Professional Documents
Culture Documents
Semester Project
Mentor approval
This is to certify that the above statement made by the candidates is correct to the best of my
knowledge and belief. This project has been submitted for presentation with my approval.
i
Acknowledgment
First and for most we would like to give great praise to our Lord, Jesus Christ, for his kindness,
forgiveness and guidance in our life. Secondly, we want to express our deepest appreciation to our
advisor Mr. Muluken Alem Who gave us advises, suggestions and comments regarding the project
during our work. Thirdly, we would like to give a thank to department of food engineering and
their lab assistances for letting us work in their lab and for helping us during our lab work.
ii
Executive Summery
Production of cotton seed ethyl ester (biodiesel) from vegetable oil for diesel substitute is
particularly important because it is renewable, ecofriendly and economical. Biodiesel is produced
by transesterification of oil and alcohol with the presence of a catalyst. Three principal variables,
molar ratio of ethanol to oil, amount of catalyst, and reaction temperature affecting the yield of
alkaline catalyzed production of ethyl ester from cotton seed oil were investigated. The reaction
variables used were ethanol/oil molar ratio(6:1,3:1), catalyst concentration(0.75,1wt%) and
temperature(60,650c). the rate of transesterification in a batch reactor increased with temperature
up to 650C. the ethyl ester with best yield and quality was produced with cotton seed ethyl ester at
6:1 molar ratio and 1wt% catalyst (NaOH). The yield was 78.4%. It was noted that greater or lower
the concentration of NaOH or ethanol than the optimal values, the reaction either fully occur or
lead to soap formation. Physical property of cotton seed ethyl ester are compared to that of
petroleum diesel and Standard biodiesel.
iii
List of Table
Table 3.1. Equipments used during and after production ………………………….…………….. 7
Table 3.2. Chemicals used during and after production ……………………………………….....7
Table 3.3. Experiment trials data ………………………………………………………………... 16
Table 4.1 Yield calculation for each trial ……………………………………………………..… 17
Table 4.2 Characterized values of each trial ………………………………………………..….. 18
Table 4.3 Property difference of trials made, Standard Biodiesel and Petrol Diesel ………...… 24
List of Figure
Figure 3.1 The experiment setup ……………………………………………………..………..... 9
Figure 3.2 Formation of Biodiesel and Glycerol ………...…………………………………..….. 13
Figure 3.3. Hydrometer measuring density of a sample a sample …………………………….… 14
Figure 3.4. VISCO STAR measuring viscosity of a sample ………………………………….… 15
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Table of Contents
Declaration ..................................................................................................................................................... i
Acknowledgment .......................................................................................................................................... ii
Executive Summery ..................................................................................................................................... iii
List of Table ................................................................................................................................................. iv
List of Figure................................................................................................................................................ iv
1. INTRODUCTION ................................................................................................................................ 1
1.1 Statement of the Problem ............................................................................................................ 2
1.2 Objective ....................................................................................................................................... 2
1.2.1 General Objective ................................................................................................................. 2
1.2.2 Specific Objective ................................................................................................................. 2
1.3 Significance of the project ............................................................................................................ 3
1.4 Scope of the Project ...................................................................................................................... 3
2. Literature Review.................................................................................................................................. 4
3. Material & Method ............................................................................................................................... 7
3.1 Material ......................................................................................................................................... 7
3.1.1 Equipments ........................................................................................................................... 7
3.1.2 Chemical ............................................................................................................................... 7
3.2 Method ......................................................................................................................................... 8
3.2.1 Raw Material Collection and Analysis ........................................................................................ 8
3.2.2 Free Fatty Acid Determination (FFA %) ..................................................................................... 8
3.2.3 Catalyst Preparation ..................................................................................................................... 8
3.2.4 Transesterification........................................................................................................................ 8
3.2.4.1 Reaction Kinetics .................................................................................................................. 9
