008). As
the solvent passes through the sample it extracts the oil and carries them into the flask. Finally
the oil obtained from 100 g of avocado peel powder was 70 ml (52.2 g) for 3 hr at 600 C and at 4
and 5 hrs 74.74 ml (55.74 g) and 80.3 ml (59.9 g) at 65 & 69 0C respectively.
Figure 3.4 Extraction of oil by Soxhlet extraction

3.7. Evaporation Process

After completed the extraction process, the flask containing the solvent and lipid is removed and
the distillation (recovered) process of oil was begun. The solvent and extractor were placed on
water bath to evaporate the solvent. The solvent was evaporated at 700c and the oil remains in the
flask because of its low volatility (Chemat et al., 2008) and the solvent (n-hexane) evaporates
through condenser and we use this solvent for other extraction.
3.8. Degumming process

In degumming process, distilled water was heated to 1000C and left to boil for several minutes.
Then crude avocado peels oil was poured into a beaker and equal volume of hot distilled water
was added and stirred vigorously to remove the gums. The mixture was allowed to settle for 5
minutes the oil -water mixture separated into layers with the oil layer on top. The oil was decant-
ed and the process repeated again.
Figure 3.5 Degumming process
3.9. Characterization (Physicochemical) properties of oil

The oil extracted by Soxhlet extraction was used after analyzing the physicochemical properties
oil. Physical properties such as density, kinematic viscosity, pH value and chemical properties
like acid value, free fatty acid value, saponification value, and iodine value, were determined for
oil physicochemical properties using optimum operating parameters.

3.9.1. Determination of density

A clean and dry density bottle of 50ml capacity was weighed in gm. Then, the bottle was filled
with water and reweighed. The water was substituted with oil and weighed again and the specific
gravity of oil was determined. The density of the sample was calculated from the specific gravity
by equation 4.3.
3.9.2. Determination of kinematic viscosity of oil

A kinematic viscosity of the oil was measured indirectly using vibro viscometer which was
available in laboratory of school of chemical and bio engineering. The sample was kept in the
water bath heated by thermostat until it reaches the equilibrium temperature. A sample of 35 ml
oil was measured and fed to a sample holder of the vibro viscometer. A sensor of the viscometer
was immersed to the oil and then a dynamic viscosity of oil was displayed on the vibro viscome-
ter screen at a temperature of 300C. This was done in triplicate and the average dynamic viscosi-
ty was recorded and calculated. The kinematic viscosity (𝜇) of the oil was calculated from equa-
tion 4.4.
3.9.3. Determination of Saponification Value

Saponification Value is defined as the numbers of milligrams of sodium hydroxide require sa-
ponified. The saponification value gives on idea of the molecular weight of the fatty acid and the
higher the saponification value, the higher the molecular weight.
2 gm of the sample was taken and added in to a 250 ml conical flask followed by the addition of
25ml of 0.5M alcoholic sodium hydroxide solution was added in to the flask. The flask was con-
nected to reflux condenser and kept on the water bath and boiled gently for 1 hour. After the
flask and the condenser were cooled, the inside of the condenser was washed with 10 ml of hot
ethyl alcohol. Then few drops of phenolphthalein indictor were added and the excess sodium hy-
droxide was titrated with 0.5 N hydrochloric acid to the end point, until the pink color of the in-
dicator just removed. The same procedure was conducted for the blank and the saponification
value (SV) expressed as the number of milligrams of NaOH required to saponified 1 gm of fat or
oil was (Nguamo, 2008). Blank determination was also conducted along with that of sample,
using the same reagents minus sample (and volume 𝑉𝑏 was recorded).

The saponification value (SV) expressed as the number of milligram of NaOH required to sapon-
ified 1g oil) was calculated using equation 4.5.
3.9.4. Determination of acid value

Acid value measure the free fatty acids present in oils. Or the number of milligram of sodium
hydroxide that is required to neutralize free fatty acids in 1 g of fat or oil. A good quality of oil
generally has low acid value (Otieno, 2011). 5 gm of the sample was weighed and poured in to
250 ml conical flask and 50 ml of hot ethyl alcohol was added to the flask. After few drops of
phenolphthalein added, the mixture was boiled for about five minutes and while it was hot titrat-
ed with 0.5N sodium hydroxide solution and then the acid value was determined.
The total acidity (acid number) in mg NaOH/g oil was calculated using equation 4.6(i). Since the
acidity is frequently expressed as free fatty acid from acid value free fatty acid was calculated
and FFA of oil was calculated from the acid value using equation 4.6(ii).
3.9.5. Determination of iodine value

Iodine value is a measure of the proportion of unsaturated acids present. Iodine value is measure
as the number of grams of iodine taken up by l00gm of fat or oil (Otieno, 2011). Generally, bio-
diesel made from low iodine value oils have a higher melting point and high iodine value oils
have lower melting points and make better cold weather biodiesel.
3.9.6. Determination of high heating value

Energy content or heat of combustion of a fuel was determined using bomb calorimeter. 1 g of
sample was taken in a crucible and made into a pellet and the initial weight was noted. It was
placed in the bomb, which was pressurized to 18atm of oxygen. The bomb was placed in a vessel
containing 2kg of water. The ignition circuit was connected and the water temperature noted. Af-
ter ignition a temperature rise was noted every minute till a constant temperature was reached.
The pressure was released and the length of unburned fuse wire was measured. The determina-
tion of the oils calorific value was conducted following the same procedure as that for standardi-
zation, except that the sample was solid fat. Including the corrections for heat transfer between
the surrounding and the apparatus, heat liberated by the glowing wire etc, the heat value of the
oil was calculated according to equation 4.7(i).

3.9.7. Determination of melting point

The melted oil was poured into a small heat resistant glass capillary and then let to solidify. After
this, the solidified glass capillary was inserted into the CHI apparatus. The melting tempera-
ture set point was assigned on the apparatus. When the first melting was observed on the watch-
ing screen, the corresponding temperature was recorded.
3.9.8. Determination of pH
The determination of pH value of avocado peel oil was determined to be 5.7; this shows the
slightly acidic nature of the oil, it meets the standard value of (5-6.7).
3.10. Transesterification Reaction

Transesterification reaction is the most commonly used method of producing biodiesel. Trans-
esterification is the reaction of oil with an alcohol to separating the fatty acids from their glycerol
backbone to form fatty acid methyl esters (FAME) and free glycerol [Abhullah et al, 2007]. Bio-
diesel can be produced in batch reactor by transesterifying triglycerides APO with lower molecu-
lar weight alcohols in the presence of a base catalyst. Biodiesel is biodegradable, non-toxic and
essentially free from sulfur, which has a correlation with sustainable development, energy con-
servation, management, efficiency and environmental preservation.
3.10.1. The Transterification procedure (making biodiesel)

Biodiesel production process by transterification reaction is made using three main components
are: avocado peel oil, alcohol, and a base catalyst have been studied in laboratory experiments. A
500ml glass three neck flask reactor equipped with magnetic stirrer, electric thermostat, and con-
denser was used in all experiments. The reactor was connected to a water bath heated with ther-
mostat, which was capable of controlling the temperature within deviation of 1⁰C. The proce-
dures for the biodiesel production by transterification reaction are:
(i). Mixing of the methanol and the catalyst in a 200 ml beaker using the mixing ratio of metha-
nol and catalyst concentration respectively. A quantity of methanol was poured in a beaker and
the sodium hydroxide pellet was placed in the weighing balance to get exactly weight and mix
with methanol to 500C (in a water bath) and stirred by manually until the catalyst is completely
dissolved in methanol. The moisture level should be kept as low as possible. Water causes the

formation of soap by saponification. It is necessary to reduce the formation of soap. Formation of

soap consumes the catalyst is consumed and complicates the separation and purification process.
Formation of soap also decreases the biodiesel yield.
(ii).The methanol and sodium hydroxide solution was poured in the warm avocado peel oil in a
500 ml three neck flask and stirred vigorously for (45-90) minutes using a magnetic stirrer at 500
rpm. The mixture was then allowed to settle for 24 hours in a separating funnel. After settling,
the upper layer which was biodiesel was poured into a separate beaker, while the lower layer (i.e.
glycerol, soap and other residual) was collected from the bottom of the funnel. The quantity of
biodiesel collected was measured and recorded in each run.
(iii). Washing biodiesel. Warm distilled water was used to wash the biodiesel to remove any im-
purities like, excess methanol, glycerol and soap that remain in the funnel. This was repeated un-
til a clear biodiesel in the separating funnel was obtained (clear water was seen below in the sep-
arating funnel).
(iv).The washed sample was dried by placing it on a hot plate (oven) to evaporate the excess wa-
ter in the biodiesel.
(v).The quantity of biodiesel was measured and collected in the sample holder and recorded in
each sample run.
Note: The above procedures were repeated by varying the mole ratio of avocado peel oil to
methanol, catalyst concentration, stirring time, and reaction temperature by design experimental
run.

