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INVESTIGATION OF BIODIESEL FUEL PROPERTIES WITH THE

DISPERSION OF CARBON NANOTUBES

DINISH S/O THEGARAJU

Report submitted in partial fulfillment of the requirements


for the award of Bachelor of Mechanical Engineering with Automotive Engineering

Faculty of Mechanical Engineering


UNIVERSITI MALAYSIA PAHANG

JUNE 2012

vii

ABSTRACT
This project reports on the use of carbon nanotubes as additive.to the biodiesel fuel and
its effects to the operational characteristics of the fuel The objective of this project is to
investigate the properties of palm oil biodiesel dispersed with carbon nanotubes in order
to achieve improved operational characteristics and performance. In this study, the
tested fuels were prepared by dispersing CNT into the fuels at five different
concentrations of 0.5 % vol, 1.0 % vol, 1.5 % vol, 2.0 % vol, 2.5 % vol and have their
properties tested and be compared against standard fuels. Experimental results have
shown that the thermal conductivities and flash points of the fuels dispersed with CNT
have increased with higher concentration of CNT. The pour point data have shown
decremental values when dispersed with CNT at higher concentrations and the
dispersion of CNT has increased the cetane number and higher heating value of the
fuels. As a conclusion, dispersion of CNT as additive has improved the properties and
the operational characteristics of biodiesel fuel and its blends.

viii

ABSTRAK

Projek ini melaporkan mengenai pengunaan carbon nanotubes sebagai bahan tambahan
untuk meningkatkan prestasi biodisel kelapa sawit. Objektif projek ini adalah untuk
menyiasat sifat-sifat biodisel yang ditambah dengan zarah CNT untuk mencapai ciri-ciri
operasi yang lebih baik. Dalam kajian ini, bahan bakar yang diuji disediakan dengan
menambah CNT dengan lima kepekatan seperti berikut, 0.5 % vol, 1.0 % vol, 1.5 %
vol, 2.0 % vol, 2.5 % vol dan sifat-sifatnya diuji dan dibandingkan dengan minyak biasa
di pasaran. Hasil uji kaji ini menunjukkan bahawa koduktiviti terma dan titik kilat bagi
biodisel meningkat dengan peningkatan kepekatan CNT. Data titik tuang menunjukkan
penurunan apabila ditambah dengan CNT dengan kepekatan yang lebih tinggi dan
penambahan CNT menunjukkan peningkatan dalam nombor cetane dan nilai bakar
tinggi biodiesel. Sebagai kesimpulan, penambahan CNT sebagai bahan tambahan akan
meningkatkan sifat-sifat biodisel konvensional dan ciri-ciri operasinya.