3.2.5 Glycerol Separation............................................................................................................. 13
3.2.6 Washing .............................................................................................................................. 13
3.2.7 Water Removal ................................................................................................................... 13
3.2.8 Characterization .................................................................................................................. 14
3.2.9 Experimental Design ........................................................................................................... 16
4. Results and Discussions ...................................................................................................................... 17
4.1 Results ......................................................................................................................................... 17
4.1.1 Free Fatty Acid.................................................................................................................... 17
4.1.2 Yield.................................................................................................................................... 17
v
4.1.3 Biodiesel Physical Characterization.................................................................................... 18
4.2 Discussion.................................................................................................................................... 18
5. Conclusion & Recommendation ......................................................................................................... 20
5.1 Conclusion ................................................................................................................................... 20
5.2 Recommendation........................................................................................................................ 20
Reference .................................................................................................................................................... 21
vi
1. INTRODUCTION
Biodiesel, an alternative diesel fuel, is made from renewable biological sources such as vegetable
oils and animal fats. It is biodegradable and non-toxic has low emission profiles and so is
environmentally beneficial. Recently, because of increases in crude oil prices, limited resources of
fossil oil and environmental concerns there has been a renewed focus on vegetable oils and animal
fats to make biodiesel fuels. Continued and increasing use of petroleum will intensify local air
pollution and magnify the global warming problems caused by carbon dioxide. [4]
Biodiesel is a renewable substitute fuel for petroleum diesel fuel which is made from non-toxic,
biodegradable, renewable sources such as refined and used vegetable oils and animal fats. It is
produced by transesterification in which oil or fat is reacted with a monohydric alcohol in the
presence of a catalyst. The process of transesterification is affected by many factors such as mode
of reaction, molar ratio of alcohol to oil, type of alcohol, nature and amount of catalysts, reaction
time, and temperature. [5]
Various studies have been carried out using different oils as the raw material and different alcohols
(methanol, ethanol, butanol), as well as different catalysts, notably homogeneous ones such as
sodium hydroxide, potassium hydroxide, sulfuric acid, and supercritical fluids or enzymes such as
lipases. Recent research has focused on the application of heterogeneous catalysts to produce
biodiesel, because of their environmental and economic advantages. [6]
Biodiesel does not contain any sulfur, aromatic hydrocarbons, metals and crude oil residues. These
properties improve combustion efficiency and emission profile. Biodiesel fuel blends reduce
particulate material (PM), hydrocarbon, carbon monoxide and sulphur oxides. However, NOx
emissions are slightly increased depending on biodiesel concentration in the fuel .Due to the lack
of sulphur biodiesel decrease, levels of corrosive sulphuric acid accumulating in engine crank case
oil. [5]
1
Global biodiesel industry is projected to grow and touch around 3,900 Million Gallon by 2014.
Coming to in our country, so far there is no observable market use of biodiesel product in our
country Ethiopia. But currently there are more than 50 projects in progress from which 14 has
started operation in five different regions (Benshangl Gumuz, Amhara, Oromia, SNNP and
Gambella). For the production of biodiesel, especially for large production plants, the availability
of customers (demanders) plays a very crucial role. If we assess the customer status in Ethiopia, it
is believed there are a significant amount of demanders looking for low cost fuel (compared with
petro-diesel). [4]
Because Diesel produce oxides of sulfur oxides (SOX), oxides of nitrogen (NOX) and oxides of
carbon (CO & CO2) which has an increasing environmental concerns and also based on world
petroleum council (WPC) earth’s capacity to give petroleum will seize under 50 years, There is a
great demand for alternative sources of petroleum-based fuel. Biodiesel, a clean renewable fuel,
has recently been considered as the best candidate for a diesel fuel substitution.
1.2 Objective
1.2.1 General Objective
To Produce Biodiesel from Cotton seed oil
1.2.2 Specific Objective
a) To determine the free fatty acid value of cotton seed oil
b) To determine the optimum parameters such as alcohol to oil ratio, temperature and catalyst
concentration for maximum yield
c) To characterize the produced biodiesel
d) To compare quality of the produced biodiesel with Standard biodiesel and petrol diesel
2
1.3 Significance of the project
Biodiesel from cotton seed is considered the best candidate for diesel fuel substitute in diesel
engines because it is non-toxic, bio-degradable and also have similar operational properties with
that of petroleum based diesel fuel. Using biodiesel as an engine fuel has many Economical and
Environmental benefits.
