iii

For my beloved mother and father

For my beloved husband

iv

ACKNOWLEDGEMENT

Alhamdulillah, I am so grateful to Allah S.W.T for giving me strength and guidance

throughout my studies and to complete this thesis. First of all, I would like to express

my gratitude to my supervisor, Assoc. Prof. Dr. Engr. Abdul Mutalib bin Leman for

becoming my motivator, inspirer through all the stages during my Master journey.

Without his supervision and invaluable time spent with me, this thesis would not been

completed successfully.

I would like to thank to Mr Supa’at Zakaria and Mr Dafit Feriyanto for their ideas and

assistance throughout this thesis.

I would like to extend my gratitude to my beloved parents and my husband who always

provided me a moral support and guidance in the completion of this thesis. I am so

grateful for the love, support and educational opportunities that they have provided for

me throughout the years.

v

ABSTRACT

Automobile exhaust emission control is one of trending issues in automotive research

field. Ceramic and metallic catalytic converters are the most common types of catalytic

converters. Most current researches focus on the modeling and characterization of

catalytic converter and there is a lack of exhaust gas conversion data of different catalyst

types that correspond to real engine operating condition. This project focuses on

comparing and analyzing the performance of ceramic and metallic catalytic converter on

its conversion efficiency. Mitsubishi 4G93 1800cc gasoline engine was attached with a

dynamometer and Kane Auto 5-1 series exhaust gas analyzer were used for emission

measurements of carbon monoxide (CO), hydrocarbon (HC) and nitrogen oxide (NOx) in

different speed and constant load. The experimental results of the engine performance

and exhaust emission were used to compare the performance of ceramic and metallic

catalytic converters in reducing the concentration of the exhaust emission without

affecting the engine performance. Based on the result, metallic catalytic converter

showed a higher 97.9% reduction of CO concentration reduction emission as compared

to the ceramic catalytic converter. The ceramic catalytic converters on the other hands

showed better reduction of NOx and HC concentration of 87.2% and 85.4% percentage

of reduction. It can be concluded that metallic catalytic converters performs a better

exhaust gas conversion on high temperature condition at reducing CO emission while

ceramic catalytic converters reduced HC and NOx emission more effectively due to its

lower thermal conductivity.

vi

ABSTRAK

Kawalan pelepasan ekzos automobil adalah salah satu daripada isu yang mendapat

perhatian dalam bidang penyelidikan automotif. Penukar pemangkin seramik dan logam

adalah jenis penukar pemangkin yang biasa digunakan. Kebanyakan kajian semasa

memberi tumpuan kepada model dan pencirian penukar pemangkin, di mana terdapat

kekurangan data berkaitan penukaran gas ekzos bagi mengkaji prestasi pemangkin yang

berbeza dan sepadan dengan keadaan operasi enjin sebenar. Projek ini memberi tumpuan

kepada perbandingan dan menganalisis prestasi penukar pemangkin seramik dan logam

dalam kecekapan penukaran. Enjin petrol jenis Mitsubishi 4G93 1800 cc yang

disambungkan dengan dinamometer dan penganalisis gas jenis Kane Auto 5-1

digunakan untuk pengukuran pelepasan gas karbon monoksida (CO), hidrokarbon (HC)

dan nitrogen oksida (NOx) dengan perubahan kelajuan dan beban yang tetap. Keputusan

eksperimen prestasi enjin dan pelepasan ekzos penukar pemangkin seramik telah

dibandingkan dengan penukar pemangkin logam dari segi kecekapan mengurangkan

pelepasan ekzos tanpa menjejaskan prestasi enjin. Berdasarkan keputusan yang

diperolehi, penukar pemangkin logam menunjukkan pengurangan CO yang lebih tinggi

iaitu sebanyak 97.9% berbanding penukar pemangkin seramik. Penukar pemangkin

seramik pula menunjukkan pengurangan yang ketara bagi kandungan NOx dan HC iaitu

87.2% dan 85.4% kecekapan penukaran. Analisis kedua-dua penukar pemangkin

seramik dan logam menunjukkan prestasi yang berbeza dalam mengurangkan pelepasan

ekzos. Kesimpulannya, penukar pemangkin menunjukkan penukaran gas ekzos yang

lebih baik pada keadaan suhu yang tinggi untuk mengurangkan pelepasan CO manakala

penukar pemangkin seramik mengurangkan pelepasan HC dan NOx yang lebih berkesan

akibat kekonduksian terma yang lebih rendah.

