Henok Dagne

Optimization and characterization of biodiesel production from leather industry fleshing wastes
Addis Ababa University
Addis Ababa Institute of Technology
School of chemical and Bio-Engineering
Optimization and Characterization of Biodiesel Production from Leather

Industry Fleshing Wastes
A thesis submitted to the school of graduate studies of Addis Ababa Institute

of Technology in partial fulfillment for the Degree of Masters of Science in
Environmental Engineering
By: Henok Dagne
Advisor: Dr. Rajan Karthikeyan
Co-advisor: Dr. Sisay Feleke
Addis Ababa, Ethiopia
November, 2015
1
ADDIS ABABA UNIVERSITY
SCHOOL OF CHEMICAL AND BIOENGINEERING ENVIRONMENTAL

ENGINEERING STREAM
A thesis submitted to the school of chemical and Bioengineering,

Addis Ababa Institute of Technology in partial fulfillment for the
Degree of Masters of Science in Environmental Engineering
By
HENOK DAGNE
Approved by Board of Examiners
_________________ ________________
Head, School of Chemical and Signature Date
Bioengineering
Dr. Rajan Karthikeyan _________________ __________________
(advisor) Signature Date
Dr. Sisay Feleke _________________ __________________
(co-advisor) Signature Date
Dr-Ing. Belay Woldeyes _________________ __________________
(Internal examiner) Signature Date
Dr. Feleke Zewge _________________ ___________________
(External examiner) signature Date
2
ACKNOWLEDGEMENT
First of all I thank our Gracious and abundantly Merciful God for the grace bestowed on me for
from him and through him and to him are all things, to him be the glory forever who is with me
through my life and enabled me to pass all the ups and downs I came across.
Indeed the completion of this thesis represents the fulfillment of a hope that many people shared
with me. There are many individuals who have been instrumental in assisting me to accomplish
this thesis work.
I am indebted to my thesis advisor, Dr. Rajan Karthikeyan, Assistant professor and Chair person,
leather Technology program, school of Chemical and Bioengineering, Addis Ababa Institute of
Technology, Addis Ababa University for his enlightening guidance and corrections since the
inception of the writing of the thesis till its completion.
I would like to express my acknowledgement to Ethiopian Environment and Forest research

institute that helped me by covering my expenses for this research work.
My special gratitude shall go to my co advisor, Dr. Sisay Feleke, researcher at Ethiopian

environment and forest research institute, for the patience he showed at the time when I was not
able to finalize the laboratory work soon. Words cannot express how much I was privileged from
his day to day guidance and intellectual acumen during the entire thesis wok. Were it not for the
tireless advice and guidance from him, completion of the thesis would be a reality today.
I would like to extend my deepest acknowledgment for laboratory staffs at Addis Ababa institute
of technology, management of the Addis Ababa tannery factory S.C. and the staffs at Forest
Product Utilization Research Center.
Although too many to mention them by name, all my family members shall take the lion’s share
of the acknowledgment for unreserved support.
Finally, my deep rooted sense of honor shall go to all my friends especially for their best wishes,
encouragement and timely comments.
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ABSTRACT
Leather industry fleshing wastes have been currently recognized as potential feed stocks for
biodiesel production due to high fat content and less competition with food production.
Moreover, utilization of industrial wastes for energy production has additional environmental
protection purposes. This research work aims at optimization of process variables of biodiesel
production from limed leather fleshing waste. Wet limed leather fleshing wastes were delimed
using 1% boric acid, dried, chopped and subjected to Soxhlet extraction. The oil after
concentrated was treated by 2% w/w orthophosphoric acid and 3% w/w distilled water to
remove gums. The pretreated oil had acid value of 1.13 mg KOH /g of oil, FFA of 0.56 %. Since
the FFA was below 2.5% direct homogenous base catalyzed transesterification was conducted.
The conversion to biodiesel by potassium hydroxide-catalyzed transesterification was achieved
above 96% under optimum conditions: a methanol-to-oil molar ratio of 6:1, catalyst amount of 1
% w/w, reaction temperature of 60 °C for an hour reaction time. The produced FAME was found
2 3
to have viscosity of 5.99 mm /s density of 880 kg/m , cetane number of 68.5, iodine value
of 65.13g I2 /100g and HHV of 42.38 MJ/kg. The results showed that majority of the fuel
properties are within the ASTM and EN standards.
Keywords: Biodiesel, fleshing oil, homogenous catalysis, pretreatment, transesterification
4
Table of Contents
ACKNOWLEDGEMENT …………………………………………..…………………………….I
ABSTRACT ........................................................................................................................... …..II
TABLE OF CONTENTS …………………………………………………………………..…....III
LIST OF ABBREVIATION ………………………………………………………….…..…... VII
LIST OF FIGURES…………...……………………………………………………… …. .....VIII
LIST OF TABLES ……………………………………..………………………………….…... IX
1. INTRODUCTION..............................................................................................1
1.1. Background of the study ...................................................................................................... 1
1.2. Statement of the problem ..................................................................................................... 3
1.3. Objectives ............................................................................................................................ 5
1.4. Significance of the study..................................................................................................... 6
2. LITERATURE REVIEW ..................................................................................6

2.1. Introduction.......................................................................................................................... 6
2.2. Leather processing ............................................................................................................... 7
2.3. Characterization of leather fleshing wastes ....................................................................... 10
2.3.1. Water Content ............................................................................................................. 10
2.3.2. pH............................................................................................................................... 10
2.3.3. Fat content................................................................................................................... 11
2.3.4. Thermal Values ........................................................................................................... 11
2.4. Biodiesel production .......................................................................................................... 11
2.4.1. Pretreatment ................................................................................................................ 12
2.4.2. Transesterification...................................................................................................... 12
2.4.3. Catalysts for Biodiesel Production............................................................................. 14
5
2.5. Leather Industry Fleshing Waste a challenge and opportunity.......................................... 15

2.6. Correlation between chemical composition and physical properties of biodiesel ............. 15
2.6.1. Specific gravity ........................................................................................................... 16
2.6.2. Low-temperature operability ...................................................................................... 16
2.6.3. Oxidative stability....................................................................................................... 17
2.6.4. Kinematic viscosity..................................................................................................... 18
2.6.5. Flash point................................................................................................................... 19
2.6.6. Higher heating value (HHV)....................................................................................... 20
2.7. Limitations in biodiesel production from leather industry fleshing wastes ....................... 20
2.8. Factors affecting biodiesel production yield and quality................................................... 21
2.9. Advantages and Disadvantages of Biodiesel ..................................................................... 21
2.10. Food versus fuel ............................................................................................................. 22
3. MATERIALS AND METHODS........................................................................ 23

3.1. Experimental Setup and Descriptions ................................................................................ 23
3.2. Physico-chemical characterization of raw material ........................................................... 25
3.2.1. pH measurement ......................................................................................................... 25
3.2.2. Moisture content of the delimed fleshing waste ......................................................... 25
3.2.3. Ash content of limed fleshing waste and volatile organic content ............................. 25
3.2.4. Total fat content of delimed fleshings ........................................................................ 26
3.3. Physicochemical characterization of leather fleshing oil and biodiesel ............................ 26
3.3.1. Determination of specific gravity ............................................................................... 26
3.3.2. Determination of kinematic viscosity ......................................................................... 26
3.3.3. Acid value (Acid Number) determination .................................................................. 27
3.3.4. Saponification value determination ............................................................................ 27
3.3.5. Determination of iodine value .................................................................................... 29
3.3.6. Determination of high heat value................................................................................ 29

3.3.7. Determination of cetane number (CN) ....................................................................... 29
3.4. Quantification of leather fleshing oil fatty acids............................................................... 29
3.5. Experiments ....................................................................................................................... 30
3.5.1. Flesh Waste Treatment and Oil Extraction ................................................................. 30
3.5.2. Pretreatment of extracted oil ....................................................................................... 30
3.5.3. Transesterification...................................................................................................... 31
3.6. Experimental Design.......................................................................................................... 34
4. RESULT AND DISCUSSION ........................................................................35

4.1. Physical characterization of raw material .......................................................................... 35
4.2. Oil extraction and physicochemical characterization ........................................................ 36
4.2.1. Physicochemical Characteristics of the Fleshing and Pretreated Oil......................... 36
4.2.1.1 Density of the extracted oil ....................................................................................... 37
4.2.1.2. Kinematic viscosity of oil and biodiesel .................................................................. 38
4.2.1.3. Acid value of the oil................................................................................................. 41
4.2.1.4. Saponification value of the oils............................................................................... 43
4.2.1.5. Iodine values of oil and biodiesel ............................................................................ 46
4.2.1.6. HHV of the oils and biodiesel.................................................................................. 47
4.3. Biodiesel production and analysis of effects of parameters............................................... 47
4.3.1. Transesterification process......................................................................................... 47
4.3.2. Statistical analysis ....................................................................................................... 47
4.3.3. Optimum conditions................................................................................................... 53
4.3.4. Main factors affecting the yield of biodiesel .............................................................. 53
4.3.4.1. Effects of individual process variables on biodiesel yield....................................... 53
4.3.4.1.1. Effect of methanol-to-oil molar ratio .................................................................... 53
4.3.4.1.2. Effect of reaction temperature .............................................................................. 54
4.3.4.1.3. Effect of catalyst mass/concentration ................................................................... 56

4.3.4.2. Effects of interaction of process variables on percent yield of biodiesel ................ 56
4.3.4.2.1. Effect of methanol to oil molar ratio and temperature on Biodiesel yield............ 57
4.3.4.2.2. Effect of methanol to oil molar ratio and catalyst on Biodiesel yield .................. 59
4.3.4.2.3. Effect of temperature and catalyst mass on Biodiesel yield ................................. 61
4.4. Optimization of process variables...................................................................................... 63
4.5. Gas chromatograph-Mass spectroscopy analysis of the produced biodiesel ..................... 64
4.6. Physicochemical properties of the FAME from goat fleshing oil ..................................... 68
4.6.1. Density of the FAME of the goat fleshing oil............................................................ 68
4.6.2. Kinematic viscosity of the FAME of the goat fleshing oil ......................................... 68
4.6.3. Acid value of the FAME of the goat fleshing oil....................................................... 69
4.6.4. Moisture and ash contents of the FAME of the goat fleshing oil ............................... 69
4.6.5. Iodine value of the FAME of the goat fleshing oil ..................................................... 69
4.6.6. Cetane number of the FAME of the goat fleshing oil................................................. 69
4.6.7. Higher heat value of the FAME of the goat fleshing oil............................................ 70
4.7. Comparison of the biodiesel properties with ASTM and EN Standards ........................... 70
5. CONCLUSION AND RECOMMENDATION ................................................. 71

5.1. Conclusion ......................................................................................................................... 71
5.2. Recommendation ............................................................................................................... 72
REFERENCE .......................................................................................................... 73
ANNEX................................................................................................................... 78
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List of acronyms and abbreviations

ASTM American standard for testing materials
CFPP Cold filter plugging point
EGR Exhaust gas recirculation
EN European Norm
EPA Environmental protection authority
FAAE Fatty acid alkyl ester
FAME Fatty acid methyl ester
FFA Free fatty acid
GCC Global climate change
GC-MS Gas chromatograph- mass spectroscopy
GDP Gross domestic productivity
LIDI Leather industry development institute
OSI Oxidative stability index
PUFA Poly unsaturated fatty acid
SFA Saturated fatty acid
TAG Triacyl glycerol
USFA Unsaturated fatty acid
WAF Waste animal fat
WCO Waste cooking oil
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Optimization and characterization of biodiesel production from leather industry fleshing wa
stes
List of figures
Figure 2.1 Sequential transesterification reaction
Figure 3.1 Preparation of waste and extraction of oil
Figure 3.2 Separation of oil and extractive
Figure 3.3 Removing gum from the crude oil
Figure 3.4 Separation of FAME from glycerol
Figure 4.1 Oil density measurement using hydrometer
Figure 4.2 Density of the sheep, goat and hide oils before and after Degumming
Figure 4.3 Determination of kinematic viscosity using viscometer
Figure 4.4 Effect of temperature on kinematic viscosity of degummed goat fleshing oil
40
Figure 4.5 effect of temperature on kinematic viscosity of goat fleshing biodiesel
Figure 4.6 Acid values of oils before and after degumming treatment
Figure 4.7 Effect of degumming on saponification value of the oils
Figure 4.8 plot of actual versus predicted percentage yield of biodesiel
Figure 4.9 Normal probability plot of residuals
Figure 4.10 Index plots of internally studentized reseduals
Figure 4.11 Effect of methanol to oil molar ratio on percentage yield of biodiesel
Figure 4.12 Effects of temperature on percentage yield of biodiesel
Figure 4.13 Effect of catalyst concentration on percentage yield of biodiesel
Figure 4.14 the effect of methanol to oil molar ratio and temperature on FAME 58
percentage
yield
60
Figure 4.15 the effect of methanol to oil molar ratio and catalyst mass on FAME
percentage
yield
Figure 4.16 The effect of temperature and catalyst mass on FAME percentage yield
Figure 4.17 Optimization of process variables for maximum conversion of oil to FAME
63
Figure 4.18 Desirability of the experimental process variables
Figure 4.19 Goat fleshing FAME chromatogram
Figure 4.20 Hide fleshing FAME chromatogram
Figure 4.21 Sheep fleshing FAME chromatogram
Figure 4.22 Density of goat leather fleshing biodiesel at different temperature
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Optimization and characterization of biodiesel production from leather industry fleshing wast
es
List of tables
Table 3.1 Independent variables used for CCD in transesterification process 3