ix

TABLE OF CONTENTS

Page
TITLE

EXAMINER DECLARATION

ii

SUPERVISOR DECLARATION

iii

STUDENT DECLARATION

iv

DEDICATION

ACKNOWLEDGEMENT

vi

ABSTARCT

vii

ABSTRAK

viii

TABLE OF CONTENTS

ix

LIST OF TABLES

xi

LIST OF FIGURES

xiii

LIST OF SYMBOLS

xv

LIST OF ABBREVIATIONS

xvi

LIST OF APPENDICES

xvii

CHAPTER 1

INTRODUCTION

1.1

Project Background

1.2

Problem Statement

1.3

Project Objective

1.4

Project Scope

CHAPTER 2

LITERATURE REVIEW

2.1

Introduction

2.2

Background of Study

2.3

Biodiesel

2.3.1

Advantages and Disadvantages of Biodiesel

2.4

Biodiesel Production

2.5

Diesel Engine

9
11

2.6

Carbon Nanotube

12

2.7

Cetane Number

15

2.8

Viscosity

19

2.9

Density

20

2.10

Higher Heating Value

23

2.11

Flash Point

23

2.12

Cold Flow Properties

25

2.13

Thermal Conductivity

25

2.14

Summary

27

CHAPTER 3

RESEARCH METHODOLOGY

3.1

Introduction

29

3.2

Flow Chart Description

31

3.2.1

Project Introduction

31

3.2.2

Literature Study

31

3.2.3

Sample Preparation

31

3.2.4

Determination of Key Fuel Properties

33

3.2.4.1 Higher heating value

33

3.2.4.2 Cetane number

34

3.2.4.3 Flash point

35

3.2.4.4Thermal conductivity

35

3.2.4.5 Weigh scale

36

3.2.4.6 Ultrasonication homogenizer

37

3.2.4.7 Glassware

39

3.5

3.6

Water Bath System

39

3.5.1

40

Water Bath System Container Design

Pour Point

CHAPTER 4

42

RESULT AND DISCUSSION

4.1

Introduction

44

4.2

Analysis of Water Bath System

44

xi

4.2.1

Effect of Stirring on Homogeneity and Temperature

44

4.3

Thermal Conductivity Analysis

46

4.4

Flash Point Analysis

50

4.5

Pour Point Analysis

52

4.6

Cetane Number Analysis

54

4.7

Higher Heating Value Analysis

56

CHAPTER 5

CONCLUSION AND RECOMMENDATION

5.1

Introduction

59

5.2

Conclusions

59

5.3

Recommendations

61

REFERENCES

63

xii

LIST OF TABLES
Table No.

Title

Page

2.1

Properties of biodiesel and vegetable oil

2.2

Properties of carbon nanotubes and other common materials

14

2.3

Cetane number of biodiesel esters

17

2.4

Oxidization effect of methyl esters on cetane number

18

2.5

Thermal conductivities of various solids and liquids

26

2.6

Thermal properties of biodiesel and diesel mixtures

27

3.1

Volume concentration of CNT in biodiesel

32

3.2

Specification of the weigh scale

37

4.1

Homogeneity of water temperature with and without stirring effect

45

xiii

LIST OF FIGURES
Figure No.

Title

Page

2.1

Emissions of biodiesel compared with petro-diesel

2.2

A schematic diagram for biodiesel production

10

2.3

Comparison of fuel prices

10

2.4

CNT shapes

13

2.5

Relationship between cetane number and ignition delay

15

2.6

Relationship between viscosity and methyl ester amount in


biodiesel fuel

20

Relationship between density and methyl ester amount in


biodiesel fuel

22

2.8

Relationship between density and temperature of biodiesel

22

2.9

Relationship between flash point and number of atoms and number


of double bonds in fuel chains

24

3.1

Final year project flow chart

30

3.2

Samples of CNT-biodiesel blends

33

3.3

Oxygen bomb calorimeter

34

3.4

Octane meter

34

3.5

Petrotset machine

35

3.6

KD2PRO apparatus and the reading probe

36

3.7

Relationship between particle size and total particle surface

38

3.8

Scientz ultrasonic homogenizer

39

3.9

Water Bath Machine

40

3.10

Sample container holding steel plate with the clamp

41

3.11

Water bath system water container design

42

3.12

K46100 pour point and cloud point apparatus

43

2.7

xiv

3.13

Sample container containing sample fuel during pour point testing

43

4.1

Dye dispersion in water without stirring effect

45

4.2

Dye dispersion in water with stirring effect

46

4.3

Thermal conductivity of D100 without CNT in relation to


temperature

47

4.4

Thermal conductivity of B100 in relation to temperature

48

4.5

Thermal conductivity of D20 in relation to temperature

48

4.6

Thermal conductivity of D10 in relation to temperature

49

4.7

Flash point of fuel blends in relation to various volume


concentrations of CNT

51

Pour point of B100 in relation to various volume


concentrations of CNT

52

Pour point of B20 in relation to various volume


concentrations of CNT

53

Pour point of B10 in relation to various volume


concentrations of CNT

53

Cetane number of fuel blends in relation to various volume


concentrations of CNT

55

Higher heating values of fuel blends in relation to volume


concentrations of CNT

57

4.8

4.9

4.10

4.11

4.12

xv

LIST OF SYMBOLS
%

Percentage

Degree Celsius

cm

Centimeter

cP

Centipoise

Grams

kg

Kilogram

Meter

mm/s

Millimeter per Square Second

Nm

Nanometer

Pa

Pascal

% vol

Volume Percentage

W/m-K

Thermal Conductivity

Density

xvi

LIST OF ABBREVIATIONS
API

American Petroleum Institutes

ASTM

American Standard of Testing Materials

CNT

Carbon Nanotube(s)

