By
Felicia 11604018
BACHELOR’S DEGREE in
CHEMICAL ENGINEERING - SUSTAINABLE ENERGY AND ENVIRONMENT FACULTY OF LIFE SCIENCES AND TECHNOLOGY
SWISS GERMAN UNIVERSITY The Prominence Tower
Jalan Jalur Sutera Barat No.15, Alam Sutera Tangerang, Banten 15143 - Indonesia
July 2020
Revision after Thesis Defense on 9 July 2020
Oxidative Stability of Biodiesel (A Review)
Felicia STATEMENT BY THE AUTHOR
I hereby declare that this submission is my own work and to the best of my knowledge, it contains no material previously published or written by another person, nor material which to a substantial extent has been accepted for the award of any other degree or diploma at any educational institution, except where due acknowledgment is made in the thesis.
Felicia
_____________________________________________
Student Date
Approved by:
Silvya Yusri, S.Si., M.T.
_____________________________________________
Thesis Advisor Date
Dr. Hery Sutanto, M.Si.
_____________________________________________
Thesis Co-Advisor Date
Dr. Dipl.-Ing. Samuel P. Kusumocahyo
_____________________________________________
Dean Date
ABSTRACT
PERFORMANCE OF SEVERAL TYPES OF ANTIOXIDANT ON THE OXIDATIVE STABILITY OF BIODIESEL (A REVIEW)
By
Felicia
Silvya Yusri S.Si., M.T., Advisor Dr. Hery Sutanto, M.Si., Co-Advisor
SWISS GERMAN UNIVERSITY
Biodiesel has been used as an alternative of petroleum diesel due to its availability, performance and clean emissions. Among those advantages, biodiesel has one major drawback regarding oxidation stability. Addition of antioxidant is one of the most common method used to improve biodiesel oxidation stability. However, different antioxidant may result in different activity on biodiesel. This review is subjected on the performances of different types of antioxidant on biodiesel from various different sources.
Previous researches regarding the application of natural antioxidants such as α-tocopherol and synthetic antioxidants propyl gallate (PG), pyrogallol (PY), tert-butylhydroquinone (TBHQ), butylated-hydroxyanisole (BHA) and butylated-hydroxytoluene (BHT) on different types of biodiesel are screened and collected. The use of antioxidants as single and binary antioxidant with the addition of surfactant are discussed. Performance of modified synthetic antioxidants are compared with the use of commercial antioxidant on biodiesel. Single use of pyrogallol (PY) and tert-butylhydroquinone (TBHQ) proved to be more efficient compared to other antioxidants on various types of biodiesel.
Keywords: biodiesel, oxidative stability, antioxidant, surfactant, modification, commercial antioxidant
Oxidative Stability of Biodiesel (A Review)
Felicia
© Copyright 2020 by Felicia
All rights reserved
DEDICATION
This thesis is dedicated to the strongest person I know: me.
Oxidative Stability of Biodiesel (A Review)
Felicia ACKNOWLEDGMENTS
First and foremost, I would like to thank God who has always guided me. Without His grace this project could not become a reality.
The completion of this thesis would not have been possible without the help and assistance of my advisor Ms. Silvya Yusri and co-advisor Mr. Hery Sutanto. Their supervision has really helped me in every phase of this thesis. I would like to use this opportunity to especially thank Ms. Silvya Yusri for her patience and guidance.
I convey my sincere gratitude to all my Swiss German University lecturers who have taught me the past four years. Thank you, not only for the useful theoretical and practical knowledge, but also for the encouragement you have given.
I am highly obliged in taking the opportunity to thank my classmates, the third batch of Sustainable Energy and Environment, especially the girls. Thank you for helping me with problems that occur during the process of writing this thesis.
A profound thank you to Kosuke – you are my happy place. Thank you for being the support system I need.
Finally, I would like to acknowledge with gratitude the support and love from my family.
To my sister Farren and brother Filbert, thank you for cheering me up whenever I was tired and weary. Also thank you for the bubble teas and chib-chib every other day I felt stuck writing this thesis review.