Economically, producing biodiesel will substitute imported petroleum products and export
earnings, which enhance agricultural development and agro processing and also will create Jobs
and improve income of the people.
This project work ranges from characterization of cotton seed oil, finding proper operational
parameters for maximum yield, characterization & comparison of the produced biodiesel with that
of petrol diesel and standard diesel.
3
2. Literature Review
Extraction cotton seed oil was performed using soxhlet extraction method using hexane as a
solvent. And using anhydrous ethanol transesterification was carried out in a laboratory with a
molar ratio of which of 6 to 1 and 0.75wt% sodium methaoxide as a catalyst. The mixture was
stirred at 500rpm and 60OC for 2hrs which biodiesel was then the decanted from the glycerol. The
conditions used are similar to the optimized system parameters established by Rashid et al.,(2009)
of 6:1 methanol/oil molar ratio (mol/mol), 0.75% sodium methoxide concentration (wt %), 65OC
reaction temperature, 600 rpm stir rate, 90 min reaction time which fetched a maximum biodiesel
yield of 96.9%. After decanting, the lighter biodiesel was washed with deionized water thrice and
then chemically dried by passing it through anhydrous sodium sulphate (Na2SO4). Finally they
concluded that because of the low free fatty acid, the cotton seed oil did not require a two stage
treatment for biodiesel production by alkaline transesterification and also found out that the
biodiesel that was produced had similar properties with that of petrol diesel but with 84.49 cetane
number which was an additional benefit. [1]
A study was carried out for the preparation of cotton seed oil Biodiesel by base transesterification
process in which totally focused on the increase in ester content by changing the basic process
parameters. Here two 0parameters are kept constant and one parameter is increased and the degree
of esterification variation is studied. In this work, oil to alcohol ratio and temperature is kept
constant and catalyst concentration has been increased which results to different degree of
esterification for different catalyst concentration. Similarly the process temperature & catalyst
concentration kept constant and oil to alcohol ratio is increased, here too yield of biodiesel varies.
The process temperature changed and remaining two parameters oil to alcohol ratio &
concentration of catalyst are kept constant which gives a different yield. From the experimental
studies , the optimum process conditions for transesterification of cottonseed oil has been
examined which results in good yield of Biodiesel which is the best alternative fuel for petro diesel.
[2]
4
After the crude cotton seed oil was extracted from the seed, Esterification on the free fatty acid
was carried out with methanol and concentrated sulphuric acid (H2SO4) as a catalyst. The oil fed
into the reactor was preheated to 55OC before the catalyst and the alcohol mixture were added.
Agitation was provided with a speed controller mechanical stirrer, at a constant speed of 464rpm,
to overcome mass transfer limitations. The optimum condition was found after a certain trials
which is Methanol to oil ratio of 1:6, catalyst concentration of 1wt%, and a reaction temperature
of 60OC, at an agitation speed of 464rpm. The total Methylester formed after the process was
66.4%. Finally concluded that the biodiesel outcome depends on the concentration of catalyst used,
oil to alcohol ratio and temperature used for the process. [3]
Biodiesel yield with respect to time for 6:1 and 4.5:1and 3:1 molar ratio respectively at different
percentage of catalyst (KOH). It has been observed that there is higher yield in case of 6:1 molar
ratio as compared to 4.5:1 and 3:1 molar ratio. It may be because of alcohol using for 6:1 molar
ratio is more than that of 4.5:1 and 3:1 molar ratio. The yield for 0.5% KOH is less as compare to
0.75% and 1% KOH in all the cases. It may be because of 0.5% KOH is not sufficient to enhance
the reaction. The maximum yield obtained is 97.82 at 1% KOH for 6:1 molar ratio. [8]
Experiment was conducted on production & analysis of biodiesel from non-edible oils. Bio diesel
has become more alternative recently because of its environmental benefits and it is derived from
renewable resources, bio degradable and non-toxic in nature. Several bio diesel production
methods have been developed among which transesterification using alkali catalyst gives high
level of conversation of transesterification is effected by the reaction condition , molar ratio of
alcohol to oil ,type of alcohol, type and amount of catalyst, reaction there temperature , purity of
reactants free fatty acids and water content of oil’s or fats. Alternative fuels for diesel engines have
become increasingly important due to decreasing petroleum resource and environmental
consequences of exhaust gases from petroleum fuelled engines. [9]
5
The overall studies based on the production, fuel characterization, engine performance of different
biodiesel blends of waste cotton seed oil methyl esters were carried out. The kinematic viscosity
of diesel, waste cotton seed oil biodiesel were found as 2.8, 3.6 centistokes respectively at 400C.
