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PREPARATION OF' CHE~nCALLY ~10DtFIED SAGO BARK FOR OIL SORPTION
Muham'sfd Farid Bin Mohammed N~lb
Master of Sciellc~ (Environmental Science)
2014
Pusat Khidmat Maklumlt Akadtmil< . I; I1VFR~ MALAYSIA S M'AK
PREPARATION OF CHEMICALLY MODIFIED SAGO BARK FOR OIL SORPTION
MUHAMAD FARID BIN MOHAMMED NOH
A thesis submitted In fulfilment of the requirements for the degree of Master of Science
(Environmental Science)
Faculty of Resource Science and Technology UNIVERSITI MALAYSIA SARA W AK
2014
DECLARATION
I hereby declare that no portion of the work referred to this thesis has been submitted in
support of an application for another degree or qualification to this or any other university
or institution of higher learning.
(MUHA AD FARID BIN MOHAMMED NOH)
Date: 28 ~~~ 2.01tt
...
11
LIST OF PUBLICATION
Ngaini, Z., Noh, F., Wahi, R. (2014). Esterified sago waste for engine oil removal in
aqueous environment. Environmental Technology. In Proceeding (Taylor & Francis).
111
LIST OF ACHIEVEMENTS
1. Patent: PI 2013002599. Ngaini, Z., Wahi., R., & Noh, M. F. M. (2013). Biodegradable
absorption material and manufacturing method thereof.
2. Noh, M. F. 1\1., Ngaini, Z., & Wahi, R. (2012). Incorporation of fatty acid derivatives
onto sago network for oil absorption, in: ASEAN sago symposium 2012: Advances in
Sago Research and Development, p. 34.
3. Noh, F., Ngaini, Z., & Wahi, R. (2013). Adsorption of spilled oil from seawater by
Metroxylon Sagu bark. 26th Regional Symposium ofMalaysia Analytical Sciences, p.
50.
4. Noh, F., Ngaini, Z., & Wahi, R. (2013). Oil spilled recovery using chemically modified
sago waste. International Festival of Science, Technology, Engineering and
Mathematics.
5. Ngaini, Z., Wahi, R., Noh, M. F. M., & Ahmad, R. R. (2013). Awarded a silver award
for the project entitled "SagoZORB: Solution to Oil Spills" at the UNIMAS Research
and Development Exposition 2013.
6. Ngaini, Z., Wahi, R., Noh, M. F. M., Chuah, L. A., Nourouzi, M. M., & Choong, T. S.
Y. (2014). Awarded a gold award for the project entitled "SagoZORB 2.0: Biomass
Filter Bed for Oil and Grease Removal" at the UNIMAS Research and Development
2014.
IV
ACKNOWLEDGEMENT
Thank Allah, the Most Merciful Most Gracious for His Guidance and kept me in
His Grace and far from astray, I am finally able to complete this thesis.
The special thank goes to my helpful supervisor, Assoc Prof Dr Zainab Ngaini.
With her enthusiasm, inspiration, and her great efforts to explain things clearly and simply,
she helped to make my research work meaningful for me. The supervision and support that
she gave truly help the progression and smoothness of my thesis. This thesis work was
enabled and sustained by her vision and ideas.
I wish to thank Mdm Rafeah Wahi for her guidance and comments on the
experiments. Her comments and suggestions were very valuable with giving wise advice,
helping with various applications, and so on.
Special appreciation goes to all lab assistant for their endless assistance throughout
my years in UNIMAS.
I would like to acknowledge the support of research grant from CoE
COESARlPK07/07/2012(Ol) and Ministry of Energy, Green Technology and Water,
Malaysia under Research Fund Mentoring Programs: 1 IPT A 1 Menteri. Special thank also
goes to Kementerian Pengajian Tinggi Malaysia for the financial assistance.
Most importantly, I wish to thank my parents, Muhammed Noh Zainal and Asnah
Abd Kadir for their supports and encouragement throughout my studies in UNIMAS. Their
continuous support and profound understanding very helpful to me for complete this thesis.
Last but not least, thanks to all postgraduate students in organic laboratory. My love
will always be with you guys.
v
ABSTRACT
•
(sago (Metroxylon spp.) bark is a waste material in the sago production industries. The bark
of sago has potential application as a low cost and effective oil sorbent. Raw sago bark
(SB) was esterified using stearic acid to afford modified sago bark (MSB) with greater
hydrophobicity compared to untreated SB. The esterification of SB was conducted by the
addition of stearic acid to the SB with ratio (2:1), in the presence of difference percentage
of catalyst (5, 10, 15 and 20 %) under refluxing ethyl acetat:J In this study, the
esterification of SB using 15 % catalyst afforded MSB with highest oil sorption capacity.