TABLE OF CONTENT
STATEMENT BY THE AUTHOR ... 2
ABSTRACT ... 3
DEDICATION ... 5
ACKNOWLEDGMENTS ... 6
TABLE OF CONTENT... 7
LIST OF FIGURES ... 9
LIST OF TABLES ... 12
1. INTRODUCTION ... 13
1.1. Background ... 13
1.2. Problem Statement ... 14
1.3. Objectives ... 14
1.4. Significance of Study ... 14
2. LITERATURE REVIEW ... 15
2.1. Energy Condition ... 15
2.2. Renewable Energy ... 15
2.3. Biodiesel... 17
2.4. Advantages of Biodiesel ... 18
2.5. Disadvantages of Biodiesel ... 19
3. METHODS ... 20
3.1. Framework ... 20
3.2. Scientific Method ... 20
4. RESULT AND DISCUSSION ... 22
4.1. Oxidative Stability ... 22
4.1.1. Biodiesel Quality Standards ... 23
4.2. Antioxidant ... 27
Oxidative Stability of Biodiesel (A Review)
Felicia
4.2.1. Tocopherol ... 28
4.2.2. Propyl Gallate ... 28
4.2.3. Pyrogallol ... 29
4.2.4. Tert-butyl-hydroquinone ... 30
4.2.5. Butylated-hydroxyanisole ... 30
4.2.6. Butylated-hydroxytoluene ... 31
4.3. Application of Antioxidant in Biodiesel ... 31
4.3.2 Single Antioxidant with Surfactant ... 47
4.3.3. Binary Antioxidant ... 53
4.3.4. Modified phenolic antioxidant ... 58
4.3.5. Commercial antioxidant ... 66
5. CONCLUSIONS AND RECOMMENDATIONS ... 70
5.1. Conclusion... 70
5.2. Recommendations ... 71
6. REFERENCES ... 73
LIST OF FIGURES
Figure 2.1 Total primary energy supply 2016 (WBA, 2018)... 16
Figure 2.2 Biofuel production in 2008 and 2018 in btoe (BP, 2019) ... 16
Figure 2.3 Transesterification reaction process (Van Gerpen et al., 2004) ... 18
Figure 3.1 Flow chart of thesis method ... 20
Figure 4.1 Primary oxidation reaction ... 22
Figure 4.2 Resonance stabilization by pyrogallol (Wahyudi, 2018) ... 28
Figure 4.3 Alpha tocopherol molecular structure ... 28
Figure 4.4 Propyl gallate molecular structure ... 29
Figure 4.5 Pyrogallol molecular structure ... 29
Figure 4.6 Tert-butylhydroquinone molecular structure ... 30
Figure 4.7 Butylated-hydroxyanisole molecular structure ... 30
Figure 4.8 Butylated-hydroxytoluene molecular structure ... 31
Figure 4.9 Induction period of soybean biodiesel with antioxidants (Luo et al., 2012) .32 Figure 4.10 Induction period of SDOB with antioxidants (Ryu, 2009) ... 33
Figure 4.11 Induction period of SDXB with antioxidants (Ryu, 2009) ... 33
Figure 4.12 Induction period of SDXC with antioxidants (Ryu, 2009) ... 34
Figure 4.13 Induction period of soybean biodiesel with antioxidants (Domingos et al., 2007) ... 35
Figure 4.14 Induction period of soybean biodiesel with antioxidants (Tang, Ng and Salley, 2011)... 36
Figure 4.15 Induction period of cottonseed biodiesel with antioxidants (Tang, Ng and Salley, 2011)... 36
Figure 4.16 Induction period of yellow grease biodiesel with antioxidants (Tang, Ng and Salley, 2011) ... 37
Figure 4.17 Induction period of poultry fat biodiesel with antioxidants (Tang, Ng and Salley, 2011)... 38
Figure 4.18 Induction period of UDOB with antioxidants (Ryu, 2009)... 38
Figure 4.19 Induction period of jatropha biodiesel with antioxidants (Subroto, 2015) .. 40
Felicia Oxidative Stability of Biodiesel (A Review)
Figure 4.20 Induction period of pongamia biodiesel blends with PY (Dwivedi and
Sharma, 2016) ... 42