Figure3.6 Mixing of NaOH and methanol and experimental transesterification reaction process
Catalyst
Catalyst
mixing Purification
(washing by Drying Biodiesel
Methanol
distilled water)
Recycled
methanol
Avocado peel oil

Transesterification
Crude biodiesel
Methanol re- Crude

Phase Separation glycerin
covery
Figure 3.7: The production process of the biodiesel by transterification reaction.

3.11. Separation process

After the reaction was completed the separation process is one of the most crucial parts of bio-
diesel production. The product from the transesterification process is normally composed of bio-
diesel, glycerine, alcohol, catalyst and unreacted glycerides. The properties of the fuel are strong-
ly influence by the purity of the biodiesel product. Normally, the biodiesel is separated from by-
product glycerine using a simple gravitational settling (density difference) method and left for 24
hours. The separation process using the separation funnel was considered to be cost effective.
After 24 hours two different layers were seen in the separating funnel. The above biodiesel layer
was separated for further purified and the lower glycerol layer was decanted off. The glycerol
phase is much denser than the biodiesel phase.
Figure 3.8 separation processes.
3.12. Washing and Drying
3.12.1. Washing (Purification) of crude biodiesel

Once phase separation has been achieved, the purification of the ester phase is necessary to en-
sure that the biodiesel meet specifications (ASTM). After the phase separation of glycerol, the
biodiesel still has an excessive amount of soaps, aggressive pH, catalyst, FFAs, water, methanol,
glycerides and other impurities. These substances, if not reduced to their limits value, this will
have effects on the biodiesel and it may not meet the ASTM. The biodiesel is washed with warm
distilled water to remove any residue, insoluble impurities left in biodiesel after the reaction and

initial settling is complete. The contaminants include (primarily) excess alcohol, excess catalyst,
soap formation glycerine and a small amount of left over lye. Water used is warmed to about
500C for the washing process, 50% (related the biodiesel volume) of water was added to the bio-
diesel in order to extract contaminants passed through the esters to allow soluble material, excess
catalyst and other impurities to stick to the water and be settled to the bottom of the vessel. The
mix was allowed to separate, forming a top biodiesel layer and a bottom aqueous layer, due to
difference in densities and immiscibility. After complete separation, the aqueous layer is re-
moved and the washing process is repeated until the aqueous layer shows no contamination and
the pH of the biodiesel becomes relatively neutral. When biodiesel is first made, it is quite with a
pH of between 8 and 9. Washing with distilled water it is sufficient to improve impurities bring-
ing the pH down biodiesel becomes relatively neutral.
Table 3.1 Effects of Impurities in biodiesel on diesel engine performance (Prah, 2010)
Impurity Effects
FFAs Corrosion and low oxidation stability.
Water Hydrolysis (free fatty acid and alcohols formation), corro-
sion, bacteriological growth (filter blockage).
Methanol Low values of density, viscosity and low flash point.
soap, catalyst Deposit in the injectors, filter blockage (sulphate ashes), and
engine weakening.
Glycerol Settling problems.
3.12.2. Drying (Evaporation) process

The last step was drying process. The biodiesel washing process sometimes leaves the biodiesel
looking a bit cloudy. This means there's still a little water in it. Drying biodiesel requires a little
more than heating up the final biodiesel at 65 0C, for 15 - 20 minutes until all any remaining
moisture (water) evaporate and removed from the sample. After the biodiesel washed and dried,
the yield of biodiesel production must be analyzed to ensure it meets any required specifications
and product was then characterized using empirical formula to confirm the biodiesel production
yield and consider the biodiesel yield with its standard.

3.13. Physicochemical Properties of Biodiesel

The production of biodiesels from avocado peel oil by the transesterification reaction was char-
acterized by their physical and chemical properties by empirical formula and gas chromatog-
raphy analysis. The extensively characterized physical properties were specific gravity, kinemat-
ic viscosity, pH, higher heating value, and cloud point. The biodiesels were, also characterized
for their chemical properties such as acid value, free fatty acid value, iodine value, saponification
value, cetane number and flash point (U.S, 2014).
3.13.1. Determination of Specific Gravity

The density of the oil (biodiesel) was determined by using density beaker. A clean and dry bottle
of 100ml capacity was weighed (W0) and then the beaker was filled with the oil (biodiesel) and
reweighed to give (W1). The oil (biodiesel) was substituted with water after washing and drying
the bottle and weighed to give (W2). The expression for specific gravity (Sp.gr) is:
Specific gravity= …………………………………………………………….3.2
Where, W1= Moil (biodiesel) + Mbeaker

Wo= Mbeaker
W2 =Mwater + Mbeaker
Sp.gr = =0.88, it meets the standard Limits of ASTM (0.86-0.9) of the specific gravity
of biodiesel.
3.13.2. Determination of density
Density influences the efficiency of the fuel for airless combustion system. It has some effect on
the break-up of fuel injected into the cylinder. Since density is strongly influenced by tempera-
ture, the quality standards state the determination of density at 15 0C. The air fuel ratio and ener-
gy content within the combustion chamber are influenced by fuel density. The denser the oil the
higher the energy content per liter. The density of oil or biodiesel was determined from specific
gravity of oil (biodiesel).
Density=specific gravity *density of water……………………….……….………..3.3
Density =0.88 × 1000 kg/m3 = 880 kg/m3. From this result the density of avocado peel methyl
ester is 880 kg/m3 which meet the ASTM Standards.

3.13.3. Determination of API Gravity of Biodiesel

API Gravity of biodiesel test is actually determined using specific gravity of biodiesel. The API
gravity is a widely used measure of fuels density. API Gravity is inversely proportional to specif-
ic gravity. As API gravity goes up, specific gravity goes down.
The formula that relates API to SG is:
API = ……………………………………………………….. (3.4)
API = =31.14
As API gravity increases energy content decreases. Since specific gravity is the inverse of API
gravity, a higher specific gravity means a higher energy content fuel. As specific gravity increas-
es, power output increase. The API limits for biodiesel are 30 to 45. This value translates to spe-
cific gravities of 0.879 to 0.802.
3.13.4. Kinematic Viscosity
Viscosity is the most important factor of fuels that affects the flow of the fuels i.e. its fluidity.
The kinematic viscosity is defined as the resistance to flow of a liquid against gravity (viscosity
is the reverse of fluidity). To define kinematic viscosity, it is useful to begin with the definition
of viscosity. Simply stated, viscosity, which is also called dynamic viscosity (η), is the ease with
which a fluid will flow and technically, it is the ratio of the shear stress to the ratio of a fluid. In
contrast, the kinematic viscosity (V) is the resistance to flow of a fluid under gravity. Therefore,
the kinematic viscosity of a fluid is related to the dynamic viscosity through the density ( ) i.e.
V= ………………………………………………….. (3.5)
Where, μ= dynamic viscosity, mpa.sec

ν= kinematic viscosity, mm2/s
ρ=density, Kg/m3
Dynamic viscosity of oil, which was red from vibro viscometer was 37.2mpa.s at a temperature
of 40 0C. Substituting the dynamic viscosity = 37.2mpa.s = 3.72×10-2kg/m.s and density of bio-
diesel (BD) is 880kg/m3.
V= = 4.22×10-5m2/s, Therefore kinematic viscosity of avocado peel methyl
ester is 4.22cSt which meets ASTM Standards.