The results indicated that the waste cotton seed oil biodiesel had the kinematic viscosity 75.69 %
more than that of diesel. The waste cotton seed oil biodiesel was found to have higher flash and
fire point than those of mineral diesel. The graphical results show that diesel has better
performance characteristics than biodiesel and biodiesel blends. Among the three different blends
of biodiesel, B10 has the better performance characteristics than B15 and B20 blend of biodiesel
when fuelled in an internal combustion engine. [10]
Cottonseed oil has enormous potential for biodiesel production. It is very clear that economics of
the product is controlled by the availability of raw materials. So, the plantation of the trees and
their usage should be properly managed to explore the benefits from this neglected plant. In
conclusion it’s found that in mechanical stirring the yield obtained at 1% KOH is higher as
compare to 0.75% KOH. Maximum yield up to 98% is obtained from CSO by using mechanical
stirrer technique. When we increase timing of stirrer the percentage of yields enhances. The overall
finding is that molar ratio 6:1 and timing of stirrer 30 minute is give good percentage of yields.
[11]
It was reported the optimal molar ratio of methanol to Cynara oil between 4.05-5.57, beyond which
either the catalytic transesterification is incomplete or glycerin separation becomes very difficult.
More than 98% conversion of vegetable oils to the methyl esters could be achieved at the molar
ratio of 6:1. [12]
6
3. Material & Method
3.1 Material
3.1.1 Equipments
3.1.2 Chemical
7
3.2 Method
3.2.4 Transesterification
Transesterification is the process of producing alkyl ester, commonly known as biodiesel, and
glycerol though the reaction of alcohol and oil in the presence of a base catalyst. Based on the trial
data given below on table 3, we mixed the catalyst solution, oil & ethanol with their perspective
8
temperature of 60 & 65OC which is below the boiling point of ethanol (78OC) in a flask. Before
sealing the flask with aluminum foil, in order to reduce ethanol escaping and better reaction
environment, we putted a stirring rod at the bottom of the flask for stirring purpose. Finally the
flask, after being sealed with the foil, was putted on a magnetic stirrer that operated with a constant
stirring speed for 90mins.
9
If it was possible it would have been recommended to remove the water from the mixture of
sodium ethoxide and water solution since water and oil reaction makes free fatty acids that may
convert to soap which is undesired reaction. But removing water is impossible since boiling point
of ethanol is lower than water. So the sodium ethoxide solution was poured into the flask that
contained oil with the respected value from table 3. Finally the catalyst-alcohol-oil solution was
constantly stirred for 90mins.
10
During transesterification process, 3 basic parameters namely oil to alcohol ratio, catalyst
concentration and temperature were used variously to determine the best possible way to gain a
better yield. The first parameter was ratio of ethanol to oil which were kept 3:1mol/mol and
6:1mol/mol. Another parameter was the concentration of catalyst i.e. NaOH which was taken
1%wt/v and 0.75%wt/v. The last parameter was temperature, for our project we used 60OC and
65OC. Every trial gave different biodiesel yield which were recorded for optimal parameter
recommendation later.