Table 3.2 CCD experimental design matrix of transesterification reaction 3
Table 4.1 Physical parameters of liming and Delimed Fleshing wastes 3
Table 4.2 Physicochemical characterization of untreated and treated fleshing oil 3
Table 4.3 Kinematic viscosity of degummed goat leather fleshing oil at different 39
temperature
Table 4.4 kinematic viscosity of goat fleshing biodiesel at different temperature 4
Table 4.5 Acid value of goat fleshing crude oil 4
Table 4.6 Acid value of degummed goat fleshing oil 4
Table 4.7 Acid value of sheep fleshing crude oil 4
Table 4.8 Acid value of degummed sheep fleshing oil 4
Table 4.9 Acid value of crude hide fleshing oil 4
Table 4.10 acid value of degummed hide fleshing oil 4
Table 4.11 Saponification value of crude goat fleshing oil 4
Table 4.12 Saponification value of degummed goat fleshing oil 4
Table 4.13 Saponification value of crude sheep fleshing oil 4
Table 4.14 Saponification value of degummed sheep fleshing oil 4
Table 4.15 Saponification value of crude hide fleshing oil 4
Table 4.16 Saponification value of degummed hide fleshing oil 4
Table 4.17 Actual and predicted value of biodiesel yield 4
Table 4.18 Analysis of variance (ANOVA) table for response surface quadratic model 4
Table 4.19 Adjusted versus predicted R squared 5
Table 4.20 Optimization of process variables 6
Table 4.21 Comparison of experimental biodiesel with standards 7
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1. INTRODUCTION
1.1. Background of the study
The human society, with its expansion and high technological development, is highly dependent
on petroleum fuel for energy generation. However, fossil fuels are non-renewable resources,
which take millions of years to form up and remained with limited reserves and high price.
Around 60 % of world’s oil consumption and one-fifth of global CO2 emissions are related to
transportation sector [1].
The demand for diesel fuel is constantly increasing, requiring its alternate that could be
sustainable, technically feasible, price competitive and ecologically acceptable. Politico-
environmental situations, emission of huge amounts of greenhouse gases, health problems,
economic concerns, cost effectiveness as well as predicted shortage of conventional fuels forced
in the exploration of alternative fuel to drive diesel engines.
The production and use of fossil fuel in engines with internal combustion causes environmental
problems such as rising carbon dioxide levels in the atmosphere and in Global Climate Change
(GCC).This decline of conventional fossil fuel reserve, growing emissions of combustion
generated pollutants, and their increasing costs make biomass sources more attractive in
the recent years to substitute the dependency on fossil fuel. Biofuel as a renewable an alternate
and ecologically acceptable substitute for the conventional fuels, biodiesel has attracted
concerned environmentalists and governments all over the world. Beside many advantages of
biodiesel over diesel fuel, such as: renewability, ready availability, portability, lower sulfur and
aromatic content, higher efficiency, higher cetane number, better emission profile and safer
handling [2].
The high cost of biodiesel production is the main reason for its limited commercial application.
The price of raw material consists of about 70–95% of the total biodiesel cost [2]. Since
biodiesel production from food-grade oils is not ethically acceptable and economically
competitive with petroleum-based diesel fuel. Therefore, it is necessary to use look for novel and
low cost oil feed stocks for its production. The use of cheap waste cooking oils (WCOs), waste
oil by-products from edible-oil refinery, non-edible oils and waste animal fats (WAFs) can be
used as low cost source in the production of sustainable and ecologically acceptable product.
12
One of these biomass sources would be the leather industry fleshing waste. The leather fleshing
waste generated from the tanneries always triggers secondary, and tertiary environmental
impacts such as ground water contamination, greenhouse gas emission effects and odor
problem.
The capacity of world leather process is around 15 million tons of hides and skins per year. Solid
waste generation from tannery process is estimated over 6 million tons/year. The disposal of
large quantity of sludge which is about 4.5 million tons from effluent treatment plants is one of
the major environmental pollution issues [3].
Leather industry plays a major role in creating employment opportunity and contributing for
national GDP in developing countries like Ethiopia. Ethiopia is relatively well endowed in its
livestock base with a share of 12, 15 and 22 percent of the world cattle, sheep and goats
population respectively. This makes the country one of the most promising leather producing
economic center in Africa. Ethiopia's livestock population is estimated at 52 million Cattle
rd
ranking 1st in Africa, 27 million Sheep population which makes 3 in Africa and 23 million
rd
Goat population which makes 3 in Africa (LIDI, 2014).
The country owns around twenty-nine tanneries with varying processing capacity, the smallest
having a soaking capacity of 3000 skins per day. According to the Ethiopian Leather Industry
Development Institute (LIDI), the 29 tanneries are processing and producing about 46451520
square meters of finished leather. About 48% of the existing tanneries in Ethiopia are operating
at Modjo area. Moreover, the government plan to setup the Modjo Leather City (MLC) at Modjo
area makes a necessity to setup a glue and edible grade gelatin plant in order to reduce the impact
of leather waste on the environment, since it generates huge amount solid waste.
The Ethiopian leather industries account for about 67% of the total manufactured exports as
depicted in the Ethiopian Federal Environmental Protection Authority, Environmental Impact
Assessment Guideline for Tanneries (EPA, 2007).
Although the leather industry contributes to the national economic growth, it has also negative
environmental impacts by generating organic and inorganic pollutants. The wastes generated by
these industries are solid, liquid and gaseous that poses a major challenge to the environment and
the ecosystem. The solid wastes that are generated in the leather industries are originated
13
from the pre-tanning stages. These wastes are mainly originated from pre-fleshing, fleshing,
shaving and trimming. These solid wastes have high amount of fat contents that can be used in
the production of bio-energy such as biodiesel. Fleshing waste has considerable amounts of
fatty acid composition as compared to the other vegetable oil fatty acid compositions.
However, these wastes are not changed in to value added products. One way to recover the
leather industry wastes is using them as feedstock in biodiesel production due to their rich
fat content [4]. Consequently, the pollution coming from the leather industry wastes can be
reduced dramatically and more value added products can be obtained by converting them to
biodiesel.
Essentially, biodiesel is non-aromatic and sulfur-free as compared with petro diesel which
contains 20 to 40 wt.% aromatic compounds and 500 ppm SO2 [5]. Biodiesel release around 50%
less smog smoke density decreased by 22.5 %, the release of CO to 17 % and CO2 to 14 %
reduced as compared to fossil fuel emission[6].
Currently, the production of oil directly from the agricultural industry has the greatest potential
for the production of biodiesel. However, producing biodiesel from virgin oil is not
commercially feasible to satisfy the need of the transportation due to the cost and dilemma of
food or energy.
On the other side, there are potential sources in oil and leather industry wastes for the
production of biodiesel. Producing biodiesel from these wastes has a dual purpose by reducing
environmental pollution and value added products.
Different researchers have investigated the potential of animal fats and waste oils for biodiesel
production [4, 7, 8]. Therefore, the purpose of the present study was to optimize parameters
for biodiesel production from low cost goat fleshing oil feed stock through performing
extensive experiments on the oil extraction, hydrolysis and trans esterification reactions
throughout the production process.
1.2. Statement of the problem
Since the mid of 19th century when fossil fuel came into exploration for energy generation, the
st
need for more energy and fossil reserve depletion in the 21 century forced to the search of new
14
energy sources. In 2012, the global petroleum consumption was estimated as 89 million barrels
per day from which about a half was used for gasoline production. At this rate of consumption,
the oil resources are predicted to run out within the next 50 years[9]. The price fluctuation and
reserve depletion of fossil fuel, rejuvenate the use of biomass as energy source of material. These
biomass resources are either generated from plant or animals.
Thermo-chemical-based biodiesel obtained from wastes can reduce carbon release by 90 %

compared to the 75 % reduction offered by usual biodiesel [10].
Although tannery industry is built upon the waste from slaughter house and can be considered as
one method of waste management and contribute to the national GDP but the solid, liquid and
gaseous wastes produced from tannery are posing serous human health and environmental
problems. These days waste is not something to be disposed off or kept out of sight. There is a
search for use, reuse and recycling of wastes and changing waste to wealth via tireless research
efforts. Production of biodiesel from leather industry fleshing wastes is therefore one of these
attempts.
Ethiopia imports petroleum with foreign currency which is earned from agricultural products.
The demand for petroleum fuel is rising rapidly due to the growing economy and increasing
infrastructures. Import of fuel grows annually by 26.6 percent and reached USD 1.7 billion. The
share of fuel import in total imports of goods was 16 percent and 20.1 percent in the years
2009/10 and 2010/11 respectively (Annual report of National Bank of Ethiopia, 2010/11).
During the fiscal year 2012/13, a total of about 2.2 million metric tons of petroleum products
worth Birr 38.7 billion were imported. The total value of imports was increased by 5.5 percent as
compared to the performance in fiscal year 2011/12 (Annual report of National Bank of Ethiopia
2012/13).
Having high capacity of animal population and thereby huge potential of tannery work which
will produce vast amount of fleshing waste which has high potential for biodiesel production,
undertaking research to manage the waste and producing value added products is crucial.
Usage of expensive substrates for biodiesel production keeps the cost higher. Low-cost feedstock
such as waste animal fat can make economically viable the production of biodiesel [11].
Although animal-derived fats have gained considerable attention across the world for the
15
production of biodiesel, sufficient studies have not been conducted in Ethiopia to attract leather
sector towards biofuel generation. This study aims to provide valuable information concerning
biodiesel production using low-cost, leather industry byproducts.
Management of industrial wastes is top priority agenda for developing countries like Ethiopia.
The primary issue being waste minimization through conversion to valuable products, therefore,
this research will focus on conversion of leather industries waste to biodiesel as an extra source
of biodiesel for the country.
The conversion of low quality residual animal fats into commercial grade biodiesel could help to
reduce environmental contamination besides contributing to overcome the fuel crisis [12].
Since many researchers have developed conceptual frame work on biodiesel production from
waste animal fat, this research, aimed at optimization of parameters for biodiesel production
from leather fleshing wastes specifically on goat fleshing oil.
1.3. Objectives
1.3.1. General objective
 Optimization of biodiesel production from leather industry fleshing wastes using

homogenous base catalyzed method and characterization of the oil and biodiesel.
1.3.2. Specific objectives
i. To undertake physical characterization of the leather fleshing waste.

ii. To determine the crude oil yield from the leather industry fleshing wastes.
iii. To undertake physicochemical and compositional analysis for the extracted oil
iv. To define optimum conditions/ parameters / i.e. Alcohol to oil ratio, catalyst
concentration and reaction temperature for maximum conversion using response
surface composite central design.
v. To determine the fuel physicochemical properties such as acid value,
saponification number, density, kinematic viscosity, cetane number, heating
value, cloud point, iodine value of the biodiesel.
16
1.4. Significance of the study

There is strong scientific evidence that the average temperature of the earth’s surface is rising, it
is attributed to the increased concentration of carbon dioxide (CO2), and other greenhouse gases
(GHGs) in the atmosphere released by burning fossil fuels [13, 14]. This global warming will
eventually lead to substantial changes in the world’s climate, which will, in turn, have a major
impact on human life and the environment. Reduction of GHG release to the atmosphere can be
achieved by minimizing the energy demand, by rational energy use, use of efficient technologies,
by recovering heat and the use of more green energies. This study is a step towards achieving
this goal.
The growing environmental concerns due to increasing carbon dioxide emissions, global
warming, declining petroleum reserves and rising crude oil prices have resulted in worldwide
attention to biodiesel. With growing human population, more land is needed to produce food for
human consumption, which poses a potential challenge to biodiesel production. Leather industry
fleshing waste could way-out of feedstock for biodiesel production.
This study will enable to know the optimum operating conditions for biodiesel production from
leather industry fleshing wastes and fill the gap in solid waste management with in leather
production factories. The significance goes far beyond waste minimization to energy production.
Furthermore the study will serve as a reference material for researchers, academicians, policy
makers, leather industry owners and managers in the management of fleshing wastes. Since
conversion of waste to energy technology is not common in developing countries including
Ethiopia the study will contribute to fill the gap in this regard.
2. LITERATURE REVIEW
2.1. Introduction
Biodiesel, a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable
oils, animal fat, and mixtures thereof, is produced by transesterification, with glycerol which has
17
many uses being produced as a byproduct. Due to the reserve depletion and increasing price of
petroleum together with environment pollution caused by the combustion of fossil fuels,
the search for alternative fuels has gained much attention [15]. Biodiesel (fatty acids
methyl ester, FAME) can be derived from the trans esterification of triglycerides (the main
component of vegetable oils or animal fats) with a short chain alcohol (mainly methanol). It
has become popular as a possible alternative to fossil fuels. The main advantages of this fuel are
renewability, cleanness and that its properties and performance are similar to conventional diesel
fuels [16].
2.2. Leather processing
Producing different types of leather requires different types of processes and chemical usage.
Consequently, leather wastes generated from each type of leather and process have different
characteristics. For the utilization of these wastes in various fields, having more specific
information about their characteristics has great importance. It is possible to divide leather
processing into four main stages. It is known that processing 1 ton of wet salted hide yields only
200-250 kg leather and 25% of becomes chrome leather waste, and remainder becomes non
tanned waste or is lost in waste water as fat soluble protein and solid suspended pollutants [17].
In order to reduce the environmental impact of leather processing, it is necessary to find a
solution for the solid and liquid wastes generated from the industry. Raw hide Trimmings, Green
Fleshings, Limed Fleshings and Trimmings are the most important non tanned wastes generated
during pretanning operations. These wastes are the good source of raw material for the
production of biodiesel.
2.2.1. Beam house processes:
The conserved hides are first subjected to a trimming process for removing the unwanted
parts, and then they are soaked to restore the lost water and to remove substances like dirt,
blood and conservation salt. After the wetted hides are fleshed they are treated with an intense
alkali solution of lime (Ca (OH) 2) and sodium sulfide (Na2S) to ensure hair and wool removal
(unhairing process). Later the hides are swelled up in liming process by immersing them in a
strong alkaline bath so as to open up the collagen structure. The hides may be treated with
18
a second fleshing process after liming in order to clean the flesh. At this stage, hides are treated
with splitting Process and split into two or three layers.
Through bating process, hides are exposed to an enzymatic effect for both opening up the
structures, and the removal of unwanted proteins from the hide. Following the bating process, a
degreasing process is applied to hides for removing the excess natural fat in their structure and
providing a homogeneous distribution of the fat in it.
Raw Trimmings
Trimming is one of the primary operations in a tannery, which involves removal of neck, leg,
and tail pieces from hides/skins to provide a shape to the final leather. The quantities of
trimmings are estimated to be around 8-10% (on raw weight) depending on the nature of the
animal. The raw trimmings are the good source of raw material for the production of edible
grade gelatin for human consumption.
Green fleshing
In some tanneries, the raw hides undergo fleshing operation yielding green fleshing and fatty
tissues. This operation is carried out before washing and soaking. The yield of green fleshing is
estimated to be 10% on the weight of the raw hide. Since these fleshing are not contaminated
with chemicals they are suitable for the production of gelatin for human consumption.
Limed Fleshing
Limed fleshing is obtained while scraping out the limed hides and skins either by hand or by
fleshing machines. The fleshing are proteinaceous in nature comprising cutaneous muscle layers
and sub cutaneous adhering tissues which are not required in the subsequent operations of leather
manufacture. The availability of limed fleshing is 35% on the wet weight of the raw hides (70%
moisture). The limed fleshing can be utilized for the production of glue.
Limed Trimmings
After the fleshing operation, the hides, skins and sides are trimmed in order to remove the ragged
and torn edges. These trimmings are proteinaceous in nature and found to be good raw material
for glue. The limed trimmings are 2-7% on the wet weight of the hides.
19
2.2.2. Tanning Processes:

The hides at this stage are first treated with pickle process in a solution composed of salt and
acids so as to obtain a homogeneous distribution of tanning materials through the cut. After the
hides are conditioned as above, the tanning process is applied with various tanning materials
(materials able to form stable bonds with collagen) in order to provide the leather with a stable
form and high thermal stability. Tanning materials such as vegetable tannins, mineral tanning
materials and syntans (synthetic organic tanning materials) are used in tannage. Among mineral
tanning materials, chrome is the most widely used in leather production due to its unique features
that it gives to the leather. Aluminum and vegetable tanning materials are also widely used in
leather production. Before the leathers are treated with further processes, the setting out and
samming process is applied, and shaving is done to obtain the desired thickness of the leather.
2.2.3. Post-Tanning Processes:
The next step for the leathers, which are tanned and standardized to a desired thickness, is re-
tanning process with various retanning agents improving the requested characteristics of
products. In this process, the structural differences within leathers are compensated to obtain
uniform structure. The Fat liquoring process is applied by using a combination of various fat
liquoring agents in order to allow the leather to be more supple and softer. In the dyeing
process leathers are dyed to the desired color. After this stage, leathers are hanged and dried, and
they are prepared for the finishing process through certain mechanical operations. The unwanted
parts are trimmed and removed.
2.2.4. Finishing Processes:
After the leathers are fat liquored and dyed following the tanning process, they are processed
with a series of coatings on the surface in order to improve their resistance and produce
appealing and uniform surface effects. After this process, leathers are trimmed for a final form
and sent to confection. Solid wastes generated by the leather industry in these stages of processes
may be classified as follows.
i. wastes from untanned hides/skins (trimmings, fleshing wastes)