3.13.5. Determination of pH Value

The pH electrode was standardized with distilled solution and the electrode immersed into the
sample and the pH value was read and recorded. Therefore the pH values read from the standard-
ize electrode is 7.8, this satisfy the ASTM which is from (7-9).
3.13.6. Cloud point (CP)

The cloud point (CP) is a measure of the temperature at which components in the biodiesel begin
to solidify out of the solution. The cloud point is reached when the temperature of the biodiesel is
low enough to cause wax crystals to precipitate. Initially, cooling temperatures cause the for-
mation of the solid wax crystal. Further decrease of temperature causes these crystals to grow.
The CP is the most commonly used measure of low-temperature operability of the fuel. The bio-
diesel cloud point is typically higher than the cloud point of conventional diesel.
3.13.7. Pour point (PP)

The pour point is the temperature at which the fuel contains so many agglomerated crystals that
it is essentially a gel and will no longer flow. This occurs if the temperature of the biodiesel
drops below CP. Similarly to the cloud point, the pour point values also depend on the feedstock.
Although CP and PP are relatively easily determined, they only provide indicative values for the
minimum temperature at which the fuel can be used.
3.13.8. Flash point (FP)

A key property determining the flammability of fuel is the flash point. It measures the tendency
of fuel to form flammable mixture with air. The flash point is the minimum temperature at which
the fuel will ignite (flash) on application of an ignition source under specified conditions. The
flash point does not affect the combustion directly; higher values make fuels safer with regard to
storage and transportation. Minimum flash point temperatures are required for proper safety and
handling of diesel fuel. FP varies inversely with the fuel‟s volatility. If the temperature is at or
above the flash point, the vapours will ignite and an easily detectable flash can be observed.
(Surma, 2008)

3.13.9. Determination of Acid Value (Number)

Free fatty acids occur naturally in vegetable oils and thus are carried over into the final product
after transesterification. The amount of free fatty acids in the biodiesel is indicated by the acid
number which is an expression of the milligrams of NaOH per gram of sample required to titrate
a sample to a specified end point. The standard established by the ASTM is a maximum of 25ml
of toluene and 25ml of methanol was mixed in beaker. The resulting mixture was added to 2g of
biodiesel in a 250ml conical flask and few drops of phenolphthalein were added to the mixture.
The mixture was titrated with 0.1M NaOH to the end point with consistent shaking for which a
dark pink color was observed and the volume of 0.1M NaOH (V) was noted.
The Acid value was calculated as:
Acid Value = ……………………………………………………….3.6
Where,
C=concentration of NaOH
V=Volume of titrated solution
M=Mass of sample
40=Molecular weight of NaOH
Acid Value = = 0.4
3. 13.10. Determination of free fatty acid value

Determination of the free fatty acid has from acid value. Therefore the free acid value was calcu-
lated using the following formula.
Free fatty acid value = ………………………………………………3.7
Free fatty acid value = = 0.2, this value satisfy the ASTM.
3. 13.11. Determination of refractive index

Refractive index was determined by using refract meter and three drops of oil (biodiesel) onto
refract meter and reading the value at specified temperature. Refractive index implies the purity
of oil. The lower the refractive index is the higher the quality of oil (Anhwange et al, 2010). A
refractive index of 1.54 at a temperature of 40 0c was obtained. The result obtained indicated that
the oil is of high quality.

3. 13.12. Cetane Number (Index)

Cetane number is a relative measure of the interval between the beginning of injection and auto
ignition of the fuel. Fuels with low cetane numbers will result in difficult starting, noise and ex-
haust smoke. Theoretically, the cetane number is defined in the range of 15-100. In general, bio-
diesel engines will operate better on fuels with cetane numbers above 51. Higher cetane numbers
indicate shorter times between the injection of the fuel and its ignition.
3. 13.13. Determination of Iodine Value
Iodine Value (IV) is the amount of iodine, measured in grams, absorbed by 100 grams of given
oil. 0.2g of avocado peel oil in each case was weighed out and placed in a dry flask. The oil was
dissolved in 20ml of carbon tetrachloride. The stoppered flask was swirled to mix the contents
and in a dark cupboard for 1 hour at normal temperature (Approx. 250C). It was removed and
20ml of a 15% potassium iodine solution was added followed by l00ml of distilled water. The
liberated iodine was slowly titrated with 0.1M thiosulphate solution until the yellow colour al-
most disappeared. At this stage 2ml of indicator was added and the blue colour which appeared
was added discharged by further slow additions of thiosulphate. The iodine value was calculated
by this formula:
Iodine value = 3.8
Where, B = blank titration

S = Sample titration
M = Molarity of sodium thiosulphate solution
12.69 = atomic weight of iodine
IV = =114.21, this satisfy the ASTM, since higher iodine value indicates a
higher quantity of double bonds in the sample and greater potential to polymerize in engine and
hence lesser stability.

3.14. Factor affecting on the Extraction of Avocado peel oil by Soxhlet extrac-
tion
The efficiency of oil extraction by Soxhlet extraction from avocado peel oil can be influced by
different factors such as particle size, solvent type used, extraction temperature, extraction time,
moisture content of the peel and solid to solvent ratio (avocado peel powder to n-hexane).
3. 14.1. Effect of Time on the extraction

In the above result obtained the oil yield (expressed in percent) was extraction time reliant. In
general, the oil yield increased with increase in extraction time and there was no considerable
increase after 5hour (Tesfaye and Tefera, 2017). Results shown from table 4.1 and figure 4.1,
Soxhlet extraction using n-hexane the time changed from 3hr to 5hrs the percent oil yield
changed from 35.6% to 40.5%. This percent indicates as the extraction time increases the percent
oil yield also increases.
3. 14.2. Effect of Temperature on the extraction of oil

From the above results (table.4.1, figure 4.1) the obtained value analysis showed that an increase
in temperature generally favors an increase in percent oil yield. This phenomenon is due to the
fact that oils are generally more soluble at elevated temperatures. At higher temperatures, the
viscosity of the solvent is reduced while the diffusivity, as well as evaporation rate is increased.
This increases the contact time between the solvent and the oil bearing material (Tesfaye and
Tefera, 2017). Temperature generally affects both the equilibrium and mass transfer rate of the
extraction process. Soxhlet extraction using n-hexane the temperature changed from 65 to 690c
the percent oil yield changed from 35.6% to 40.5%. This percent indicates as the extraction tem-
perature increases the percent oil yield also increases.
3. 14.3. Particle size

The Particle size influences oil extraction by the Soxhlet extraction rate in many ways. The
smaller the particle size, the greater is the interfacial area between the solid and liquid, and there-
fore the higher is the rate of transfer of material and the smaller is the distance the solute must
diffuse within the solid as already indicated. On the other hand, the surface may not be so effec-
tively used with a very fine material if circulation of the liquid is impeded and separation of the

particles from the liquid and drainage of the solid residue are made more difficult (Richardson et
al., 2002).
To obtain adequate oil release, particle diameters or thicknesses in the 0.2 - 5 mm range usually
represent a good choice for scale up extractions (Henry, 1983). For our cause we use the mean of
the two sizes, i.e. [(0.2+ 5)] / 2 =2.6 mm.
3. 14.4. Solvent Type

The liquid chosen should be a good selective solvent and its viscosity should be sufficiently low
for it to circulate freely. Generally, a relatively pure solvent will be used initially, although as the
extraction proceeds the concentration of solute will increase and the rate of extraction will pro-
gressively decrease, first because the concentration gradient will be reduced, and secondly be-
cause the solution will generally become more viscous (Richardson et al., 2002). The most sol-
vent extraction methods that we use during extraction are a trial and error approach. The most
commonly used solvents for avocado peel are commercial n-hexane. N-hexane is solvents desir-
able to be cheap, noncorrosive, nonflammable, non-explosive, nontoxic, easily removable, and
easily recoverable. It obviously may be impossible to meet all these objectives (Henry, 1983). `
3.15. Factor affecting on the production of biodiesel
3. 15.1. Purity of reactants

The impurities present in the vegetable oil affect ester conversion significantly. The vegetable oil
(crude oil) is filtered before the transesterification reaction. The oil settled at the bottom of the
flask during storage would give lower yield because of deposition of impurities such as wax.
3. 15.2. Water Content