vii

TABLE OF CONTENTS

TITLE i

DECLARATION ii

DEDICATION iii

ACKNOWLEDGEMENT iv

ABSTRACT v

ABSTRAK vi

TABLE OF CONTENTS vii

LIST OF TABLES x

LIST OF FIGURES xii

LIST OF SYMBOLS AND ABBREVIATION xvi

LIST OF APPENDICES xviii

CHAPTER 1 INTRODUCTION 1

1. 1 Background of Study 1

1.2 Problem Statement 4

1.3 Objectives of Study 5

1.4 Scopes of Study 5

1.5 Significant of Study 6

1.6 Thesis Organization 6

CHAPTER 2 LITERATURE REVIEW 7

2.1 Introduction 7

2.2 Regulation of Vehicles Emission 7

2.3 Performance and Emission of RON 95 and RON 97

Gasoline

9

2.4 Emission of Gasoline Engine 11

viii

2.4.1 Emission of Nitrogen Oxides (NOx) 11

2.4.2 Emission of Carbon Monoxide (CO) 12

2.4.3 Emission of Hydrocarbon (HC) 12

2.5 Emission Standard of Gasoline Engine 13

2.6 Factors Affecting Exhaust Emission 14

2.6.1 Air-to-Fuel Ratio 15

2.6.2 Cold-Start Condition 17

2.6.3 Exhaust Temperature 19

2.7 Catalytic Converter 19

2.7.1 Substrate 21

2.7.2 Washcoat 22

2.7.3 Catalyst 23

2.8 Ceramic Catalytic Converter 23

2.9 Metallic Catalytic Converter 26

2.10 Advanced Material Development 28

2.11 Experimental Analysis of Exhaust Emission

Testing

29

2.12 Research Gap 35

CHAPTER 3 METHODOLOGY 37

3.1 Introduction 37

3.2 Research Flowchart 37

3.3 Catalytic Converter Selection 39

3.4 Experimental Facilities and Equipment 40

3.4.1 Exhaust system Modification 40

3.4.2 Engine Test Bench 41

3.4.3 Eddy Current Dynamometer 43

3.4.4 Fuel Measurement 46

3.4.5 Temperature Measurement 47

3.4.6 Exhaust Gas Analyzer 48

3.5 Operating Conditions and Testing Sequence 50

3.6 Analysis of Engine Performance 52

ix

3.6.1 Brake Power Calculation 52

3.6.2 Brake Mean Effective Pressure 52

3.6.3 Brake Specific Fuel Consumption 52

CHAPTER 4 RESULTS AND DISCUSSION 54

4.1 Introduction 54

4.2 Engine Performance Analysis 54

4.2.1 Effect of Brake Power On Engine

Performance

55

4.2.2 Effect of Brake Mean Effective Pressure on

Engine Performance

57

4.2.3 Effect of Brake Specific Fuel Consumption

on Engine Performance

59

4.2.4 Effect of inlet and outlet temperature on

Engine performance

61

4.3 Analysis of Engine Emission 63

4.3.1 Effect of Engine Speed on Engine Out

Emission

63

4.3.1.1 CO Emission 64

4.3.1.2 NOx Emission 67

4.3.1.3 HC Emission 69

CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS 72

5.1 Conclusions 72

5.2 Recommendations for Future Works 73

REFERENCES 75

APPENDICES 85

x

LIST OF TABLES

1.1 Estimated average contributions of vehicle emissions to

ambient levels of major air pollutants in developed

countries

2.1 California emission standard for passenger cars 9

2.2 Comparison between vehicle emission control legislation

United State and European Union (EU)

9

2.3 Gasoline properties and its effect on fuel and exhaust

emission

10

2.4 Typical exhaust gas compositions at the common gasoline

engine

12

2.5 Light Duty Vehicles (LDVs) Emission Standard in

ASEAN countries

13

2.6 Air fuel mixture and emission relationship 16

2.7 Previous research which highlighted the gaps of this

research

35

3.1 Properties of metallic and ceramic substrates support 39

3.2 Engine specification summary 43

3.3 K-type thermocouple specifications 47

3.4 Technical Specifications of Kane Auto 4-1 Gas Analyzers 49

4.1 Brake power (Nm) of ceramic and metallic CAT with and

without catalytic converter using RON 95 and RON 97

55

4.2 BMEP (kPa) of ceramic and metallic CAT with and

without catalytic converter using RON 95 and RON 97

57

4.3 BSFC (kg/kwhr) of ceramic and metallic CAT with and

without catalytic converter using RON 95 and RON 97

59

2

xi

4.4 Inlet and outlet temperature (oC) of ceramic and metallic

catalytic converter using RON 95 and RON 97

62

4.5 CO concentration (%) at inlet and outlet of ceramic and

metallic using RON 95 and RON 97

65

4.6 NOx concentration (ppm) at inlet and outlet of ceramic and

metallic catalytic using RON 95 and RON 97

67

4.7 HC concentration (ppm) at inlet and outlet of ceramic and

metallic catalytic using RON 95 and RON 97

69

xii

LIST OF FIGURES

1.1 Catalytic Converter Monolith of Ceramic and metallic

Material

3

2.1 European particular matter (CO) and nitrogen oxides

(HC) emission standards for gasoline light passenger

cars.