ii. Wastes from tanned leather (shaving wastes, buffing dust)
20
iii. Wastes from dyed and finished leather (trimmings from leather)
Data obtained from research reveals that 80% of solid wastes are generated during pre-
tanning
processes, while 20% of the wastes are caused by post-tanning processes[18].
2.3. Characterization of leather fleshing wastes
The variety and quantity of solid wastes depends on animal species, breeding conditions
,
slaughterhouse practices, conservation conditions, leather process stages, mechanical operations
,
Type of limed % Water pH Fats & oils Nitrogen % Salt % SO2 Calorific
fleshing waste content % (ppm) value
Kcal/kg
Sheep 61.65 12.5 53 13.1 1.77 439 4852
Goat 83.72 10.06 25 25 0.87 243 4916
Hide lime 57.13 12.5 6.5 25 2.84 65 5450
qualification of the personnel, and chemicals used in processes. Yet this fact causes uncertainties
in reusing the generated wastes. First of all, solid wastes should be characterized so that they ca
n
be reused.
2.3.1. Water Content
Water content of solid wastes differs to a great extent in accordance with how and where the
y
are collected, storage conditions, and climate. Due to the fact that fleshing wastes are generate
d
during leather process steps called beam house processes, in which leathers are processed i
n
watery environments where fleshing wastes have higher amounts of water.
2.3.2. pH
The pH of the fleshing wastes show similarities in parallel with the process stages disclosing th
Tablee 2.1.Mean values of some characteristics of limed leather fleshing wastes.
pH values of solid wastes, and the pH values at which these processes are carried out; and i
t
was found that liming fleshing waste has the highest pH value, since the liming process is don
e
21
(Adapted
at around from, Ozgunay
pH 11-12. [19])to protect the current ecosystem, wastes should be subjected to a
In order
neutralization process before they are disposed to the environment.
2.3.3. Fat content
According to Bienkiewiczk [20] fat content varies between 0.5% and 4% in cattle and horse
hides, 3% and 30% in sheep skin, 4% and 40% in pig skin, and 3% and 10% in goat skin over
dry weights. Another fat source in solid wastes is the natural or synthetic fats used in the
fat liquoring process in order to provide the leather with features like softness, elasticity and
resistance, and to allow the leather fibers to slide easily over one another depending on the
leather type and purpose of use. The fat content of leathers consists of the remaining natural fat
after degreasing process, and the fat used in fat liquoring process. Due to this reason, different fat
proportions may be detected in leather wastes. Pre-fleshing and lime fleshing wastes from the
processes before degreasing include higher amounts of fat compared to other waste samples (40-
70%). In addition, it should be kept in mind that wastes were generated at the end of the fleshing
process that was applied to remove the hypodermis layer of the hide, which is the layer including
the highest amount of fat. It should also be taken into consideration that flesh and fat layers left
on hides may differ greatly, depending on slaughter and flaying techniques, which in turn
directly affects the fat amount in waste.
The fat obtained from lime fleshing waste is generally regarded to be of low quality due to its
dirty color and bad smell resulting from sulfide contact.
2.3.4. Thermal Values
Due to their high content of fat, fleshing wastes with an average of 5872 kcal/kg thermal value
have higher thermal values than that of other wastes with an average of 4493 kcal/kg [19].
Thermal treatment of leather scrap must be justified not only by its high calorific value, but by
taking into account as much as possible of the consequences of it, namely (i) pollutants and their
levels in the released gasses; (ii) characteristics of the ashes and factors that influence
changes in the chromium oxidation state during the burning process as well as in some of the
further ash treatment options [21].
2.4. Biodiesel production
22
2.4.1. Pretreatment
The high FFA acid content of the waste animal fat renders it inadequate for the most traditional
direct one-step base-catalyzed transesterification process to biodiesel due to soap formation.
However, an indirect multistep process allows the use of these feed stocks with high FFA
concentrations by first carrying out an acid-catalyzed esterification of the FFA before the base-
catalyzed triglyceride trans esterification.
Moreover, the low quality of the animal fat used as feedstock as source of energy influenced
with problems like higher nitrogen and sulfur contents of the animal fat indicate that still some
protein and phosphoglycerides (usually called gums) remain in the feedstock; the
phosphoglycerides are essential constituents of the animal cell membranes and they concentrate
in the lipids fraction. For this reason, a degumming process to eliminate the phosphoglycerides
has been proposed as the first step of this multistep process.
The esterification of the FFA was carried out at different temperatures, catalyst concentration
and alcohol to oil molar ratio with stirring (750 rpm) for a period of one hour. Among the acids
of choice to catalyze this esterification of the FFA, concentrated hydrochloric acid (ca.35 wt. %)
would introduce an undesirable amount of water in the reaction.
2.4.2. Transesterification
There are usually three main steps for biodiesel production from waste oils including
pretreatment, transesterification, and separation processes. Some types of oil usually needs
pretreatments to reduce the viscosity and the content of water and free fatty acids (FFAs) which
can influence trans esterification process negatively [22]. Even by carrying out a pretreatment on
used oil, it is still more economical and can reduce the direct production costs in comparison
with pure oils [23].
Transesterification is an equilibrium reaction which takes place in three consecutive steps.

It is usually affected by variables such as molar ratio, temperature, catalyst type and catalyst
amount, reaction time etc. [24]
Pretreatment is the first step in biodiesel production from waste oils in order to remove the
impurities and solid particles or decrease the water content and acidity value [25]. The required
23
pretreatments in most cases are filtration and heating; however, pretreatments such as steam
injection, neutralization, vacuum evaporation, degumming, esterification and vacuum filtration
can be applied as well.
In the second step, transesterification reaction should be performed in which glycerides are
converted into esters in the presence of a catalyst and an alcohol. However, in this step, using
non-catalytic conversion techniques are also possible. In fact, each mole of lipid reacts with two
or three moles alcohol to produces the respective alkyl esters (biodiesel) and a mole glycerol
[26].There are three basic chemical processes used to produce biodiesel from oils and fats
industrially; base catalyzed trans esterification of the oil with alcohol usually methanol, direct
acid catalyzed esterification of the oil with methanol or conversion of the oil to fatty acids (acid
pretreatment) and then to alkyl esters with acid catalysis.
Generally biodiesel is generated through transesterification of animal fats, which can be

classified into catalyzed (using various chemical catalysts), enzymatic methods and non-
catalyzed (supercritical alcohol conditions) reactions. The fats/oils are chemically esterified with
an alcohol such as methanol or biochemically with an enzyme [27]. Based on the reaction state
esterification process categorized into homogenous, heterogeneous, enzymatic and non-catalyzed
systems [28]. One-step and two-step trans esterification reactions are applied to feedstock with
low and high acid numbers, respectively [29].
Homogeneous reactions generally involve alcohol: fat molar ratio of 6:1, catalyst concentration
of about 1% and reaction temperature of 60 °C for 1 h. Sulfuric acid constitutes the most
commonly used acid catalyst whereas both KOH and NaOH are typically used as base catalysts
for homogeneous transesterification[29]. Heterogeneous transesterification involves
comparatively high catalyst concentration and reaction temperature with longer reaction time
than its homogeneous equivalent.
Regardless of being a time-consuming procedure, enzymatic transesterification can be

conveniently used for the processing of feedstock having high acid number without acid pre-
treatment. Supercritical transesterification is considered as economically prejudicial due to
involvement of extremely high temperature and pressure conditions. Although both
homogeneous as well as heterogeneous transesterification methods are currently being applied
24
for the successful conversion of animal fats into biodiesel, introduction of novel techniques using
ultrasonic irradiation, microwaves, enzymes and radiofrequency heating will further extend the
global biodiesel production from animal-derived byproducts.
In general, depending on the presence of the catalyst in the process, there are two methods of
transesterification of TAGs into biodiesel: catalyzed and non-catalyzed. According to the type of
catalyst employed, the reactions can be classified into three groups: homogeneously-,
heterogeneously- and enzymatically catalyzed. The transesterification reactions are
conventionally performed using homogeneous base or acid catalysts. Different groups of
heterogeneous catalysts such as: metallic, solid bases, solid acids and natural catalysts can be
also applied for efficiently converting oil or fat to ester [30].
2.4.3. Catalysts for Biodiesel Production

Biodiesel is produced commercially using homogenous basic catalysts such as sodium or
potassium hydroxide or methoxide because the trans esterification reaction is generally faster,
less expensive, and more complete with these materials than with acid catalysts[31].
The biodiesel industry currently uses sodium methoxide, since methoxide cannot form water
upon reaction with alcohol such as with hydroxides. Other alkoxides, such as calcium ethoxide,
have also effectively catalyzed the biodiesel production, albeit with higher methanol and catalyst
requirements [32]. Furthermore, base-catalyzed reactions are performed at generally lower
temperatures, pressures, and reaction times and are less corrosive to industrial equipment than
acid-catalyzed methods. Therefore, fewer capital and operating costs are incurred by biodiesel
production facilities in the case of the base-catalyzed transesterification method [16].
However, the homogenous acid-catalyzed reaction holds an important advantage over the base-
catalyzed method in that the performance of acid catalysts is not adversely influenced by the
presence of FFA. A wide range of catalysts may be used for biodiesel production, such as
homogenous and heterogeneous acids and bases, sugars, lipases, ion exchange resins, zeolites,
and other heterogeneous materials.
In general, acids are more appropriate for feed stocks with high FFA content. Homogenously
catalyzed reactions generally require less alcohol, shorter reaction times, and more complicated
purification procedures than heterogeneously catalyzed transesterification reactions.
25
Heterogeneous lipases are generally not tolerant of methanol, so production of ethyl or higher
esters is more common with enzymatic methods.
Feedstock quality dictates the catalyst media or process is needed to produce FAAE that satisfies
relevant biodiesel fuel standards such as ASTM D6751 or EN14214. If the feedstock contains a
significant percentage of FFA (>3 wt.%), typical homogenous base catalysts such as sodium or
potassium hydroxide or methoxide will not be effective as a result of an unwanted side reaction
in which the catalyst will react with FFA to form unreacted TAG, soap, DAG, MAG, biodiesel,
glycerol, water, and/or methanol [33].
2.5. Leather Industry Fleshing Waste a challenge and opportunity
Solid wastes created from leather industry, constitutes about 56-60% of the pre-tanned solid
wastes [34]. Disposal of leather industry fleshing wastes to the environment may harbor
pathogenic microorganisms resulting in environmental pollution and health risks. Therefore,
especial attention is given to these wastes on handling and converting to value added materials.
Leather industry which plays a crucial role in the country’s economy, contributes to
environmental pollution by dumping the solid wastes into the land and the water bodies.
Even though disposal methods such as landfill disposal, thermal incineration and anaerobic
digestion are available, they again contribute to pollution and cause additional economic
burden to the tanners.
One way to recover the leather industry wastes is using them as feedstock in biodiesel
production due to their rich fat content [7]. Consequently, the pollution coming from the leather
industry wastes can be reduced dramatically and more value added products can be obtained by
converting them to biodiesel.
2.6. Correlation between chemical composition and physical properties of

biodiesel
The fatty ester composition, along with the presence of contaminants and minor components,
dictates the fuel properties of biodiesel fuel. Because each feedstock has a unique chemical
composition; biodiesel produced from different feed stocks will in turn have different fuel
properties. Important properties of biodiesel that are directly influenced by fatty ester
26
composition and the presence of contaminants and minor components include low-temperature
operability, oxidative and storage stability, kinematic viscosity, exhaust emissions, cetane
number, and energy content. In the context of biodiesel, minor components are defined as
naturally occurring species found in vegetable oils and animal fats and may include tocopherols,
phospholipids, steryl glucosides (also called sterol glucosides, steryl glycosides, sterol
glycosides, or phytosterols), chlorophyll, fat soluble vitamins, and hydrocarbons (such as
alkanes, squalene, carotenes, and polycyclic aromatic hydrocarbons). Contaminants are defined
as incomplete or unwanted reaction products, such as free fatty acid, soaps, triacyl glycerol,
diacyl glycerol, monoacyl glycerol, alcohol, catalyst, glycerol, metals, and water.
2.6.1. Specific gravity

Density is a key fuel property, which directly affects the fuel performance, as some of the engine
properties, such as cetane number, heating value and viscosity of biodiesel. The density of the
fuel also affects the quality of atomization and amount of fuel injected into the combustion
chamber and thus, the air-fuel ratio. This is because fuel injection pumps meter fuel by volume
not by mass and a denser fuel contains a greater mass in the same volume. Densities of biodiesel
fuels are generally higher than those of petro diesel and are dependent on fatty acid composition
and purity. Since density is strongly influenced by temperature, the quality standards state the
determination of density at 15°C. Density limits in the European EN norm are in the range of
860-900 kg/m³. Contamination of the biodiesel significantly affects its density; therefore, density
can also be an indicator of contamination in the fuel. Experimental data showed that biodiesel
density decreased with increasing unsaturation levels of FAMEs [35].
2.6.2. Low-temperature operability

Low-temperature operability is normally determined by three common parameters: cloud point,
pour point, and cold filter plugging point (CFPP).
The cloud point (CP) is defined as the temperature at which crystal growth is large enough
(diameter≥0.5μm) to be visible to naked eye. At temperatures below the CP, larger crystals fuse
together and form agglomerations that eventually become extensive enough to prevent pouring
of the fluid.
27
The lowest temperature at which the fluid will pour is defined as the pour point (PP). The CFPP
is defined as the lowest temperature at which a given volume of biodiesel completely flows
under vacuum through a wire mesh filter screen within 60 s. The CFPP is generally considered to
be a more reliable indicator of low-temperature operability than CP or PP, since the fuel will
contain solids of sufficient size to render the engine inoperable due to fuel filter plugging once
the CFPP is reached. It should be noted that it is inappropriate to measure CP, PP, and CFPP of
chemically pure compounds (pure methyl oleate, for instance). Instead, determination of melting
point (MP) as a means to measure low-temperature operability is appropriate for chemically pure
compounds. The CP, PP, CFPP, and LTFT attempt to quantify low-temperature behavior of
complex mixtures (such as biodiesel) that are composed of constituents that generally exhibit a
relatively wide range of melting point.
The low-temperature behavior of chemical compounds is dictated by molecular structure.

Structural features such as chain length, degree of unsaturation, orientation of double bonds, and
type of ester head group strongly influence MP of individual chemical constituents of biodiesel.
As the chain length of saturated fatty acid alkyl ester (FAAE) increases, a corresponding increase
in melting point is observed. With respect to unsaturation, compounds of similar chain length but
increasing levels of unsaturation display lower melting point.
The orientation of the double bond(s) is another important factor influencing melting point.
Nearly all naturally occurring unsaturated fatty acids contain cis-oriented double bond. However,
trans isomers may be chemically introduced through catalytic partial hydrogenation. Constituents
that contain trans double bonds generally exhibit higher melting point than the corresponding
cis- isomers.
With respect to ester head group, the melting point of FAEE is generally lower with larger alkyl
head groups up to about eight carbons.
2.6.3. Oxidative stability

Oxidative stability of biodiesel is determined through measurement of the oil stability index
(OSI) by the Rancimat method (EN 14112). The Rancimat method indirectly measures oxidation
by monitoring the gradual change in conductivity of a solution of water caused by volatile
oxidative degradation products that have been transported via a stream of air (10 L/h) from the
28
vessel (at 110°C) containing the biodiesel sample. The OSI is mathematically determined as the
inflection point of a computer-generated plot of conductivity (μS/cm) of distilled water versus
time (h). The units for OSI are normally expressed in hours. Biodiesel fuels with longer OSI
times are more stable to oxidation than samples with shorter values.
Oxidation initiates in the case of lipids at methylene carbons allylic to sites of unsaturation [36].
Autoxidation of lipids, including biodiesel, produces free radicals through hydrogen abstraction
in the presence of various initiators such as light, heat, peroxides, hydro peroxides, and transition
metals. These free radicals further react exothermically with molecular oxygen to produce
peroxides, which react with un oxidized lipids to produce additional free radicals [36]. Generally,
the rate-limiting step in the autoxidation of lipids is initial hydrogen abstraction. The rate of
autoxidation is dependent on the number and location of methylene interrupted double bonds
contained within FAAE. Materials that contain more methylene carbons allylic to sites of
unsaturation (such as polyunsaturated esters) are particularly vulnerable to autoxidation.
Structural features such as degree of unsaturation, double bond orientation, chain length, and
type of ester head group influence the OSI of FAAE. Esters that are otherwise similar but contain
a greater number of methylene interrupted double bonds undergo oxidative degradation at
progressively faster rates [37]. Consequently, superior oxidative stability is expected from
biodiesel fuels prepared from feed stocks relatively high in saturated fatty acid content or
relatively low in polyunsaturated fatty acid content.
Oxidative stability and low-temperature operability are normally inversely related: structural
factors that improve oxidative stability adversely influence low-temperature operability and vice
versa. Ester head group is the only exception to this relationship, as larger ester head groups tend
to improve both low-temperature performance and oxidative stability.
2.6.4. Kinematic viscosity

Kinematic viscosity is the primary reason why biodiesel is used as an alternative fuel instead of
neat vegetable oils or animal fats. The high kinematic viscosities of vegetable oils and animal
fats ultimately lead to operational problems such as engine deposits when used directly as fuels.
The kinematic viscosity of biodiesel is approximately an order of magnitude less than typical
vegetable oils or animal fats and is slightly higher than petro diesel.
29
Kinematic viscosity is determined following ASTM D445 at 40°C. Several structural features
influence the kinematic viscosities of FAAE, such as chain length, degree of unsaturation, double
bond orientation, and type of ester head group. Factors such as longer chain length and larger
ester head group result in increases in kinematic viscosity. Increasing the degree of unsaturation
decreases kinematic viscosity. Kinematic viscosity at 40°C is the parameter required by biodiesel
and petro diesel standards. In a diesel engine, the liquid fuel is sprayed into compressed air and
atomized into small drops near to the nozzle exit. The liquid fuel, usually, forms a cone shaped
spray at the nozzle exit and its viscosity affects the atomization quality, size of fuel drop and
penetration. The viscosity of the fuel increases with chain length (number of carbon atoms).
Fuels with high viscosity tend to form larger droplets on injection which can cause poor fuel
atomization during the spray, increases the engine deposits, needs more energy to pump the fuel
and wears fuel pump elements and injectors. Kinematic viscosity is the resistance to flow of a
fluid under gravity. It is the time taken for a fixed volume of fuel to flow under gravity through
the capillary tube viscometer immersed in a thermostatically controlled bath at 40ºC. It is the
product of measured time flow and calibration constant of viscometer.
The kinematic viscosity is a basic design parameter for the fuel injectors used in diesel engines.
Fuel viscosity has influence on fuel droplet size and spray characteristics. Viscosity is inversely
proportional to temperature. Viscosity increases with chain length and degree of saturation. Fuel
specification viscosity upper limit ensure that fuel will flow readily during cold starting. Higher
viscosity leads to poor atomization, incomplete combustion and increases carbon deposits. More,
higher viscosity fuel needs higher pumping power also. Fuels with lower viscosity leaks past
plunger through the clearance between plunger and barrel during fuel compression [38]
2.6.5. Flash point