Water content is one of the variables that significantly affect the performance of the transesterifi-
cation reaction when present in the feed stock oil and also the final biodiesel product. All materi-
als involved in the transesterification process should be waterless because it decreases the bio-
diesel yield in the transesterification reaction, can lead to corrosion and also promotes bacteria
growth in biodiesel and simultaneously contributes to the formation of soap. The produced soap
increases the viscosity of the reaction mixture leads to difficulty in the separation process. A lim-

it of water in the product is a maximum of 0.05 volume % is set as a standard in ASTM (Prah,
2010).
3. 15.3. The kinetics and mechanism of transesterification reaction
Kinetic of the transesterification reaction of oils provide the extent of reaction by predicting pa-
rameters at any given time under particular reaction conditions. Kinetics usually includes the de-
termination of rate constant and reaction rate equation as well as activation energy. The overall
transesterification reaction consists of a number series, of three equivalents, consecutive and re-
versible reactions, in which mono and diglycerides are formed as intermediates. Transesterifica-
tion is, in principle, the action of one alcohol displacing another from an ester, referred to as al-
coholysis. In transesterification reaction oils, triacylglycerol react with an alcohol, to produce
esters and glycerin. Transesterification is conducted to produce biodiesel with the objective to
reduce the viscosity of the parent vegetable oil fat, since it is an order of magnitude greater than
that of the biodiesel. The kinematic viscosity of avocado peel oil significantly reduces after
transesterification.
A mole of ester is liberated at each step. The triglyceride is converted stepwise to di-glyceride,
mono-glyceride and finally to the by-product which is called glycerol. The reactions are reversi-
ble, although the equilibrium lies toward the production of fatty acid esters glycerol (Ecky,
1956).

CHAPTER FOUR
4. RESULTS AND DISCUSSIONS
4.1.1 Determination of moisture (water) content of the avocado peels
The total weight of the avocado peel we use (weight of sample before dry) was 10 Kg, but
weight of sample after dry from this mass of peel was 2.9 Kg. The percent moisture content of
the peel was calculated by substituting these values in to equation 4.1.
% Moisture content = 4.1
Where, 𝑊1 = Original weight of the sample before drying.
𝑊2 = Weight of the sample after drying.
% Moisture content = =71 %.
This meets the physicochemical properties of avocado skin. Therefore, 71 % of the avocado peel
was moisture and drying by oven or sun drying for five days used for oil extraction using n-
hexane.
4.1.2. Determination of the percentage of oil yield extracted from avocado peel
100 g (W1) of the sample was placed in the thimble and about 500ml of n-hexane was poured
into the round bottom flask. The apparatus was heated at 70 0C and allowed for 5hrs for extrac-
tion process. After the extraction, the solid avocado powdered was dried in the oven at 105 0C
and weighed until the constant weight (W2) is attained and the percentage of oil extracted was
determined as:
% crude oil yield = ………………………………………………….4.2
Where, W1 =weight of sample before extraction
W2 = weight of sample after extraction

Table.4.1: show result of Soxhlet extraction with particle size 2.6mm at different temperature
and time with the above formula.
Trial Temperature Time weight of sample weight of sample Oil yield Average
(0c ) (hr) before extraction(g) after extraction(g) (%) (%)
1 60 3 100 64.6 35.6
2 65 4 100 62.8 37.8 38
3 69 5 100 59.4 40.6
Figure 4.1 oil yield (%) of oil extraction by Soxhlet extraction at different temperature and time.
4.1.3. Physicochemical properties of avocado peel oil

Avocado peel oil was first characterized before produce biodiesel. The details of the properties
are discussed below as follows:
4.1.4. Specific gravity

The oil sample was brought to a test portion was transferred to the measuring cylinder. Densime-
ter was inserted in to the cylinder. Then, the reading was taken.

The specific gravity observed was 0.91. Hence, the density of the oil is determined using the
specific gravity.
SG = = ρoil 4.3
Where, ρoil = Density of avocado peel oil
𝑤= Density of equal volume water =1 g/ml
Therefore, the density of the oil was 0.91g/ml or 910kg/m3.
4.1.5. Kinematic viscosity

Viscosity refers to the thickness of the oil, and is determined by measuring the amount of time
taken for a given measure of oil. The viscosity of oil was measured using Vibro viscometer. The
device detects the dynamic viscosity, which is resistance to flow with vibration. The observed
dynamic viscosity was at 40 0c was 47.2mpa.s
V = ………………………………………………….. (4.4)
Where, μ= dynamic viscosity, mm2/s

ν= kinematic viscosity, mpa.sec
ρ=density, Kg/m3
V= = = 5.2 *10-5m2/s, which is in agreement with literature data.
4.1.6. Saponification value

Generally the SV is inversely proportional to the mean molecular weight of the fatty acid in oil.
The saponification number was determined by using titration. Solutions were prepared with the
required concentration. In order to know the exact concentration, the solution was standardized.
Hence, primary and secondary standardization was used.
Mass of NaOH =N*equivalent weight*Volume of solution in liter
= 0.5mol/l *40g/mol*1 lit = 20 g
Mass of HCl = N*equivalent weight*Volume of solution in liter

=0.5*36.5*1l =18.25g
VHCl= m/ρ=18.25/1.16 =15.73ml
2g of oil was dissolved in ethanolic NaOH and titrated with HCl. Similarly blank titration was
done. In both cases, the volume of HCl was recorded. The saponification value was then calcu-
lated using equation 4.5.
SV = 4.5
Where, w = weight of oil used, 2g
N= normality of HCL solution, 0.562N
Va= volume of HCl solution used in the test, 29.4 ml
Vb= volume of HCl solution used in blank, 47.2 ml
Values for unknowns in equation 4.5 were substituted; hence the SV was calculated. The ob-
served value was 200 mg of NaOH/g of oil, which is satisfy the literature data. The ranges of SV
of avocado peel oil are 170-200 mg/NaOH/g in AOCS. (1998).The experimental result was at-
tached in Appendix C.
4.1.7. Acid value

Acid value is the measure of total acidity of the lipid involving from all the constituent fatty ac-
ids that make up the glyceride molecule (Indhumathi P et al, 2014). Titration method was used to
determine the acid value. The required solutions were prepared with the required concentration
as follows. The titrant volume was observed to be 11ml. The acid value of the oil was calculated
as:
Acid Value = ……………………………………………………….4.6(i)
Where,
C=concentration of NaOH
V=Volume of Titrated Solution
M=Mass of Sample

40=Molecular Weight of NaOH
Acid Value = = 8.8 mg NaOH/g of oil
The % FFA value was calculated from the acid value using the relation:
𝐴V =𝐹𝐹A 2 4.6(ii)
Therefore, % FFA = AV/2= 8.8/2 = 4.4 %, the % FFA value was far beyond the required limit
for biodiesel transesterification.
4.1.8. Higher heating value

Heating Value or Heat of combustion is the amount of heating energy released by the combus-
tion of a unit value of fuels. It was determined by using bomb calorimeter. 1g of benzoic acid
was used as a calibrating substance (Tesfaye, July, 2011). The amount of water used to fill the
calorimetric container was 2000g. Equation 4.8(i) was used to calculate the HHV of the oil.
–
HHV = 4.7 (i)
Where: HHV= Higher heating value, cal/g
m =Mass of the fuel, g
𝑤 = Mass of the calorimeter water, g
𝐶 𝑤=Specific heat of the calorimeter water, 𝐶 𝑤 = 1cal/g0C
𝑡𝑜= First temperature reading of main test, 0C
𝑡 = Last temperature reading of main test, 0C
𝑐 = Correction for heat exchange between calorimeter and the surrounding, min*0C.
Σ𝑏=Correction for heat exchange between calorimeter and the surrounding, cal
The correction, c was calculated from the formula in equation 4.7 (ii).
𝑐 =m′Δn − (Δn + Δν) F 4.7 (ii).