Figure 4.21 Induction period of palm oil biodiesel (Gunawan et al., 2020; Ajie et al., 2020; Rafif et al., 2020; Naufal et al., 2020) ... 43
Figure 4.22 Viscosity of palm oil biodiesel (Wahyudi, 2018) ... 44
Figure 4.23 Acid number of palm oil biodiesel (Wahyudi, 2018) ... 45
Figure 4.24 Iodine value of palm oil biodiesel (Wahyudi, 2018) ... 46
Figure 4.25 Schematic figure of surfactant ... 47
Figure 4.26 HLB scale (Aulton, 2002) ... 48
Figure 4.27 Surfactants molecular structure ... 49
Figure 4.28 Acid number of antioxidant and surfactant mixtures (Sutanto, Susanto and Nasikin, 2018; Yusri, Nasikin, Sutanto, 2020) ... 51
Figure 4.29 Iodine value of antioxidant and surfactant mixtures (Sutanto, Susanto and Nasikin, 2018; Yusri, Nasikin, Sutanto, 2020) ... 52
Figure 4.30 Induction period of jatropha biodiesel with the addition of PY and PD (Subroto, 2015) ... 53
Figure 4.31 Induction period of palm oil biodiesel with the addition of binary antioxidants (Gunawan et al., 2020; Ajie et al., 2020; Rafif et al., 2020; Naufal et al., 2020) ... 55
Figure 4.32 Induction period of safflower biodiesel with the addition of TBHQ + BHA adapted from (Nogales-Delgado, Encinar and González, 2019) ... 57
Figure 4.33 1.1’-(4,5,6-trihydroxy-1,3-phenylene)bis(hexadecane-1-one) molecular structure (Belinda, 2018) ... 59
Figure 4.34 1-(2-(tert-butyl)-3,6-dihydroxyphenyl)hexadecan-1-one molecular structure (Pramastiani, 2018) ... 60
Figure 4.35 (9E,11E)- 13-(2,6-dihydroxyphenoxy)octadeca-9,11-dienoate molecular structure (Sutanto, 2019) ... 61
Figure 4.36 (10E,12E)- 9-(2,6-dihydroxyphenoxy)octadeca-10,12-dienoate (Sutanto, 2019) ... 61
Figure 4.37 (10E,12Z)-9-(2,3,4-trihydroxyphenyl)octadeca-10,12-dienoate molecular structure (Handayani, 2019) ... 62
Figure 4.38 (9Z,11E)-13-(2,3,4-trihydroxyphenyl)octadeca-9,11-dienoate molecular structure (Handayani, 2019) ... 63
Figure 4.40 (9Z,11E)-13-(4-(tert-butyl)-2,5-dihydroxyphenyl)octadeca-9,11-dienoate molecular structure (Putri, 2019)... 64 Figure 4.41 Induction period of biodiesel, BAYNOX and modified products (Sutanto,
2019; Handayani, 2019; Putri, 2019) ... 65 Figure 4.42 Induction period of soybean biodiesel with IB (Tang, Ng and Salley, 2011)
...67 Figure 4.43 Induction period of cottonseed biodiesel with IB (Tang, Ng and Salley,
2011) ... 67 Figure 4.44 Induction period of yellow grease biodiesel with IB (Tang, Ng and Salley,
2011) ... 67 Figure 4.45 Induction period of poultry fat biodiesel with IB (Tang, Ng and Salley,
2011) ... 68
Felicia Oxidative Stability of Biodiesel (A Review)
LIST OF TABLES
Table 4.1 ASTM D6751 ... 23
Table 4.2 EN 14214... 24
Table 4.3 SNI 7182:2015 ... 25
Table 4.4 Comparison of different biodiesel quality standards ... 26
Table 4.5 Types of antioxidants used on jatropha biodiesel (Subroto, 2015)... 39
Table 4.6 Delta absorbance of biodiesel samples (Sutanto, Susanto and Nasikin, 2018; Yusri, Nasikin, Sutanto, 2020) ... 48
Table 4.7 Combinations of different binary antioxidants concentrations and ratios (Gunawan et al., 2020; Ajie et al., 2020; Rafif et al., 2020; Naufal et al., 2020) .... 54
Table 4.8 Concentration combinations of TBHQ + BHA (Nogales-Delgado, Encinar and González, 2019) ... 56