The flash point is the minimum temperature calculated to a barometric pressure of 101.3 kPa at
which the fuel will ignite (flash) on application of an ignition source under specified conditions.
Flash point helps to monitor the safe handling and storage of fuel. The flash point does not affect
the combustion directly; flash point varies inversely with the fuel’s volatility. For biodiesel the
minimum flash point is 93°C in the United States, 100°C in Brazil and 120°C in Europe. The
flash point indicates the residual alcohol present in biodiesel samples. For example, the presence
of 0.5% methanol in biodiesel reduces biodiesel flash point from 170°C to 50°C.
30
2.6.6. Higher heating value (HHV)

The higher heating value (HHV) is an important property defining the energy content and
thereby efficiency of fuels, such as vegetable oils and biodiesels. The higher heating value of a
fuel increases with increasing carbon number in fuel molecules and also increases as the ratio of
carbon and hydrogen to oxygen and nitrogen increases. Higher heating value (HHV) and
composition of biomass are important properties which define the energy content and determine
the clean and efficient use of these fuels.
The high heating value (HHV) is not specified in the EN 14214 and ASTM D6751 biodiesel
standards. However, European standard for using biodiesel as heating oil (EN 14213) specifies a
minimum HHV of 35MJ/kg. The HHV increases with increasing chain length and decreases with
increasing unsaturation, and it is important for estimating the fuel consumption: the greater the
HHV, the lower the fuel consumption.
Biodiesel fuels do not contain aromatics, but they contain methyl esters with different levels of
saturation. Unsaturated esters have lower energy content on a weight basis, but due to their
higher density, they have more energy per unit volume. The higher heating value (HHV) is an
important property defining the energy content and thereby efficiency of fuels, such as oils and
biodiesels. The HHV of biodiesel is approximately 10% less than that of petrodiesel. There exists
a variety of correlations for predicting HHV from ultimate analysis of fuels. Energy content is an
important indication of the suitability of a fuel.
2.7. Limitations in biodiesel production from leather industry fleshing wastes
The production of biodiesel from WAFs has certain limitations and concerns that have to be
overcome, such as the presence of proteins, phosphoacylglycerols, water, FFAs, SFAs,
pathogens etc. The major technical constraints associated with processing of waste animal fats
include the presence of relatively high content of water, free fatty acids, saturated fatty acids,
phosphoacylglycerols and pathogens. Desiccation, drying or gravitational settling can be used for
the exclusion of excessive humidity. Two-step acid/base transesterification helps to cope with
the relatively high concentration of free fatty acids [39]. Compared to vegetable oils, animal fats
contain high amount of saturated fatty acids which diminish the efficacy of resultant biodiesel in
cold weather. Nevertheless this problem can be overcome by suitable additives or winterization
31
process [40]. Phosphoacylglycerols can be eliminated from animal fats through degumming
process using 60% orthophosphoric acid followed by centrifugation [41]. Pathogenic prions
involved in the contamination of biodiesel thereby offering a risk towards the environment and
public health could be effectively inactivated via esterification at high temperature catalyzed by
sulfuric acid [42].
2.8. Factors affecting biodiesel production yield and quality
The main factors affecting transesterification are the molar ratio of glycerides to alcohol, reaction
temperature and time, catalyst, acid pretreatment and mixing intensity. Methanol is the preferred
alcohol for biodiesel production because of low cost and easy distinct layer formation between
the biodiesel and the byproduct glycerol [43].
Fig. 2.1 Transesterification reaction
Animal fats are categorized into three distinct types: high quality fat has less than 2% of free
fatty acids; medium and low-grade fats exhibit 3-5% and above 5% free fatty acids respectively
and can be effectively used for biofuel production. Beef fat, lard, poultry fat and fish oil
constitute the chief products of animal origin primarily used for biodiesel production [44].
Feather meal, duck fat, lamb fat and leather industry fleshing wastes can also be used as
feedstock to generate biodiesel.
2.9. Advantages and Disadvantages of Biodiesel
Biodiesel has attracted considerable interest as an alternative fuel or extender for petrodiesel for
combustion in compression–ignition (diesel) engines. Biodiesel is miscible with petrodiesel in
any proportion and possesses several technical advantages over ultra-low sulfur diesel fuel
32
(ULSD, <15 ppm Sulfur), such as inherent lubricity, low toxicity, derivation from a renewable
and domestic feedstock, superior flash point and biodegradability, negligible sulfur content, and
lower overall exhaust emissions.
The major disadvantages of biodiesel include high feedstock cost, inferior storage and oxidative
stability, lower volumetric energy content, inferior low-temperature operability versus petro
diesel, and in some cases, higher NOx exhaust emissions [37]. Many of these deficiencies can be
mitigated through cold flow improver and antioxidant additives, blending with petro diesel
and/or reducing storage time [45].
Additional methods to enhance the low-temperature performance of biodiesel include

crystallization fractionation [46] and transesterification with long or branched-chain alcohols.
Strategies to improve the exhaust emissions of biodiesel include various engine or after-
treatment technologies such as selective catalytic reduction (SCR), exhaust gas recirculation
(EGR), diesel oxidation catalysts, and NOx or particulate traps.
2.10. Food versus fuel

By means of continuous efforts to produce biodiesel from non-food sources, it has been
established that fats produced as a waste in leather industries offer a promising feedstock. The
raw material of animal fat derived biodiesel is rejected for food, so its use for biodiesel
production offers an added environmental perspective. It can avoid disposal problem in leather
industries by minimizing the environmental impact associated with the accumulation of these
residues. The economics of biodiesel production totally depend upon the cost of utilized
feedstock. Therefore high vegetable oil prices are very unfavorable, whereas non-food, waste
animal fats could solve the problem of the biodiesel industry by frequently providing
inexpensive and abundant, high-quality feedstock.
33
3. MATERIALS AND METHODS
The leather fleshing wastes were collected from Addis Ababa Tannery S.C located in Addis
Ababa, Ethiopia as main raw materials. Moisture content of the flesh was 65%. The flesh
waste was washed with distilled water so as to remove the impurities. All chemicals used in this
study were analytical grade. Sample preparation, extraction of oil, analysis and characterization
of oil and its product were done at the Forest Products Research Center of the Ethiopian
Environment and Forest Research Institute and at the Chemical and Bioengineering School of
the Addis Ababa Institute of Technology.
a/ fleshing waste b/waste soaked in 1% c/ chopped dried waste d/oil extraction using Soxhlet
wt. /wt. boric acid
Fig.3.1 Preparation of waste and extraction of oil
3.1. Experimental Setup and Descriptions

The GC-MS analysis was carried out at Ethiopian leather industry development institute (LIDI)
Addis Ababa. The pH, high heat value, viscosity, density and ash content were done in school of
Chemical and Bioengineering reaction laboratory. All the other analysis was done at Ethiopian
forest product utilization research center, Addis Ababa Ethiopia. Soxhlet extraction was used to
extract the oil from the flesh (fig.1. d). A weighed amount of flesh waste was charged into the
Soxhlet. The heating mantle was heated to the desired temperature of boiling point of the
o
solvent. Then, the extracted oil and solvent i.e. petroleum ether 60-80 C was separated by
rotator vapor (fig 3.2. b).
34
a/ oil and extractive b/ separation of oil and extractive using rota vapor
Fig 3.2. Separation of oil and extractive
The concentrated oil was subjected to degumming process to remove the phospholipids with
centrifuge model TD3, at 800 rpm to separate the oil from the mixture. Finally the
fleshing oil was washed several times with distilled water and dried to keep it in moisture free
container.
a/degumming b/ centrifuging c/gum and oil separation d/ storage of oil in
moisture free container
Fig.3.3. removing gum from the crude oil
All the pretreatment and transesterification experiments were performed in a laboratory scale
glass reactor. Hot plate magnetic stirrer was used to heat and agitate the reaction mixture. When
O
the crude oil temperature is reached 70 C, a defined amount of orthophosphoric acid previously
dissolved in distilled water was added to the heated oil. The mixture was stirred with magnetic
stirrer at 200 rpm for 1h. After cooling the reaction mixture was centrifuged with centrifuge
model TD3, 800 rpm for 20 minutes to separate the gum and oil mixture. The degummed
O
fatty acid was further heated to 105 C to remove any remaining water. The acid and FFA
35
values of the oil before and after degumming were determined and recorded. After obtaining the
desired FFA level, the transesterification reaction experiment was performed in the same reactor.
Weight of dried sample (g)
Vacuum Filter was% used for separation of the oils and the biodiesel from impurities.
moisture
3.2. Physico-chemical characterization of raw material
3.2.1. pH measurement
The pH of the hide, goat and sheep fleshing waste samples were determined by shaking five
gram of sample of solid wastes in 100ml of distilled water for 16 – 24 hours followed by direct
measurement of the pH.
3.2.2. Moisture content of the delimed fleshing waste
Weight of ash (g)
Moisture content of solid waste
% isAsh
usually expressed as the mass of moisture per unit mass of wet
or dry materials. In order to determine the moisture content of the solid wastes, samples of the
solid waste was first weighed and(Weight
0
put in of
ansample
oven attaken
105Weight
C forof24
ashhours.
(g) It was kept in
% volatile organic content
desiccators for about 30 minutes and then weighed and recorded. The wet-mass moisture content
is expressed as follows.
100%…………………………(3.1
Weight of sample taken (g)
3.2.3. Ash content of limed fleshing waste and volatile organic content
About 1g of the oven dried LFW was taken in a silica crucible. The crucible containing the
sample was ignited on the hot plate till the sample gets charred. Then the crucible along with the
sample was kept in a muffle furnace and heated at 550-600°C for 4 h. Finally, it was
allowed to cool and the ash formed was weighed. The percent of ash and volatile organic
contents were calculated using the following formulae
100%………………… (3.2)
100%……(3.3)
weight of the fat (g)
Total fat%
36
3.2.4. Total fat content of delimed fleshings

The Total Fat content of DFs was determined using A.O.A.C, 2005 method. About 1g of the
DF sample was placed in the Soxhlet extraction apparatus and 150 ml of petroleum ether
was added and the sample was extracted for 6 hours at the boiling point of the solvent. It
was then allowed to cool and the ether was evaporated. The weight of the extraction flask
along with the dried extract minus the weight of the empty extraction flask gives the
weight of the total fat being extracted.
The % of total fat in de-limed fleshing wastes was calculated using the following formula-
x 100%………………(3.4)
weight of sample (g)
3.3. Physicochemical characterization of leather fleshing oil and biodiesel
The physiochemical properties of the oil before and after pretreatment and after biodiesel
production were conducted to identify the effects of the different pretreatments i.e. degumming
dynamic viscosity
and acid catalyzed esterification. The physicochemical characterization of the biodiesel produced
kinematic viscosity
was performed to compare the results with the EN and ASTMD standards. The physicochemical
parameters that have been investigated include specific gravity, kinematic viscosity, acid value,
ester value, FFA content, iodine number, high heat value and saponification number.
3.3.1. Determination of specific gravity
The specific gravity of the oils extracted and biodiesel produced was determined by inserting
O
hydrometer into a graduated cylinder containing 500ml samples heated to 25 C.
3.3.2. Determination of kinematic viscosity
Digital sine-wave (SV-10, 2011, Australia) vibrio viscometer was used to determine the viscosity
of the oil and the biodiesel. The viscosities were determined at different temperatures. Since the
reading of the vibrio viscometer is dynamic viscosity the kinematic viscosity was determined
using the following empirical formula.
……………..(3.5)
density of oil
37
M N Vfrom leather industry fleshing wastes
Optimization and characterization of biodiesel production
AV
3.3.3. Acid value (Acid Number) determination

The acid value (AV) is the number that expresses, in milligrams the quantity of potassium
hydroxide required to neutralize the free acids present in 1 g of the substance. The acid value
may be overestimated if other acid components are present in the system, e.g. amino acids or
acid phosphates. The acid value is often a good measure of the breakdown of the triacylglycerol
into free fatty acids, which has an adverse effect on the quality of many lipids.
For acid value determination of oil a titration solution of 0.1N KOH was prepared and stored in
O
brown bottle for five days. Two grams of oil was added to a beaker and heated at 70 C for three
minutes. Next 20ml of anhydrous ethanol (99.5% W/W), 20 ml of diethyl ether and 5 drops of
phenolphthalein were added to the titration beaker containing
AV the 2 gram oil sample. The
% FFA
solution was mixed thoroughly and titrated with 0.1 N KOH by adding a drop at a time until pink
color appeared. The acid value was determined by using the following correlation.
………………………………….(3.6)
W
Where N = Normality of KOH
V = volume of titrant i.e. KOH used for titration (ml)
M = Molecular weight of KOH

W = Weight of the oil sample
3.2.1. Free fatty acid (FFA) determination

The free fatty acid of the oil was determined using acid value previously determined using the
following equation.
……………………………..(3.7)
2
Where % FFA = percentage of free fatty acid, AV= acid value of the oil
3.3.4. Saponification value determination

The saponification value is the amount of mg of potassium hydroxide required to neutralize the
free acids and to saponify the esters in 1 g of the substance. The saponification number is a
38
measure of the average molecular weight of the triacylglycerol in a sample. Saponification is the
process of breaking down a neutral fat into glycerol and fatty acids by treatment with alkali. The
smaller the saponification number the larger the average molecular weight of the triacylglycerol
present i.e. Saponification value is inversely proportional to the mean molecular weight of fatty
acids (or chain length).
O M N (Vb Vs)
H 2C OH
H 2C O C R SV O
O +
+ 3 KOH HC OH 3 R C OK
HC O C R
O
H 2C OH
H 2C O C R
Saponification reaction
Twenty-five milliliter of 0.5 ml ethanoic solution of KOH was added to 2 g of previously

O
extracted oil of LFW. The mixture was heated to 70 C for 30 minutes in reflex condenser. Then
the heated mixture was cooled immediately and 5 drops of phenolphthalein was added for
indicator subsequently the sample was titrated with 0.5 mol/l HCl solution. Titration was stopped
when color change was observed. The same procedure was also performed using blank level test
i.e. without the presence of oil sample in parallel to the above activity. The saponification was
then determined by using the following equation.
……………………………..(3.7)
W
Where SV= Saponification value, mg KOH/g oil
M= Molecular weight of KOH
N= Normality of HCl solution
Vb =Volume of HCl solution used in blank
Vs = Volume of HCl solution used in the sample

MI (Vb Vt) N
IV
W= Weight of the oil used
39
3.3.5. Determination of iodine value

The iodine value determination was done by measuring one gram of biodiesel/oil and
dissolving it in 10ml of chloroform. 25ml of Hanus solution (which was prepared by
dissolving 13.6g of iodine in 400ml glacial acetic acid by adding 6ml of bromine liquid) and
(0.041 SV 0.015 IV
allowed to stand in darkHHVplace49.43
for 30min. Ten milliliter of 15% KI (15g of KI dissolved
in100 ml) added to the oil sample and titrated against 0.1N sodium thiosulfate until yellow
solution turns in to almost colorless.
……………………………..(3.8)
Ma
Where, IV = Iodine value (g I2 / 100 g amostra), Vt = volume of sodium thiosulfate

5458
solution for the sample (mL), Vb = volume
CN 46.3of sodium thiosulfate solution for the blank (ml),
N = standard sodium thiosulfate solution concentration (N); Ma= mass of the biodiesel sample
(g), MI= molar mass of iodine.
3.3.6. Determination of high heat value