Where, m′= duration of main test, min
Δn = Average temperature fall for every minute of the pre-test
Δν =Average temperature rise for every minute of the pre-test
The factor F can be approximated to: F = 1.0, 1.25 and 1.5, and if the temperature rise in 1 st mi-
nute of the main test is higher than in the 2nd, temperature rise in the 1st minute and 2nd minutes
of the main test are about the same, and temperature rise in the 1st minute of the main test is less
than in the 2nd minute respectively.
The correction summation of b (Σ𝑏) consists of heat value added by glowing of the ignition wire
1cm = 1.5cal.
The HHV of benzoic acid was known with a guaranteed heat of combustion of 6324 Cal/g. The
recorded higher heating value of the oil is 40MJ/kg. The result is in agreement with literature
data. See Appendix C for more experimental calculations.
4.1.9. Iodine Value

Iodine value is the measure of the degree of unsaturation of a particular oil or fat. It was deter-
mined using empirical equations given in equation 4.9.
HHV = 49.43− [0.041(SV) + 0.015(IV)] 4.8(i)
IV = 4.8(ii)
The iodine value of the oil was calculated equal to 82 g I2/100g.
4.1.10. Melting point

The melting point of the solidified oil was determined by UCH Melting Point -540. 1 g of
APO was introduced into the capillary tube. Then the temperature set of the apparatus was ad-
justed to heat to 45 0C. The first melting was observed on the watching screen and the tempera-
ture was recorded, and it was 38.5 0C.

4.1.11. Molecular Weight Determination

To determined molecular weight of oil the saponification value and acid value of avocado peel
oil was used (Indhumathi P, 2014). The molecular weight of the oil was calculated as:
MW = 4.9
Where, MW-molecular weight of oil
SV- Saponification value of oil
AV- acid value of oil
 MW = = 880 g / mol
Table 4.2: Physico-chemical of Properties of the obtained biodiesel and avocado peel oil and the
standards of biodiesel in the United States and Europe
Property Avocado Biodiesel EN 14214 ASTM D-6751

peel oil Yields
Density at 15 0C, kg/m3 910 880 860-900
Flash point, (0C) 161 >120 >130
PH 6.2 7.8 5- 6.7 7-9
API 31.14 30-45
Specific gravity 0.91 0.88 0.86-0.9
kinematic viscosity at 40 0C, cSt 5.1 4.22 3.5-5.0 1.9-6.0
Esters content % 38 95.2
HHV (MJ/kg) 40 41.25 36– 40 40-42
Melting point (0C) 38.5
Fire Point (0C) 250 190 -
Iodine value , g I2/100 g 82 114.21 < 120
Cetane number 54 >51 >47
Acid value , mg NaOH/g 8.8 0.4 <0.5
Free fatty acids 4.4 0.2 < 0.24
Refractive index @400c 1.54 1.4-1.7
Saponification value (mgKOH/g) 200

4.2. Statistical Analysis of the Experimental Results

Statistical analysis of the model was performed to evaluate the analysis of variance (ANOVA).
The analysis of variance will be used as one of the primary tools for statistical data analysis. The
Design Expert 6.8.0 program was used in the regression analysis and analysis of variance. The
Statistical software program was used to generate surface plots, using the fitted equation ob-
tained from the regression analysis, holding one of the independent constant variables.
The predicted values of percentage conversion of the oil to biodiesel at the design points are
shown in table 4.5. All 26 run were conducted by the experimental design expert 6.8.0 software.
The actual yield of biodiesel produced at different process parameters was calculated. The yield
of the transesterification processes were calculated as final weight of FAME produced to weight
of total feed used, multiplied by 100.The formula is given as:
Yield of FAME (biodiesel %) = …………………………….4.9
Table 4.3 Result using Experimental design expert 6.8.0 software
Run Factor 1 Factor 2 Factor 3 Factor 4 Biodiesel

NO. A:molar ratio of B:reaction tem- C:reaction D:amount of yield (%)
oil: methanol (ml) perature(0c) time(min) catalyst(g)
1 1:3 50 45 0.6 67.6
2 1:8 50 45 0.6 72.9
3 1:3 65 45 0.6 69.5
4 1:8 65 45 0.6 73.7
5 1:3 50 90 0.6 69.5
6 1:8 50 90 0.6 73.3
7 1:3 65 90 0.6 78.4
8 1:8 65 90 0.6 79.6
9 1:3 50 45 1.82 68.7
10 1:8 50 45 1.82 70.9
11 1:3 65 45 1.82 72.9
12 1:8 65 45 1.82 74.2

13 1:3 50 90 1.82 68.5

14 1:8 50 90 1.82 69.3
15 1:3 65 90 1.82 71.6
16 1:8 65 90 1.82 77.6
17 1 : 5.25 57.5 67.5 1.21 87.1
18 1:6 60 67.5 1.21 95.2
19 1 : 5.5 56.75 67.5 1.21 90.7
20 1 : 5.5 58.25 67.5 1.21 92.9
21 1 : 5.5 57.5 65.25 1.21 92.7
22 1 : 5.5 57.5 67.5 1.21 93.2
23 1 : 5.5 57.5 69.75 1.21 93.8
24 1 : 5.5 57.5 67.5 1.15 91.5
25 1 : 5.5 57.5 67.5 1.27 92.9
26 1 : 5.5 57.5 67.5 1.21 93.2
Table 4.4 Design Summary of factorial designs.
Design Summary of Design expert® 6.8.0 software

Study type Response surface
Initial design CCD
Design model Quadratic, polynomial
Run 26

Table 4.5 Actual versus Predicted model of biodiesel yield
Standard Residual Leverage Student Cook's Outlier Run Actual Predicted

Order Residual Distance T Order Value Value
1 -0.22 0.687 -0.244 0.009 -0.233 3 67.60 67.82
2 1.36 0.687 1.484 0.323 1.582 10 72.90 71.54
3 -0.70 0.687 -0.767 0.086 -0.752 18 69.50 70.20
4 -0.37 0.687 -0.407 0.024 -0.391 7 73.70 74.07
5 -0.71 0.687 -0.774 0.088 -0.758 21 69.50 70.21
6 -0.32 0.687 -0.354 0.018 -0.340 20 73.30 73.62
7 1.71 0.687 1.864 0.509 2.149 4 78.40 76.69
8 -0.66 0.687 -0.719 0.076 -0.702 25 79.60 80.26
9 -0.29 0.687 -0.319 0.015 -0.306 22 68.70 68.99
10 -0.76 0.687 -0.826 0.100 -0.814 2 70.90 71.66
11 1.28 0.687 1.392 0.284 1.462 9 72.90 71.62
12 -0.24 0.687 -0.265 0.010 -0.253 16 74.20 74.44
13 1.32 0.687 1.440 0.304 1.525 12 68.50 67.18
14 -0.24 0.687 -0.266 0.010 -0.254 26 69.30 69.54
15 -2.31 0.687 -2.517 0.928 -3.687 * 13 71.60 73.91
16 1.17 0.687 1.277 0.239 1.319 1 77.60 76.43
17 -0.88 0.901 -1.696 1.740 -1.882 23 87.10 87.98
18 0.26 0.976 1.040 2.981 1.044 6 95.20 94.94
19 -2.24 0.145 -1.475 0.025 -1.571 11 90.70 92.94
20 -0.50 0.144 -0.330 0.001 -0.317 8 92.90 93.40
21 -0.36 0.400 -0.279 0.003 -0.267 17 92.70 93.06
22 0.53 0.400 0.414 0.008 0.398 15 93.80 93.27
23 -0.68 0.400 -0.536 0.013 -0.518 5 91.50 92.18
24 0.85 0.400 0.671 0.020 0.653 14 92.90 92.05
25 1.51 0.119 0.979 0.009 0.977 19 93.20 91.69
26 1.51 0.119 0.979 0.009 0.977 24 93.20 91.69
* exceeds limits

The model equation that correlates the response (yield of the oil to biodiesel) to the transesterifi-
cation process variables in terms of actual value after excluding the insignificant terms was given
below. The predicted model for percentage of biodiesel % final equation in terms of Coded fac-
tors is shown in equation 4.10 below:
biodiesel yield = + 91.69 + 1.56 * A +2.32 * B+1.09 * C - 0.67* D-356.10 * A2 +147.62 * B2