The untreated SB and MSB were characterised by Fourier-Transform Infrared (FTlR)
analysis, Scanning Electron Microscopy (SEM) analysis and Brunauer-Emmett-Teller
(BET) analysis. The physical properties such as proximate analysis, hydrophobicity,
buoyancy, surface area and pore size of untreated SB and MSB were also investigated. The
esterification of SB has successfully increased the buoyancy and hydrophobicity up to 60
%. Sorption study indicated that both untreated SB and MSB were excellent oil adsorbent
in the absence of water. Sorption tests with used engine oil (UEO) were also conducted in
deionized and sea water media in different systems namely wet static system and wet
dynamic system. The MSB afforded higher oil sorption capacity in deionized water up to
2.8 gig in wet static system and 2.5 gig in wet dynamic system compare to untreated SB
(static: 0.12 gig, dynamic: 0.68 gig). In seawater condition, untreated SB showed slightly
higher oil sorption capacity in wet static system (2.0 gig) compare to MSB (1.9 gig). MSB,
however, showed higher oil sorption capacity in wet dynamic system (4.3 gig) at seawater
compared to untreated SB (0.76 gig). The finding indicated on the potential application of
MSB as oil adsorbing material in both deionized and sea water conditions.
vi
PENYEDlAAN KIMIA KULIT KAYU SAGU YANG TERUBAHSUAI UNTUK PENYERAPAN MINYAK
ABSTRAK
Kulit pokok sagu (Metroxylon spp.) adalah bahan buangan di dalam industri-industri
pengeluaran sagu. Kulit pokok sagu mernpunyai potensi untuk diaplikasi sebagai
penjerapan minyak yang berkos rendah dan efektif. Kulit pokok sagu (SB) diesterkan
menggunakan asid sterik untuk menjadikan kulit sagu terubahsuai (MSB) yang mernpunyai
sifat hidrofobik yang tinggi berbanding SB yang tidak dirawat. Pengesteran SB telah
dijalankan dengan penambahan asid sterik ke SB dengan nisbah (2:1), dalam kehadiran
peratusan pernangkin yang berbeza (5, 10, 15 dan 20 %) di bawah refluks etil asetat.
Dalarn kajian ini, pengesterifikasian SB dengan menggunakan 15 % pernangkin
menghasilkan kapasiti penyerapan minyaknya yang tinggi. SB tidak dirawat dan MSB
dicirikan oleh ana lis is FTIR, analisis SEM dan analisis BET. Ciri-ciri jizikal seperti
analisis proksimat, hidrofobik, keapungan, luas permukaan dan saiz liang juga dikaji.
Proses pengesteran SB berjaya meningkatkan sifat apungan dan hidrofobik sehingga 60
%. Ujian penyerapan minyak dengan menggunakan minyak enjin yang telah digunakan
(UEO) menunjukkan kedua-dua sarnpel mernpunyai kapasiti penyerapan rninyak yang baik
di dalam sistem tanpa kehadiran air. Ujian penyerapan juga dijalankan di dalam sistem
yang mengandungi media air ternyahion dan air laut dengan dua sistem yang berbeza
dinamakan sistem statik lembap dan sistem dinarnik lernbap. MSB menunjukkan kapasiti
penyerapan minyak yang tinggi di dalam air ternyahion sehingga 2.8 gig di dalam sistem
statik lembap dan 2.5 gig di dalam sistern dinarnik lembap berbanding SB tidak dirawat
(statik: 0.12 gig, dinamik: 0.68 gig). Di dalam keadaan air laut, SB tidak dirawat
menunjukkan kapasiti penjerapan minyak yang agak sedikit tinggi di dalan:z sistem statik
Vll
lembap (2.0 gig) berbanding MSB (1.9 gig). Walaubagaimanapun, MSB menunjukkan
kapasiti penjerapan minyak yang tinggi di dalam sistem dinamik lembap (4.3 gig) di air
laut berbanding SB tidak dirawat (0.76 gig). Keputusan yang diperoleh menunjukkan MSB
berpotensi untuk diaplikasi sebagai bahan penjerap minyak di dalam kedua-dua keadaan
air tenyahion dan air laut.