Determination of HHV was conducted using empirical equation available. Therefore, for
calculation of the HHVs (MJ/kg) of oils, the following equation was suggested [47].
……………………………..(3.9)
Ma
3.3.7. Determination of cetane number (CN)
Cetane number determination was done using empirical formula suggested [7]. The calculation
was based on the results from saponification number (SN) and Iodine value (IV) of oils. The CN
was calculated as below:
0.225IV……………………………..(3.10)
SV
3.4. Quantification of leather fleshing oil fatty acids

Gas chromatography stands out among other methods of analysis of fatty acids because it allows
their easy separation and quantification. However to analyze fatty acids by this technique, it is
40
necessary to increase the volatility of the fatty acids by converting them in to methyl ester
derivatives[48]. The esterification procedure followed was the method described by Bannon et al
[49]. Approximately 300 mg each from the sheep, goat and hide fleshing oil were weighed.
About 10 ml of KOH in 0.5 mol/L methanol was added to each sample. The mixture was heated
under reflux for 3 minutes. Total weihgt of dried oil
Yield(%Next 10 mL BF3 (14%) in methanol was added. Then the mixture
was heated under reflux for another 3 minutes. After cooling 6 ml heptane and approximately 30
mL saturated NaCl were added and vigorously stirred for 15 seconds. After phase separation, the
top phase was collected and 2.5 µL for each samples were injected into the gas chromatographer.
3.5. Experiments
3.5.1. Flesh Waste Treatment and Oil Extraction

One percent (Wt. / Wt.) boric acid was added with sufficient water in order to neutralize the pH.
The flesh was soaked with the acid for an hour at atmospheric conditions. Then, the flesh was
chopped into smaller sizes and the oil was extracted in a Soxhlet extraction apparatus a little
above the boiling point of the extraction solvent. Finally, the oil and the solvent mixture was
subjected to rotatory vapor for separation using the boiling point differences. The yield of the
fleshing oil was calculated as:
x100%............................. (3.11)
Total weight of flesh waste sample
3.5.2. Pretreatment of extracted oil
In this study degumming was used as options of oil pretreatment. Degumming is the pre-
treatment of Feedstock for separation of gums, solid, water and free fatty acid. Technically,
degumming is referred as an operation of purification of oil, which normally contains impurities
in the colloidal state or dissolved in them. In more simple words, degumming is a process of
removing the unwanted gums, which will interference the stability of the oil product (like Bio-
diesel). In refining, physical and chemical processes are combined to remove undesirable natural
as well as environmental-related components from the crude oil. These components comprise for
example phosphatides, odors etc. The emulsifying action of phospholipids increases oil losses
during alkali refining. Above all gums lead to brown discoloration of oil after heating during
deodorization. They are also known causes of accelerated oxidative degredation of oil. Different
41
degumming processes are carried out to remove phosphatides. The four known categories of
degumming techniques are water degumming, acid degumming, enzymatic degumming and
membrane degumming. A large part of the phosphatides (gums) can be hydrated quickly and
easily. If the extracted oil contains a considerable quantity of gums the oil is subjected to the
water degumming process immediately following extraction. In this process, water is added to
the oil. After a certain reaction period the hydrated phosphatides can be separated either by
decantation (settling) or continuously by means of centrifuges. In this process step a large part of
hydratable and even a small proportion of the non-hydratable phophatides are removed.
Dry acid degumming is particularly suit-able for processing oils with low gum contents such as
palm oil, coconut oil, palm kernel oil or animal fats. Intensive mixing is implemented following
addition of acid to the pre-heated crude oil. The benefits of the dry acid degumming process are
high efficiency as a result of low energy consumption, low operation and maintenance costs
(sturdy and reliable control system), long service life (the components are acid proof), low
investment costs, environmental-friendly as no wastewater or soap stock occur.
The degumming technique employed in this study was chemical degumming using 2% v/v
o
(orthophosphoric acid/oil) and 3% v/v (distilled water/oil) at 70 C, 200 rpm mixing intensity for
an hour. Then the gum was separated from the oil using a centrifuge at the speed of 800 rpm for
20 minutes. The acid value, FFA, pH and saponification values of the degummed and non-
degummed oil were measured. The results obtained were tabulated for comparison.
3.5.3. Transesterification
After degumming pretreatment experimental work that lowered the FFA below 1% the next
experimental stage in the production of biodiesel was transesterification. In this study alkali
catalyzed transesterification was employed to convert the purified and pretreated oil. The
catalyst (KOH) and the alcohol (CH3OH) were mixed via vigorous stirring. Fifty milliliters of
O
pretreated oil was charged to the experimental reactor. It was heated for 30 minutes at 100 C to
dehumidify the oil to avoid parallel saponification reaction. The alcohol-catalyst mixture was
charged to the reactor containing dehumidified, pretreated oil. The alcohol-catalyst-oil mixture
was agitated at 750 rpm using magnetic stirrer for an hour. The temperature of reaction, catalyst
to oil weight basis ratio and alcohol to oil molar ratio were varied, to obtain a large range of
methyl ester yields. Heating and stirring were then stopped, and the product was allowed to
42
Total weihgt of fatty acid methyl Ester
Yield(%
settle, to allow the two phases to be separated. The top phase consists of biofuel, whereas the
lower phase contained a mixture of impurities. The upper layer was purified using distilled water
and then dried over anhydrous sodium sulfate (Na2SO4). In this sense, 0.5 g of anhydrous
Na2SO4 was added for every 100 mL of fatty acid methyl ester, stirred for 15 min, and then was
allowed to settle and be decanted. To remove solid traces from biofuel after the purification step,
a filtration process was needed. This step was performed with the help of a vacuum pump and a
27-µm diameter filter paper. For each oil sample, three replications were performed. The
optimum of each parameter involved in the process was determined while the rest of them
remained constant. After each optimum was attained, this value was accepted and considered to
be constant during the optimization of the next parameter. Ester yield results (given as
percentages) were related to the weight of oil at the start (weight of ester/weight of oil). The
biodiesel yield was determined as:
x 100%.......................... (3.12)
Total weight of oil in the sample
a/separation of the glycerol and FAME b/Purified FAME
Fig. 3.4. Separation of FAME from glycerol
43
4 1 1.50 9.00 55.00

5 2 0.50 3.00 65.00 Table
17 3 1.00 6.00 60.00 3.1: I
13 4 1.00 6.00 55.00 ndep
3 5 0.50 9.00 55.00 ende
nt va
14 6 1.00 6.00 65.00 riabl
19 7 1.00 6.00 60.00 es us
1 8 0.50 3.00 55.00 ed fo
9 9 0.50 6.00 60.00 r CC
D in
7 10 0.50 9.00 65.00 trans
20 11 1.00 6.00 60.00 ester
12 12 1.00 9.00 60.00 ificat
16 13 1.00 6.00 60.00 ion p
15 14 1.00 6.00 60.00
roces
s
6 15 1.50 3.00 65.00
11 16 1.00 3.00 60.00
8 17 1.50 9.00 65.00
2 18 1.50 3.00 55.00
10 19 1.50 6.00 60.00
18 20 1.00 6.00 60.00
Variable symbol Coded levels
-1 0 +1
Catalyst % (wt. /wt.) A 0.5 1 1.5
Methanol to oil molar ratio B 3:1 6:1 9:1
Temperature ( oC) C 55 60 65
Table 3.2. CCD experimental design matrix of transesterification reaction
Std. Run Catalyst (% wt. /wt.) Methanol : oil Temperature (oC) % Yield
44
3.6. Experimental Design
Response surface methodology (RSM) is a useful statistical technique which has been applied in
research into complex variable processes. It employs multiple regression and correlation analyses
as tools to assess the effects of two or more independent factors on the dependent variables.
Optimization of transesterification reaction was undertaken. Where the alcohol to oil molar ratio,
catalyst amount and reaction temperature were investigated within one hour and 750 rpm mixing
intensity. In order to optimize the central composite experimental design (CCD), a three-level-
three-factor central composite design was employed in this study, which generates 20
experimental runs. The factors investigated in this study were catalyst concentration, temperature
(°C), and oil/methanol ratio. Considering the treatments as in dependent variables, difference in
means of each treatment were compared at a significance level of p < 0.05 was considered
throughout the study.
o
S.N Parameters Limed fleshing waste Delimed fleshing waste
.
sheep hide goat goat hide sheep
1. Color Greyish Greyish Greyish Pinkish Pinkish Pinkish

brown brown brown brown brown brown
2. Odor pungent pungent pungent normal normal normal
3. Moisture 63% 58% 82% 61% 60% 80%

Content
4. Ash content 3.06% 3% 2.8% 2.05% 1.8% 1.6%
5. Total fat content NA NA NA 23.08% 12.05% 26.7%
6. pH 10.6 10.6 12.5 6.5 6.5 8.6
45
4. RESULT AND DISCUSSION
4.1. Physical characterization of raw material
The raw material used in this study had unique characteristics, its color was greyish brown with a
characteristic pungent odor. The odor decreases markedly after each consecutive water washing
and deliming using boric acid. The pH of the hide and sheep fleshing wastes was found to be
10.6 whereas the goat flesh had originally a pH of 12.25. The pH values are attributed to the
basicity values of soaking conditions. The tannery fleshing wastes with this high amount of limes
should be first neutralized with boric acid. After washing with water to neutralize and wash out
the alkalis about 1% (wt. /wt.) boric acid was added with sufficient water in order to neutralize
the pH. The flesh was soaked with the acid for an hour at atmospheric condition. Then, the flesh
was chopped into small size and dried with the atmospheric air before extraction was
commenced. It was possible to reduce the pH of hide and sheep fleshing waste to 6.5 and that of
goat to 8.6.
Table 4.1.Physical parameters of liming and Delimed Fleshing wastes
46
o
S.N Parameters Unit Fleshing oil before Fleshing oil after
. treatment treatment
goat sheep hide goat sheep hide
3
1. Density @ Kg/m 911 905 900 906 900 895
298.15 K
2. Water content % mass 0.4 0.3 0.15 0.32 0.24 0.04

@ 378.15 K
2
3. Kinematic mm /s 70.8 40.2 30.9 57.8 27.65 21.23
viscosity @
313.15 K
Deliming made the fleshings vulnerable for fermentation with different species like probiotic
bacterium Lactobacillus plantarum. Therefore, the delimed fleshing waste was kept in a
refrigerator i.e. controlled environment that does not allow the growth of the bacterium.
4.2. Oil extraction and physicochemical characterization

About 2.5 liter i.e. 2.76 kg of goat fleshing oil was obtained from 10 kg delimed chopped and
dried goat leather fleshing waste. The total fat content of DFs was determined using A.O.A.C,
2005 method. It was calculated based on equation 3.4 on page 28.
4.2.1. Physicochemical Characteristics of the Fleshing and Pretreated Oil

3 2
The density of the goat fleshing oil was reduced to 906 kg/m , viscosity to 57.8 mm /s, acid
value to 1.13 mg KOH /g of oil, free fatty acid to 0.56 %, at the oil pretreatment stage. The
experimental results of the physicochemical characteristics of fleshing oil and pretreated oil are
shown in Table 4. In this study biodiesel was produced using goat fleshing oil because on other
fleshing wastes two researchers have conducted studies at different times using different
methods. The physicochemical parameters are performed to see the effect of pretreatment i.e.
degumming for all the three types of leather fleshing wastes.
Table 4.2 Physicochemical characterization of untreated and treated fleshing oil
47
4. Acid value mg 6.1 3.5 3.25 1.13 2.8 2.7
KOH/g
5. FFA % 3.05 1.75 1.63 0.56 1.4 1.35
6. Saponification mg 165.6 198.6 191.57 148.1 170.5 171.3

value KOH/g
7. Higher heating MJ/Kg 42.2 40.2* 42.43** 42.38 40.86* 43.13**

value
8. Iodine value g/100g 66 74* 80** 65.13 65* 75**
* adapted from Abebe Reda [8]
**adapted from Eshetu Getahun and Nigus Gabiyye [7]
4.2.1.1 Density of the extracted oil

The densities of the untreated and treated fleshing oils were measured by hydrometer and the
results of the experiment were recorded.
Fig 4.1 Oil density measurement using hydrometer
As depicted in table 3 degumming has reduced the density of the oil. The density of the oil is
affected by contamination. It also shows the unsaturation level. Density values of oil samples
depend on their fatty acid composition, as well as on their purity. On the one hand, density
increases with decreasing chain length and increasing number of double bonds, explaining high
values for fuels rich in unsaturated compounds, The higher the unsaturation the higher the
48
density of fuels. A widely used method for density prediction of vegetable oils was developed by
Lund and discussed by Halvorsen et al [50]. The Lund relationship is: sg (298.15 K) = 0.8475 +
0.00030 SV + 0.00014 IV where sg is the specific gravity of oil at 298.15 K, SV is the
saponification value, and IV is the iodine value of the oil. The results obtained experimentally
are in close agreement to the values calculated by using the suggested correlation. The density of
the oil is inversely related to the temperature. Higher density values may increase the required
fuel/air mixture, which increases emission of pollutants, including hydrocarbons, carbon
monoxide and particulate matter. Low values may favor the formation of a lean air/fuel ratio,
leading to loss of engine power and consequent increased fuel consumption Experimental data
showed that biodiesel density decreased with increasing unsaturation levels of FAME [35]. The
results obtained from this experiment agree with this fact.
915
910
905
Density before
900
treatment
895 Density after
treatment
890
885
Sheep fleshing Goat fleshing Hide fleshing
oil oil oil
Fig 4.2 Density of the sheep, goat and hide oils before and after Degumming
4.2.1.2. Kinematic viscosity of oil and biodiesel

Viscosity is the measurement of a fluid’s resistance to flow defined as the force in required to
move a surface one square centimeter in area past a parallel surface at a speed of one centimeter
per second, with the surfaces separated by a fluid film one centimeter thick. Laboratory
measurements of viscosity normally use the force of gravity to produce flow through a
capillary tube (viscometer) at a controlled temperature. This measurement is called kinematic
49
0
Temperature ( C) 30 35 40 45 50 55 60
Specific gravity 0.901 0.895 0.889 0.893 0.881 0.875 0.869
Dynamic viscosity ( m. pa. s) 80.9 63.3 51.4 42.5 34.7 28.6 22.5
2
Kinematic viscosity (mm /S) 89.8 70.7 57.8 47.6 39.4 32.7 25.9
viscosity. Kinematic viscosity is absolute viscosity of a fluid divided by its density at the same
temperature of measurement. It is the measure of a fluid’s resistance to flow under gravity, as
determined by test method ASTM D 445. To determine kinematic viscosity, a fixed volume of
the test fluid is allowed to flow through a calibrated capillary tube (viscometer) that is held at a
closely controlled temperature.
Fig 4.3.Determination of kinematic viscosity using viscometer
The dynamic viscosity of the treated oil and the biodiesel was measured at different
temperatures. The kinematic viscosities were calculated using equation 3.5 under section 3.3.2
and the results are presented using graphs on figures 4.4 and 4.8.
Table 4.3. Kinematic viscosity of degummed goat leather fleshing oil at different temperature
50
0
Temperature ( C) 20 25 30 35 40 45 50 55 60
Specific gravity 0.880 0.875 0.872 0.868 0.865 0.862 0.859 0.850 0.848
Dynamic viscosity 8.32 7.06 6.90 5.85 5.18 4.24 3.80 3.70 3.30
( m. pa. s)
Kinematic viscosity 9.45 8.06 7.91 6.74 5.99 4.90 4.42 4.35 3.91
kinematicviscosity(mm2/s)
2
(mm /S)
As clearly observed from figure 4.4 below temperature and kinematic viscosity are inversely
related.
100
90
80
70
60
50
40
30
20
10
0
0 20 40 60 80
Temprature (oc)
Fig.4.4 Effect of temperature on kinematic viscosity of degummed goat fleshing oil
Table 4.4 kinematic viscosity of goat fleshing biodiesel at different temperature

51
kinematicviscosity
9
8
(mm2/s
7
6
5
4
3
2
1
0
0 20 40 60 80
Temprature (oc)
Fig. 4.5 effect of temperature on kinematic viscosity of goat fleshing biodiesel
4.2.1.3. Acid value of the oil