FKM

Faculty of Mechanical Engineering

FTP

Federal Test Procedure

FYP

Final Year Project

SWNTs

Single-Walled Nanotubes

MWNTs

Multi-Walled Nanotube

SAE

Society of Automobile Engineers

xvii

LIST OF APPENDICES
Appendix

Title

Page

A1

Gantt chart for Final Year Project 1

66

A2

Gantt chart for Final Year Project 2

67

B1

Thermal conductivity of D100 in relation to temperature

68

Thermal conductivity of B100 in relation to temperature

68

Thermal conductivity of D20 in relation to temperature

69

Thermal conductivity of D10 in relation to temperature

69

Fuel blends flash point in relation to various volume


concentration of CNT

70

Fuel blends pour point in relation to various volume


concentration of CNT

71

Fuel blends cetane number in relation to various volume


concentration of CNT

72

Fuel blends higher heating value in relation to various volume


concentrations of CNT

73

B2

CHAPTER 1

INTRODUCTION

1.1

PROJECT BACKROUND
The worlds energy demand and supply has been pressurizing the availability of

crude oil. The dependence on fossil fuel is now in its critical stage as most the logistics
of the world require crude oil in order to move. The increasing usage of this fossil based
fuel has a degrading effect on the environment and climate through its polluting
combustion product. As the demand increases renewable form of fuel that is compatible
with current diesel engine (compression ignition engine) must be identified and the
potential candidate is the biodiesel from vegetable oils through transesterification.
Malaysia is a major producer of vegetable oils such as palm oil and palm oil can be
converted to biodiesel. Biodiesel has promising properties such as better cetane number,
flash point and emissions compared to fossil fuels but biodiesels suffer from metal
corrosion (Fazal et al., 2011) as oxygen content is higher in the fuel. Properties such
viscosity, higher heating value and cold flow properties are also lower than
conventional fossil fuel which affects its performance on a diesel engine. Biodiesel is
completely miscible with diesel allowing blending the fuels in any proportion without
modification of current engines. CNT is a form of pure carbon arranged in a cylindrical
shape in nanoscale dimensions and the dispersion in the blended fuel may improve the
fuel properties and the engine performance to CNT mix ratio in fuels is to be performed.

1.2

PROBLEM STATEMENT

Biodiesel fuels derived from vegetable oils comparatively have lower heating
value compared to the diesel due to the excess of oxygen in biodiesel fuels. This reduces
the amount of power generated when biodiesel is used, and thus increasing fuel
consumption for the same power generation from a diesel engine. In order to improve
the properties of the biodiesel, CNT is prepared to be dispersed within the dieselbiodiesel fuel mixture in order to produce better fuel performance such as the higher
heating value and cetane number. Dispersion of CNT will also increase the ratio of
carbon-oxygen in the fuel, thus improve the properties further. Existing research on the
CNTs effect on biodiesel fuels has not been fully established

1.3

PROJECT OBJECTIVE

For this project, the objectives to be achieved are listed as follows;

i.

To investigate various properties of diesel and biodiesel fuel blends.

ii.

To quantify the effect of CNT dispersion on the properties of diesel and


biodiesel fuels.

iii.

To develop a water bath system to find the effect of temperature on CNT


added diesel and biodiesel blends on thermal conductivity.

1.4

PROJECT SCOPE

In this study, CNT particles are selected as additive due to their high thermal
conductivity. It is proposed to determine operational characteristics of biodiesels in
concentrations of 0.5 % vol, 1.0 % vol, 1.5 % vol, 2.0 % vol and 2.5 % vol. Testing of
the fuel will be evaluated as per the American Standards of Testing Materials (ASTM).
The following tests are planned to be conducted.

i.

The Cetane number of a fuel is to be measured the quality of the fuel and
is used to determine the ignition delay of the fuel.

ii.

The Higher heating value is the energy contained by one gram of fuel
during combustion.

iii.

Thermal Conductivity of biodiesel is to be measured under transient


conditions. This method of measurement is undertaken by many
researchers. The measurement of temperature change with time is used in
the determination of thermal conductivity of biodiesel.

iv.

The Cold flow properties or the pour point is the lowest temperature at
which no movement of the specimen is observed is to flow out of the
container under the influence of gravity.

v.

The flash point temperature of biodiesel is the lowest temperature at


which an ignition source causes the vapors of the biodiesel to ignite
under specific conditions.