14

2.2 Air-fuel ratio for exhaust SI gasoline emission 15

2.3 Response of oxygen sensor used in exhaust pipeline 17

2.4 The Integrated Model structure of combined engine,

emissions, exhaust and after treatment system model

18

2.5 Schematic view of three way catalyst converter 20

2.6 Ceramic and metallic monolith 21

2.7 Fabrication of monolith honeycomb substrates 22

2.8 Washcoat and catalyst development focused area in

catalytic converter

24

2.9 Honeycomb structure of ceramic substrates in three

dimensional

25

2.10 Schematics illustrating shape selectivity in zeolite

catalysis

26

2.11 Design and production of early metallic substrates 27

2.12 Structure of metallic substrates 28

2.13 Experimental setup that is commonly used for SI engine

emission testing

30

2.14 Flow chart of a preliminary quality assurance

methodology

31

2.15 Schematic diagram of chassis dynamometer emission

test facility

32

xiii

2.16 The exhaust emission test routine 33

2.17 Experimental setup of exhaust emission measurement 34

3.1 Research flowchart of the study 38

3.2(a) Ceramic catalytic converter 39

3.2(b) Metallic catalytic converter 40

3.3 New modified exhaust system 40

3.4 New exhaust piping with thermocouple sensor and gas

analyzer probe

41

3.5 Automotive Engineering Centre (AEC), University

Malaysia Pahang, Pekan Campus

41

3.6 Schematic View of Experimental Setup of Mitsubishi

4G93

42

3.7 Engine Test Bed 42

3.8 Mitsubishi 4G93 engine with eddy current

dynamometer

44

3.9(a) Dyno cooling tank 45

3.9(b) Dynamometer cooling tower 45

3.10(a) Control room 45

3.10(b) Dynalec Dynamometer Controller 45

3.11(a) AIC fuel flow meter 46

3.11(b) Board Computer BC 3033 (BC-3033) 46

3.12 Testo 922 with K-Type Thermocouples 47

3.13 Thermocouples position on the exhaust pipe 48

3.14(a) Kane Auto 5-1 Gas Analyzer 49

3.14(b) Position of analyzer probe on the exhaust pipe 49

3.15 Adapted View of Kane Auto 5-1 Exhaust Emission

Software

50

4.1 Effects of engine speed on brake power for ceramic and

metallic CAT when using RON 95

56

4.2 Effects of engine speed on brake power for ceramic and

metallic CAT when using RON 97

56

xiv

4.3 Effects of engine speeds on brake mean effective

pressure for ceramic and metallic CAT when using

RON 95

58

4.4 Effects of engine speeds on brake mean effective

pressure for ceramic and metallic CAT when using

RON 97

58

4.5 Effects of engine speeds on brake specific fuel

consumption for ceramic and metallic CAT when using

RON 95

60

4.6 Effects of engine speeds on brake specific fuel

consumption for ceramic and metallic CAT when using

RON 97

60

4.7 Effects of engine speed on inlet and outlet temperature

of catalytic converter on engine performance using

RON 95

63

4.8 Effects of engine speed on inlet and outlet temperature

of catalytic converter on engine performance using

RON 97

63

4.9 Concentrations values of CO emission (%) for ceramic

and metallic catalytic against engine speed when using

RON 95

65

4.10 Concentrations values of CO emission (%) for ceramic

and metallic catalytic against engine speed when using

RON 97

66

4.11 Concentrations values of NOX emission (ppm) for

ceramic and metallic catalytic against engine speed

when using RON 95

68

4.12 Concentration values of NOX emission (ppm) for

ceramic and metallic catalytic against engine speed

when using RON 97

68

xv

4.13 Concentration value of HC emission (ppm) for ceramic

and metallic catalytic against engine speed when using

RON 95

70

4.14 Concentration value of HC emission (ppm) for ceramic

and metallic catalytic against engine speed when using

RON 97

70

xvi

LIST OF SYMBOLS AND ABBREVIATIONS

2WCC - Two-Way Catalytic Converter

γ-Al2O3 - Gamma Alumina

Al2O3 - Alumina

CeO2 - Ceria

Cu(NO3)2 - Copper nitrate

CO - Carbon Monoxide

CuO - Copper oxide

CrO2 - Cerium oxide

DOE - Department of Environment

EGR - Exhaust Gas Recirculation

EHC - Electrical Catalytic Converter

EICHC - Electrically Initiated Chemically Heated Catalytic

Converter

EPA - Environmental Protection Agency

E.U - European Union

FeCrAl - Ferum Chromium Aluminium

FTP - Federal Test Procedure

H2 - Hydrogen

HC - Hydrocarbon

HCl - Hydrochloric Acid

H2O - Hydrogen Dioxide

ICE - Internal Combustion Engine

kHz - Kilo Hertz

LDV - Light Duty Vehicles

xvii

LEV - Low Emission Vehicle

NaOH - Sodium Hydroxide

NEDC - New European Drive Cycle

NiO - Nickel Oxide

NOx - Nitrogen Oxides

O2 - Oxygen

OEM - Original Engine Manufacture

PC - Personal Computer

Pd - Palladium

PGEs - Platinum Group Elements

PM - Particulate Matter

PPM - Parts Per Million

Pt - Platinum

Rh - Rhodium

rpm - Rotation Per Minute

SCR - selective catalytic reduction

SI - Spark Ignition

SO2 - Sulphur Dioxide

TLEV - Transitional Low Emission Vehicle

TWC - Three Way Catalyst

ULEV - Ultra Low Emission Vehicle

ZEV - Zero Emission Vehicle

ZrO2 - Zirconia

xviii

LIST OF APPENDICES

APPENDIX TITLE PAGE

A Specifications of AIC Fuel Flow

Meter

85

B1 Testo 922 Manual 86

B2 Kane Auto 5-1 Gas Analysers

Manual

87

B3 Exhaust System Modification 89

B4 List of Publication 91

CHAPTER 1

INTRODUCTION

1.1 Background of Study

Air pollution has been known to be a major risk to health and environment. Outdoor

air pollution is estimated to cause 1.3 million annual deaths worldwide

(WHO, 2011). All over the world, mobile sources stand out as the largest

contributors of a number of air pollutants which produced about 70 to75 % of the

total air pollutions.

One automobile exhaust can release gas that contains nearly 200 different

components into the atmosphere (Mishakov, 2011). The emission potential of

gasoline-powered vehicles are carbon monoxide (CO, 0.5 vol.%), unburned

hydrocarbons (HC, 350 ppm), nitrogen oxide (NOx, 900 ppm), hydrogen (H2, 0.17

vol.%), water (H2O, 10 vol.%), carbon dioxide (CO2, 10 vol.%), and oxygen (O2, 0.5

vol.%) (Bharat and Kuldeep, 2012). Table 1.1 shows the estimated average

contributions of vehicle emissions of major air pollutants.

2

Table 1.1: Estimated average contributions of vehicle emissions to ambient levels of

major air pollutants in developed countries (Greenbaum, 2013)

Pollutant Contribution (%) Reference

Carbon monoxide ~90 EPA (2000)

PM2.5 ~25–30 DEFRA (2012)

Nitrogen oxides ~40 EPA (2000)

Volatile organic compounds ~35 EPA (2000)

Average air toxics ~21 EPA (1999)

Urban air toxics ~42 EPA (1999)

Over the recent years, exhaust after treatment for automobile presents a range

of advanced technologies based on oxidation and three-way catalyst, adsorption,

storage and filtration processes. This enables the reduction of CO, HC, NOx and

particulate emissions (PM) from any gasoline or diesel engine in order to meet the

demands of current and future of exhaust emission regulations. Catalytic converters

were first introduced in the market of the United States in the mid-1970s in order to

comply with the strict Environmental Protection Agency (EPA) on automobile

exhaust emissions (Pankaj and Manish, 2012). Catalytic converter has been known as

a built-in device in the exhaust system of an automobile to reduce the amount of CO,

NOx and unreacted HC in automotive emissions (Sebayang et al., 2007). These gases

are eliminated by the basic reactions occur inside a catalytic converter through

oxidation of CO, HC and reduction for NOx. This catalytic converter is mounted

along the exhaust pipe of the engine and has a base mesh or substrate to enable the

exhaust gas to flow inside the container (Mansha, 2012).

The act of simultaneous reaction of oxidation and reduction is referred as

Three Way Catalyst (TWC) and it has become the most common type of catalytic

converter (Sebayang et al., 2007 and Heck et al., 2009). Catalytic converters come in

many concepts, structures and even the materials; nevertheless, it continues to evolve

depending on different vehicle requirements. Catalytic converter is consisted of three

basic components such as substrate, washcoat and catalyst (Sebayang et al., 2006).