+147.09 * C2 + 42.09 * D2 + 0.039 * A * B - 0.075 * A * C -0.26 * A * D
+1.03 * B * C + 0.063 * B * D -1.05 * C * D ……………..………….. 4.10
Where, A – molar ratio of oil to methanol
B – Reaction temperature
C- Reaction time
D-amount of catalyst
The coefficients of the response surface model, as provided by the above quadratic model equa-
tion, were also evaluated. From ANOVA for the quadratic model for esterification is listed in
table 4.6 below. From the ANOVA for response surface quadratic model for transterification re-
action, the Model F-value of 70.65 implies the model is significant. There is only a 0.01%
chance that a "Model F-Value" this large could occur due to noise. Values of "Prob > F" less
than 0.0500 indicate model terms are significant. In this case A, B, C, A2, B2 and the interaction
BC and CD are significant model terms. From this Prob > F Values greater than 0.1000 indicate
the model terms are not significant.
Table 4.6 Analysis of variance (ANOVA) for the quadratic model of esterification
Source Sum of DF Mean F Prob > F

Squares Square Value
Model 2661.13 14 190.08 70.65 < 0.0001 Significant
A 38.88 1 38.88 14.45 0.0029
B 85.97 1 85.97 31.95 0.0001
C 19.14 1 19.14 7.11 0.0219
D 7.09 1 7.09 2.64 0.1327

A2 19.78 1 19.78 7.35 0.0202

B2 22.65 1 22.65 8.42 0.0144
C2 6.84 1 6.84 2.54 0.1391
D2 0.56 1 0.56 0.21 0.6570
AB 0.024 1 0.024 8.857E-003 0.9267
AC 0.090 1 0.090 0.033 0.8582
AD 1.10 1 1.10 0.41 0.5352
BC 16.81 1 16.81 6.25 0.0295
BD 0.063 1 0.063 0.023 0.8816
CD 17.64 1 17.64 6.56 0.0265
Residual 29.59 11 2.69
Lack of Fit 29.59 10 2.96
Pure Error 0.000 1 0.000
Cor Total 2690.72 25
As can be seen from the above table 4.6, F-values of the model coefficients, the value of the re-
action temperature in both linear and quadratic is less than 0.0001. This indicated that reaction
temperature is the most significant in determining the model than rest and the value of the meth-
anol to oil molar ratio is the second. However, in order to minimize error, all of the coefficients
were considered in the design. The Lack of Fit F-value of 2.96 implies its insignificance relative
to the pure error. Non-significant lack of fit is good because we want the model to fit.
Table 4.7 Model adequacy measures
Std. Dev. 1.64 R-Squared 0.9890

Mean 80.05 Adj R-Squared 0.9750
C.V. % 2.05 Pred R-Squared 0.8528
Press 396.15 Adeq Precision 22.281
The "Pred R-Squared" of 0.8528 is in reasonable agreement with the "Adj R-Squared" of 0.9750
in less than 0.15 difference as one might expect. "Adeq Precision" measures the signal to noise

ratio due to random error. A ratio of 22.281 indicates an adequate signal. Therefore, this model
can be used to navigate the design space.
The regression coefficients and the corresponding 95% CI (Confidence Interval) Low and High
were presented in table 4.8 below. If zero was in the range high and low 95% Confidence inter-
val, the factors has no effect. From the 95% CI High and Low values of each model term, it
could be concluded that the regression coefficients of catalyst concentration and the interaction
terms of molar ratio of oil to methanol and reaction time have highly significant effect in bio-
diesel production.
Table 4.8: Regression coefficients and significance of response surface quadratic model for
transterification.
Factor Coefficient DF Standard 95% CI VIF

Estimate Error Low High
Intercept 91.69 1 0.57 90.45 92.94
A 1.56 1 0.41 0.66 2.46 1.00
B 2.32 1 0.41 1.41 3.22 1.01
C 1.09 1 0.41 0.19 1.99 1.00
D -0.67 1 0.41 -1.57 0.24 1.00
AB 0.039 1 0.41 -0.86 0.94 1.00
AC -0.075 1 0.41 -0.98 0.83 1.00
AD -0.26 1 0.41 -1.17 0.64 1.00
BC 1.03 1 0.41 0.12 1.93 1.00
BD 0.063 1 0.41 -0.84 0.97 1.00
CD -1.05 1 0.41 -1.95 -0.15 1.00

Table 4.9 Sequential model sum of squares and model summary statistics of the response quad-
ratic model for transesterification reaction
Source Sum of DF Mean F Val- P-value Std. R2 Adj. Pred. press

Squares Square ue Prob > F Dev. R2 R2
Mean 1.666E+ 1 1.666
005 E+005
Linear 181.24 4 45.31 0.38 0.8209 10.93 0.0674 -0.1103 -0.3360 3594.85
2FI 35.85 6 5.98 0.036 0.9997 12.84 0.0807 -0.5322 -2.7127 9989.75
Quadratic 2444.04 4 611.01 227.11 < 0.0001 1.64 0.9890 0.9750 0.8528 396.15
Cubic 25.98 9 2.89 1.60 0.4431 1.34 0.9987 0.9832 +
Residual 3.61 2 1.81
Total 1.693E+ 26 6512.1
005 1
The quality of the model developed was evaluated based on the correlation coefficient value, R2.
The R2 value for equation 4.10 was 0.989. This indicated that 98.9% of the total variation in the
biodiesel yield was attributed to the experimental variables studied. The closer the R2 value to
unity, the better the model will be as it will give predicted values which are closer to the actual
values for the response. From the ANOVA and regression analysis on table 4.6 and table 4.8,
respectively it can be seen that the linear terms of A, B and C, the quadratic term A2 and B2 were
significant (because Prob > F less than 0.05), but the interactions BC and CD were insignificant.

Figure 4.2 Yield Plot for the actual vs. predicted of FAME yield
The graph of the predicted vs. actual values was obtained using the experimental data run corre-
lation shown in figure 4.2 above. The plot contains a line of unit slope (i.e. the line of perfect fit)
with points corresponding to zero error between predicted values and actual. This plot therefore
indicates the performance of the correlation in an evident way. Hence, the regression model
equation granted a very accurate description of the experimental data, in which all the points are
very close to the line of perfect fit. This outcome indicates that it was successful in creating the
correlation between the four process variables to the FAME.

Figure 4.3 Normal plots of residuals
From the plot as shown above, the normal probability plot indicates the residuals following a
normal distribution, in the case of this experiment the points in the plots shows fit to a straight
line in the figure, this shows that the quadratic polynomial model satisfies the assumptions anal-
ysis of variance (ANOVA) i.e. the error distribution is approximately normal.

Figure 4.4 Residual vs. predicted values
From the model, the residuals should be structure less; in particular, they should be unrelated to
any other variable including the predicted response. A plot of the residuals versus the rising pre-
dicted response values tests the assumption of constant variance. The plot shows random scatter
which justifying no need for an alteration to minimize personal error.
4.3. Main Factor affecting on the Yield of Biodiesel Production
4.3.1. The effect of molar ratio oil to methanol

The effect of molar ratio of oil to alcohol is one of the main significant factors affecting the yield
of biodiesel. An excess of alcohol is used in biodiesel production to ensure that the oils or fats
will be completely converted to esters and a higher alcohol triglyceride ratio can result in a
greater ester conversion in a shorter time. The yield of biodiesel is increased when the alcohol to
triglyceride ratio was increased and reaches a maximum biodiesel yield.
Further increasing the alcohol amount beyond the optimal ratio will not increase the yield but
will increase cost for alcohol recovery. The molar ratio of methanol to oil increased from 1: 3 to

8, the production yield also increased. From this ratio methanol to oil molar ratio was determined
as 6:1, for maximum biodiesel yield (95.2%) of biodiesel than other molar ratio. Figure 4.5 was
shown the effect of molar ratio on the biodiesel yields.
Figure 4.5 The individual effect of ratio methanol to oil
4.3.2. The effect of catalyst concentration

The effect of catalyst concentration affects the yield of the biodiesel production in a positive
manner up to a certain concentration. As the catalyst concentration increases the conversion of
the yield of biodiesel increase. This is because an insufficient amount of catalysts result in an
incomplete conversion of the triglycerides into the fatty acid esters.
From the results, the maximum yield of biodiesel can be obtained at 1.21g of NaOH concentra-
tion and then decreases a little with a further increase in catalyst concentration. The reduction of
the yield of the biodiesel is due to the addition of excessive alkali catalyst causing more triglyc-
erides to react with the alkali catalyst and form more soap (Leung and Guo, 2006). It reached
95.2 % of the biodiesel yield. Figure 4.6 was shown the effect of catalyst concentration on the
biodiesel yields.