The acid values of the treated and the untreated the goat, sheep and hide fleshing oils were
measured in triplicate for each and the average values were taken.
7
6
5
4 Acid value of crude
3 oil
2 Acid value of
1 degummed oil
0
Goat fleshing Sheep Hide fleshing
oil fleshing oil oil
Fig 4.6. Acid values of oils before and after degumming treatment
The following consecutive tables show the acid values of oils of crude and degummed goat,
sheep and hide fleshing wastes. It is possible to observe that degumming has reduced the acid
values of the crude oils. The acid values and FFA are calculated based on section 3.3.3 using
equations 3.6 and 3.7 respectively.
52
Run Mass of oil Titrant (KOH) volume Color change Acid value FFA
number (g) (ml) (mg KOH/g oil) %
1. 2.010 1.300 Yellow to pink 3.628 1.814
2. 2.050 1.200 Yellow to pink 3.284 1.642
3. 2.000 1.280 Yellow to pink 3.588 1.794
Average 2.020 1.260 Yellow to pink 3.500 1.750
1. 2.130 0.400 Yellow to pink 1.054 0.527
2. 2.050 0.500 Yellow to pink 1.368 0.684
3. 2.300 0.400 Yellow to pink 0.976 0.488
1. 2.044 2.200 Yellow to pink 6.040 3.020
2. 2.016 2.20 Yellow to pink 6.120 3.060
3. 2.050 2.250 Yellow to pink 6.160 3.080
Table 4.5 Acid value of goat fleshing crude oil
Table 4.6. Acid value of degummed goat fleshing oil
Table 4.7. Acid value of sheep fleshing crude oil

53
1. 2.050 0.9 Yellow to pink 2.463 1.232
2. 2.040 1.1 Yellow to pink 3.025 1.512
3. 2.140 1.0 Yellow to pink 2.621 1.310
1. 1.998 1.150 Yellow to pink 3.229 1.614
2. 2.030 1.100 Yellow to pink 3.040 1.520
3. 1.999 1.250 Yellow to pink 3.508 1.754
1. 2.174 1.090 Yellow to pink 2.813 1.406
2. 2.000 0.980 Yellow to pink 2.749 1.374
3. 1.980 1.000 Yellow to pink 2.833 1.417
Table 4.8 Acid value of degummed sheep fleshing oil
Table 4.9.Acid value of crude hide fleshing oil
Table 4.10: acid value of degummed hide fleshing oil
4.2.1.4. Saponification value of the oils

The procedure followed to calculate the saponification value of the crude and degummed oils is
discussed in section 3.3.5. The results obtained are illustrated in the subsequent tables.
54
Run Mass of oil VbHCl VsHCl VbHCl - VsHCl Saponification value
number (g) (ml) (ml) (ml) (mg KOH/g oil)
1. 2.000 25.5 11.340 14.160 198.6
2. 1.964 25.5 11.500 14.000 200.0
3. 2.036 25.5 11.200 14.300 197.2
average 2.000 25.5 11.346 14.15 198.6
1. 2.50 25.5 12.3 13.2 148.1
2. 2.50 25.5 11.9 13.6 152.8
3. 2.54 25.5 12.5 13.0 143.4
average 2.47 25.5 12.23 13.27 148.1
1. 2.100 25.5 13.1 12.4 165.6
2. 2.200 25.5 12.7 12.8 169.4
3. 2.098 25.5 13.4 12.1 161.8
average 2.13 25.5 13.06 12.44 165.6
Table 4.11. Saponification value of crude goat fleshing oil
Table 4.12. Saponification value of degummed goat fleshing oil
Table 4.13. Saponification value of crude sheep fleshing oil

55
1. 2.02 25.5 13.42 12.08 167.7
2. 1.98 25.5 13.50 12.00 170.0
3. 2.00 25.5 13.00 12.50 175.3
average 2.00 25.5 13.30 12.20 171.0
1. 2.00 25.5 11.50 14.00 196.35
2. 1.95 25.5 12.45 13.04 187.50
3. 2.05 25.5 11.5 14.00 190.86
average 2.00 25.5 11.85 13.65 191.57
1. 1.99 25.5 13.4 12.1 170.5
2. 2.00 25.5 13.5 12.0 168.3
3. 2.01 25.5 13.12 12.38 172.7
average 2.00 25.5 13.34 12.16 170.5
Table 4.14 Saponification value of degummed sheep fleshing oil
Table 4.15 Saponification value of crude hide fleshing oil
Table 4.16.Saponification value of degummed hide fleshing oil

56
The effect of degumming on saponification values of the oils can be easily observed using bar
graph depicted below.
250
200
150
Saponification value
of crude oil
100
Saponification value
of degummed oil
50
0
Goat Sheep Hide
fleshing oil fleshing oil fleshing oil
Fig. 4.7.Effect of degumming on saponification value of the oils
4.2.1.5. Iodine values of oil and biodiesel

The iodine values of the crude and degummed oil samples were measured using the method
discussed on section 3.3.6 using equation 3.8. The average value of the triplicate result was
recorded.
Iodine value is a measure of total unsaturation within a mixture of fatty acid. It is expressed in
grams of iodine which react with 100 g of the respective sample when formally adding iodine to
the double bonds. The iodine value of a vegetable oil or animal fat is almost identical to that of
the corresponding methyl esters [51]. Iodine value is a measure of total unsaturation of fatty
acids. The more unsaturation is present in the oil, the higher the iodine value [52]. The lower
iodine value i.e. superior oxidative stability of the sheep fleshing oil dictates it to be more
preferable for biodiesel production. All the fleshing oils have iodine value limits below the
maximum value expressed by EN-norm. This result is similar with the result obtained by Eshetu
Getahun and Nigus Gabiyye [7]. The low iodine index indicates less susceptibility to oxidation
by oxygen. Decreasing the chain length and/or increasing the number of double bonds (i.e.
higher iodine value (IV)) of FAAE results in an increase in NOx emissions [53].
57
4.2.1.6. HHV of the oils and biodiesel

The high heating value (HHV) is not specified in the EN 14214 and ASTM D6751 biodiesel
standards. However, European standard for using biodiesel as heating oil (EN 14213) specifies a
minimum HHV of 35MJ/kg. The HHV increases with increasing chain length and decreases with
increasing unsaturation, and it is important for estimating the fuel consumption: the greater the
HHV, the lower the fuel consumption. Factors that influence the energy content include the
oxygen content and carbon to hydrogen ratio. Generally, as the oxygen content of FAAE is
increased, a corresponding reduction in energy content is observed.
4.3. Biodiesel production and analysis of effects of parameters
4.3.1. Transesterification process
The transesterification process was carried out using the method described in section 3.6. In this
study biodiesel was produced from goat leather fleshing oil using homogenous base catalysis.
Since the oil extracted was of high quality grade i.e. significantly low acid value, direct base
catalyzed transesterification after degumming was selected to produce the biodiesel. The acid
values of the sheep and hide fleshing oils obtained in this study is significantly different from the
values reported by Eshetu Getahun, Nigus Gabiyye [7] and Abebe Reda [8]. This variation might
be due to the extraction method used. While Getahun and Gabiyye used extractive boiler, Reda
used heating and decantation. In this study Soxhlet extraction was employed. Using Soxhlet
extraction high quality oils were obtained. Only degumming was enough to reduce the acid
values to go for direct transesterification reaction. Fifty milliliters of degummed goat fleshing oil
was used for each run.
4.3.2. Statistical analysis
The Design Expert 7.0.0 software was used for the regression and graphical analysis of the data.
The maximum values of percentage of yeild of biodesiel were taken as the response of the design
experiment for transesterification process. The experimental data obtained by the above
procedure was analyzed by the response surface regression using the following second-order
polynomial equation.
58
Factors Biodiesel (ml) % Biodiesel
yield Residuals
Catalyst Methanol to Temperatur Actual Predicte Actua Predicte
(wt. /wt. oil molar ratio e d l d
0
%) C
1 1.50 9.00 55.00 38.20 38.230 76.4 76.46 -0.061
2 0.50 3.00 65.00 36.00 35.970 72 71.94 0.059
3 1.00 6.00 60.00 48.55 48.405 97.1 96.81 0.290
4 1.00 6.00 55.00 45.00 45.015 90 90.03 -0.025
5 0.50 9.00 55.00 34.70 34.670 69.4 69.34 0.035
6 1.00 6.00 65.00 44.00 43.985 88 87.97 0.035
7 1.00 6.00 60.00 48.25 48.405 96.5 96.81 -0.310
8 0.50 3.00 55.00 35.50 35.525 71 71.05 -0.051
9 0.50 6.00 60.00 44.50 44.495 89 88.99 0.015
10 0.50 9.00 65.00 34.00 34.04 68 68.08 -0.081
11 1.00 6.00 60.00 48.40 48.405 96.8 96.81 -0.011
12 1.00 9.00 60.00 43.00 42.985 86 85.97 0.035
13 1.00 6.00 60.00 48.50 48.405 97 96.81 0.190
14 1.00 6.00 60.00 48.20 48.405 96.4 96.81 -0.410
15 1.50 3.00 65.00 34.40 34.430 68.8 68.86 -0.061
16 1.00 3.00 60.00 42.75 42.765 85.5 85.53 -0.025
17 1.50 9.00 65.00 35.75 35.725 71.5 71.45 0.049
18 1.50 3.00 55.00 35.9 35.86 71.8 71.72 0.079
Run
19 1.50 6.00 60.00 45.5 45.505 91 91.01 0.000

20 1.00 6.00 60.00 48.52 48.405 97.05 96.81 0.240
k
k k
k
2
y B0 ∑ BiXi BiiXi ∑ ∑ BijXiXj………………………..(4.1)
i 1
∑ j
i 1
i j
Where; y is the response, i and j are the linear and quadratic coefficients respectively, xi and xj
are the uncoded independent variables, β0 is the regression coefficient, k is the number of factors
studied and optimized in the experiment. Statistical analysis of the model was carried out to
evaluate the analysis of variance (ANOVA). The equation was also validated by carrying out
confirmatory experiments. The actual results obtained from average values of triplicate of the 20
runs were recorded in table 4.17 below.
Table 4.17: Actual and predicted value of biodiesel yield

59
Source Sum of Squares df Mean Square F value P-value Significance
Prob > F
Model 2492.56 9 276.95 5790.64 < 0.0001 Significant

A 10.2 1 10.2 213.29 < 0.0001
B 0.48 1 0.48 10.12 0.0098
C 10.61 1 10.61 221.82 < 0.0001
AB 20.8 1 20.8 434.92 < 0.0001
AC 7.03 1 7.03 147.01 < 0.0001
BC 2.31 1 2.31 48.32 < 0.0001
2
A 127.76 1 127.76 2671.19 < 0.0001
2
B 336.75 1 336.75 7040.95 < 0.0001
2
C 167.99 1 167.99 3512.5 < 0.0001
Residual 0.48 10 0.048
Lack of Fit 0.036 5 7.24E-03 0.082 0.9921 Not significant
Pure Error 0.44 5 0.088
Cor Total 2493.03 19
From different models such as the linear, 2F1, quadratic and cubic, quadratic is selected on the
bases of p-values, Lack of fit test and R-Square. A P-value (P< 0.0001) indicates the
signifficance of quadratic model. In addition, absence of any lack of fit (P> 0.05) strengthened
the reliability of the model.
The predicted model equation that relates the response to the parameters affecting the response
interms of actual and coded factors is desplayed below.
Final equation in terms of coded factors:
% biodiesel yeild 96.81 1.01 A 0.22 B 1.03 C 1.61 AB 0.94 AC 0.54 BC
2 2 2
6.82 A 11.07 B 7.82 C
Where: A- Catalyst
B- methanol to oil molar ratio
C- temperature
Final equation in terms of actual factors:
% biodiesel yeild 96.81 1.01 catalyst 0.22 methanol to oil molar ratio 1.03 temperature
1.61 catalyst methanol to oil molar ratio 0.94 catalyst temperature
- 0.54 methanol to oil molar ratio. temperature -
2 2 2
6.82 catalyst – 11.07 methanol to oil molar ratio – 7.82
Std. Dev. 0.22 R- squared 0.9998
Mean 83.96 Adjusted R- squared 0.9996
C.V. % 0.26 Predicted R- squared 0.9995
PRESS 1.34 Adequacy Precision 185.787
60
Table 4.18 Analysis of variance (ANOVA) table for response surface quadratic model
The Model F-value 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 0.0100 indicate
2 2 2
model terms are significant. In this case A, B, C, AB, AC, BC, A , B , C are significant model
terms. The "Lack of Fit F-value" of 0.08 implies the Lack of Fit is not significant relative to the
pure error. There is a 99.21% chance that a "Lack of Fit F-value" this large could occur due to
noise. Non-significant lack of fit is good; we want the model to fit. As it can be seen from p-
values of the model coefficients, the value of temperature and catalyst mass in both linear and
quadratic is much more less than 0.001. This indicated that both parameters are more significant
than the third parameter i.e. methanol to oil molar ratio. The non-significant lack of from the
ANOVA indicated that the model represent the actual relationships of reaction parameters.
Table 4.19 Adjusted versus predicted R-squared

The predicted R- squared of 0.9995 is in reasonable agreement with the adjusted R- squared of
0.9996. A rule of thumb is that the adjusted and predicted R-squared values should be within 0.2
of each other. Here the values are within the order of 0.0001. Adequacy precision measures the
signal to noise ratio. A ratio greater than 4 is desirable. The ratio of 185.787 indicates an
adequate signal. This model can be used to navigate the design space. The plot between
predicted vs. actual (fig. 4.8) is a good tool to study the significance of suggested model. The
responses predicted from the empirical model are in agreement with the observed values in the
range of the operating variables. Maximum points are on the line.
The normal probability plot is shown in( Fig. 4.9). The general impression from examining this
display is that as the plot resembles a straight line so there is not much of a problem with the
Predicted
normality of the data. Outlier detection was done using index plots of externally studentized
residuals (Fig. 4.10).
Linearity and quadratic effect of the independent variables and their interactions on the response
variable were evaluated by analysis of variance (Table 4.18). The ANOVA of the regression
61
model showed that the model was highly significant due to a very low probability value (P<
0.0001).
The P-values were used as a tool for checking the significance of each coefficient, which in turn
might indicate the interaction patterns between the variables. The smaller the P-value, the more
significant was the corresponding coefficient.
Design-Expert® Software Predicted vs. Actual

FAME 98.0
Color points by value of

FAME:
90.5
97.1
68.0
83.0
75.5
68.0
68.0 75.3 82.5 89.8 97.1
Actual
Fig.4.8 plot of actual versus predicted percentage yield of biodesiel
Normal%Probability
62
InternallyStudentizedResiduals
Design-Expert® Software Normal Plot of Residuals

FAME
99.0
FAME: 95.0
97.1 90.0
80.0
68.0 70.0
50.0
30.0
20.0
10.0
5.00
1.00
FAME

Fig.4.9 FAME:
97.1
Design-Expert® Software 68.0

-2.00 -
1.15 -0.299 0.553
1.41
Inter 1.50
nally Studentized Residu

als
0.000
Normal probability plot
of residuals.
-1.50
Residual
s vs. Run
3.00 -3.00
1.00 4.00 7.00 10.0 13.0 16.0 19.0
Run Number
Fig4.10.Index plots of internally studentized reseduals
63
4.3.3. Optimum conditions

As the fitted model presented in equation 4.1 offered a good estimate to the experimental
conditions, so the given model was employed to predict the best possible values of the
transesterification process variables for obtaining a maximum yield of FAME. Optimum
conditions are depicted by bold font in bold in table 4.17.
The optimal experimental conditions for biodiesel production using goat leather fleshing oil
acquired using the model were as follows: catalyst concentration (%) on weight basis 1, reaction
o o
temperature ( C) 60 C, and molar ratio of methanol to oil 6:1 for 1 hour reaction time and 750
rpm mixing intensity. Under these optimal conditions, the model predicted a maximum response
of 96.81 percentage yield of biodiesel from the oil.
4.3.4. Main factors affecting the yield of biodiesel

The effects of individual parameters and interaction factors are subsequently discussed in the
proceeding subsections. The factors selected for this study are temperature, catalyst
concentration and methanol to oil molar ratio.
4.3.4.1. Effects of individual process variables on biodiesel yield
4.3.4.1.1. Effect of methanol-to-oil molar ratio

