Table of Contents

CHAPTER ONE..............................................................................................................................1
INTRODUCTION...........................................................................................................................1
1.1 BACKGROUND OF THE STUDY............................................................................1
1.2 PROBLEM STATEMENT...........................................................................................4
1.3 AIM...............................................................................................................................4
1.4 SCOPE OF THE STUDY.............................................................................................4
1.5 CONTRIBUTION TO STUDY....................................................................................4
CHAPTER TWO.............................................................................................................................5
LITERATURE REVIEW................................................................................................................5
2.1 EXTRACTION OF CASTOR OIL FROM SEED........................................................5
2.2 CHARACTERIZATION OF THE EXTRACTED CASTOR OIL..............................9
2.3 PRODUCTION OF BIODIESEL FROM VARIOUS SOURCES.............................12
2.4 DESCRIPTION, PREPARATION AND CHARACTERIZATION OF CATATLYST
24
CHAPTER THREE.......................................................................................................................32
METHODOLOGY........................................................................................................................32
3.1 GENERAL OVERVIEW OF THE METHODOLOLGY..........................................32
3.2 REAGENTS................................................................................................................32
3.3 APPARATUS..............................................................................................................32
3.4 PREPARATION OF ANTHILL CATALYST..........................................................33
3.4.1 CHARACTERIZATION OF ANTHILL CATALYST......................................33
3.4.2 ACTIVATION OF ANTHILL DERIVED CATALYST.......................................33
3.5 EXPERIMENTAL SETUP.........................................................................................33
3.5.1 TRANSESTERIFICATION PROCESS.................................................................34
3.5.2 DETERMINATION OF BIODIESEL YIELD.......................................................34
CHAPTER FOUR.........................................................................................................................35
RESULT AND DISCUSSION......................................................................................................35
4.1 EFFECT OF TIME.........................................................................................................44
4.2 EFFECT OF TEMPERATURE......................................................................................44
4.3 EFFECT OF CATALYST CONCENTRATION...........................................................45
CHAPTER FIVE...........................................................................................................................48
CONCLUSION AND RECOMMENDATION............................................................................48
5.0 CONCLUSION...............................................................................................................48
5.1 RECOMMENDATION..................................................................................................48
REFERENCES..............................................................................................................................49
 CHAPTER ONE

INTRODUCTION

1.1 BACKGROUND OF THE STUDY

After the disaster of Fikushima’s nuclear power plant on 11th of March 2011 in

Japan, the role of atomic energy to protect global warming has been under consideration (Le

Tu et al, 2012 ). Other sources of energy such as solar battery, wind energy power generation,

geothermal power generation, biomass energy resources (methane, ethanol and biodiesel fuel

(BDF)) have attracted much attention to serve as substitute for disastrous atomic energy as

green energy for the mitigation of global warming due to the advantage of carbon neutrality

of biomass (Le Tu et al, 2012). Many scientists have challenged the effectiveness of biomass

energy as in the case of bio-ethanol produced in Brazil which was considered to have

increased global warming because it was produced from plants cultivated at tropical forest

area (Le Tu et al, 2012). The term bio-fuel refers to solid (bio-chair), liquid (ethane and

biodiesel), or gas (biogas, bio-hydrogen and biosynthetic gas) fuels that are predominantly

produced from biomass (Demirbas, 2009). Biofuels such as ethanol from sugar cane, corn,

wheat or cassava and biodiesel from sunflower, soybean, canola, castor seed oil are the most

popular ones produced from food crops that require good quality land for plantation

(Demirbas A., 2009).

Biodiesel is an oxygenated, sulphur-free, biodegradable, non-toxic and eco-friendly

alternative to diesel fuel oil (Murchana et al, 2015). Biodiesel is composed of mono-alkyl

ester of long chain fatty acids derived from renewable sources like vegetable oil, animal fat

and used cooking oil (Murchana et al, 2015). It possesses a high flash point, better lubrication

and has closed physical and chemical characteristics with that of conventional diesel fuel

(Sani et al, 2017).

1
 Biodiesel sources such as vegetable oil and animal fat can be subjected to trans-

esterification reaction to undergo change in viscosity and volatility (Sani et al, 2017). Sani et

al (2017) explained further that, this transesterification can be carried out with a simple

alcohol in the presence of catalyst which can be either homogeneous or heterogeneous and

catalyzed by an acid, base or enzymes. Heterogeneous solid catalyst has advantage of being

easy and cheap in term of regeneration when carrying out separation process.

Jatropha seed is also a good source of biodiesel. It is a non-edible, oil bearing and

drought-hardy shrub with ecological advantages, belonging to the Euphorbiaceae family and

it was found to be the most appropriate renewable alternative source of biodiesel (Tint and

Mya, 2009). The extracted oil could not be used directly in diesel engine because of its high

viscosity. High viscosity of pure vegetable oils would reduce the fuel atomization and

increase engine deposit and thickening of lubricating oi (Tint and Mya, 2009).

The study of Adejumo et al, (2015) established that watermelon seed oil is also a

source of biodiesel. Watermelon is a drought tolerant crop which belongs to the cucurbitaceae

family of flowering plants generally considered to be of the citrullus species and has been

referred to as citrullus vaulgaris. It is found in Southern Africa in diversity such as sweet,

blend and bitter forms (Adejumo et al, 2015). Watermelon juice is very tasty, it supplies both

food and water at the same time. It is vary in shape and colour. Watermelon fruit is rich in

vitamin A and C with small amount of vitamin B1, B2, B6, folate, and niacin. It is very rich in

potassium and also contains other minerals like iron, calcium, magnesium and phosphorus in

traces but free of fats and cholesterol. Its seed averagely consist of 31.9% protein, 4.4%

carbohydrates, 5.71% fat, 8.2% fibre, 6.2% ash, 130mg calcium, 456mg phosphorus, and

7.5mg iron. It also contain the necessary amino acids such as leucine, isoleucine, tryptophan

and valine (Adejumo et al, 2015). The seeds are removed from the rinds, sun dried to reduce

its moisture content. The dried seeds are then pressed to extract the useful oil.

2
Castor plant (Ricinus Communis) is a member of the Euphorbiaceae, which contains plants

mostly native to the tropics (Oluwole et al, 2012). In Nigeria, castor seed can be found

abundantly in almost every part of the country. It contains 40 to 60% oil (Oluwole et al,

2012). Depending on locality where it is found, it is being called different names like Lara in

Yoruba, Zurma in Housa, Kwolakwola in Kanuri, Kpikpi in Igbo (Oluwole et al, 2012).

Castor oil is pale amber viscous liquid sometimes known as ricinus oil (Akpan et al, 2006).

Castor oil and its derivatives can be used in the production of paints, vanishes, lacquers and

other protective coatings, lubricants and grease, hydraulic fluids, soaps, printing inks, and as

a raw material in the production of plasticizer and nylon (Akpan et al, 2006 ).