CHAPTER 2

LITERATURE REVIEW

2.1

INTRODUCTION

A plethora of experiments and studies were devoted by researchers on fuels and this
chapter discusses the findings of other researchers publications and by doing so, the
foundation and development of this project is paved by giving a better understanding of
fuel properties and its characteristics. The focus of the literature study is on biodiesel and
the dispersion of CNT as an additive.

2.2

BACKROUND OF STUDY

Nanomaterials are now in the forefront of the additive development of fluids


because of their unique properties and performance increase has been achieved in spark
ignition engines by dispersing CNT in gasoline in terms of octane number and anti-knock
properties. Nanomaterials can act as a burning rate catalyst because when dispersed into
liquids as they accelerate the burning rate and promote clean burning, also particulate
matters and carbon monoxide are reduced (Kish et al., 2009). Biodiesels are a viable choice
as a fuel source because it has no aromatics and is 10 % to 20 % more in oxygen content
and also, biodiesel improves the lubricity which results in longer component life as it does
not undergo desulfurization unlike common fossil fuel which reduces emission but it loses
its lubricity. (Alptekin and Canakci., 2008). Ertan also postulated that biodiesel has higher
cost due to the cost of virgin oil but Malaysia as a producer of vast quantities of palm oil is
capable of producing cheap oil compared to expensive corn or soy derived biodiesels.

Biodiesel is also nontoxic, renewable, biodegradable and environmentally friendly


(Verduzco et al., 2011). In addition, unlike oil and gas which have heavy foreign contents,
palm oil production is virtually 100% local. (Kalam and Masjuki., 2002)

2.3

BIODIESEL

The increasing awareness in the deteriorating properties of the ever growing


emissions and pollutants by combustion and the hike in fossil fuel cost due to its scarcity
will make biodiesel more acceptable. (Thielemann et al., 2007). Experts computed that
fossil fuel reserve depletion times for oil, coal and gas is approximately 35, 107 and 37
years which denotes that coal are available up to 2112 and the existing fossil fuel will
remain up until 2042. (Shafiee and Topal., 2008). To compensate for the rising energy
demand and the inevitable fossil fuel depletion, fuels such as biodiesel are in the pinnacle
alternative technologies as a viable replacement for diesel engines. The methyl ester of
palm oil, also known as palm oil diesel (POD) which is pure, made of 100% monoalkyl
ester is called neat fuel and is branded B100. Biodiesel blends can be designated by the
call sign BXX. The XX denotes the percentage of biodiesel in the blend (i.e., B90
describes a blend with 90% biodiesel and 10% diesel). . The comparison of properties of
vegetable oil biodiesel and standard specifications of diesel is given in Table 2.1. (Bajpai
and Tyagi., 2006). Table 2.1 indicates the properties of biodiesel in terms of kinematic
viscosity, cetane number, flash point, lower heating value and pour point for common types
of biodiesel and diesel.

Table 2.1: Properties of biodiesel and vegetable oil

Vegetable
oil
Peanut
Soybean
Sunflower
Palm
Diesel
20 %
biodiesel
blend

Kinematic
viscosity at
38 (C)
(mm2/s)
4.9
4.5
3.6
5.7
3.06
3.2

Cetane
number

Flash
point
(C)

56.4
45
63
62
50

176
178
127
164
76

Lower
heating
value
(MJ/Kg)
33.6
33.5
31.8
33.5
43.8

51

128

43.2

Cloud
point
(C)

Pour
point
(C)

5
1
4
13
-

-7
-16

-16

Source: (Bajpai and Tyagi., 2006)

2.3.1 ADVANTAGES AND DISADVANTAGES OF BIODIESEL

It is a fact that the transportation network of the world are the highest consumer of
fossil fuel such as gasoline, diesel fuel, liquefied petroleum gas (LPG) and natural gas (NG)
and the alternative to this fuel must be feasible, economical relative to current production
techniques, environmentally acceptable and has good availability. However it is not wise to
look only at biodiesel, it is important to take into account other crucial factors such as raw
material and vehicle technology in order to assess the feasibility of biodiesel as a fuel.
Biodiesel is 100 % renewable and being plant based it does not emit sulfur and carbon
monoxide on burning and is nonpolluting, biodegradable and environmentally safe. The
cytotoxic and mutagenic effects of diesel engine using biodiesel shows that particulates and
vitro cytogenic and mutagenic effects were lower compared to diesel fuel. In view of the
environmental considerations, biodiesel is considered carbon neutral as all the carbon
dioxide released from the atmosphere are used for the growth of vegetable oil crops (carbon
is exhausted and absorbed in a closed cycle thus there will be no addition of carbon to the
atmosphere compared to diesel fuel as it releases trapped carbons to the atmosphere). It is

