UNIVERSITI PUTRA MALAYSIA

ODEIGAH, EDITH ANWUNLI

FK 2012 91

CHEMICAL ADDITIVES AS COLD FLOW IMPROVERS FOR PALM OIL AND JATROPHA OIL BIODIESEL

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CHEMICAL ADDITIVES AS COLD FLOW IMPROVERS FOR PALM OIL AND JATROPHA OIL BIODIESEL

By

ODEIGAH, EDITH ANWUNLI

Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia, in Fulfilment of the Requirements for the Degree of Master of Science

November 2012

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This work is dedicated to my mother Mrs. Victoria C. Odeigah (R.I.P)

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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfilment of the requirement for the degree of Master of Science

CHEMICAL ADDITIVES AS COLD FLOW IMPROVERS FOR PALM AND JATROPHA BIODIESEL

By

EDITH ANWUNLI ODEIGAH

November 2012

Chair: Rimfiel B. Janius, PhD

Faculty: Engineering

Palm oil and jatropha oil biodiesel are attractive renewable energy source, which could

be used as a suitable substitutes for the non-renewable petroleum diesel. Biodiesel

produced from these two sources are more environmentally friendly than petroleum

diesel and could reduce a nation’s dependence on crude oil imports. However, both

biodiesel fuels exhibit very poor cold flow behavior causing engine start-up and fuel

filter plugging problems in cold weather. Jatropha oil comparing to palm oil is a very

promising source of biodiesel as it is non-edible and can grow in wasteland with very

little nutrient requirement and has very high oil yield. Both are the two most widely used

oil seeds for biodiesel production in Asia.

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This study was conducted to evaluate the possibility of using hexane, ethanol,

chloroform and kerosene as a cold flow improving component for jatropha and palm

biodiesel. 1v/v%, 5v/v%, 10v/v%, 15v/v% and 20v/v% concentrations of these additives

in palm and jatropha biodiesels were tested for their effects on the cold flow behavior of

the biodiesel fuels as well as on other basic fuel properties such as viscosity, density,

flash point and energy content. Performance tests of a Yanmar L48N model single

cylinder 4-stroke compression-ignition engine running on palm and jatropha biodiesel

containing these additives were then conducted.

Among the selected additives, chloroform was found to be the most effective in

improving the cold flow behavior of the biodiesel fuels. At 10 v/v% additive

concentration, the reduction in cloud point for palm and jatropha biodiesels were

respectively 5oC and 6oC with chloroform, 4oC and 5oC with hexane, 4oC and 4oC with

ethanol and 3oC and 2oC with kerosene. Kerosene and hexane resulted in good engine

performance with about 6.36% and 5.01% increase in brake power at 10v/v%, while

ethanol produced a 5.01% increase and chloroform produced a 3.87% decrease in engine

brake power at the same concentration. However, overall, ethanol blends seemed to be

the most favorable with a good balance between fuel analytical properties and engine

performance. Cloud point and pour point were reasonably reduced with ethanol as

additive and engine performance was also good because of its higher oxygen content.

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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai memenuhi keperluan untuk ijazah Master Sains

BAHAN TAMBAH KIMIA SEBAGAI PENAMBAHBAIK ALIRAN SEJUK BAGI BIODIESEL KELAPA SAWIT DAN JATROPHA

Oleh

EDITH ANWUNLI ODEIGAH

November 2012

Pengerusi: Rimfiel B. Janius, PhD

Fakulti: Kejuruteraan

Biodiesel Kelapa sawit dan minyak jatropha adalah sumber tenaga boleh diperbaharui

yang menarik, yang boleh digunakan sebagai pengganti sesuai bagi diesel petroleum

yang tidak boleh diperbaharui. Biodiesel yang dihasilkan daripada kedua-dua sumber

adalah lebih mesra alam daripada diesel petroleum dan dapat mengurangkan

kebergantungan sesuatu negara kepada import minyak mentah. Walau bagaimanapun,

kedua-dua bahan api biodiesel mempamerkan sifat yang lemah dalam aliran sejuk,

menyebabkan masalah penjanaan enjin dan petrasangan penapisminyak semasa cuaca

sejuk. Minyak Jatropha berbanding dengan kepada kelapa sawit merupakan sumber yang

sangat menjanjikan biodiesel kerana ia tidak boleh dimakan dan boleh tumbuh di tanah

terbiar dengan keperluan nutrien yang sangat sedikit dan mempunyai keberhasilan

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minyak yang sangat tinggi. Kedua-duanya adalah dua jenis bijian minyak yang

digunakan dengan paling meluas untuk pengeluaran biodiesel di Asia.