The application of solid-based catalysts in the field of renewable energy to produce

renewable fuel has become a significant area of research due to environment concern

resulting from the continual reliance on fossil fuel sources, current industrial energy demands

and upswing in the world population. Due to the cost associated with production of biodiesel

as a result of dependence on ready-made catalyst, there is an increase in interest in searching

for naturally occurring minerals and domestic waste materials as heterogeneous catalyst as a

result of their low cost and availability (Yusuff et al, 2018). Many of these materials have

been reported to be effective option in production of biodiesel through heterogeneous

transesterification, these materials provide a clean, almost glycerol free biodiesel and reduce

its production cost (Yusuff et al, 2018). Studies have shown that, some of these catalyst used

in production of biodiesel like CaO which can be derived from waste carbonaceous materials

(chicken eggshell, ostrich eggshell, waste animal bone) while an anthill is a form of fired clay

which is made up of silica (SiO2), alumina (Al2O3), iron oxide (Fe3O4) and many other metal

oxides (Yusuff et al, 2018).

Heterogeneous acid catalysts can simultaneously catalyze both esterification and

trans-esterification showing much higher tolerance to free fatty acids (Feng and Zhen, 2011).

3
The features of this heterogeneous acid catalyst make possible continuous fixed-bed

operation which can in-turn minimize product separation and purification cost, also make the

product economically viable to compete with commercial petroleum-based diesel fuel.

In this study

1.2 PROBLEM STATEMENT

This project work was done to determine the availability, abundance, effectiveness

and cost of solid catalyst (anthill) used on the yield of biodiesel produced.

1.3 AIM

The aim of this work is to enhance biodiesel production from castor oil using anthill catalyst.

This will be achieved through the realization of the following objectives.

(i) Preparation and characterization of raw anthill for biodiesel production

(ii)Evaluation of the production conditions that optimize the yield of biodiesel.

(iii) Estimation of the kinetics and thermodynamics parameters of the biodiesel

production

1.4 SCOPE OF THE STUDY

This study was limited to the use of anthill as solid catalyst for the production of

biodiesel from castor seed oil. Catalyst was characterized for mineralogical and elemental

composition using X-ray diffractometer and X-ray fluorescence while the microstructural

analysis was carried out by using Scanning Electron Microscope.

1.5 CONTRIBUTION TO STUDY

This study established the possibility of reduction of biodiesel production cost,

viability with petroleum-based diesel and also its public acceptability and environmental

friendliness.

4
 CHAPTER TWO

LITERATURE REVIEW

2.1 EXTRACTION OF CASTOR OIL FROM SEED

Oluwole et al, (2012), worked on traditional way of extracting castor oil, he established that

traditional procedures of castor oil extraction presently practice permits the extraction of

about 20% oil from the kernel, which is very inefficient and time consuming. These

procedures involve the following steps:

Cleaning: unwanted materials such as stones and dirt are removed from the dehulled seeds by

hand picking

Boiling: the decorticated seed is then heated in water to a temperature of about 96 oC for

about 10minutes

Drying: the boiled seed is spread in the sun to dry. The drying process reduces the moisture

content to about 5-7 %

Grinding: grinding to form paste is done using manually operated grinding machine

Mixing with water: the paste is then mixed with water in the proportion of 1kg of paste to 2

liters of water

Cooking: the castor pastry is then placed on fire for heating, as the water evaporates and the

product becoming sticky, oil start gushing out and settled on the surface

Scooping: the extracted oil is then scooped to separate container and the cake is collected for

drying.

Drying of Oil: the scooped oil is then dried by heating to reduce the moisture in the extracted

oil

According to Oluwole et al, (2012), the procedures were repeated nine times and presented

the result in a table where he observed that about 19.42% oil was obtained, which is about

38.84% of the oil present in the kernel.

5
From the table below Oluwole et al, (2012), was able to show that traditional method of

castor oil extraction is inefficient, tedious and time consuming. He explained further that it is

necessary to develop an appropriate technology for the processing of castor oil to provide the

needed solutions to problems facing the local processors of the oil.

6
Table 2.1: The Result of the Extraction Process.
Trials Mass of seed Mass of oil Volume of oil Density of oil mass of cake after
oil
after grinding extracted extracted (ml) extracted (kg/m3) extraction (kg)
(kg) (kg)
1 1.4 0.28 285 0.982 0.92

2 1.8 0.48 490 0.98 1.25

3 1.64 0.39 395 0.987 1.14

4 1.0 0.193 200 0.965 0.79

5 1.2 0.231 241 0.963 0.82

6 3.0 0.578 598 0.967 2.01

7 1.6 0.229 228 0.97 1.2

8 1.2 0.179 185 0.97 0.9

9 2.67 0.445 460 0.967 1.7

Sum 15.51 3.005 3082 10.73

Av 1.72 0.334 342.44 0.975 1.19

Akpan et al, (2006) on the other hand process castor seed by making it (seeds) to undergo

various processing in the course of its preparation for extraction. He also explained the

following unit operation involved:

Clearing: the castor beans had some foreign materials and dirt which was separated by hand

picking.

Drying: The cleaned beans were sun dried in the open, until the casing splits and sheds the

seeds. The beans were further dried in the oven at 60°C for 7hrs to a constant weight in order

to reduce its moisture content, which was initially at about 5 to 7%.

Winnowing: The separation of the shell from the nibs (cotyledon) was carried out using tray

to blow away the cover in order to achieve very high yield.

7
Grinding (size reduction): Mortar and pestle were used to crush the beans into a paste (cake)

in order to weaken or rupture the cell walls to release castor fat for extraction.

Akpan et al, (2006) employed soxhlet extractor where 300ml of normal Hexane was poured

into round bottom flask. 10g of the sample was placed in the thimble and was inserted in the

centre of the extractor. The Soxhlet was heated at 60oC. When the solvent was boiling, the

vapour rises through the vertical tube into the condenser at the top. The liquid condensate

drips into the filter paper thimble in the centre, which contains the solid sample to be

extracted. The extract seeps through the pores of the thimble and fills the siphon tube, where

it flows back down into the round bottom flask. This was allowed to continue for 30 minutes.

It was then removed from the tube, dried in the oven, cooled in the desiccators and weighed

again to determine the amount of oil extracted. Further extraction was carried out at 30

minutes interval until the sample weight at further extraction and previous weight becomes

equal. The experiment was repeated by placing 5g of the sample into the thimble again. The

weight of oil extracted was determined for each 30minutes interval. At the end of the

extraction, the resulting mixture (miscella) containing the oil was heated to recover solvent

from the oil.

Moisture content was determined by Akpan et al, (2006), he weighed 40g of the

cleaned sample and dried it in an oven at 80°C for 7hrs and the weight was taken after every

2hrs. The procedure was repeated until a constant weight was obtained. After each 2 hours,

the sample was removed from the oven and placed in the desiccator for 30 minutes to cool. It

was then removed and re-weighed. The percentage moisture in the seed was calculated from

the formula: Moisture = 100(W1- W2)/W2 %, where W1 = Original weight of the sample

before drying; W2 = Weight of the sample after drying.

The findings of Akpan et al, (2006) established that the percentage oil extracted was

33.2% which was higher than that obtained by Olwole et al, (2012) (19.42%). This validate

8
the claim of Oluwole et al, (2012) that tradition way of extraction yield low quantity and it is

not advisable to process with the method.

2.2 CHARACTERIZATION OF THE EXTRACTED CASTOR OIL

Oluwole et al, (2012) went further to characterize the extracted oil and the results obtained

were given in the tables below.