CH2COOR CH2 - OH
| |
NaOH
CH2COOR + 3C2H5OH 3C2H5COOR + CH - OH
| Ethanol Ethyl Ester |
CH2COOR (Biodiesel) CH2 - OH
Triglyceride (Oil) Glycerol
Based on the stoichiometry of the process above, amount of oil and ethanol used for the production
process was determined as follows.
11
Average molecular Wight of Cotton Seed Oil (CSO) = ∑MiXi = 256.42*0.211 + 284.4*0.036 +
282.52*0.201 + 280.45*0.552 = 270.26g/mol
12
3.2.5 Glycerol Separation
After 90mins of stirring process, we turned off the stirrer and the biodiesel-glycerol mixture was
allowed to settle over a night for the reaction to be completed and gain maximum yield. Separation
process was accomplished by gravity separating the mixture into biodiesel and glycerol. After
complete conversion we got a light yellow color biodiesel and a very viscose glycerol. Because of
its higher density property, glycerol settled down under the biodiesel. So using syringe, we pumped
the biodiesel out of the beaker carefully without any movement not to mix the two products.
3.2.6 Washing
Then the biodiesel was washed with 1/3rd volume of distilled water to remove unreacted catalyst
and soap formations, based on volume of biodiesel, and allowed to settle for 4hrs.
13
3.2.8 Characterization
After the produced biodiesel have been separated, we measured its properties and first compare
each of the trials with one another and take the best one of the trials and compare it to petrol diesel
and standard biodiesel.
A. Density
It is measure of the power output of a diesel engine per unit volume of fuel consumed. It
was measured using hydrometer at atmospheric temperature (i.e. 25OC) by immersing the
hydrometer in to each trial biodiesel sample and the density value was read at the level of
the oil.
B. Viscosity
Viscosity is the important fuel property because it influences the atomization of the fuel
being inserted into the engine combustion chamber. For complete combustion, a very small
fuel drop is required. High viscosity causes poorer atomization of the fuel spray and less
accurate operation of the fuel injectors. Lower viscosity of the biodiesel helps to pump and
atomize easily and achieve finer droplets. It was measured using a device called VISCO
STAR plus. There is a rotating shaft that has a small disc at the end of it and this end was
inserted on the sample which is brought near to it, so when the shaft rotates, the disc with
a sensor will measure the viscosity and displayed on the digital screen. The measurement
14
that VISCO STAR gave was dynamic viscosity at atmospheric temperature (i.e. 25OC) of
the sample. From that result and the samples respective density, we calculated kinematic
viscosity.
C. Yield
Yield of biodiesel is the amount of biodiesel produced per a certain of amount of cottonseed
oil used.
D. Flash point
Flash point is the lowest temperature at which application of an ignition source causes the
vapor of a specimen to ignite. Due to material shortage we used Cleveland open-cup
method to determine the flash point of the biodiesel. First 50ml of biodiesel was poured
into a cup and putted on a heater with a thermometer dipped in the sample which was fixed
by stand. Then heat was applied gradually until flash was observed and the temperature at
which flash was observed were recorded.
15
3.2.9 Experimental Design
a) Number of Runs (NR = LP= 2^3 = 8)
Where L – Levels
P – Parameters
b) Number of Parameters with Levels(P = 3 and L = 2)
a) Temperature (60O and 65OC)
b) Catalyst concentration (1%wt/v and 0.75%wt/v)
c) Alcohol to oil ratio (3:1 and 6:1)
16
4. Results and Discussions
4.1 Results
4.1.1 Free Fatty Acid
Free fatty acid in cotton seed oil was determined using titration and its value calculated from the
equation given in the method which was approximately 0.66% which was below 2.5% of
standard value so one step transesterification process was enough.