Fig.4.6.Effect of catalyst concentration on the biodiesel Production
4.3.3 Effect of Reaction time

The reaction time was an important factor, which influence the biodiesel yield. According to the
result, the biodiesel yields are directly proportional to the reaction times. In other words, the bio-
diesel yields increase with increasing reaction times.
Experimental results presented in figure 4.7 show the biodiesel yield versus reaction time that
the increase of the reaction time shifts the reaction equilibrium to the products, thus increasing
biodiesel yield. Moreover, excess reaction time will lead to a reduction in the product yield and
then remains relatively constant with a further increase in the reaction time due to the backward
reaction of transesterification, resulting in a loss of esters as well as causing more fatty acids to
form soaps (Alamu, 2007).

Figure 4.7 Effect of the reaction time on the biodiesel yield
4.3.4. Reaction temperature

The effect of temperature is significantly influences the transesterification reaction and yield of
the biodiesel product. The boiling point of methanol is 64.7 0C and in order to avoid alcohol
evaporation, reaction temperature must be less than boiling point. Increasing a reaction tempera-
ture above the boiling point would reduce the viscosity of the oil which leads to a sufficient re-
sult in an increased reaction rate and a shortened reaction time between the oil and the methanol.
Results obtained in these experiments show that increasing of temperature clearly influences the
biodiesel yield and the maximum yield of biodiesel was obtained at 600C. Further increasing of
temperature did not lead to significant rising the biodiesel yield due to the evaporation of metha-
nol, this indicating that the reaction is close to equilibrium and further increasing temperature
decreases the product.

Figure 4.8.Effect of reaction temperature on biodiesel yield
Effect of interactive parameters on biodiesel yield
Contour plots and 3D surface (fig 4.9 a & b and fig 4.10 a & b below), show the relationships
between dependent and independent variables of the developed model. Each contour curve pre-
sented the effect of two variables on the methyl ester yield, holding the third variable at constant
level. The third variable is held at zero level. However, the interaction factor also must be con-
sidered as the individual effect plot does not give information regarding the significant interac-
tion involved. Remarkable the interaction between the independent variables could be observed
if the contour plots had an elliptical profile.

(a)
(b)
Figure 4.9 methanol to oil ratio vs. reaction temperature when concentration of catalyst is at 1.21
%

(a)
(b)
Figure 4.10 methanol to oil ratio vs. amount of catalyst when the reaction temperature is 600c

4.4. Analysis of Fourier transforms infrared (FT-IR)

Fourier transform infrared spectroscopy, FT-IR was to analysis the main function group presence
in the produced biodiesel and it‟s the raw material avocado peel oil. The FT-IR techniques were
used for qualitative analysis of the product. FT-IR analysis was performed using instrument,
Perkin Elmer, model spectrum one for detection of transesterification efficiency of oil by deter-
mination of the active groups produced from these process. The FT-IR spectra will be recorded
at ambient temperature in the wave number between 4000-400 cm-1.
Figure 4.11 The FT-IR produced biodiesel process
An analysis of FT-IR spectrum showed in the above figure 4.11. The oil, biodiesel prepared from
avocado peel oil was analyzed by FT- IR. The major change that takes place during the conver-

sion from triglyceride oil to biodiesel was the gain of a CH3 carbon in the methyl ester (bio-
diesel) product, which is found in the range of 1438- 1459 cm-1 which is not present in the spec-
tra of the oil. Biodiesel results in the formation of carbon hydrogen bonds at 2855-3008 cm-1,
ester functionality at 1738-1759 cm-1, the carbons at 1438-1459 cm-1, and carbon oxygen bonds
at 1171-1197 cm-1. C= O carbonyl compound (aldehydes, acids, etc) are the strong C=O stretch-
ing absorption bands in the region of 1870-1540 cm-1.If ester this band appears in the 1705 cm-1
and 1658 cm-1. C-O-C (Ethers), these stretching vibrations produce a strong band in the 1200-
900 cm-1 region. C-H, adsorption bands as an example 2931 cm-1 and 2954cm-1 correspond to the
asymmetric and symmetric vibration modes of methyl group, ethylene groups respectively, H2O
the adsorption bands of water can be between 1800 -1200 cm-1. Other identifying peaks found in
the oil were at 2926 cm-1 and 2855 cm-1 that represents sp3 hybridized carbon molecules that are
found in the long carbon chain of the biodiesel (Hiwot, 2017).

CHAPTER FIVE
5. CONCLUSION AND RECOMMENDATION
5.1. Conclusion
In this thesis biodiesel produced from avocado peel oil is obtained by transesterification process
using sodium hydroxide as a catalyst. The process parameters affecting yield of FAME conver-
sion has been studied and the statistical analysis and experimental design run was done by using
design expert 6.8.0 software. The outputs of the experimental run conducted have been analyzed
by using physicochemical parameter determination. The overall results showed that the avocado
peel oil could be used to produce biodiesel as waste management and recycled process. The stud-
ied physicochemical properties of the produced biodiesel from APO, methyl ester could be used
as an alternative energy resource in diesel engine. The conclusions from biodiesel feedstocks
(APO) are as follows: -
Biodiesel is an important alternative fuel and it possesses properties like renewability,

non-toxicity biodegradability, and environmentally friendly benefits, since the model re-
siduals would be structure less.
The fuel property of biodiesel production is strongly affected by parameters such as ef-
fects of molar ratio of oil to alcohol; reaction temperature; reaction time and amount of
catalyst concentration were observed. The density and the viscosity were indicators of the
biodiesel quality against the process variables. Generally the ester yield, increased with
increased molar ratio, catalyst concentration and reaction temperature until the optimum
conversion. The best result was obtained at molar ratio of oil to methanol 6:1, reaction
temperature of 60 0C, the reaction was complete at about 67.5 min and 1.21g catalyst
concentration amount has played an important role in improving the biodiesel yield.
Transesterification was the most commonly employed method for FAME production.
The purpose of this method is to reduce the viscosity of oil using base catalyst in the
presence of methanol. The ester yield obtained from the transesterification process ranged
from 67.8 to 95.2%. The yield is strongly dependent on the product of the transterifica-
tion step.

5.2. Recommendation
The present study in this thesis work, there are some further important studies that need to be investi-
gated., In this work we recommended in order to find more optimum conditions for transesterifica-
tion reaction, the main reaction parameters which affect to the biodiesel conversion has been studied
and good results were achieved. However, further investigations effect studies have to be done to im-
prove the reaction conditions, yield and increasing reaction time may give more good results, which
could offer more opportunities for increasing income. In addition to this, in order to get a better yield
in both quantity and quality of biodiesel:-
There must be careful selection of catalyst and the reactor
Appropriate characterization studies like density, viscosity, flashpoint measurement must be
carried out on biodiesel.
Moreover, in order to decrease the cost of chemicals, recycling is important. Therefore, the
catalysts and also the excess alcohol should be reused. Sufficient laboratory equipment
should be provided for the production of biodiesel.
However, the produced oil from avocado peel was not used until for food consumption or other pur-
pose. So we recommend that all the extracted oil must be used for biodiesel production, which intro-
duces more profit. Finally we recommended that the government should encourage the production of
biodiesel from non-edible oil resources particularly from wastes using transesterification process be-
cause this process was less complex, require less investment cost and it needs less energy for produc-
tion.