Table 2.2: Physical Properties of the Crude and Refined Castor Oil
Property Crude Castor Oil Refined Castor Oil
Specific gravity 0.9587 0.9587

Viscosity at 28°C [St] 9.42477 6.4842

Refractive Index at 28°C 1.4686 1.4674

P H 6.11 6.34

Colour Amber Amber

Table 2.3: Chemical Properties of the crude and refined castor oil

________________________________________________________________________

Property Crude Castor Oil Refined Castor Oil

________________________________________________________________________

Acid Value [mg NaOH/g of Oil] 1.148 0.869

Saponification Value [mg KOH/g of Oil] 185.83 181.55

Iodine Value [g I2 /100g of Oil] 87.72 84.8

_________________________________________________________________________

9
Table 2.4: Determination of Percentage Oil Extracted

_________________________________________________

Determination Value (g)

_________________________________________________

Weight of empty flask (M1) 108.6

Weight of thimble (W1) 3.13

Weight of sample + thimble (W2) 33.13

Weight of Sample (W2-W1) 30

Weight of empty flask +Oil (M2) 160.15

Weight of Oil (M2-M1) 51.55

2nd Weight of Sample 35.1

3-rd Weight of Sample 40.2

4-th Weight of Sample 50

_______________________________________________

10
Table 2.5: ASTM Specification for Quality Castor Oil

___________________________________________________________________________

Property Ranges Selected

___________________________________________________________________________

Specific gravity 20/25°C 0.957-0.968 0.962

Refractive Index, nD 1.476-1.479 -

Saponification Value 175-187 181

Un-saponification Value 0.3-0.7 0.7 (Max %)

Iodine Value 82-88 85

Hydroxyl Value 160-168 160(Minimum)

Viscosity at 25°C 6.3-8.8 St -

Acid Value 0.4-4.0 3

Colour (Gadner) Not darker than 2-3 3.0 (Maximum)

It was reported by Oluwole et al, (2012) that the best method for extraction of castor

oil at present is by the use of hydraulic pressing. He came to conclusion that there was no

difference between the specific gravity of crude oil and refined one (0.9587). Differences

were observed between the values obtained for the viscosity of crude oil (9.42477st) which

was outside the recommended standard (6.38.8st) and refined oil (6.4842st) which was quite

within the range. This may be attributed to the fact that some impurities and other

components were removed during reifining ( Oluwole et al, 2012). He came to conclusion

that refined castor oil was of good quality and could be recommended suitable for industrial

usage.

11
2.3 PRODUCTION OF BIODIESEL FROM VARIOUS SOURCES

Vegetable oil and animal fat are triglycerides, which are esters of Free Fatty Acid

(FFA) with glycerol (Le et al, 2012). The triglyceride typically contains several FFA, and

thus different FFA can be attached to one glycerol backbone (Le et al, 2012). Le et al, (2012)

reported that FFA composition is the most important factor influencing the corresponding

properties of vegetable oil and animal fats. Because vegetable oils or animal fats have high

viscosity, i.e., 35–50 mm2/s, it is necessary to reduce the viscosity in order to use them in a

common diesel engine. There are four methods used to solve this problem: blending with

petro-diesel, pyrolysis, microemusification (co-solvent blending) and transesterification.

Among these methods, only the transesterification reaction creates the products commonly

known as biodiesel (Le et al, 2012).

Sani et al, (2017) study also go along with that of Le et al, (2012) in which he found

out that high Free Fatty Acid (FFA) reduces catalyst effectiveness and decreases the

production yield of biodiesel. He therefore recommended that amount of FFA in waste

cooking oil (WCO) should not exceed 1wt%. He also established that, biodiesel has a high

flash point, better lubrication, high cetane number and has a quite resemblance in regard to

physical and chemical characteristics with that of conventional diesel fuel. Sani et al, (2017)

experiment with waste cooking oil taking from the fryer which was used for frying potatoes

and other vegetables based food in Sokoto State. According to Sani et al, (2017), the used

vegetable oil was mainly contaminated with water and solid particles. Some analysis were

conducted by Sani et al, (2017) on the waste oil to determine the quality of the oil and pre-

treatment was conducted to remove the solid impurity through filtration. The analyses of the

oil were given in the table below:

12
Table 2.6: Physicochemical Properties of Waste Cooking Oil

_________________________________________________

Property name value

_________________________________________________

Acid value (mg of KOH/gm of oil) 3.47

Kinematic viscosity at 35.10C (mm2/s) 42.2

Density (g/cm3) 0.9

Free fatty acid content (%) 1.73

Specific gravity 0.9

Moisture content (%) 0.1

Odour mild flavor

Colour light brown

___________________________________________________

13
Murchana et al, (2015) made use of waste cooking oil collected from restaurants in

Guwahati, refined the oil and subjected it to transesterification process. The reaction involved

was established by Murchana et al, (2015) as:

CH2 –OOC –R1 R1 –COO –R CH2 –OH

| Catalyst | |

CH –OOC –R2 + 3ROH R2 –COO –R + CH –OH

| | |

CH2 –OOC –R3 R3 –COO –R CH2 –OH

Tryglyceride Alcohol Ester Glycerol

According to Murchana et al, (2015), glycerol is the by-product of the

transesterification process and it is highly viscous, odorless, transparent, colourless and has

low toxicity and can also be used for making soaps, explosives, cosmetics, ointments and

certain inks. The table below obtained by Murchana et al, (2015) shows comparison of the

properties of diesel, biodiesel and blended biodiesel.

14
Table 2.7: Comparison of Diesel, Biodiesel and Blended Biodiesel

___________________________________________________________________________

S/N Properties Diesel Blended Blended Pure

Sample Biodiesel(B10) Biodiesel(B20) Biodiesel(B100)

________________________________________________________________________________________________________________

1 Density (gm/cc) at 150C 0.8442 0.8471 0.8521 0.8875

2 Kinematic Viscosity (cs) 2.25 2.83 3.57 4.57

3 Dynamic viscosity (cs) 2.67 3.37 4.18 5.19

4 Flash point (°C) 42 44 44 44.5

5 Pour point (°C) -9 -12 -12 -7

6 Sulphur content (ppm) 345 363 268 13

7 Cetane index 46.9 46.95 46.51 47.07

8 Calorific value (KJ/kg) 10903.39 10893.09 10875.24 10745.92

___________________________________________________________________________________________________

15
Murchana et al, (2015) deduce from table 2.8 above, that density and viscosity is highest in

pure biodiesel followed by blended form and standard diesel in the decreasing order.

Biodiesel has a higher flash point than standard diesel, thus making it less volatile and safe to

transport or handle than standard diesel. The cetane index of blended biodiesel and standard

diesel was found to be nearly similar but lower than that of pure biodiesel. Also, the sulphur

content of biodiesel (B100) is very less compared to that of blended biodiesel and standard

diesel. The calorific value is highest in standard diesel, followed by blended and pure

biodiesel.

The author concluded that, used cooking oil that generally goes to waste can be

utilized for producing biodiesel, which is both economically and environmentally favorable.