Vlll
Pusat Khidmt MakJumlt Akademik UNlVERSffi MALA SIA SARAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF PUBLICATION
LIST OF ACHIVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
TABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF ABBREVIATIONS
CHAPTER 1
INTRODUCTION
1.1 Research background
1.2 Problem statement
1.3 Justification of study
1.4 Research objectives
1.5 Scope of study
CHAPTER 2
LITERATURE REVIEW
2.1 Nature ofoil and its toxicity
2.2 Oil spills in coastal-marine environment
Page
11
iii
iv
v
VI
vii
IX
Xlll
XIV
XVI
4
5
5
6
7
8
IX
.,
I 2.2.1 The causes of oil spills 10
2.2.2 Effect of oil spilts on aquatic ecosystem and human health 11
2.3 Oil removal and recovery technologies 13
2.3.1 Oil removal by sorption techniques 17
2.4 Natural fibrous oil sorbent 19
2.5 Chemical modifications of natural fibres 22
2.6 Metroxylon sagu as potential oil sorbent 24
2.6.1 Sago residues and the potential applications 26
CHAPTER 3
MATERIALS & METHOD
3.1 Materials 29
3.2 Sample preparation 29
3.3 Chemical modification ofSB 30
3.3.1 Pre-treatment of SB 30
3.3.2 Esterification of SB 31
3.4 Characterisation of untreated SB and modified sago bark (MSB) 32
3.4.1 Moisture content 32
3.4.2 Ash content 32
3.4.3 Volatile content 33
3.4.4 Buoyancy and hydrophobicity analysis 34
3.4.5 Measurement of BET surface area and pore volume 35
3.4.6 Fourier-Transform Infrared (FTIR) analysis 35
3.4.7 Scanning electron microscopy (SEM) and elemental compositions
analysis 36
x
,....
3.5 Sorption experiments procedure 36
3.5.1 Water uptake 36
3.5.2 Oil sorption capacity 37
3.6 Reusability test of untreated SB and MSB 38
CHAPTER 4
RESUL TS & DISCUSSION
4.1 Esterification of sago bark (SB) 40
4.1.1 Pre-treatment of SB using NaOH 41
4.1.2 Esterification of SB using CaO 42
4.2 Chemical and physical properties of untreated SB and MSB 45
4.3 Water uptake study of untreated SB and MSB 48
4.3.1 Water uptake in the static system 48
4.3.2 Water uptake in the dynamic system 49
4.4 Oil sorption capacity of untreated SB and MSB 51
4.4.1 Oil sorption capacity in the wet static system 51
4.4.2 Oil sorption capacity in the wet dynamic system 55
4.4.3 Oil sorption capacity in the dry system 58
4.5 The effect of reusability 60
4.6 Comparison with other natural sorbents for removal of oil 61
CHAPTERS
CONCLUSION & RECOMMENDATION
5.1 Conclusion 63
5.2 Recommendation 65
Xl
Table 2.1
Table 2.2
Table 2.3
Table 2.4
Table 2.5
Table 4.1
Table 4.2
Table 4.3
LIST OF TABLES
Page
Some major oil spill cases around the world and the 8 corresponding effects and clean-up techniques
Oil spill incidents in Malaysia 9
Composition of the Prestige fuel oil and toxicity of its 12 components
Methods for oil spill clean-up based on previous 14 study
The composition of sago hampas 28
Yield of MSB obtained under different percentage of 43 catalyst and response
Chemical and physical characteristics of untreated SB 46 andMSB
Studied natural sorbents for removal of oil 62
Xlll
,... I
Figure 2.1
Figure 2.2
Figure 2.3
Figure 2.4
Figure 2.5
Figure 3.1
Figure 3.2
Figure 4.1
Figure 4.2
Figure 4.3
Figure 4.4
Figure 4.5
Figure 4.6
Figure 4.7
Figure 4.8
Figure 4.9
L •
LIST OF FIGURES
Millions gallons of spilled oil in marine environment from different sources
Proposed mechanism of adsorption
Sago palms in Pusa, Sarawak
Production of sago starch
The abundance production of (a) sago bark, (b) sago hampas and wastewater after starch extraction process
Preparation of (a) raw SB after debarking process, (b) shredded SB, and (c) ground SB
Different sorption systems in (a) dry system (b) wet static system and (c) wet dynamic system (on orbital shaker)
FTIR spectra of (a) untreated SB, (b) pre-treated SB with NaOH and (c) esterified pre-treated SB
FTIR spectrum ofMSB (sample 4)
SEM micrographs of (a) untreated SB and (b) MSB before oil adsorption
The buoyancy of (a) untreated SB and (b) MSB in water system
Water uptake of untreated SB and MSB in static system: (a) deionized water, and (b) seawater
Water uptake of untreated SB and MSB in dynamic system: (a) deionized water, and (b) seawater
Sorption capacity of untreated SB and MSB in the mixture of oil and water static system: (a) deionized water, and (b) seawater medium