The active catalyst layer is applied on the surface of the monolith walls. The coating,

called ‘washcoat’, is composed of porous, high surface area inorganic oxides such as

γ-Al2O3 (gamma alumina), CeO2 (Ceria) and ZrO2 (Zirconia). Noble metal catalysts,

3

such as Platinum (Pt), Palladium (Pd) and Rhodium (Rh), are deposited on the

surface and within the pores of the washcoat (Pontikakis, 2003).

In the last few years, the monolith or honeycomb structure catalyst has been

the most dominant catalyst used for gasoline engine. This type of catalyst is a

mixture of alkaline earth-metals, oxides and platinum group elements (PGEs) such as

Pt, Pd and Rh in which are all coated with highly porous washcoat of 90% γ-Al2O3

(Paraskevas, 2012). Ceramic and metallic substrates are the most common catalytic

converter used in regard to the catalyst type (Kaspar et al., 2003). In spite of extruded

ceramic monoliths being the most widely used substrate material, mainly because of

its relatively low manufacturing costs, foil metallic monolith substrates has become

more advanced in after-treatment market. It is selected as the substrate due to its

high thermal conductivity, lower heat capacity, greater thermal and mechanical shock

resistant, thinner wall lower pressure drop (Wu et al., 2005), higher coefficient of

thermal expansion (CTE) (Zhao et al., 2003) high temperature oxidation resistance

and is able to achieve larger specific surface area as shown in Figure 1.1.

As many researchers have been focused on the modeling and characterization

of the catalytic converter, there is a need for experimental testing on both ceramic

and metallic converters. In this project, the experimental measurement of exhaust

emission of both ceramic and metallic catalytic converter were compared in order to

examine the conversion efficiency of the exhaust gases in respond to the real engine

operating conditions such as engine speed and load.

Figure 1.1: Catalytic converter monolith of (1) ceramic and (2) metallic material

(Putrasari et al., 2010).

4

1.2 Problem Statement

The contribution of exhaust emissions reduction via sophisticated engine system is

relatively limited; however, increased environmental awareness has led to the

demand for products and processes which are more compatible with the environment

(Hasan, 2011). The most common type of after treatment used for the petrol engine is

the ‘three-way catalyst’ (TWC) which caters for a simultaneous oxidation and

reduction of exhaust gas components. Ceramic and metallic catalytic converters are

the most commonly used products available in the exhaust after treatment market

(Bode, 2002). There have been a vastly increased interest in experimental studies that

investigated the performance of the catalytic converters. Martin et al. (1998) has

experimentally investigated the effects of flow distribution, space velocity and light-

off temperature on the performance of catalytic converters. Buchner et al. (2001)

have gathered an experimental data base from test bench and dynamometer in order

to determine the heat transfer coefficients in catalytic converters. Silva et al. (2006)

evaluated the conversion efficiency of a catalytic converter under steady operating

condition. The inlet and outlet chemical species concentration, temperature and air

fuel ratio (A/F) were measured as a function of the brake mean effective pressure

(BMEP) and engine speed (rpm). Pannone and Mueller (2001) and Santos and Costa

(2008) have compared catalyst system using ceramic and metallic substrates in order

to assess the influence of various substrate parameters on the exhaust gas conversion

efficiencies. Despite that, there is still lack of literature on the exhaust gas conversion

data for different catalyst types for two different gasoline fuels (RON 95 and RON

97).

Thus, the present study attempts to analyze the performance of the ceramic

and metallic catalytic converter on its conversion efficiency. Ceramic and metallic

three way catalytic converter have been compared to assess the influence of physical

parameters and fuel properties on the engine parameters and exhaust gas conversion

for several different operating conditions. The inlet and outlet chemical species

concentration and temperature were measured as a function of the engine speed

(rpm).

5

1.3 Objectives of Study

The objectives of this study are:

i. To examine the conversion efficiency of the substrate materials in

reducing CO, HC and NOx of gasoline engine through experimental

measurement.

ii. To analyze the influence of ceramics and metallic substrate properties

towards the engine performance and emission of a gasoline

iii. To investigate experimentally the performance of engine and the

characteristics of emission using RON 95 and RON 97.

1.4 Scopes of Study

Several points are listed here to elucidate the scopes of the study as follows:

i. Experimental study is conducted to measure the emission and engine

performance data from the tested engine.

ii. Mitsubishi 4G93 gasoline engine with eddy current dynamometer

used as test engine.

iii. Two type of catalytic converter which is ceramic and metallic

catalytic converter.

iv. Two type of petrol fuel were used which is RON 95 and RON 97.

v. The emission testing was conducted at different engine speeds from

1000 rpm to 4000 rpm at constant engine loads of 25%

vi. The exhaust emission of carbon monoxide (CO), nitrogen oxide (NOx)

and hydrocarbon (HC) are measured during the engine test.

6

1.5 Significant of Study

The significant of this research are:

i. The outcome of this research is expected to contribute in the development

of ceramic and metallic substrate.

ii. The intent is to further clarify the performance of metallic and ceramic

substrates under different engine conditions.

1.6 Thesis Organization

This thesis consists of several chapters which contain different discussion as follows:

Chapter 1: Consists of the background of the study, problem statement,

research objectives, significant research, expected results and scope or limitation of

the project.

Chapter 2: Review about the terminology of catalytic converter, the

development material and method for developing catalytic converter and the

experimental studies from the past research.

Chapter 3: Described the current method and material used in this research

and also the analysis and equipment used to achieve the research objectives.

Chapter 4: Discuss a result of the experimental result of exhaust emission

testing in order for determining the effectiveness of the new catalyst and technique

approach applied in this project.

Chapter 5: Consist of conclusions of this research which answer the

objectives and also recommendation to continue this research for the next researcher.

CHAPTER 2

LITERATURE REVIEW

2.1 Introduction

This chapter presents overview of regulation of vehicle emission standard and the

theoretical background and previous research related to the component of catalytic

converter and its development in after treatment application. It discusses on the

development of ceramics and metallic substrate and its properties in which affect the

overall performance of the catalytic converter in reducing the vehicle exhaust

emission.