Methanol-to-oil molar ratio is one of the important factors that affect the transesterification
process. The stoichiometric ratio for transesterification requires three moles of alcohol and one
mole of triglyceride to yield three moles of FAME and one mole of glycerol. However,
transesterification is an equilibrium reaction in which a large excess of alcohol is required to
drive the reaction to the right side of reaction products [54].
In the present work, the effect of a methanol-to-oil molar ratio was varied from 3:1 to 9:1 on
conversion to biodiesel was studied. When the methanol-to-oil molar ratio was 3:1, the
conversion to biodiesel was 85.5% (Figure 4.17). The maximum conversion to biodiesel was
obtained at 6:1 and a further increment did not result in higher conversion to biodiesel since the
excess of methanol deactivated the catalyst [55]. The excess methanol, with one polar hydroxyl
group, could act as an emulsifier and thereby increase the solubility of glycerol in the ester
phase, making the separation more difficult. The glycerol that remained in solution could drive
the equilibrium back to the left, reducing the ester conversion. Consequently there will be
FAME
64
recombination of esters and glycerol to MAGs in the excess of methanol [56]. However, at
industrial scale increasing the amount of methanol is not a problem in terms of yield, since
methanol is recovered from ester and glycerol phases [57]. Even in industrial set up further
increase in the amount beyond the optimal ratio will increase the cost of alcohol recovery. The
use of excess methanol will shift the equilibrium to the right and improve FAME yield, but
beyond a certain value (6:1 in this case) the excess methanol causes dilution.
68.0
Design-Expert® Software
98.0
FAME
Design Points
90.5
X1 = B: Methanol : oil
Actual Factors 83.0

A: Catalyst = 1.00
C: Temprature = 60.0
75.5
One Facto
r 2 2
3.00 4.50 6.00 7.50 9.00
B: Methanol : oil
Fig. 4.11. Effect of methanol to oil molar ratio on percentage yield of biodiesel
4.3.4.1.2. Effect of reaction temperature

Temperature clearly influences the reaction and yield of the biodiesel product. The reaction
temperature was varied at six different levels to determine the effect of reaction temperature on
GLFO biodiesel production. As can be seen from table
2 4.17, when the reaction temperature was
60°C, the conversion to biodiesel reached 97.1%.
Initially increased biodiesel yield was observed as temperature increased due to the fact that
viscosity of oils decreases at high temperature which results in an increased reaction rate. With
65
further increase in reaction temperature, there was little increase in conversion to biodiesel. The
reaction temperature above the boiling point of methanol (65°C) should be avoided since at
higher temperature, methanol tends to be lost and high temperature accelerates saponification of
FAME
the glycerides by alkaline catalyst [58].
The results obtained in this study confirmed that higher a temperature of 65 °C was not
beneficial for transesterification a decrease in conversion to biodiesel was observed.
o
The temperatures in the range from 62 to 70 C caused evaporation of methanol and reduced the
overall ester yield [56].
Although a reflux condenser was used to avoid methanol losses, the ester yield significantly
decreased at temperatures of greater than 60 °C, probably because of a negative interaction
between temperature and catalyst concentration, due to side reactions, such as soap formation
completion of the alcoholysis.
Design-Expert® Software FAME

FAME = 88.0 98.0
One Factor 3
Design Points 90.5 2
X1 = C: Temprature = 65.0 2
Actual Factors 83.0

A: Catalyst = 1.00
B: Methanol : oil = 6.00
75.5
68.0
55.0 57.5 60.0 62.5 65.0
C: Temprature
2
Fig. 4.12. Effects of temperature on percentage yield of biodiesel
FAME
66
2
4.3.4.1.3. Effect of catalyst mass/concentration
The biodiesel yield was increased as the catalyst concentration increased up to a certain level.
Further increasing catalyst concentration beyond optimum values caused a decreased biodiesel
yield. The addition of an excessive amount of catalyst, gives rise to the formation of an
emulsion, which increases the viscosity and leads to the formation of gels. These hinder the
glycerol separation and, hence, reduce the apparent ester yield. These results are in good
agreements obtained by other investigators [59].
Design-Expert® Software One Factor

98.0 3
FAME
Design Points 90.5

2
X1 = A: Catalyst 68.0
Actual Factors 83.0

75.5
2
0.500 0.750 1.00 1.25 1.50
A: Catalyst
Fig.4.13 Effect of catalyst concentration on percentage yield of biodiesel
4.3.4.2. Effects of interaction of process variables on percent yield of biodiesel

The 3D and contour plots of interaction effects of process variables over the FAME yield were
drawn and subsequently descriptions are given. Each contour curve represents effects of two
process variables while holding the third at constant level.
67
FAME
4.3.4.2.1. Effect of methanol to oil molar ratio and temperature on Biodiesel yield
The following consecutive interaction, 3D and contour plots show the effect of varying
temperature and methanol to oil molar ratio while the catalyst concentration i.e. weight by
weight catalyst to oil is at 1. Initially the effect of low level of methanol to oil molar ratio and
temperature produces low level of FAME percentage yield. Further increase of both process
variables will enable optimum amount of yield where as an increase beyond some levels
decreases the yield. The effect of increasing temperature beyond the boiling point of methanol
will decrease the interaction of the oil with methanol which leads to a decreased yield.
Design-Expert® Softw are Interaction

FAME C: Temprature
98
3
Design Points
C- 55.000
C+ 65.000 90.5
X2 = C: Temprature
Actual Factor 83
A: Catalyst = 1.00
75.5
68
3.00 4.50 6.00 7.50 9.00
B: Methanol : oil
A/ interaction plot
FAME
68
Design-Expert® Softw are
FAME
97.1
68
98
X2 = C: Temprature
92.5
Actual Factor
A: Catalyst = 1.00
87
C:Temprature
81.5
76
65.00 9.00
62.50 7.50
60.00 6.00
57.50 4.50
C: Temprature B: Methanol : oil
55.00 3.00
7. X1 = B: Methanol : oil
1 X2 = C: Temprature
Actual Factor
Design-Expert® Softw are A: Catalyst = 1.00
8
FAME
Design Points
83.3358
/3
D
plo
t
65.00 86.7127 86.7127
6
62.50
A
M
60.00
E
93.4664
83.3358
83 83.3358
.335 90.0896
57.50 8 3.00 4.50 6.00 7.50 9.00
B: Methanol : oil
55.00
69
C/ contour plot
Fig.4.14 the effect of methanol to oil molar ratio and temperature on FAME percentage yield
4.3.4.2.2. Effect of methanol to oil molar ratio and catalyst on Biodiesel yield
The individual effects of methanol to oil molar ratio and weight by weight catalyst ratio have
FAME
been discussed in their respective sub sections. Here, the effect of the interaction of the two
variables is depicted using contour, interaction and 3D plots. It is possible to see from the plots
that initially percentage FAME yield increases with increasing catalyst and methanol to oil molar
ratio. Further increase of both the methanol and the catalyst decreases the percent yield. This
might be due to the fact that increasing catalyst mass favors formation of soap than the biodiesel
and an increase in methanol beyond the limit will hinder the conversion of fatty acids to FAME.
This might be due to the inactivation of the catalyst or emulsification of the glycerol by the
alcohol.

Actual
FAME 98
or
Design Points C:
ure
B- 3.000
B+ 9.000 90.5
X1 = A: Catalyst
83.2996
B:Methanol:oil
79.9133
70

9.00
FAME
79.9133 86.6859
FAME
FAME
Design Points
97.1
68
7.50
X1 = A: Catalyst
X2 = B: Methanol : oil 90.0722
Actual Factor 6.00

C: Temprature = 60.00 Design-Expert®
Softw
FAME
4.50
3.00
6 6.6
1.25 1.50
859
0.50 A: Catalyst
93.4585 0.75
1.00 B/contour plot

83.2996 83.2996
98
X1 = A: Catalyst
92.5
Actual Factor
87
81.5
76
9.00 1.50
7.50 1.25
6.00 1.00
4.50 0.75
B: Methanol : oil 3.00 0.50
A: Catalyst
C/3D plot
Fig. 4.15 the effect of methanol to oil molar ratio and catalyst mass on FAME percentage yield
FAME
71
4.3.4.2.3. Effect of temperature and catalyst mass on Biodiesel yield

It can be observed from the following plots that initial increase in both the temperature and the
catalyst increases the yield of FAME. As both the temperature and the catalyst increases the
FAME percent yield starts to decline. The result might be due to the fact that an increase in
temperature will lead to evaporation of the alcohol and an excessive amount of catalyst, gives
rise to the formation of an emulsion, which increases the viscosity and leads to the formation of
gels that hinder the glycerol separation and, hence, reduce the apparent ester yield.
The contour, interaction and 3D plots of the interaction effect of catalyst and temperature is
depicted in the subsequent figures below.
Design-Expert® Softw are X2 = C: Temprature

X1 =
FAME Actual Factor
A: C B: Methanol : oil = 6.00
Design Points
atal
C- 55.000
C+ 65.000 yst
83
Interaction
C: Temprature
98
3
2
75.5
90.5
68
0.50 0.75 1.00 1.25 1.50
A: Catalyst
FAME
A/ interaction plot
72
FAME
C:Temprature
97.1
68
98
X1 = A: Catalyst
X2 = C: Temprature
93.75
Actual Factor
89.5
85.25
81
65.00 1.50
62.50 1.25
60.00 1.00
57.50 0.75
C: Temprature 55.00 0.50
A: Catalyst
B/ 3D plot

FAME 65.00
FAME
83.711 88.9789
Design Points 86.345
86.345
97.1
68
62.50
X1 = A: Catalyst
X2 = C: Temprature
Actual Factor
60.00 6
57.50
88.9789 94.2469
86.345
88.9789
91.6129
83.711
86.345
55.00
0.50 0.75 1.00 1.25 1.50
A: Catalyst
C/ Contour plot
Fig. 4.16. The effect of temperature and catalyst mass on FAME percentage yield
73
Constraints Lower Upper Lower Upper
Name Goal Limit Limit Weight Weight Importance
Catalyst in range 0.5 1.5 1 1 3
Methanol to oil
in range 3 9 1 1 3
molar ratio
Temperature in range 55 65 1 1 3
FAME maximize 68 97.1 1 1 5
Solution Catalyst Methanol to oil Temperature % yield of Desirability Remark
number molar ratio FAME
1 1.04 6.05 59.64 96.891 0.993 selected
4.4. Optimization of process variables
The optimization of process variables with in the selected ranges for maximum conversion of the
oil to FAME was evaluated using Design Expert 7.0.0. The optimum result predicted by the
model was found to be 96.891% FAME at catalyst weight by weight percent of 1.04, temperature
O
of 59.64 C and methanol to oil molar ratio of 6.05.
Table 4.19 optimization of process variables
Solution
0.5 Catalyst 1.04 1.5 55 Temperature 65

o
59.64 c
0.5 Methanol to oil molar 1.5

ratio 6.05 :1
68 FAME 97.1
74
96.891
Desirability = 0.993
Fig 4.17. Optimization of process variables for maximum conversion of oil to FAME
Desirability
Fig 4.18. Desirability of the experimental process variables
4.5. Gas chromatograph-Mass spectroscopy analysis of the produced biodiesel
The samples for sheep, goat and hide fleshing FAMEs were prepared according to the method
described in section 3.4. The method employed for identification of species was the internal
standard. Individual fatty acids of the oil were identified by comparing retention time i.e. the
time at which the peak is observed and the chromatographic profiles of the samples. The gas
chromatograms of FAMEs of the sheep, goat and hide fleshing oils are presented subsequently in
the following figures. The peak values of the corresponding FAMEs are presented in the annex.
75
Fig.4.19. Goat fleshing FAME chromatogram
76
Fig 4.20. Hide fleshing FAME chromatogram
77
Fig 4.21. Sheep fleshing FAME chromatogram
78
4.6. Physicochemical properties of the FAME from goat fleshing oil

Density(mg/l)
The physicochemical analysis of the biodiesel was conducted. The procedures followed were
those discussed in the materials and methods section.
4.6.1. Density of the FAME of the goat fleshing oil
The density of the biodiesel was measured at different temperature using pycnometer. The result
of the biodiesel density measurement at different temperatures is depicted by figure 4.22.
The density of biodiesel is a factor which influences the efficiency of atomization and depends
o
on alkyl ester content and remained amount of alcohol. The density value of biodiesel at 25 C is
3 3
adopted to be between 860 and 900 kg/m by EN14214 standard and between 875 and 900 kg/m
3
ASTM D 6751-02. The result obtained from the experiment i.e 880 kg/m was found to be
within the range.
0.89
0.88
0.87
0.86
0.85
0.84
20 25 30 35 40 45 50 55 60
Temprature (oc)
Fig. 4.22 Density of goat leather fleshing biodiesel at different temperature
4.6.2. Kinematic viscosity of the FAME of the goat fleshing oil

The viscosity of biodiesel is influenced primarily by the experimental conditions and the extent
of transesterification reaction [60]. Therefore it is possible to find different viscosity values for
esters originated from the same type of feedstock due to incomplete reaction i.e presence of acyl
glycerol and inherent biodiesel purification. The kinematic viscosity of the treated oil and the
79
biodiesel was measured and the result was depicted under section 4.2.1.2. The method to
calculate the kinematic viscosity was discussed under section 3.3.2.
o 2
The standard values for kinematic viscosity biodiesel at 40 C are EN14214 (3.5-5.0 mm /s) and
2 2
the ASTM D6751 (1.9-6.0 mm /s). The experimental result 5.9 mm /s was slightly higher than
the limits dictated by EN.
4.6.3. Acid value of the FAME of the goat fleshing oil

The acid value of the biodiesel was determined employing the similar procedure stated under
section 3.3.3. The result obtained was 0.48 mg KOH/g.
4.6.4. Moisture and ash contents of the FAME of the goat fleshing oil
The moisture and ash contents of the produced biodiesel were measured using procedures
mentioned under sections 3.2.2 and 3.2.3. The moisture and ash contents were 0.023 and 0.021
respectively.
4.6.5. Iodine value of the FAME of the goat fleshing oil

The iodine value of the produced biodiesel was calculated using equation 3.8 that was discussed
under section 3.3.6. Iodine value is a measure of total unsaturation within a mixture of fatty acid.
It is expressed in grams of iodine which react with100 g of biodiesel when formally adding
iodine to the double bonds. It is limited to 120 g I2/100 g in the European biodiesel standard EN
14214. The iodine value of the biodiesel was found to be 65.13 g I2/100g.
4.6.6. Cetane number of the FAME of the goat fleshing oil