known that the combustion of 1 liter diesel fuel gives 2.6 Kg of CO2 against 1 kg of
CO2/Kg of biodiesel (Bajpai and Tyagi., 2006). The literature states that the combustion of
biodiesel emit lesser pollution compared to diesel in which the emission of SO2, soot, CO,
hydrocarbons (HC), polyaromitic hydrocarbons (PAH), and aromatics as shown in Figure
2.1 which indicates the engine exhaust contains no SO2, and shows decreasing emissions of
pollutants. The NOx emissions are reported to be in the range between 10% compared to
diesel depending on engine combustion characteristics. This shows that biodiesel is similar
to diesel fuel in chemical and physical properties and has favourable engine performance
that makes it a better substitute for diesel fuel compared to battery power and hydrogen
power.

Figure 2.1: Emissions of biodiesel compared with petro-diesel

Source: (Bajpai and Tyagi., 2006)

Hydrocarbons are reduced with biodiesel in diesel engines along with carbon
monoxide and particulate matter. The exhaust emission of total hydrocarbon is at an
average of 67 % lower for biodiesel, carbon monoxide at 48 % lower and particulate matter
at 47 % lower than diesel. This nulls the perspective that the dispersion of CNT will
increase pollution compared to diesel fuel as only a small percentage of CNT is dispersed.

However nitrous oxide emissions stayed or are slightly increased. The melting temperature
of palm oil biodiesel (POD) is about 20 C which forms a clear liquid when blended with
diesel fuel. The fraction of POD in blends does not create any separation or any layering on
the inside wall of the fuel tank. This investigation was done in Malaysia, when the ambient
environmental temperature was 25 C 35 C. It is assumed that POD could be a good
alternative to partially replace the conventional diesel fuel (Kalam and Masjuki., 2002).
Biodiesels are subjected to oxidation through contact with the oxygen in the air and
hydroperoxides are formed by the reaction of oxygen with carbon atoms and most
vegetable oils contain anti-oxidants such as vitamin E that inhibit oxidation until it is
depleted causing the oxidation to process rapidly beyond the depletion of vitamin E. With
the presence of two or more double bonds in the fatty acid chain, biodiesel oxidize more
rapidly compared to biodiesel with one double bond thus the tendency to oxidize is greater
with the increase in the number of double bonds in the biodiesel chain. The important
consequence of oxidization is that the hydroperoxides are very unstable and tend to attack
the elastomers and it induces polymerization of esters and form insoluble gums and
sediments which causes filter plugging. This phenomenon is called fuel stability problem
and the oxidization is accelerated by heat and light. When biodiesels are distilled to remove
high boiling point materials such as glycerin, the natural antioxidants are also removed
causing accelerated oxidation. Biodiesel also show degradation when stored for a long time
along with humidity, pigments and enzymes which reduces oxidative stability. (Dantas et
al., 2010). The lubricating properties of the biodiesel increases the engine efficiency and
can eliminate the use of additives and reduce the failure of fuel injection pump which is
caused by inadequate fuel lubricity. Drivability is another important advantage of the
biodiesel where, the use of biodiesel causes smoothing of the engine where it runs quieter
and produces less smoke and existing engines can be used without any modification up to
20 % biodiesel in the fuel blend.