2.2 Regulation of Vehicles Emission

Automobile emission has always been a major source of atmospheric pollution.

Kaspar et al., (2003) suggested that automobile exhaust composition is depended on

a variety of factors such as type of engine, driving conditions and vehicle speed. The

creation of pollutants may result from a number of chemical changes that take place

from the mixture of hydrocarbons or gasoline and air which is ignited through

combustion process (Kaleli, 2003). In the 20th century, the pollutants released from

internal combustion engines had raised serious health and environmental issues

(Seinfeld, 2004). In response to this concern, a stringent legislation regulating

emissions has been developed in many countries. Table 2.1 shows the current

8

summary of the California emission standard for passenger cars which involve

Transitional Low Emission Vehicle (TLEV), Low Emission Vehicle (LEV), Ultra

Low Emission Vehicle (ULEV) and Zero Emission Vehicle (ZEV).

Table 2.1: California emission standard for passenger cars (EPA, 2000)

Category Durability Basis

(miles)

NMOG

(g/mile)

CO (g/mile) NOx

(g/mile)

TLEV 50, 000

120, 000

0.125

0.156

3.4

4.2

0.4

0.6

LEV 50, 000

120, 000

0.075

0.09

3.4

4.2

0.05

0.07

ULEV 50, 000

120, 000

0.04

0.055

1.7

2.1

0.05

0.07

ZEV -0- -0- -0- -0-

The Environmental Protection Agency (EPA) has established a vehicle test

procedure namely the Federal Test Procedure (FTP) which stimulates the average of

the driving conditions of vehicles in the United State where the pollutant emission

gases such as CO, NOx and unburned HC are measured and analysed. The FTP cycle

is conducted by attaching a dynamometer to a vehicle. The FTP test also measure

gases emitted from vehicle exhaust during conditions such as cold start conditions,

hot start and combination of urban and highway driving conditions (Heck and

Farrauto, 2009). The United State (U.S) and the European Union (E.U) have different

specification for vehicle emission control in terms of test cycle conducted to the

vehicles, fuel quality and type of pollutants as shown in Table 2.2.

9

Table 2.2: Comparison between vehicle emission control legislation United State and

European Union (EU) (EPA, 2000)

United State (U.S) European Union (E.U)

Test

Cycle

Federal Test Procedures + Supplemental

Cycles:

• FTP-75 (city cycle, includes cold start)

• US06 (high speed)

• SC03 (air conditioning)

• HWFET (highway cycle, fuel economy

only)

New European Drive Cycle:

• NEDC (city and extra urban, cold start)

World-Harmonized Light-Duty Vehicle

Test Procedure:

• WLTP (cold start, low, medium, high

and aggressive driving in a single cycle)

• Expected implementation in 2017

Fuel

Quality

Gasoline: 30 ppm sulphur average / 80

max

(2006); 10 ppm average / 80 max (2017)

• Diesel: 15 ppm sulphur max (2007)

• Gasoline & diesel: 50 ppm sulphur max

(2005)

• Gasoline & diesel: 10 ppm sulphur max

(2009)

Pollutants

Emissions:

• NOx + NMOG and CO (bin certification,

fleet

averaging)

• HCHO (limit value)

• PM mass (limit values, phased in)

GHG:

• CO2 (fleet average)

• CH4, N2O (limit values)

Emissions:

• NOx, HC, NOx+HC (diesels), PM and

PN (limit values per vehicle category)

CO2:

• CO2 (fleet average)

2.3 Performance and Emission with RON 95 and RON 97 Gasoline

Gasoline is the most widely used fuel for on-road vehicles worldwide and therefore

the main power source for this energy user. Demand for gasoline is continually

expanding with the increasing number of on-road vehicles supported by the

development of fuel efficient direct gasoline injection and hybrid engines. Table 2.3

shows the parameter for gasoline RON 95 and RON 97.

10

Table 2.3: Gasoline properties for RON 95 and RON 97 (Owen and Tao, 2015)

Description RON 95 RON 97

Research octane number 95 97

Initial Boiling Point (oC) 35.7 35.7

Final Boiling Point (oC) 197.2 200.5

Density @ 15oC (kg/.L) 0.764 0.7639

Reid vapor pressure 66 65.5

Gasoline engine formulation is mainly indexed with respect to octane

numbers; RON or MON. Rating of the octane numbers is considered to be one of the

important parameters in deciding the quality of the fuel as it influences the vehicles

engine performance and emission (Nagai, 2000). Octane number is also an

impartment parameter for vehicle combustion. Farayedhi (2002) showed decreases in

CO and HC emissions along with but higher NOx emission with increasing octane

number of the fuel. The combustion duration becomes prolonged as octane number

increases; longer combustion duration may result in low thermal efficiency and

increased fuel consumption Shen et al. (2008).

Many studies have been conducted to investigate the effects of RON number

to engine performance and emissions. Sayin (2005) has found that the use of RON

which is higher than the engine requirement not only reduces brake thermal

efficiency but also increased brake specific fuel consumption, CO and HC emission

but can be reduced with a more advanced spark timing. However, recent study by

Mohamad and Geok (2014) has found that RON95 produced higher engine

performance for all part-load conditions within the speed range. RON95 produced an

average of 4.4% higher brake torque, brake power, and brake mean effective pressure

as compared to RON97. The difference in engine performance was more significant

at higher engine speed and loads. Cylinder pressure and ROHR were evaluated and

correlated with engine output. With RON95, the engine produced 2.3% higher fuel

conversion efficiency on average but RON97 was advantageous with 2.3% lower

brake specific fuel consumption throughout all load condition. In terms of exhaust

emissions, RON95 produced 7.7% lower NOx emission but higher CO2, CO and HC

emissions by 7.9%, 36.9% and 20.3% respectively. Higher octane rating of gasoline

may not necessarily be beneficial on engine power, fuel economy and emissions of

11

polluting gases. Even though RON97 proves to be beneficial in terms of emission

reduction of CO2, CO and HC, the price is 38% higher and higher NOx emission is

more expensive in the long run.