His Comparison to petroleum based diesel revealed that, biodiesel has a more favorable

combustion emission profile, such as low emission of carbon monoxide, particulate matter

and unburned hydrocarbons. Carbon dioxide produced by combustion of biodiesel can be

recycled by photosynthesis, thereby minimizing the impact of biodiesel combustion on the

greenhouse effect. Murchana et al, (2015) explained further that, biodiesel provides

lubricating properties that can reduce engine wear and extend engine life. In brief, these

merits of biodiesel make it a good alternative to petroleum based fuel and have led to its use

in many countries especially in environmentally sensitive areas. It could been clearly seen

that Murchana et al, (2015) work agreed with that of Sani et al, (2017) in which they both

concluded that the produced biodiesel is both economically and environmentally favorable.

Olutoye et al, (2016) contributes to the study by synthesizing biodiesel from palm

kernel oil using materials such as liquid methanol, powdered chicken eggshell and fine clay.

Anhydrous methanol (analytical grade, ~99.5%) was purchased from a chemical laboratory

while refined palm kernel oil was purchased from Kure ultra modern market (Minna, Niger

State) according to (Olutoye et al, 2016). Palm kernel oil was transformed to its methyl ester

16
via transesterification. He explained further that the reaction was carried out in a batch

reactor (a 250ml two way round bottom flask). For every run, 250ml of the palm kernel oil

was measured into the reaction flask and the required volume of methanol solvent was added.

The reaction was catalyzed at room temperature, covered and mixed vigorously (Olutoye et

al, 2016). The reactor was fitted with a reflux condenser to return most part of the vaporized

methanol as reaction took place at temperatures higher than its boiling point. Stirring was

initiated at a reasonable using magnetic stirrer (close to 500rpm) (Olutoye et al, 2016). After

Olutoye et al, (2016) carefully followed those procedures he highlighted, he obtained a

mixture which he cloth filtered to remove the catalyst and then poured into a separating

funnel to allow to settle. The catalyst was in order to avoid clogging at the exit of the

separating funnel. After settling, the product mixture was separated into two liquid layers:

crude methyl ester (biodiesel) layer abοve and glycerοl layer at the bοttοm since the biοdiesel

layer is lighter than the glycerοl layer. Unreacted methanοl was seen abοve in cases οf

incοmplete reactiοn οr when in true excess. Οn separatiοn frοm the glycerοl by-prοduct, the

biοdiesel was washed by adding an equal amοunt (to the volume of the biodiesel) οf warm

distilled water tο it in the separating funnel, the separating funnel was swirled severally and

clamped οn a retοrt stand fοr sοme minutes till water layer was separated frοm diesel layer.

The water (nοw impure) was drained οff frοm the bοttοm οf the funnel.

After washing, the biοdiesel was dried by heating οn a hοt plate and the yield recorded. The

yield was calculated theoretically as thus,

Biodiesel volume (ml)

Yield % = ___________________ x100

Oil volume (ml)

In his work, Yusuff et al, (2017) also made use of vegetable oils where he established

five major techniques used in lowering the viscosity of vegetable oils for practical use in

17
engines. These methods are pyrolysis, microemulsification, blending, transesterification or

esterification and supercritical process. He clarified further that blending and

microemulsification are not production processes. Blending is achieved through physical

mixing of vegetable oil with fossil diesel while microemulsification is colloidal equilibrium

dispersion spontaneously from two immiscible fluids. Lower viscosity is achievable through

these methods. However, similar engine performance is still encountered using these two

techniques:

Pyrolysis or thermal cracking is the breaking down of organic matter in the absence of air. In

this case, heat and catalyst are involved in thermal cracking of vegetable oils or fat into

smaller components at temperature ranging between 400 and 450oC (Yusuff et al, 2017).

Diesel –like fuel is thus obtained with similar properties to fossil diesel. The diesel fuel

derived from pyrolysis of vegetable oil or animal fat contains mostly olefins, paraffin, and

esters. Unlike blending and microemulsification techniques, diesel fuel derived from

pyrolysis process is clean and does not suffer engine performance issues; it is energy

consuming and needs expensive separation unit. More so, the sulphur and ash contents make

pyrolysis technique less environmental friendly (Yusuff et al, 2017). Yusuff et al, (2017) also

reported that in the past, blending, microemulsification and pyrolysis techniques have been

successfully employed for diesel oil production from vegetable oil or fat, today,

transesterification process is a commonly used method for the biodiesel production. Yusuff et

al, (2017) defined transesterification as the direct conversion of one ester to another through

interchange of special functional group called alkoxy moiety. In this method of biodiesel

production, the triglycerides present in vegetable oil or fat react with monohydric alcohol

(methanol, ethanol, and butanol) in the presence of a catalyst. In the

transesterification process. Yusuff et al, (2017) gave three consecutive reactions as:

18
 The first reaction is the one between triglyceride (TG) molecules present in oil and

excess methanol (A) usually methanol which gives di-glyceride (DG) (intermediate) and

methyl ester (ME). The di-glyceride (DG) then reacts with part of the remaining methanol

leading to the formation of another intermediate (mono-glyceride [MG]) and more methyl

ester (ME). The intermediate formed in the second reaction then also combines with

remaining methanol to give more methyl ester (ME) and glycerol (G). Occasionally the

mono-glyceride (MG) (intermediate) is destroyed in the last reaction step.

catalyst

TG + CH3 OH (A) DG +ME (1)

catalyst

DG + CH3OH (A) MG + ME (2)

catalyst

MG + CH3OH (A) G + ME (3)

catalyst

TG + 3CH3OH (A) G + 3ME (4) (Overall reaction)

(a) Equations (1) - (3) are transesterification reaction steps (b) Equation (4) is the overall

transesterification with methanol. Meanwhile, there is another advanced form of

transesterification process called non-catalytic supercritical transesterification. Yusuff et al,

(2017) reported that, there is another method which does not require catalyst to speed up the

reaction rate known as advanced form of transesterification process called non-catalytic

supercritical transesterification. Non-catalytic supercritical transesterification is usually

carried out in a homogeneous phase by subjecting solvents such as water, methanol, ethanol,

propanol, as well as butanol to high temperatures and pressures in order to make them act as

19
super acids (Yusuff et al, 2017). Under supercritical conditions, alcohol performs the roles of

catalyst and reactant (Yusuff et al, 2017). Saka and Kusdiana, (2001) had investigated a non-

catalytic biodiesel production process by using supercritical method. A conversion of

rapeseed oil of 98.5% was achieved under favorable supercritical conditions of 350 oC

temperature of reaction, 43mPa pressure, 240s reaction time and 42:1 molar ratio of methanol

to oil. In spite of high product yield and purity, the high cost of production makes this

technique not viable for commercial production

Para rubber seed oil was used for biodiesel production by Chanatip et al, (2015)

through transesterification of Recently Para Rubber Seed Oil (RSO) at a 16:1 M ratio of

methanol: oil. 5g of RSO was mixed with 3g of methanol and catalyst (wt% of oil) then

transferred to 100ml round-bottom flask equipped with a condenser while the cooling water

was set at 10-15oC using thermostatic bath. The reaction was carried out at stirring condition

of 750 rpm, time and temperature condition were set up. At the end of the reaction time, the

reaction was terminated by quenching in an ice-water bath. The excess methanol and catalyst

were separated by evaporation band filtration, respectively (Chinatap et al, 2015).