Reference
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an palm kernel oil
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Appendix
Table A1: Specification of EN 14214 comparing biodiesel to conventional diesel
Properties Diesel Biodiesel
density,150c 0.82 -0.86 0.86 -0.90

viscosity,400c 2.0 -4.5 3.5 -5.0
Flash point, 0c > 377 > 130
Sulfur, % mass < 0.2 < 0.01
sulphated ash (% mass) < 0.01 < 0.02
water (mg/Kg) < 200 < 500
Carbon residues ( % wt) < 0.3 < 0.03
Cetane number > 45 > 51
Acid Value(mg KOH/g) < 0.8
Methanol(% mass) - < 0.2
MG content (% mass) - < 0.8
DG content (% mass) - < 0.2
TG content (% mass) - < 0.4
free glycerin (% mass) - < 0.02
Total glycerin - < 0.25
Iodine number - <120
Cloud Point Report to the customer
Pour point Report to customer
Phosphorus (mg/Kg) - < 10

Table B1: Physico-Chemical Properties of Biodiesel from Different oil raw material
Feed stock Kinematic Density Saponification Iodine Acid val- Cetane Heating
Viscosity (kg/m3) value value ue (mg Number value
(at 400C KOH/g) (MJ/kg)
Soybean 4.08 885 201 138.7 0.15 52 40
Rapeseed 4.3-5.83 880-888 0.25-0.45 49-50 45
Sunflower 4.9 880 200 142.7 0.24 49 45.3
Palm 4.42 860-900 207 60.07 0.08 62 34
Peanut 4.42 883 200 67.45 54 40.1
Corn 3.39 880-890 202 120.3 58-59 45
Camelina 6.12-7 882-880 152-157 0.08-0.52
Canola 3.53 880-900 182 103.8 56 45
Cotton 4.07 875 204 104.7 0.16 54 45
Pumpkin 4.41 884 202 115 0.48 38
jatropha 4.78 864 202 108.4 0.496 61-63 40-42
Pongamina 4.8 883 0.62 60-63 42
pinnata
Palanga 3.99 869 41
Tallow 856 244.5 126 0.65 59
Nile tilapia 88.1 1.4 51
Poultry 867 251.23 130 0.25 61
used cook- 4 0.15
ing oil
Table C1: Saponification value of APO
Run N HCl VbHCl VaHCl 𝑉𝑏 𝑉 ) Mass of oil (g) SV
1 0.562 47.2 29.4 17.8 2 200

2 0.562 47.2 27.9 19.3 2 216.9
3 0.562 47.2 30.9 16.3 2 183.212
Mean 200

Table C2: Infrared Correlations by Wavenumber
Functional Group Frequency (cm-1) Appearance

Free O-H 3590 – 3600 sharp
Alcohol O-H (H bonded) 3300 – 3500 medium to strong
Carboxylic acid O-H 2400 - 3600 variable, broad*
Amide N-H 3200 - 3400 medium, sharp, often two bands
sp C-H (C≡C-H) 3260 - 3390 strong
sp2 (C=C-H) 3000 - 3100 medium
Aromatic C-H 3000 - 3050 weak (see below)
sp3 C-H (C-C-H) 2850 - 2960 medium to strong
Aldehyde C-H 2700 - 2900 weak, two bands
Nitrile C≡N 2200 - 2270 medium
Alkyne C≡C 2100 - 2250 weak, may be absent if symmetric
Anhydride C=O 1800 - 1850 strong, two bands**
1740 – 1790
Acid chloride C=O 1790 – 1810 strong**
Ester C=O 1730 – 1750 strong**
Aldehyde and ketone C=O 1695 - 1740 strong**
Carboxylic acid C=O 1700 - 1730 strong, usually broad**
Amide C=O 1640 - 1690 strong**
Alkene C=C 1640 - 1680 often weak, may be absent
Conjugated C=C 1600 - 1650 intensity increased by conjugation
Aromatic C=C 1500 - 1600 medium, two or three bands
Nitro NO2 1500 - 1570 strong, two bands
1320 – 1360
Amine C-N 1180 - 1360 strong
Chloride C-Cl 700 – 800 strong
Aromatic C-H 650 – 850 may distinguish substitution pattern
Monosubstituted benzene 690 – 710 strong, two bands
730 – 770
1, 2-disubstituted benzene 735 – 770 strong
1, 3-disubstituted benzene 690 - 710 strong, two bands
750 - 810
880 sometimes observed
1,4-disubstituted benzene 810 - 833 Strong
*generally strong, but hydrogen bonded carboxylic acids may show a very weak O-H stretch
**lowered by 15-30 cm-1 by unsaturation (e.g. unsaturated aldehydes & ketones ca. 1670-
1700cm-1)

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ADDIS ABABA UNIVERSITY

ADDIS ABABA INSTITUTE OF TECHNOLOGY (AAiT)

SCHOOL OF CHEMICAL AND BIO- ENGINEERING

PRODUCTION AND CHARACTERIZATION OF BIODIESEL FROM AVO-

A thesis submitted to the school of graduate studies of Addis Ababa University in

Advisor: Dr. Eng. Abubeker Yimam

School of chemical and Bio-Engineering Page i

ADDIS ABABA INSTITUTE OF TECHNOLOGY (AAiT)

SCHOOL OF CHEMICAL AND BIO- ENGINEERING

A Thesis submitted to Addis Ababa Institute of Technology, In Partial

By: Tafere Aga

Approved By the Examining Board Signatures Date

Dr. Eng. Abubeker Yimam

Dr. Eng. Abubeker Yimam

Dr. Eng. Zebene Kifile

School of chemical and Bio-Engineering Page ii

School of chemical and Bio-Engineering Page iii

School of chemical and Bio-Engineering Page i

School of chemical and Bio-Engineering Page ii

List of Tables ..................................................................................................................................x

List of abbreviations and symbols ............................................................................................xi-xii

List of Annexes ........................................................................................................................... xiii

CHAPTER ONE ........................................................................................................................... 1

1.7. Study outline of the Thesis ................................................................................................... 8

School of chemical and Bio-Engineering Page iii

2.7.2. Review of avocado production in Ethiopia ..................................................................... 19

School of chemical and Bio-Engineering Page iv

3.1. Materials and Methods ........................................................................................................ 45

School of chemical and Bio-Engineering Page v

3.13.4. Kinematic Viscosity ...................................................................................................... 58

School of chemical and Bio-Engineering Page vi

4.1.11. Molecular Weight Determination.................................................................................. 71

School of chemical and Bio-Engineering Page vii

List of Figures Page

Figure 2.1: Worldwide fossil, nuclear and renewable energy consumption……………………..13

Fig 2.2: percentage of avocado production in the world……………………………..………….19

Figure 2.3 Yield seeds (liters oil/ha)………………………….…………….…………........……24

Figure 2.4 Solvent extraction……………………………………………….………………...….26

Figure 2.6 Soxhlet extractor set up………………………………………….………………..….28

Figure 2.7 Catalytic transesterification…………………………………….…………...….….…30

Figure 2.8: Flow chart for biodiesel production by homogenous catalyst.............................…....35

Figure 2.9.The production process of biodiesel…………………………………….…….…..….39

Figure 2.10- Potential emissions reductions from biodiesel……………………….…….………41

Fig 3.1: Avocado and avocado peel……………………………………………….….…………46

Figure 3.4 Extraction of oil by Soxhlet extraction…………………………….………...….……48

Figure 3.5 Degumming process….................................................................................................49

Figure3.6 Mixing of NaOH and methanol and experimental transesterification

Figure 3.7: The production process of the biodiesel by transterification reaction…....................54

Figure 3.8 separation processes………………………………………………………………….55

School of chemical and Bio-Engineering Page viii

Figure 4.3 Normal plots of residuals…………………………………….…………….…………80

Figure 4.4 Residual vs. predicted values……………………………….……………….……… 81

Figure 4.5 The individual effect of ratio methanol to oil………………….……………………..82

Fig.4.6.Effect of catalyst concentration on the biodiesel Production………….……………….. 83

Figure 4.7 Effect of the reaction time on the biodiesel yield…………………………………….84

Figure 4.8.Effect of reaction temperature on biodiesel yield ………………………………….. 85

Figure 4.11 The FT-IR produced biodiesel process……………………………………………...88

School of chemical and Bio-Engineering Page ix

List of Tables Page