2.4 Emission of Gasoline Engine

Emission of gasoline engine has been known as a major source of air pollution along

urban traffic routes in developed countries. In Malaysia, it was estimated that nearly

51% from 12 milions of registered vehicles used gasoline engine (Kalam, 2011).

Generally, gasoline engines are referred to as internal combustion engine (ICE)

where initiation of the combustion process of air–fuel mixture is ignited within the

combustion chamber which is done either by spark ignition (SI) or compression

ignition (CI) (Bera, 2010) . Emission from gasoline engine can be reduced through

improvement of engine design, combustion conditions and catalytic after treatment

devices (Faiz, 2006). Table 2.4 listed the common gasoline exhaust gas composition

at different operating condition.

Table 2.4: Typical exhaust gas compositions at the common gasoline engine

operating conditions ( GM Research& Development, 2006)

Gas Cold-Start Warm-up

CO 0.2 to 6% (̴ 1.5 % avg.) ̴ 0.8 % avg.

HC 400 to 1200 ppm (C3) ( ̴650 ppm avg.) ̴450 ppm (C 3) avg.

H2 1/3 CO 1/3 CO

NO 100 to 1200 ppm (̴ 500 ppm avg.) ̴500 ppm avg.

O2 0.5 ̴ 2.5% (̴1.2 % avg.) ̴0.7% avg.

SO2 20 ppm or lower 20 ppm or lower

2.4.1 Emission of Nitrogen Oxides (NOx)

Motor vehicles are usually the major sources of nitrogen oxides in urban areas. NOx

primarily is a mixture of nitric oxide (NO) and lesser quantities of nitrogen dioxide

(NO2). The NOx gases are formed by oxidation of nitrogen in air at high combustion

temperatures. When oxidised to NO2 in ambient air, NO plays a major role of the

12

formation of photochemical oxidants (such as ozone) and particles (such as nitrates).

Zhao et al., (2004) referred the reduction of NOx to nitrogen and oxygen caused by

temperature as thermal mechanism which derived the NO reaction under reducing

conditions as Eq. 2.1.

Nitrogen dioxide appears to exert its effects directly on the lung, leading to an

inflammatory reaction on the surfaces of the lung (Streeton, 1997).

2.4.2 Emission of Carbon Monoxide (CO)

CO is a product of incomplete combustion, which simply means that there was a lack

of oxygen for burning when the combustion process took place (Kaleli, 2003). The

conversion of CO is as Eq. 2.2 (Kaspar et al., 2003):

2CO + O2 ↔ 2CO2 (2.2)

CO is a highly toxic, colourless, odourless gas that is dangerous to those who

inhale it. This is because CO has a high affinity to blood, and when inhaled, it

combines with the haemoglobin in blood to produce carboxyl haemoglobin, which is

an extremely toxic substance (Narendran, 2013).

2.4.3 Emission of Hydrocarbon (HC)

Hydrocarbons react in the presence of nitrogen oxides and sunlight to form ground-

level ozone, a major component of smog. It is our most widespread and intractable

urban air pollution problem. A number of exhausts HC are also toxic, with the

potential to affect human health. HC includes many toxic compounds that cause

cancer and other adverse health effects (WHO, 2003). The conversion of HC gas is

shown as in Eq. 2.3:

CxH4x + 2xO2 → xCO2 + 2xH2O (2.3)

2NOx → xO2 + N2 (2.1)

13

2.5 Emission Standard of Gasoline Engine

Every country has its own strict regulation for vehicle emissions which are varied

significantly. In 2005, the first major reductions in all emitted pollutants are gained

by electronic optimization of the combustion process when gasoline-powered vehicle

is restricted to emitting between 1% to 3% CO of a comparable size unit in 1970

(Martyr and Plint, 2012). The United States (US) and European Union (EU)

regulation standards have been recognized and used worldwide. Table 2.5 presented

the comparison of EU Vehicle Emission Standard in ASEAN countries while Figure

2.1 illustrates the EU emission standard for exhaust emission gases of HC and CO for

gasoline powered vehicles.

Table 2.5: Light Duty Vehicles (LDVs) Emission Standard in ASEAN countries

(Silitonga et al., 2012)

14

Since Euro 1, vehicles have to be tested for emission not only to gain type

approvals new vehicles, but also after a number of miles in service. EU recently state

that the original equipment manufacturer (OEM) is responsible for assuring that

vehicles meet emission standard for 80,000 kilometers, in the US which the rules use

160,000 km.

2.6 Factors Affecting Exhaust Emission

Consideration of several variables and parameters can control exhaust emission. A

complete combustion in engine cylinder is needed in order for the engine to work

efficiently. Barry (2006) stated that in order to ensure a complete combustion in an

engine, several matters such as the accurate amount of air and fuel must be mixed

with the correct amount of heat at the correct time. These two factors, air-to fuel ratio

and cold-start seems to be the most important factors that could affect exhaust

emission.

Figure 2.1: European Carbon Monoxide (CO) and hydrocarbon (HC) emission standards

for gasoline light passenger cars (EPA,2000)

15

2.6.1 Air-To-Fuel Ratio

The air-fuel ratio is known as the mass ratio of air to gasoline, which is required to

ensure the operation of injection system of an engine (Halderman, 2012). The

emission of pollutant can be caused by improper ratio of air to fuel during the

combustion process. Thus, it is important to ensure a correct air-fuel ratio in order to

control the exhaust emission, good drivability and prevention internal damage of

engine parts (Barry, 2006). All three pollutants can be converted (essentially

equilibrated to CO2, H2O and N2) with high efficiency over a single catalyst if the

air–fuel ratio can be controlled sufficiently close to the stoichiometric value. Figure

2.2 shows the illustration of the total effect of the air-fuel ratio on engine emission.

Table 2.6 list the relationship between the air-fuel-ratio condition and its effect on the

emission gases.