Adejumo et al,(2015) worked on watermelon. They got the seed from Kure market,

Minna Nigeria. The initial moisture content was determined to be 4.31% using standard

methods and calculated amount of water was added to vary the percentage moisture content

to 10%, 20% and 30% for sample A, B and C. the oil was extracted using solvent extraction

method in which soxhlet apparatus was employed and the oil yield for each samples

calculated to be:

20
Table 2.8: The Effect of Moisture Content on Percentage Oil Yield of Watermelon seed

______________________________________________________________

Parameter Control Sample Sample Sample

A B C

______________________________________________________________

Weight of sample

before extraction 10 10 10 10

Weight of sample

after extraction 7.19 7.46 7.99 8.44

Weight of oil 2.18 2.54 2.01 1.56

Oil yield(%) 46.71 43.96 38.71 34.11

________________________________________________________________

Where control sample = seed with 4.31% moisture content, sample A = seed with

10% moisture content, sample B = seed with 20% moisture content, and sample C = seed

with 30% moisture content. The weights are in milligrams. The physical properties given in

the table below:

21
Table 2.9: Physical Properties of Watermelon Seed Oil

___________________________________________________________________________

Properties Control Sample Sample Sample Standard

A B C for edible

oil

__________________________________________________________________________

Viscosity

40oC(mm/s) 1.78 1.28 1.22 1.21 60

Specific gravity 0.99 0.98 1.01 1.01 1.16

Refractive index 1.45 1.45 1.45 1.45 1.46± 0.05

___________________________________________________________________________

The characteristics of the evaluated oil are: acid values (Mg/KOH/g), iodine values

(g/100), peroxide values (M/Mol/kg), saponification values (Mg/KOH/g), free fatty acid

value (Mg/KOH/g), specific gravity , and viscosity (Kg/m3) Adejumo et al,(2015).

22
Table 2.10: Chemical Properties of Watermelon Seed Oil

Properties Control Sample Sample Sample

Standard for

A B C edible oil

___________________________________________________________________________

Saponification

Value (Mg/KOH) 196.53 308.55 316.35 325.38 181.4±2.60

Iodine value

(g/100g) 135.60 122.60 126.32 131.00 80-106

Acid value

(Mg/KOH/g) 5.61 6.17 7.86 10.10 4

Peroxide value

(M/Mol/Kg) 2 4 12 16 10

Free Fatty Acid

(Mg/KOH/g) 11.22 12.34 15.71 20.20 5.61-7.28

___________________________________________________________________________

Tint and Mya, (2009) in their own study made use of Jatropha oil for the production

of biodiesel using methanol and ethanol each with different reaction conditions.

With methanol, the experiment was carried with optimum molar ratio (6:1) keeping the

catalyst concentration (1% NaOH), reaction temperature (65oC) and reaction time (1hour).

With ethanol, the experiment was conducted with optimum ratio (8:1) keeping the catalyst

concentration (1% KOH), reaction temperature (70oC) and reaction time (3½ hours)

The required amount of jatropha oil was filtered, measured with measuring cylinder

and then it was poured into the three-necked round bottom flask. Heating of the oi was done

23
at the required temperature using electric metal. Alkoxide solution was prepared while the

jatropha oil was heated (Tint and Mya, 2009).

Prepared solution of alkoxide was introduced into the reaction vessel and mixed

thoroughly during the reaction. At the end of the reaction time, the reaction was stopped and

the mixture was allowed to settle in the separating funnel for 12 hours or overnight. After

these, the mixture separated into two layers, the bottom one was crude glycerine which could

be drawn off from the bottom of the separating funnel. The biodiesel layer was purified by

washing with warm water to remove methanol, residual catalyst, and soaps. The PH of the

biodiesel layer was measured and phosphoric acid added to the biodiesel layer to neutralize

the catalyst residue. After neutralization process, the washing was done with gentle agitation

to avoid emulsion. After separation of the layer for 30 minutes, the wash water layer was

drained off from the bottom of the separating funnel. The washing process was repeated until

the ester layer became clear (Tint and Mya, 2009). After washing, PH of the biodiesel layer

was measured again and when it was found to be 7, the washing process was completed.

After washing process, the biodiesel was introduced to the sand filter and salt filter. The end

product, biodiesel was obtained as a clear amber-yellow liquid with a viscosity similar to that

of petro-diesel (Tint and Mya, 2009).

2.4 DESCRIPTION, PREPARATION AND

CHARACTERIZATION OF CATATLYST
According to the study of (Nur and Sarina, 2016), there are three categories of

catalysts used for biodiesel production which are alkalis, acids and enzymes catalyst. Acid

and alkali catalyst are more commonly used in biodiesel production and they were further

categorized as homogeneous and heterogeneous catalyst. Nevertheless, enzyme catalysts

have become more attractive in recent years since it can avoid soap formation and the

24
purification process is simple accomplish, although they are not commercially used because

of the longer reaction time and higher cost, some researchers developed new biocatalyst in

recent years that needs no purification.

Table 2.11: Reaction for Various Type of Catalyst

______________________________________________________________________________

Reaction conditions

Catalyst ____________________________________________ Biodiesel yield Remark

Temp Type of Catalyst Reaction Mixing

o
C alcohol loading time, h rpm

(alcohol to wt%

molar ratio)

______________________________________________________________________________

Homogeneous catalyst

Sodium soybean oil Batch

Hydroxide 40 Ethanol (9:1) 1.3 1.33 _ 95% reactor

(NaOH)

Sodium

Hydroxide 55 Methanol (3:1) 0.5 2 250 waste soybean Shake

(NaOH) cooking oil,68.5% flask

Sodium

Hydroxide 60 Methanol (475:1) 0.1 1 _ rapeseed, 88.8% Soxhlet

(NaOH)

Potassium pongamia pinnata _

Hydroxide 60 Methanol (4:1) 0.1 1 550 seeds, 978.5%

(KOH)

Potassium Jatropha seed Three

Hydroxide 50 Methanol (6:1) 0.075 5 800 87% necked

25
(KOH) rbf

Potassium calophyllum _

Hydroxide 55 Methanol (9:1) 1 _ inophyllum

(KOH) 98.53%

Sodium sesamum Batch

Methoxide 50 Methanol (6:1) 0.75 0.5 _ indicum L. reactor

(NaOCH3) seed oil, 87.8%

Heterogeneous catalyst

Bone 60 Methanol (20:1) 18 4 600 rapeseed oil, 96% Batch

Peanut oil, 94% reactor

Rice Husk 65 Methanol (24:1) 4 3 300 soybean oil, 95.5%Shake

flask

Snail shells 60 Methanol (6.03:1) 2 7 _ waste frying oil, 99.58% _

Eggshells Palm olein oil, _

and 60 Methanol (15:1) 10 2 _ 94.1%

snail shell

______________________________________________________________________________

Another table that comprises of the advantages and disadvantages of various types of catalyst

was tabulated below by (Nur and Sarina, 2016):

26
27
Table 2.12: Advantages and Disadvantages of Different Types of Catalyst used in Transesterification

___________________________________________________________________________________________________

Type of catalyst Advantages Disadvantages

____________________________________________________________________________________________________

Homogeneous base -Do not form water during transesterification reaction -Sensible to FFA content in the oil

Catalyst -4000 times faster reaction rate than acid catalyzed -Saponification can occur if the FFA content

transesterification in the oil is more than 2wt%

-Two-step alkaline-catalyzed transesterification -Saponification will decrease the biodiesel yield

from used vegetable oil is an economic method and cause problem during product purification

for biodiesel production -Produce more wastewater from purification

-Reaction can occur at mild reaction condition

and thus less energy required

-NaOH and KOH are economically feasible and

and widely available

Heterogeneous base -Reusable -Poisoning of the catalyst when expose to

ambient

catalyst -Easy to separate from product air

-Relatively faster reaction rate than acid- -Sensitive to FFA content in the oil due to its

catalyzed transesterification basicity property

-Reaction can occur at mild reaction cond- -Saponification can occur if the FFA content in the

ition and relatively lower energy oil is more than 2wt%

-Long catalyst life times -Saponification will decrease the biodiesel yield

and problem during product purification.