The cetane number (CN) is a dimensionless number for diesel just as the octane number is for
gasoline and is associated with ignition delay time, i.e., the time between fuel injection the
beginning of ignition. The shorter the ignition time, the higher the cetane number.it is the
calculated value based on equation 3.10 under section 3.3.8. Cetane number (CN) is determined
in accordance with ASTM D 613 and is one of the primary indicators of diesel fuel quality. It is
related to the ignition delay time a fuel experiences once it has been injected into a diesel
engine’s combustion chamber. Generally, shorter ignition delay times result in higher CN and
vice versa. Hexadecane, also known as cetane (trivial name), which gives the cetane scale its
name, is the high-quality reference standard with a short ignition delay time and an arbitrarily
assigned CN of 100 [61]. The cetane number of the biodiesel was calculated to be 68.5.
80
Optimization and characterization of biodiesel production from leather industry fleshing waste
s
4.6.7. Higher heat value of the FAME of the goat fleshing oil
The higher heat value of the biodiesel was calculated using equation 3.9 under section 3.3.7. Th
e
calculated value was 42.38 MJ/kg.
4.7. Comparison of the biodiesel properties with ASTM and EN Standards
The general comparison of the biodiesels produced in this experiment with internation
al
standards is illustrated in Table 4.20. As it can be observed in the table, majority of t
he
physicochemical properties of the fleshing oil biodiesel were in agreement with the internation
al
standards.
Table 4.20 Comparison of experimental biodiesel with standards
Physicochemical Unit Experimental EN ASTM D Diesel Test method

properties biodiesel 14214 6751-10
o 3
Density at 25 C kg/m 880 860-900 875-900
840-860 (EN ISO 3675 &
ASTM D 5002)
2
Kinematic
o
viscosity at 40 C
Acid value mg KOH/g 0.48 ≤ 0.5 ≤ 0.8 - ASTM D 664
HHV MJ/kg 42.38 - - 43.3-46.7 -
Iodine value g I2/100g 65.13 120 max - - ASTMD 5558
Cetane number - 68.5 - 46 - 70 47 - 55 ASTM D613
Moisture content % w/w 0.023 - < 0.03
Ash content % w/w 0.021 <0.02 <0.03 ASTM D482
mm /s 5.99 3.5-5.0 1.9-6.0 1.9 - 3.8 ASTM D 445
81
5. CONCLUSION AND RECOMMENDATION
5.1. Conclusion
The fat obtained from the leather industry fleshing wastes was used successfully for the
production of acceptable quality biodiesel. It was proved that fleshing wastes from tanneries that
storage and disposal are both troublesome and costly could be transformed to a fuel with low
emission values and a performance close to diesel fuel.
The GC-MS analysis result showed that all the three types of wastes i.e goat, sheep and hide
fleshing wastes can be acceptable candidates for producing biodiesel. In this research the
experimental oil yield obtained from washed, delimed and dried goat fleshing waste was 23.08%.
Degumming only was sufficient to reduce the FFA level to proceed with direct homogenous base
catalyzed transesterification.
Three major factors and their interaction effects on transesterification were studied. The
optimum conditions were evaluated using design expert 7.0.0 software. The transesterification
reaction yield was 97% at 1% catalyst concentration on weight basis, reaction temperature of 60
o
C, and methanol to oil molar ratio of 6 :1 for one hour reaction time and 750 rpm mixing
intensity.
3
The produced biodiesel has density, kinematic viscosity, iodine value and HHV of 880 kg/m ,
2
5.99 mm /s, 65.13 g I2/100g and 42.38 MJ/kg respectively. The physicochemical analysis result
shows that majority of the parameters fall within the range of values established by EN and
ASTM. Therefore environmental polluting leather fleshing waste can be converted to useful
energy generating product.
82
5.2. Recommendation
In this study of biodiesel production from leather industry fleshing wastes using Soxhlet
extraction was employed, although it was possible to produce high quality oil, Soxhlet cannot be
used for large scale industrial application. Further study on other ways of oil extraction is
therefore essential.
Effect of blending the oils from goat, sheep and hide fleshing oils at different proportions and
blending with other feed stocks should be studied to use the advantage of the qualities each of
them have individually.
This study has focused on homogenous base catalyzed transesterification; a complimentary

heterogeneous, super critical and biological catalysis should be tried for better environmental
protection. Exhaust gas emission profile studies, engine performance studies and should be
carried out.
The economic feasibility study on large scale production and commercialization should be
undertaken. Since gum, glycerol and compostable waste residues are produced as side products
during the production process additional studies on using these products for different
applications shall be initiated.
83
REFERENCE
1. Kırtay. E, Recent advances in production of hydrogen from biomass Energy Conversion
Management 2011. 52 (4): p. 1778-1789.
2. Balat. M and Balat. H, Progress in biodiesel processing. Appl Energy, 2010. 87: p. 1815-
35.
3. IULTCS, I.C.o., Technical guidelines for environmental protection aspects for the world
leather industry, 2008.
4. Alptekin E et al, Evaluation of leather industry wastes as a feedstock for biodiesel
production. . Fuel, 2011.
5. Demirbas.A, Biofuels, in: Green Energy and Technology. 2009: Springer London. 103-
230.
6. Utlu, Z., Evaluation of biodiesel fuel obtained from waste cooking oil, part A. Energy
Sources 2007. 29: p. 1295.
7. Eshetu Getahun and Nigus Gabiyye, Experimental investigation and characterization of
biodiesel production from leather industry fleshing wastes International Journal of
Renewable and Sustainable Energy 2013. 2(3): p. 120-129
8. Abebe Reda, Production and characterization of biodiesel from the traditional tannery
fleshing wastes. Ethiopian Journal of Science & Technology, 2014 7(1): p. 1- 13.
9. ArifinY., et al., A second generation biofuel from cellulosic agricultural by-product
fermentation using clostridium species for electricity generation Energy Procedia 2014
47 (310-315).
10. Patumsawad.S, 2nd generation biofuels: technical challenge and R&D opportunity in
Thailand SustainABLE Energy and Environment, 2011 p. 47-50.
11. Bhatti HN, MA.Hanif, and M.Qasim, Biodiesel production from waste tallow. Fuel,
2008. 87: p. 2961-2966.
12. JanaunJ and N.Ellis, Perspectives on biodiesel as a sustainable fuel. Renewable and
Sustainable Energy Reviews, 2010. 14: p. 1312-1320.
13. Robinson G, Changes in construction waste management. Waste Management World,
2007: p. 43-49.
84
14. Omer AM., Renewable energy resources for electricity generation in Sudan. Renewable
and Sustainable Energy Reviews 2007. 11: p. 1481-1497.
15. DiasJM, Alvim-FerrazMCM, and AlmeidaMF, Mixtures of vegetable oils and animal
fat for biodiesel production: influence on product composition and quality. Energy Fuel,
2008. 22: p. 3889-93.
16. Demirbas.A, Current technologies in biodiesel production. 2008: p. 161-73.
17. Tahiri S and G. MDL, Treatment and valorization of leather industry solid wastes: a
review. . J Am Leather Chem Assoc, 2009 104: p. 52-56.
18. Puntener A, The Ecological Challenge of Producing Leather. .JALCA, 1995. 90(7 ): p.
206.
19. Ozgunay, H., Characterization of leather industry wastes. Polish Journal of
Environmental studies, 2007. 16(6): p. 867-873.
20. Bienkiewiczk, Physical Chemistry of leather Making. 1983.
21. FerreiramJ and Xarae, Using ashes from Incineration of Chromium Sulphate Tanned
leather Scrap. Part I: Characterization of ashes and Chromium Extraction JSlTC, 2000.
84: p. 271.
22. Araújo.CD, M.d., et al., Biodiesel production from used cooking oil: a review
Reneweable Sustainable Energy 2013: p. 445-452.
23. Zhang.Y, et al., Biodiesel production from waste cooking oil: Economic assessment and
sensitivity analysis Bioresource Technology 2003. 90(3): p. 229-240.
24. Akhihiero E.T, Oghenejoboh K.M, and Umukoro P.O, Effects of Process Variables on
Transesterification Reaction of Jatropha Curcas Seed Oil for the Production of Biodiesel.
International Journal of Emerging Technology and Advanced Engineering 2013. 3( 6).
25. Costa.J, et al., Biodiesel production using oil from fish canning industry wastes. Energy
Conversion Management 2013 74: p. 17-23.
26. Zhang.X, et al., Energy balance and greenhouse gas emissions of biodiesel production
from oil derived from wastewater and wastewater sludge Reneweable Energy 2013
55392-403(55): p. 392-403.
27. Hemmat.Y, et al., Biodiesel fuel production from resdual animal fat as an inedible and
inexpensive feedstock. International Research Journal of Applied and Basic Sciences,
2013. 5: p. 84-91.
85
28. Banković-IlićIB, et al., Waste animal fats as feedstocks for biodiesel production. 2014.
32: p. 238-254.
29. Chakraborty R, AK Gupta, and R. Chowdhury, Conversion of slaughterhouse and
poultry farm animal fats and wastes to biodiesel: Parametric sensitivity and fuel quality
assessment. Renewable and Sustainable Energy Reviews, 2014. 29: p. 120-134.
30. Salvi BL and P. NL, Biodiesel resources and production technologies -a review. Renew
Sust Energy Rev 2012 16: p. 3680-3689.
31. Boocock D. G. B, et al., Fast one-phase oilrich processes for the preparation of
vegetable oil methyl esters Biomass. Bioenerg, 1996a. 11: p. 43-50.
32. Liu.X, et al., Calcium ethoxide as a solid base catalyst for the transesterification of
soybean oil to biodiesel. Energ. Fuel 2008. 22: p. 1313-1317.
33. Lotero.E, et al., Synthesis of biodiesel via acid catalysis. Industrial Engineering Chemical
Research 2005. 44: p. 5353-5363.
34. B.Thazeem, K.Preethi, and M. Umesh, Characterization and fermentative utilization of
tannery fleshings Using Lactobacillus Plantarum International Journal of Recent
Scientific Research 2015. 6(3): p. 3037-3041
35. Pratas.M.J, et al., Biodiesel Density: Experimental Measurements and Prediction Models
Energy Fuels 2011. 25 p. 2333-2340.
36. Frankel.E. N, Lipid oxidation. The Oily Press. Vol. 2 2005.
37. Knothe G., “Designer”biodiesel: optimizing fatty ester composition to improve fuel
properties. . Energy and Fuel 2008. 22: p. 1358-1364.
38. Rao, G.L.N., et al., Relationships among the physical properties of biodiesel and engine
fuel system design requirement International Journal of Energy and Environment 2010
1(5): p. 919-926
39. Sawangkeaw R and S.Ngamprasertsith, A review of lipid-based biomasses as feedstocks

for biofuels production Renewable and Sustainable Energy Reviews 2013 25: p. 97-108.
40. Lebedevas.S, et al., Use of waste fats of animal and vegetable origin for the production of
biodiesel fuel: quality, motor properties, and emissions of harmful components Energy &
Fuels 2006. 20: p. 2274-2280.
86
41. Canoira L, et al., Biodiesel from low-grade animal fat: production process assessment
and biodiesel properties characterization. Industrial and Engineering Chemistry
Research, 2008. 47: p. 7997-8004.
42. Seidel B, et al., Safety evaluation for a biodiesel process using prion-contaminated
animal fat as a source Environmental Science and Pollution Research 2006. 13(125-
130).
43. Thamsiriroj.T and Murphy.JD, How much of the target for biofuels can be met by
biodiesel generated from residues in Ireland? Fuel 2010. 89: p. 3579-89.
44. Encinar.J, et al., Study of biodiesel production from animal fats with high free fatty acid
content. Bioresource Technology, 2011. 102: p. 10907-10914.
45. Bondioli.P, et al., Biodiesel stability under commercial storage conditions over one year.
European Journal of Lipid Science Technology, 2003. 105: p. 35-74.
46. Kerschbaum.S, Rinke.G, and Schubert.K, Winterization of biodiesel by mirco process
engineering Fuel 2008. 87: p. 2590-2597
47. Cocks, L.V. and C. Vanrede, Laboratory Hand book foroil and Fat analysis. 1984, New
York: Lawson press.
48. Milinsk, M.C., et al., influence of esterification method on quantification of olive oil fatty
acids. Semina Cliencias Exatas e Technologicas Londrina, 2011. 32(2): p. 139-150.
49. Bannon C.D, et al., analysis of fatty acid methyl esters with high accuracy and reliability.
II methylation of fats and oils with oron triflouride metanol. journal of chromatography,
Amsterdam, 1982a. 243(1): p. 63-69.
50. Halvorsen J. D, et al., Density estimation for fatty acids and vegetable oils based on their
fatty acid composition Journal of American Oil Chemistry Society 1993 9(70): p. 875-
880
51. Knothe G, Gerpen J.V, and Krahl J, The Biodiesel Handbook. . 2005 Champaign, Illinois
AOCS Press
52. Lin C-Y, Lin H-A, and Hung L-B, Fuel structure and properties of biodiesel produced by
the peroxidation process. Fuel 2006 85 p. 1743-1749.
87
53. Knothe G, Sharp C. A, and Ryan T. W. III, Exhaust emissions of biodiesel, petrodiesel,
neat methyl esters, and alkanes in a new technology engine. . Energ. Fuel, 2006 20: p.
403-408
54. Dennis Y.C. Leung, Xuan Wu, and M.K.H. Leung, A review on biodesiel production
using catalyzed transesterification. applied energy, 2010.
55. Chung KH, Kim J, and L. KY, Biodiesel production by transesterification of duck tallow
with methanol on alkali catalysts Biomass Bioenergy 2009 33 p. 155-8.
56. Ivana B, et al., Waste animal fats as feedstocks for biodiesel production. Elsevier, 2014.
57. Panneerselvam S.I, Parthiban R, and M. L.R, Poultry fat-a cheap and viable source for
biodiesel production. In: Proceedings of the 2nd International Conference on
Environmental Science and Technology IPCBEE. Singapore:. IACSIT Press 2011 6 p.
371-374.
58. Junhua Zhang, Lei Zhang, and L. Jia, Variables seed oil with high free fatty acids
affecting biodiesel production from Zanthoxylum bungeanum Industrial & Engineering
Chemistry research, 2012 51 p. 3525−3530.
59. Meng, X., G. Chen, and Y. Wang, Biodiesel production from waste cooking oil via alkali
catalyst and its engine test Fuel Process Technology 2008 89 (9): p. 851-857.
60. Enweremadu CC and Mbarawa MM, Technical aspect of production and analysis of
biodiesel from used cooking oil- a review. Renew Sust Energy Rev, 2009. 13: p. 2205-
2224.
61. Knothe G, Bagby M. O, and Ryan T. A. III, Cetane numbers of fatty compounds:
influence of compound structure and of various potential cetane improvers SAE Tech.
Pap. , 1997: p. 127-132
88
ANNEXES
Annex A: Qualitative GC-MS analysis test result for goat fleshing FAME
89
90
91
92
93
Annex B: Qualitative GC-MS analysis test result for hide fleshing FAME
94
95
96
97
98
Annex B: Qualitative GC-MS analysis test result for sheep fleshing FAME
99
100
101
102
103
104

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Optimization and characterization of biodiesel production from leather industry fleshing wastes

Addis Ababa University

Addis Ababa Institute of Technology

School of chemical and Bio-Engineering

Optimization and Characterization of Biodiesel Production from Leather

A thesis submitted to the school of graduate studies of Addis Ababa Institute

By: Henok Dagne

Advisor: Dr. Rajan Karthikeyan

Co-advisor: Dr. Sisay Feleke

Addis Ababa, Ethiopia

ADDIS ABABA UNIVERSITY

SCHOOL OF CHEMICAL AND BIOENGINEERING ENVIRONMENTAL

A thesis submitted to the school of chemical and Bioengineering,

Approved by Board of Examiners

I would like to express my acknowledgement to Ethiopian Environment and Forest research

My special gratitude shall go to my co advisor, Dr. Sisay Feleke, researcher at Ethiopian

Keywords: Biodiesel, fleshing oil, homogenous catalysis, pretreatment, transesterification

ABSTRACT ........................................................................................................................... …..II

TABLE OF CONTENTS …………………………………………………………………..…....III

LIST OF ABBREVIATION ………………………………………………………….…..…... VII

LIST OF FIGURES…………...……………………………………………………… …. .....VIII

LIST OF TABLES ……………………………………..………………………………….…... IX

1.1. Background of the study ...................................................................................................... 1

1.2. Statement of the problem ..................................................................................................... 3

1.3. Objectives ............................................................................................................................ 5

1.4. Significance of the study..................................................................................................... 6

2. LITERATURE REVIEW ..................................................................................6

2.2. Leather processing ............................................................................................................... 7

2.3. Characterization of leather fleshing wastes ....................................................................... 10

2.3.1. Water Content ............................................................................................................. 10

2.3.3. Fat content................................................................................................................... 11

2.3.4. Thermal Values ........................................................................................................... 11

2.4. Biodiesel production .......................................................................................................... 11

2.4.1. Pretreatment ................................................................................................................ 12

2.4.3. Catalysts for Biodiesel Production............................................................................. 14

2.5. Leather Industry Fleshing Waste a challenge and opportunity.......................................... 15

2.6.1. Specific gravity ........................................................................................................... 16

2.6.2. Low-temperature operability ...................................................................................... 16

2.6.3. Oxidative stability....................................................................................................... 17

2.6.4. Kinematic viscosity..................................................................................................... 18

2.6.5. Flash point................................................................................................................... 19

2.6.6. Higher heating value (HHV)....................................................................................... 20

2.8. Factors affecting biodiesel production yield and quality................................................... 21

2.9. Advantages and Disadvantages of Biodiesel ..................................................................... 21

2.10. Food versus fuel ............................................................................................................. 22

3. MATERIALS AND METHODS........................................................................ 23

3.2. Physico-chemical characterization of raw material ........................................................... 25

3.2.1. pH measurement ......................................................................................................... 25

3.2.2. Moisture content of the delimed fleshing waste ......................................................... 25

3.2.4. Total fat content of delimed fleshings ........................................................................ 26

3.3. Physicochemical characterization of leather fleshing oil and biodiesel ............................ 26

3.3.1. Determination of specific gravity ............................................................................... 26

3.3.2. Determination of kinematic viscosity ......................................................................... 26

3.3.3. Acid value (Acid Number) determination .................................................................. 27

3.3.4. Saponification value determination ............................................................................ 27

3.3.5. Determination of iodine value .................................................................................... 29

3.3.6. Determination of high heat value................................................................................ 29

3.4. Quantification of leather fleshing oil fatty acids............................................................... 29

3.5. Experiments ....................................................................................................................... 30

3.5.1. Flesh Waste Treatment and Oil Extraction ................................................................. 30