2.4

BIODIESEL PRODUCTION

Biodiesel can be produced by chemically reacting vegetable oil or animal fat with
alcohol such as methanol. This reaction requires a catalyst such as sulfuric acid, sodium or
potassium hydroxide. This produces compounds called methyl esters. It is these esters that
came to be known as biodiesel. Biodiesel from vegetable oil is interesting for several
reasons such as it can replace diesel oil in boilers and internal combustion engines without
major adjustments, only a small decrease in performance was reported, almost zero
emission of sulfates, a small net contribution of carbon dioxide when whole life cycle is
considered from cultivation to conversion of biodiesel. In general, vegetable oils contain
triglycerides and monoglyserides and fatty acids. However the production cost of biodiesel
is not economically competitive with petroleum based fuels due to relatively high cost of
the lipid feedstock which are usually edible grade refined oils. The process of removal of
all glycerol and the fatty acid from the vegetable oil is called transesterification.
Trasesterification is a better method because it is a simple and an easy operation. Figure 2.2
shows the chemical reaction between triglycerides and alcohol in the presence of the
catalyst to produce mono-esters. Depending on the fatty acid composition of the oil, its
cetane number can be determined at the starting stage. (Halek et al., 2009)

10

Figure 2.2: A schematic diagram for biodiesel production

Source: (Bajpai and Tyagi., 2007)

In some European countries, biodiesel oil are sold commercially, however in other
countries, biodiesels are not available commercially due to high cost and is primarily used
mainly for practical purposes and in reduce dependency on imported fuels. In Asia,
Malaysia produces 3000 metric tonnes per year for transit fleet, bus and cars therefore the
demand of biodiesel is there and is increasing. Although the general interest in using and
producing biodiesel is dependent on the regional prices of biofuel, labor, land, processing
plant and economic considerations must be evaluated. Figure 2.3 shows the comparison of
the cost of diesel fuel to the cost of the energy equivalent amount of palm oil and other
vegetable oil (Kalam and Masjuki., 2002) and from the figure it is clear that it is not yet
economical to use palm oil as well as other biodiesels.

11

Figure 2.3: Comparison of fuel prices

Source: (Kalam and Masjuki., 2002)

2.5

DIESEL ENGINE

A diesel engine is a type of internal combustion engine where the standard diesel
engine operates on the principal that air in the engine cylinder is compressed to an
extremely high pressure and temperature at which time the fuel is injected into the
combustion chamber causing ignition. This is different from a gasoline engine which
compresses both the air and fuel at the same time. Once the air and fuel is compressed, the
gasoline engine relies on a spark to ignite the mixture causing combustion. The spark
ignition or gasoline engines need for electrical ignition requires the use of many
components such as spark plugs, ignition coil, distributor, and a carburetor. The mechanical
nature of the diesel engines design makes it simpler, more rugged, more versatile, and its
higher compression ratio makes it more efficient than the gasoline engine. It is because of
these basic principles of the diesel engines design that make it such a good candidate for a
near term solution to our renewable energy needs (Engine Manufacturers Association.,
2002).

12

2.6

CARBON NANOTUBES
CNT were discovered by Sumio Iijima in 1991. CNTs are a particular arrangement

of carbon atoms similar in structure to graphene, a two dimensional counterpart of graphite.


A CNT is formed when the two-dimensional sheet of graphene is rolled into a seamless
cylinder. CNTs can range from 1 nm to 100 nm in diameter and have lengths in the
micrometer range. Based on the chemical arrangement of carbon atoms, a discrete number
of unique CNTs can be formed. Normally, these different types of CNTs are classified by
their chiral vector as displayed in Figure 2.4. The chiral vector is related to the
circumference of the nanotube, and based on the chiral vector, the nanotubes are
categorized as either semi-conducting or metallic. CNTs can also be classified as singlewalled, double-walled or multi-walled. A single-walled CNT is formed by a rolling a single
sheet of graphene into a cylinder. Double-walled and multi-walled CNTs are formed by
forming concentric cylinders from multiple layers of graphene. Dresselhaus provides a very
detailed description of the chemical arrangement of CNTs as well as the phonon transport
and related thermophysical properties (Eklund., 2000). Figure 2.4 is a schematic
representation of the construction of a nanotube by rolling up and infinite strip of graphene.
In (A) the chiral vector Ch = na1+ma2 connects two lattice points O and A on the graphene
sheet. An infinite strip is cut from the sheet through these two points, perpendicular to the
chiral vector. The strip is then rolled up into a seamless cylinder. T=t1a1 +t2a2 is the
translation vector of the tube. All different nanotubes have angles between 0 and 30.
Armchair tubes have angles of 30 (Ba), zigzag have angles of 0 (Bb) and all other tubes
are called chiral and have angles within 0 to 30 (Bc) as shown in Figure 2.4 (Popov.,
2004).