-Higher molar ratio of alcohol to oil

-Produce more wastewater from purification

-Diffusion limitation

Homogeneous acid -Insensitive to FFA and water content in the oil -Low reaction rate

Catalyst -Preferrred-method if low-grade oil is used -Can lead to equipment corrosion

-Esterification and transesterification occur -Harder separation of catalyst from product

simultaneously

-Saponification can be avoided

28
 -Produce high yield of biodiesel

Heterogeneous acid -Insensitive to FFA and water content in the oil -Low reaction rates

Catalyst -Preferred-method if low-grade oil is used -Unfavorable side reaction

-Esterification and transesterification occur -Higher cost

simultaneously -High reaction condition and longer reaction times

-Easy separation of catalyst from product -More energy requirement

-High possibility to reuse and regenerate the -Leaching of catalyst active sites may result to product

catalyst contamination

-Recyclable

Enzyme catalyst -Prevent saponification -Very slow reaction rate

-Only simple purification step is required -High cost

-Environmental friendly and nonpolluting -Sensitive to alcohol, typically methanol that

deactivate the enzymes

-Inactivation and denaturation of enzyme can lead to

decreasing yield of biodiesel

____________________________________________________________________________________________________

Yusuff et al,(2018) prepared composite anthill-egg (CAE) shell they used for the

production of biodiesel using anthill which was ground into powder and screened to obtain a

particle size of 150-220µm. This anthill powder was kept in an enclosed container. The waste

chicken eggshells were first soaked for a day and washed thoroughly with tap water to

remove impurities and the inner white membrane, then washed again with distilled water.

The chicken eggshell were dried in the oven at 120oC for 6 hours to eliminate water. The

dried eggshell were ground to a powder and sieved to obtain 150-220µm particle size. This

powder was kept in a sealed plastic container. 200g mixture of anthill and eggshell powder

were formulated through incipient wetness impregnation in 20-80% proportion of anthill to

eggshell on mass bases. Required quantity of distilled water was added to the mixture and

stirred for 90 minutes on a temperature controlled magnetic stirrer for homogenization. The

mixture was filtered and the residue was dried in an oven operating at 125 oC for 2 hours. The

29
resulting dried powder mixture was calcined in the furnace at a temperature of 100 oC for 4

hours (Yusuff et al,2018).

Yusuff et al,(2018) went further to characterize the catalyst they prepared. They

determined the basicity of the raw and calcined catalyst through the colorimetric titration

method and they were found to be 2.05 and 10.80mmol/g catalyst, respectively. This basicity

result showed that the basicity strength of the calcined catalyst was higher than that of the

raw catalyst. According to the x-ray fluorescence (XRF) analysis shown in the Table 2.13

below, high content of calcium and other stearate metals were partly responsible for the

basicity of the calcined CAE.

30
Table 2.13: Chemical Composition Analysis of Raw Anthill and Synthesized CAE

__________________________________________________________________________

Compound Chemical Composition of Sample (wt%)

Raw Anthill CAE

___________________________________________________________________________

Aluminum oxide (Al2O3) 13.64 0.66

Silicon oxide (SiO2) 58.46 1.80

Phosphorus oxide (P2O5) 0.29 0.42

Trioxosulphate (SO3) 0.38 0.47

Potassium oxide (K2O) 3.17 -

Calcium oxide (CaO) 0.21 76.71

Titanium oxide (TiO2) 0.38 -

Iron (III) oxide (Fe2O3) 6.47 0.84

Molybdenum oxide (MoO2) 0.24 0.30

Tin oxide (SnO2) 1.19 0.53

Antimony oxide (Sb2O3) 1.21 0.49

Nickel oxide (NiO) 0.059 0.034

Copper oxide (Cuo) 0.059 0.034

Zinc oxide (ZnO) 0.11 0.061

Manganese oxide (MnO2) 0.068 0.0039

Tungsten oxide (WO3) 0.037 0.025

Loss on ignition (LOI) 14.03 17.62

___________________________________________________________________________

Total 100 100

___________________________________________________________________________

31
 Yusuff et al,(2018) deduced that the external surface of the calcined catalyst was

dominated by the active ingredient and this could enhance the mass transfer of methanol onto

the catalyst surface due to the expanded pore diameter. However, the pore diameters of both

the raw and calcined CAE catalysts, which were found to be 2.261 Å (or 2.261 nm) and 13.24

Å (13.24 nm) respectively indicated that they are mesoporus materials, as both values fall

within the range of 2-50 nm. Yusuff et al,(2018) then concluded that the termal treatment of

CAE has poisitive and synergetic effects on its performance.

32
 CHAPTER THREE

METHODOLOGY

3.1 GENERAL OVERVIEW OF THE METHODOLOLGY

The execution of the set objectives of this study were carried out in the following phases

i. Experimental

ii. Formulation of models

iii. Optimization and validation of the formulated models

3.2 REAGENTS

These reagents were used in carrying out the experimental analysis of this research work:

i. Castor oil

ii. Anthill

iii. Methanol

iv. Distilled water

3.3 APPARATUS

The apparatus used in the course of this research are:

i. Heater

ii. Shaker

iii. Furnace

iv. Magnetic stirrer

v. Conical flask

vi. Stirrer

vii. Measuring cylinder

viii. 500ml flat bottom flask

ix. Beaker

33
x. Thermometer

xi Spatula

3.4 PREPARATION OF ANTHILL CATALYST

The harvested anthill used was collected around school field of Ladoke Akintola

University of Technology and it was ground into powder to obtain a fine particle size (Yusuff

et al, 2018)

3.4.1 CHARACTERIZATION OF ANTHILL CATALYST

The mineralogical and elemental composition of the catalyst prepared from anthill

was carried out using X-Ray Fluorescence (XRF) and Fourier Transform Infrared

spectroscopy (FTIR).

3.4.2 ACTIVATION OF ANTHILL DERIVED CATALYST

The catalyst was prepared according to Yusuff et al, (2018) or Olutoye et al, (2016).

The prepared catalyst was calcined at about 600oC-700oC in a muffle furnace under static air.

All calcined samples were kept in the closed vessel to avoid reaction with carbon dioxide

(CO2) and humidity in air before used (Yusuff et al, 2018) or (Olutoye et al, 2016).