4.1.2 Yield
8 trials with 3 different molar ratios were studied for achieving maximum yield and their respective
yield was determined as followed. From our experimental results, higher yields were achieved at
molar ratio of 1:6(78.4%, 66.7%and 70.23%) and the catalyst effect was also observed that at 1%
catalyst concentration was better than 0.75% on the yield. The temperature also affected the yield
in such a way that increased temperature facilitated the transesterification reaction. In our trails we
observed that as the temperature increased from 60 to 650C, higher yield was obtained according
to the table below.
17
4.1.3 Biodiesel Physical Characterization
Based on their respective method density, viscosity and flash point of each trial were measured
and recorded.
4.2 Discussion
Out of all parameters used, molar ratio of oil/ethanol had a great influence on the production
process of the biodiesel with the best result being recorded at 1:6 oil to alcohol ratio, 1% catalyst
concentration and 65OC temperature with 78.4% conversion rate. This result’s property were then
compared with standard biodiesel and petrol diesel.
Table 4.3 Property difference of trials made, Standard Biodiesel and Petrol Diesel
Property Experimental Value Standard Biodiesel Petrol Diesel
Density (gm/cm3) 0.887 0.875 0.831
Viscosity (mm/s) 4.5 5.2 3.01
Flash Point (OC) 145 142 61
18
Since our best trial properties were close to that of ASTM standards, we can say that the experiment
was done to a satisfactorily level. And also properties such as density and viscosity were more
improved than that of petrol diesel which makes it a good result.
19
5. Conclusion & Recommendation
5.1 Conclusion
Cotton seed has huge capability for biodiesel production, because it has low free fatty acid, so it
does not need two stage transesterification which makes it economical to produce it at industrial
level. Maximum biodiesel is noticed by optimizing ethanol to oil ratio, temperature and catalyst
concentration. The optimal parameter that gave maximum yield of biodiesel was found at 1:6
molar ratio, 65Oc reaction temperature and 1% catalyst concentration.
5.2 Recommendation
The result could be better if the following things can be improved such as equipment malfunction
specifically the magnetic stirrer, the reactor we used were not standard, if methanol was used, the
result could be enhanced and it would be better if caloric value, cetane number could be measured,
but due to unavailability of those measurements and chemicals we couldn’t to determine them.
20
Reference
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Department of Mechanical Engineering, Federal University of Technology, Akure,
Nigeria, 2015
2. Ajaygiri K., Goswami, G. A. Usmani, Study of parameters of Biodiesel Production from
cotton seed oil, University Institute Chemical Technology, North Maharashtra University,
Jalgon, India, 2014
3. Lebnebiso, J.S., Aberuaba, F., Ndagana, S. F. and Okeye, Transesterification of Esterified
crude cotton seed (Gossypium hirsutum) oil, Department of Chemical Engineering,
Moddibo Adama University of Technology, Yola, Nigeria, 2015
4. Derib Gashawu, Investigation of Biodiesel Production Using Solid Catalyst, Addis Ababa
Institute of Technology, Addis Ababa, Ethiopia, 2010
5. Gerhard Knothe, Jon Van Gerpen, Jürgen Krahl, The Biodiesel Handbook, by AOCS Press,
2005
6. S. T. Jiang, F. J. Zhang and L. J. Pan Sodium phosphate as a solid catalyst For biodiesel
preparation, Brazilian Journal of Chemical Engineering, School of Biotechnology and
Food Engineering, Vol. 27, No. 01, pp. 137 - 144, January
- March, 2010
7. Vineet Kumar, Manish Jain, Amit Pal, an experimental study on biodiesel production of
cotton seed oil through conventional method, Mechanical Engineering Department, Delhi,
India, December 2014
8. Raghu Rajesh, Ranjith Kumar, Performance and Emission Analysis of Bio Diesel from
Cotton Seed and Rice Bran Oil, Venkateshwara College of Engineering Mechanical
Department, Bengaluru
9. Sandeep Singh, Sumeet Sharma & S.K. Mohapatra, Department of Mechanical
Engineering, Thapar University, Patiala, 2008
10. Yogendra Prasad Upadhyay, R. B. Sharma, Amit Pal, Tekanpur, Department of
Mechanical Engineering, Delhi, India, 2003
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2009
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