Figure 2.2: Air-fuel-ratio for exhaust SI gasoline emission (Heywood, 1998)

16

Table 2.6: Air fuel mixture and emission relationship (Barry, 2006)

Air-Fuel Mixture Effect on Vehicle

Too Lean

Increase NOx emissions

Poor Engine Power

Misfiring at cruising speed

Burned valves

Burned pistons

Slightly Lean

Low exhaust emissions

High gas mileage

Reduced engine power

Slight tendency to knock or ping

Stoichiometric Best all-around performance and

emission levels

Slightly Rich

Increased CO emissions

Increased HC emissions

Maximum engine power

Higher fuel consumption

Less tendency to knock or ping

Too Rich

Increased CO emissions

Increased HC emission

Poor fuel mileage

Misfiring

Oil contamination

Black exhaust

SI engines operate normally at stoichiometric conditions (λ = 1). This is to

ensure that the TWC operation is satisfactory. If the mixture is too lean, NOx will not

be converted to nitrogen and oxygen and if the mixture is too rich, the CO and

unburned HC will not be converted to carbon dioxide and water (Mansha et al.,

2013). Ferguson (2004) and Stone Richard (1999) state that the allowable air-fuel-

ratio for efficient catalytic operation is ±0.25% to ±1% of stoichiometric. This occurs

when the air-fuel-ratio is between 14.6 and 14.8 for gasoline. Within this window,

the conversion of all three polluting emissions is almost complete, although outside

this window the efficiency decreases rapidly. Only at stoichiometric conditions are

appropriate amounts of reducing and oxidizing agents present in the exhaust to carry

out the catalytic reactions by using oxygen sensor as shown in Figure 2.3.

17

Figure 2.3: Response of oxygen sensor used in exhaust pipeline

(Farrauto and Heck, 1999)

2.6.2 Cold-Start Condition

Cold start condition in engine plays an important role in producing exhaust emission.

Cold start or unstable engine running period is the time period required for the

catalyst to reach its light-off temperature (Raja and Arasu, 2015). Favez et al., (2009)

define cold start as emission in SI engine that begin after a minimum halt time of 12

hours or more. During cold start condition, CO and HC are emitted in large quantities

in the first few minutes after the spark ignition (SI) of the engine due to less active or

inactive catalytic converter (Iliyas et al., 2007). It has been found that the conversion

efficiency in catalytic converter is more effective only after the catalyst reaches

above 150 ̊C, which is the light-off temperature (Singer et al., 1999).

18

Recently, automobile manufacturers and researchers were forced to undertake

extensive investigation on reducing the cold start emission. Andrianov et al., (2012)

has presented a methodology for minimizing emissions constrained for cold start

emissions. This study has developed an Integrated Model for the optimization of

spark ignition engine control strategies. The Integrated Model is a warm-up model in

which describes a thermodynamics processes in a gasoline fuel spark ignition engine.

Using the dynamometer control system model, Integrated Model provides an

alternative way for calculation of instantaneous fuel consumption, as well as the mass

flow rates of the legislated CO, NOx and HC tailpipe emissions under transient

driving conditions, specified by engine torque and speed trajectories by using the

dynamometer control system model as shown in Figure 2.4.

Figure 2.4: The Integrated Model structure of combined engine, emissions, exhaust

and after treatment system model (Adrianov et al., 2010)

Chang et al., (2014) has developed a new technology of gasoline Cold Start

Concept (gCSCTM) for cold start or low temperature emission control. This new

concept uses the novel of mixed oxide Al2O3/CeO2/ZrO2 in which has a higher

oxygen storage capacity especially at low temperatures in which reduced the light-off

temperature of catalyst. It also combines low temperature TWC with extruded zeolite

substrates to further reduce the cold start emissions.

19

2.6.3 Exhaust Temperature

Exhaust gas temperature is the indication of the combustion quality in the

combustion chamber (Sureshkumar et al., 2008). The exhaust of vehicles gas

temperature may vary from 300oC to 400oC from idling to around 900oC at full load

condition in internal combustion engine. However, the common temperature of

exhaust gas lies between 400oC to 600oC. It requires lower temperature for unburned

HC to be oxidizing compare for the oxidation of CO in which normally oxidizes at a

specific residence time (Mansha et al., 2012). Without having a catalyst for the

conversion of pollutant gases, the temperature in the exhaust pipeline will exceed

600oC and the residence time to oxidize HC is greater than 50ms while the

temperature that are required to oxidize CO is more than 700oC (Heywood, 1988).

Temperature in the catalytic warm-up also plays a vital role for the oxidation

of the gases. In reference to the previous research, Ferguson (2004) states that the

conversion will be efficient at fully warmed up catalytic conditions about 98% to

99% for CO and 95% for unburned HC depending on HC components. Willard

(2003) state that at temperature of 400oC or higher, the catalytic converter is fully

warmed up and will eliminate about 98-99% of CO, 95% of NOx and more than 95%

of unburned HC from the engine out exhaust. Conversion process in the catalytic

does not occur at NOx, CO and unburned HC is not observed. The rate of oxidation

of CO and HC increases and NOx decreases as exhaust gasses increases. 50%

conversion efficiency is referred as light off of catalyst (Mansha et al., 2013).

2.7 Catalytic Converter

Catalytic converter is a stainless steel container mounted along the exhaust pipe of

the engine that incorporates a honeycomb monolith made of ceramic or metal

(Ganesan, 2004). Today, most vehicles with gasoline-fuelled engines achieve the

emissions limits by using the three-way catalysts, which are installed a part of the

exhaust system. These devices are designed to convert CO, NOx and HC engine-out

emissions to much less harmful CO2, H2O and N2 as shown in Figure 2.5.

20

Figure 2.5: Schematic view of three way catalyst converter (Zi et al., 1996)

Catalytic Converters are important post combustion after treatment devices

mounted in the exhaust system of engines to reduce the engine exhaust emissions and

are classified as either Two-Way or Three-Way. Two-Way Catalytic Converter

(2WCC) works on two gases, CO and unburned HC while the NOx is controlled

though exhaust gas recirculation (EGR) by retarding the ignition timing (Mansha et

al., 2013). A catalytic converter is consisted of three basic components, which are

substrate, washcoat and catalyst (Sebayang et al., 2009).