Kajian ini dijalankan untuk menilai kemungkinan menggunakan heksana, ethanol,

kloroform dan minyak tanah sebagai komponen penambahbaikan aliran sejuk bagi

biodiesel jatropha dan kelapa sawit. Kepekatan 1 v/v%, 5 v/v%, 10 v/v%, 15 v/v% dan

20 v/v% bahan tambah ini dalam biodiesel minyak sawit dan jatropha tulin diuji untuk

mengkaji kesan mereka ke atas tabiat aliran sejuk bahan bakar biodiesel itu serta juga ke

atas sifat-sifat lain bahan bakar seperti kelikatan, ketumpatan, takat kilat dan kandungan

tenaga. Ujian prestasi enjin Yanmar model L48N dengan 4-lejang dan cucuhan

mampatan yang menggunakan biodiesel minyak sawit dan jatropha yang mengandungi

bahan tambah ini kemudiannya dijalankan.

Di antara bahan tambah itu, kloroform didapati paling berkesan dalam menambah baik

tabiat aliran sejuk bahan bakar biodiesel. Pada kepekatan 10 v/v%, penurunan takat

keruh untuk biodiesel sawit dan jatropha adalah masing-masing 5 oC dan 6 oC dengan

kloroform, 4 oC dan 5 oC dengan heksana, 4 oC dan 4 oC dengan ethanol dan 3 oC dan 2

oC dengan minyak tanah. Minyak tanah dan heksana menghasilkan prestasi enjin yang

baik dengan peningkatan kuasa brek sebanyak 6.36% dan 5.01 pada 10 v/v%, sementara

ethanol menghasilkan peningkatan 5.01% dan kloroform pula 3.87% penurunan pada

kepekatan yang sama.

Walau bagaimana pun, secara keseluruhannya, campuran ethanol ternampak paling baik

dengan keseimbangan yang baik di antara sifat analitk bahan bakar dan prestasi enjin.

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Takat keruh dan takat tuang diturunkan dengan agak memuaskan dengan ethanol sebagai

bahan tambah dan prestasi enjin adalah juga baik disebabkan oleh kandungan

oksigennya yang lebih tinggi.

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ACKNOWLEDGEMENTS

I would like to express my sincere gratitude to my supervisor Dr. Rimfiel Janius for his

guidance, suggestions, patience, kindness and assistance during the course of this study.

My deep appreciation and gratitude goes to my co-supervisor, Prof. Dr. Robiah Yunus,

for her guidance and assistance.

My Special thanks goes to Mr. Zainal Abidin b. Abdul Ghani and all technical staffs of

Faculty of Engineering, Universiti Putra Malaysia, who have, in one way or the other,

provided the technical support needed to complete this research and graduate study. I

also would like to send out my gratitude to my lecturers and friends who motivated and

supported me in this study.

My greatest appreciation and heartfelt gratitude goes to my beloved husband, Hyginus

C. Ugwumba; my son Chikanayo Ugwumba; my daughter Chigoziem Ugwumba; my

parents and all my family members for their patience, understanding, support and

sacrifices throughout this study.

Lastly and most importantly, I want to express my sincere gratitude to the almighty God,

without whom, this study would not have been a possibility.

Thank you all.

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I certify that an Examination Committee has met on date of viva voce to conduct the final examination of name of student on her degree thesis entitled "CHEMICAL ADDITIVES AS COLD FLOW IMPROVERS FOR PALM OIL AND JATROPHA OIL BIODIESEL " in accordance with Universiti Pertanian Malaysia (Higher Degree) Act 1980 and Universiti Pertanian Malaysia (Higher Degree) Regulations 1981. The Committee recommends that the student be awarded the Master of Science. Members of the Examination Committee were as follows: Khalina bt. Abdan, PhD Associate Professor Faculty of Engineering Universiti Putra Malaysia (Chairman) Azmi bin Dato Haji Yahya, PhD, P.Eng Associate Professor Faculty of Engineering Universiti Putra Malaysia (Internal Examiner) Tinia Idaty bt. Mohd. Ghazi, PhD Associate Professor Faculty of Engineering Universiti Putra Malaysia (Internal Examiner) Masjuki bin Haji Hassan, PhD Professor Faculty of Engineering Universiti Malaya Malaysia (External Examiner)