3.5 EXPERIMENTAL SETUP

The 500 ml flat bottom flask (the reactor) was setup with stopper containing cotton

wool placed on it to avoid explosion due to build-up of pressure, the setup was mounted on

the hot plate magnetic stirrer. The stopper was also placed to limit the loss of methanol

during the transesterification reactions

3.5.1 TRANSESTERIFICATION PROCESS

Transesterification reaction was carried out based on the experimental runs predicted

with design expert using refined castor oil with methanol in the presence of activated anthill

as catalyst with varying methanol oil ratio, amount of catalyst, agitation rate, controlled

34
temperature and time. Each experiment was carried out using 20ml of refined castor oil. A

glass reactor (round bottom flask) was used for the transesterification reaction. The reaction

conditions were selected according to the revised literature and previous performed work.

The reaction temperature and time were selected as the most important variables to study,

taking into account the inconsistencies found in the revised studies regarding the influence on

biodiesel production. The range of the reaction condition were limited to a maximum of 3h

and 62.5oC. The selection of methanol to oil molar ratio and the catalyst amount were made,

also taking into account the objective of using minimum amount of catalyst (to reduce cost)

and methanol (to reduce cost associated with its recovery after reaction).

3.5.2 DETERMINATION OF BIODIESEL YIELD

The yields of biodiesel produced was determined in terms of fatty acid methyl esters

(FAME%) using the following euqation:

weight of biodiesel produced

FAME% = × 100% 3.1
original weight of castor oil used

Or Design Expert.

35
 CHAPTER FOUR

RESULT AND DISCUSSION

The software package Design Expert was used for statistical data manipulation and

analysis. The software was used to generate the combination of statistic level for parameters.

The responses and the combinations of statistic level were used to generate 3d plots which

indicate interactions among parameters. The program uses the sum of squares method to

compute constants for a quadratic equation that relates parameters or process variables to the

yield of FAME.

36
Table 4.1: Result of the Experimental Runs

____________________________________________________________________________________________________
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5 Response1
Std Run A:Methanol:oil B:Agitation rate C:Reaction time D:Reaction temp. E:Catalyst loading Biodiesel
yield
Rpm hrs. o
C g wt %x10
________________________________________________________________________________________________
31 1 35 1200 1 50 9 12
44 2 35 1200 2 50 5 4
25 3 10 1200 2 40 5 6.2
3 4 10 2000 2 50 5 1
27 5 10 1200 2 60 5 11
29 6 35 1200 1 50 1 4
41 7 35 1200 2 50 5 4
39 8 35 400 2 60 5 21.01
5 9 35 1200 1 40 5 6.34
15 10 10 1200 3 50 5 1
11 11 35 400 2 50 9 18
1 12 10 400 2 50 5 8.3
20 13 35 1200 2 50 9 16
10 14 35 2000 2 50 1 6
16 15 60 1200 3 50 5 1.7
30 16 35 1200 3 50 1 7
26 17 60 1200 2 40 5 1.6
14 18 60 1200 1 50 5 1.8
34 19 60 1200 2 50 1 5
22 20 35 2000 1 50 5 3
7 21 35 1200 1 60 5 6
32 22 35 1200 3 50 9 18
42 23 35 1200 2 50 5 4
17 24 35 1200 2 40 1 5
36 25 60 1200 2 50 9 19
33 26 10 1200 2 50 1 7.32
37 27 35 400 2 40 5 3.5
12 28 35 2000 2 50 9 18.1
6 29 35 1200 3 40 5 3
13 30 10 1200 1 50 5 2
46 31 35 1200 2 50 5 4.2
9 32 35 400 2 50 1 9.4
19 33 35 1200 2 40 9 18.23
45 34 35 1200 2 50 5 4
24 35 35 2000 3 50 5 4.2
28 36 60 1200 2 60 5 9.9
4 37 60 2000 2 50 5 1.8
23 38 35 400 3 50 5 5.96
21 39 35 400 1 50 5 3.3
8 40 35 1200 3 60 5 11.4
2 41 60 400 2 50 5 8.3
18 42 35 1200 2 60 1 18.29
40 43 35 2000 2 60 5 4.8
43 44 35 1200 2 50 5 4
38 45 35 2000 2 40 5 8.5
35 46 10 1200 2 50 9 10.2
____________________________________________________________________________________________________

37
Table 4.2: Analysis of Variance (ANOVA) for Response Surface Model

___________________________________________________________________________
Sum of Mean F pvalue
Source Squares df Square Value Prob> F
__________________________________________________________________________________
Model 1395.29 20 69.76 25.09 < 0.0001
significant
A-Methanol:oil 0.27 1 0.27 0.097 0.7577
B-Agitation rate 57.65 1 57.65 20.74 0.0001
C-Reaction time 11.94 1 11.94 4.29 0.0487
D-Reaction temp. 140.81 1 140.81 50.65 < 0.0001
E-Catalyst loading 308.87 1 308.87 111.10 < 0.0001
AB 0.16 1 0.16 0.058 0.8124
AC 0.20 1 0.20 0.073 0.7895
AD 3.06 1 3.06 1.10 0.3040
AE 30.91 1 30.91 11.12 0.0027
BC 0.53 1 0.53 0.19 0.6653
BD 112.47 1 112.47 40.45 < 0.0001
BE 3.06 1 3.06 1.10 0.3040
CD 19.10 1 19.10 6.87 0.0147
CE 2.25 1 2.25 0.81 0.3769
DE 21.39 1 21.39 7.69 0.0103
A 2 7.42 1 7.42 2.67 0.1149
B 2 20.13 1 20.13 7.24 0.0125
C 2 16.56 1 16.56 5.96 0.0221
D 2 131.45 1 131.45 47.28 < 0.0001
E 2 453.75 1 453.75 163.22 < 0.0001
Residual 69.50 25 2.78
Lack of Fit 69.47 20 3.47 521.02 < 0.0001
Pure Error 0.033 5 6.667E-003
Cor Total 1464.79 45
__________________________________________________________________________________
The Model F-value of 25.09 implies the model is significant. Values of "Prob > F" less

than 0.0500 indicate model terms are significant. In this case B, C, D, E, AE, BD, CD, DE,

B2, C2, D2, E2 are significant model terms. Values greater than 0.1000 indicate the model

terms are not significant.

38
Table 4.3: Analysis Summary

_____________________________________________________________________________________

____

Std. Dev. 1.67 R-Squared 0.9526

Mean 7.64 Adj R-Squared 0.9146

C.V. % 21.83 Pred R-Squared 0.8055

PRESS 284.92 Adeq Precision 16.938

_________________________________________________________________________________

The "Pred R-Squared" of 0.8055 is in reasonable agreement with the "Adj R-Squared" of

0.9146."Adeq Precision" measures the signal to noise ratio. A ratio greater than 4 is

desirable. The ratio of 16.938 indicates an adequate signal. This model can be used to

navigate the design space.