The Three-Way Catalytic Converter (TWCC) will convert all the three

gaseous pollutant that are mainly CO, unburned HC and NOx. TWCC typically

contains active catalytic materials of Pt, Rh and Pd, which promote the oxidation of

CO and unburned HC and reduction of NOx. Pt and Pd are functioning as an

oxidation catalyst while Rh (Rhodium) act as a reducing catalyst for NOx reduction

(Kamble et al., 2008).

The efficient conversion of CO, unburned HC and NOx are simultaneously

carried out on the same catalyst bed. The maximum conversion efficiency can be

achieved by operating the engine near stoichiometric condition through precise

control of A/F ratio mixture. The TWCC is at most efficient when the exhaust gas

composition from the engine is cycling around stoichiometric conditions. A ceramic

or metallic honeycomb monolithic substrate, particularly cylindrical or oval shaped)

is the common option for most environmental applications that requires high flow

rates and low pressure drop (Santos, 2007).

21

2.7.1 Subtrate

Monolithic substrate supports are uni-body structures composed of interconnected

repeating cells or channels. They are most commonly composed of ceramic or metal

materials but some can also be made of plastic (Heck et al.,2002) as shown in Figure

2.6. The monolith parts itself can be produced in a number of sizes and shapes,

typically round or oval cross-sectional areas for automotive applications, or square

for stationary emission uses. Cross-sectional part diameters for single pieces up to 35

cm have been produced commercially for heavy duty vehicle uses.

The honeycomb or also called “catalyst support” are capable to support the

catalyst as it can increase the amount of surface area (Mizanuzzaman et al., 2013). In

mid 1970s, the United States has been the first country to use ceramic substrates

(Heck and Farrauto, 1995). Each ceramic monolith is coated with a washcoat and a

catalyst coating made from precious metal.

In the automotive and stationary emission control area, monolith substrate is a

common component that is used for selective catalytic reduction (SCR) of nitrogen

oxides. Thus, the usage of the monolith substrates is increasingly used under

Figure 2.6: Ceramic and metallic monolith (Heck et al., 2002)

22

development and for evaluation in new reactor application such as ozone abatement,

chemical process system, refining industries and other types of industries usage as

(Jimme, 2001). The manufacturing of monolith substrate consists of several steps

that need to be followed by referring the flow in Figure 2.7.

Figure 2.7: Fabrication of monolith honeycomb substrates (Jimme, 2001)

For the first steps, the raw materials need to undergo mixing process where

the materials are mixed in the binder. The result of the mixing process is continued

with the second steps, the plasticizing steps where the raw materials are plasticized

with solvent, which is usually water. The plasticizing step requires the materials to

undergo extrusion process (Jimme, 2001). The extrusion processes usually use

unique dies to fabricate monolith structure. After extrusion process, the monolith

substrate will be dried at elevated temperature in order to ensure that moisture

elimination is done without cracking the monolith substrates. In the final steps, the

component will undergo firing steps; the monolith is placed at elevated temperature

to complete the solid-state reactions and to obtain the desired physical condition of

the complete monolith substrates. The monolith type substrate has been widely used

due to the catalyst coating method, flexibility in reactor design, low pressure drop

and high heat and mass transfer (Nijhuis, 2001).

2.7.2 Washcoat

The washcoat is a type of ceramic layer (oxide layer) with specific surface area and

acts as a support for catalyst materials. The waschoat also acts as a barrier from high

temperature corrosion (Cueff et al., 2004). Alumina (Al2O3) is one of the most

23

applied washcoat materials (Heck, et al., 2009). The washcoat is a thin layer of

alumina (Al2O3) coating, typically 20-150 μm thick with a high surface area on the

top of substrate. Cross section image of the coating, called ‘washcoat’ is composed of

porous, high surface area inorganic oxides such as γ-Al2O3 (gamma alumina), CeO2

(Ceria) and ZrO2 (Zirconia). Alumina is chosen due to its high surface area and

relatively good thermal stability under the hydrothermal conditions of the exhausts

(Kaspar et al., 2003).

2.7.3 Catalyst

In the last few years, the most dominant catalyst for gasoline vehicles has been the

monolith or honeycomb structure catalyst. This catalyst is consisted of a skeleton

coated with highly porous washcoat of about 90% γ-Al2O3 and a mixture of alkaline-

earth metals, oxides and noble metals such as Pt, Pd and Rh which are fixed in the

washcoat surface as shown in Figure 2.8. Noble metal catalysts are deposited on the

surface and within the pores of the washcoat (Pontikakis, 2003).

2.8 Ceramic Catalytic Converter

Ceramics materials are mainly processed from clay products such as sewer tiles,

bricks for building usage, and sewer pipes. According to Keane (2003) ceramic is a

Figure 2.8: Washcoat and catalyst development focused area in catalytic

converter (Twigg, 2007).

24

combination between non-metallic and metallic elements such as Alumina Oxide

(Al2O3) Calcium Oxide (CaO) and Silicon Nitride (Si3N4). Advanced ceramic

production includes structural materials used for engine components, machining

cutting tools and bio-ceramics for hospitality usage such as tooth and bone

replacements. Ceramic has wide range of application areas and catalysis of catalytic

converter is one of it (Hart el al., 1989).

Ceramic has high potential in withstanding high temperatures, exhibit

chemical durability and wear resistance in which is suitable for catalytic use for

various operating conditions. The applications of ceramic can be divided into

catalysts usage and materials support such as substrates to diffuse a variety of active

metals. The investigation had been made on direct synthesis and stabilization of

nano-crystalline ceramic materials for automobiles catalytic usage. Nano powders

fabrication from ceramic improved the properties of the materials, resulting in

production of advanced nanophase materials which may conduct heat, electrons and

ions more efficient compared to conventional materials.

The application of ceramic materials in ceramic substrates for automobiles

exhaust component possesses a large surface area for gas conversion process that

improves the efficiency of pollutant gases filtering and also acts as good thermal

shock resistance. It is one of the important components in conversion process in term

of performance balancing, pressure drop and maintaining strength of catalytic

materials. Ceramic substrates in commonly manufactured with honeycomb structures

which has high mechanical strength with low thermal expansion coefficient shown in

Figure 2.9.

Figure 2.9: Honeycomb structure of ceramic substrates in three dimensional

(Keane, 2003)

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