SEOW HENG FONG, PHD Professor and Deputy Dean School of Graduate Studies Universiti Putra Malaysia Date:

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This thesis was submitted to the Senate of Universiti Putra Malaysia and has been accepted as fulfillment of the requirement for the degree of type of degree. The members of the Supervisory Committee were as follows:

Rimfiel B. Janius, PhD Lecturer Faculty of Engineering Universiti Putra Malaysia (Chairman)

Robiah Binti Yunus, PhD Professor Faculty of Engineering Universiti Putra Malaysia (Member)

BUJANG BIN KIM HUAT, PhD Professor and Dean School of Graduate Studies Universiti Putra Malaysia

Date:

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DECLARATION

I declare that the thesis is my original work except for quotations and citations which

have been duly acknowledged. I also declare that it has not been previously, and is not

concurrently, submitted for any other degree at Universiti Putra Malaysia or at any other

institution.

ODEIGAH, EDITH ANWUNLI

Date: 9 November, 2012

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TABLE OF CONTENTS Page

ABSTRACT iii ABSTRAK v ACKNOWLEDGEMENTS viii APPROVAL ix DECLARATION xi LIST OF TABLES xiv LIST OF FIGURES xvi LIST OF APPENDICES xx LIST OF ABBREVIATIONS xxi

CHAPTER 1 INTRODUCTION 1

1.1 Research Background 1 1.2 Problem Statement 3 1.3 Research Aim and Objectives 5 1.4 Scope and Limitations 5

2 LITERATURE REVIEW 7

2.1 Introduction to Biodiesel 7 2.2 Biodiesel Production Techniques 12

2.2.1 Pretreatment of Oil for Biodiesel Production 14 2.2.2 Post Treatment of the Biodiesel Produced 16

2.3 Fuel Properties of Biodiesel Compared to Petroleum Diesel 16 2.3.1 Viscosity 16 2.3.2 Energy Content 17 2.3.3 Density 18 2.3.4 Cetane Number 18 2.3.5 Handling and Storage 20 2.3.6 Lubricity and Cold Flow 20

2.4 Properties and Characterization of Cold Flow of Biodiesels 21 2.5 Improving the Cold Flow of Biodiesels 27

2.5.1 Blending with Petroleum Diesel 28 2.5.2 Trans-Esterification with Branched Chain Alcohol 28 2.5.3 Winterization 30 2.5.4 Use of Chemical Additives 32

2.6 Engine Performance on Biodiesel 34 2.7 Basis for Choice of Biodiesel 36 2.8 Basis for Choice of Selected Chemical Additives 38

3 EXPERIMENTAL APPARATUS, MATERIALS AND METHODS 41 3.1 Research Design 41

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3.2 Materials 42 3.3 Production of Jatropha Biodiesel 43 3.4 Biodiesel Pretreatment and Sample Preparation 47

3.4.1 Pretreatment 47 3.4.1 Sample Preparation 48

3.5 Analytical Tests 51 3.5.1 Cloud Point 51 3.5.2 Pour Point 53 3.5.3 Flash Point 54 3.5.4 Density 55 3.5.5 Kinematic and Dynamic Viscosity 57 3.5.6 Energy Content 58

3.6 Engine Test 59 3.6.1 Engine Test Procedure 62

4 RESULTS AND DISCUSSION 65

4.1 Introduction 65 4.2 Fuel Blending and Physical Examination 65 4.3 Cloud Point and Pour Point Studies 68 4.4 Density Studies 77 4.5 Viscosity Studies 80 4.6 Energy Content Studies 83 4.7 Flash Point Studies 86 4.8 Engine Performance on Diesel and the Biodiesel Fuels 88 4.9 Engine Performance on Biodiesel- Hexane Blends 98 4.10 Engine Performance on Biodiesel- Chloroform Blends 110 4.11 Engine Performance on Biodiesel- Ethanol Blends 122 4.12 Engine Performance on Biodiesel- Kerosene Blends 134 4.13 Summary Discussion on Engine Performances 145

5 SUMMARY, CONCLUSION AND RECOMMENDATIONS 148

5.1 Summary 148 5.2 Conclusion 149 5.3 Recommendations 150

REFERENCES 152 BIODATA OF STUDENT 186 LIST OF PUBLICATIONS 187

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