39
Table 4.4: Design Solution

__________________________________________________________________________________________

Number Methanol:oil Agitation Reaction Reaction Catalyst Biodiesel Desirability

Rate time temp. loading yield

__________________________________________________________________________________________

1 26.0146 1882.428 2.185204 40.36295 8.839972 21.90959 1 Selected

2 38.89044 434.6796 2.435549 56.43832 8.139014 21.72388 1

3 54.68385 413.9143 2.028868 59.74775 1.623934 22.10732 1

4 42.53748 1541.177 1.934366 40.53546 8.887676 21.13249 1

5 54.33219 463.1418 2.36066 56.5634 8.932893 26.07669 1

6 30.76474 702.7243 2.38061 59.56212 1.424529 21.39629 1

7 50.17189 773.9772 2.527281 54.04401 8.903206 21.04026 1

8 42.95886 1786.782 1.817137 40.8702 8.941727 22.91974 1

9 23.0237 400.4765 1.557233 59.97692 8.061678 21.18762 1

10 42.9259 440.953 2.658649 59.58493 5.937182 21.43703 1

__________________________________________________________________________________________

40
Final Equation in Terms of Coded Factors:

Biodiesel yield =

+4.04

+0.13 *A

-1.90 *B

+0.86 *C

+3.14 *D

+4.49 *E

+0.20 *A*B

+0.23 *A*C

+0.88 *A*D

+2.78 *A*E

-0.37 *B*C

-5.30 *B*D

+0.88 *B*E

+2.19 *C*D

+0.75 *C*E

-2.82 *D*E

-0.91 * A2

+1.51 * B2

-1.37 * C2

+3.99 * D2

+7.40 * E2

41
 Final Equation in Terms of Actual Factors:

Biodiesel yield =+70.09160 - 0.23637* (A) + 0.024315*(B) -5.30155* (C) -3.09058* (D)

-1.65213 * (E)

+ 1.00000E-005* (A*B) + 9.00000E-003*(A*C) + 3.50000E003*(A*D) + 0.027800(*A*E)

- 4.56250E-004(*B*C) - 6.62813E-004*(B*D) + 2.73437E-004*(B *E) +0.21850*(C*D) +

0.18750* (C*E) - 0.070491*(D*E) - 1.46321E-003*(A2)+ 2.35363E-006 * (B2) - 1.36618

*(C2) + 0.039931*(D2) + 0.46230*(E2) equation 4.1

Biodiesel yield= 21.90959

From equation 3.1 FAME was determined to be

21.90959
FAME% = × 100%
26.0146

= 84.22%

42
 All diagnostic plots are also tested for all responses for adequacy of the models (normal

plot of residuals, residuals vs predicted value, residuals vs factor, box cox plot, studentized

residuals, leverage, etc.). Fore example figure 4.1 shows how precisely the oil yield is

modeled, because all the points line up and the deviation of points for oil yield from

normality is insignificant.

Figure 4.1: Predicted vs Actual Plot of Biodiesel Produced

43
Figure 4.2: Normal Plot of Residuals of Biodiesel Produced

44
Biodiesel yield

Biodiesel yield

Figure 4.3: Effect of Some Factors on Biodiesel Yield

4.1 EFFECT OF TIME

It was observed in Figure 4.3A that optimum reaction time was 2 hours and an

additional time would cause a decrease in the yield. This was also in agreement with the

study of Babatunde et al (2016) which found out that biodiesel yield was constant at a

reaction time of 120 minutes. A drop in biodiesel yield was also observed in his study, Yusuff

et al (2018) likewise Naidoo (2016) got its own optimum reaction time to be 1.9 hours

4.2 EFFECT OF TEMPERATURE

The effect of temperature with biodiesel conversion is shown in Figure 4.3B

Temperature increase clearly influences the reaction rate and biodiesel yield in a positive

manner. The temperature increase affected the biodiesel yield in a positive manner till 60°C

45
and after that it decreased. The increase in the yield of FAME at higher reaction temperature

is due to higher rate of reaction. Naidoo et al (2016) observed that a reaction temperature of

68.4oC gave a good yield which is very close to that observed in this study. The optimum

biodiesel yield of 98.1% was obtained at a reaction temperature of 60 oC (Muhammad et al,

2017). At a reaction temperature of 55oC Wu et al (2011) obtained a yield of 98.6% while

Yusuff et al (2018) found its own maximum yield at 60oC

4.3 EFFECT OF CATALYST CONCENTRATION

It was observed in figure 4.3C below that the catalyst concentration influenced the

biodiesel yield in a positive manner up to a certain concentration (say 5g) this was better

explained in 3D diagram shown in figure 4.3A and 4.3D below. Beyond this concentration,

the biodiesel yield decreased with increase in methanol concentration. When the catalyst

mount was improved, the interactive (active) site of the catalyst was increased; thus, the

transesterification reaction was accelerated and biodiesel yield was increased. Naidoo (2016)

observed in his study that any increase in catalyst concentration beyond 1g results in decrease

in biodiesel yield, this was far from what observed in this study and it may be as a result of

the combination of materials and reaction conditions he subjected the experiment to. Wu et

al (2011) prefer a catalyst loading of 1.25g but Yusuff et al (2018) study was in line with this

study with a catalyst loading of 5g.

46
 19
20
B io d ie s e l y ie ld

14.5

B io d ie s e l y ie ld
15.25

10

A
10.5
B
5.5 5.75

1
1

60.00

9.00 60.00 55.00 1600.00

50.00 1200.00
7.00 47.50
45.00 800.00
5.00 35.00 D: Reaction temp. B: Agitation r
40.00 400.00
3.00 22.50
E: Catalyst loading A: Methanol:oil
1.00 10.00
B io d ie s e l y ie ld

14 24

B io d ie s e l y ie ld
10.5 17.75

7 11.5

3.5 5.25

0 -1

60.00 3.00 9.00

55.00 2.50 7.00 55.00
50.00 2.00 5.00 50.00
45.00 1.50 3.00 45.00
D: Reaction temp. C: Reaction time E: Catalyst loading D: Reaction te
40.00 1.00 1.00 40.00

Figure 4.4: Interaction between Factors

47
From Figure 4.4A above, it was observed that an increase methanol volume and catalyst

loading caused an increase in biodiesel yield but a fall in the yield occur at a catalyst

concentration greater than 5g. In Figure 4.4B, increase in temperature and agitation rate

increased biodiesel yield.

48
 CHAPTER FIVE

CONCLUSION AND RECOMMENDATION

5.0 CONCLUSION

Box-Behnken design was employed to evaluate and optimize the process parameters

such as temperature, time, catalyst loading, agitation rate and methanol to oil weight ratio for

biodiesel production through transesterification process using castor seed oil. According to the

range analysis, the FAME yield of biodiesel increased sharply with increasing the amount of

methanol used and catalyst concentration but was slightly reduced after the optimal point. FAME

yield also increased with temperature. Transesterification occurred at a temperature below the

boiling point of methanol (65 oC) which led to the choice of temperature range between 40 and

60oC. After the whole statistical analysis, the optimum biodiesel yield of was obtained at an

agitation rate of 1882 rpm, time of 2 hours

5.1 RECOMMENDATION

Based on the challenges encountered in the course of this project work, the following are

recommended

 Ordinary anthill should not be used in biodiesel production because it produced lower

quantity

 An apparatus that can accommodate condenser should be used in order to limit the

escape of methanol so as to have excellent result and prevent health hazard

49
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