The evaluation of oil sorption capacity for untreated SB and MSB in static system: (a) deionized water, and (b) seawater medium
20 x 20 cm sorbent kit consisted of untreated SB or MSB
XIV
Page
10
19
24
25
26
30
38
42
44
45
48
49
50
52
53
54
,.. I
Figure 4.1 0 The process of clean-up UEO in deionized water: (a) 55 sorption after an hour, and (b) sorption after 24 h
Figure 4.11 Sorption capacity of untreated SB and MSB in the 56 mixture of oil and water dynamic system: (a) deionized water, and (b) seawater medium
Figure 4.12 The evaluation of oil sorption capacity for untreated 57 SB and MSB in dynamic system: (a) deionized water, and (b) seawater medium
Figure 4.13 Oil sorption capacity of untreated SB and MSB in the 59 dry system
Figure 4.14 SEM micrographs of (a) untreated SB and (b) MSB 59 after oil adsorption from UEO
Figure 4.15 Reusability and oil sorption capacity of untreated SB 60 and MSB
xv
l
LIST OF ABBREVIATIONS
SB Sago Bark
MSB Modified sago bark
UEO Used engine oil
ASTM American Society for Testing Materials
FTIR Fourier Transfonn Infrared
SEM Scanning electron microscopy
EDX Electron dispersive X-ray
BET Brunauer-emmett-teller
PAH Polycyclic aromatic hydrocarbon
NBS N-bromosuccinimide
WPG Weight per cent gain
S.D Standard deviation
K Kelvin
XVI
CHAPTERl
INTRODUCTION
1.1 Research background
Water pollution caused by oil spills has been receiving a great attention due to its adverse
environmental effects. Approximately 224,000 tonnes of oil spilled reported in marine
environment globally between 2000 and 2011 (ITOPF, 2011). Oil pollution occurs due to
tanker disaster, wars, operation failure, accidents, and natural disaster during the operation,
transportation and storage of oil (Rengasamy et ai., 2011). Domestic and industrial activities
have also contributed significantly to oil pollution in environment.
Oil pollution has given both immediate and long-term environmental damages. Oil spills have
damaged the beaches, marshlands and marine ecosystem (Annunciado et ai., 2005). It also
gives negative impact to marine mammals, birds and fish, and destroyed wildlife habitat and
breeding grounds. The oil not only severely pollutes the marine environment, but also poses a
serious threat to marine life (Wang et ai., 2010). The formation of oil-in-water emulsion or
floating film occurs during oil spill could be toxic to ~icroorganisms for oil biodegradation
process (Karan et ai., 2011).
Due to the serious oil pollution problems in water bodies, many oil removal technologies have
been introduced and improved. The aims are to return the functions of an ecosystem and re
establish the biological community in the ecosystem (Karana et ai., 2011). Examples of
1
I
I
available oil removal techniques are in-situ burning, bioremediation, mechanical methods,
chemical methods, and sorbents. However, these techniques are not available for all types of
spilled oil. There are some factors that might affect oil spilled control such as type of oils, the
surface on which it spills, the soil and subsoil conditions, and the weather conditions (AI
Majed et ai., 2012).
Adsorption using appropriate oil sorbent seems to be the best solution for oil spill recovery
due to its effectiveness, feasibility, simplicity and easy handling (Wahi et ai., 2013). A good
sorbent usually possess high oleophilic and hydrophobic property (Deschamps et al., 2003),
high oil sorption capacity, buoyancy and retention over time, durability in aqueous media,
reusability and biodegradability (Karana et aI., 2011), environmental friendly, and low-cost
method (Shavandi et al., 2012). There are three classes of oil sorbents which are commonly
reported. It includes synthetic organic, inorganic mineral and agricultural (organic) products
(Deschamps et aI., 2003; Radetic et al., 2008; Sun et al., 2003; Wahi et aI., 2013). The most
often reported on synthetic organic sorbents are polyurethane (Li et al., 2012) and
polypropylene (Lin et aI., 2010). The example of inorganic sorbents are organoclay (Cannody
et al., 2007), calcium carbonate (Arbatan et al., 2011). Kapok (Abdullah et aI., 2010; Lim and
Huang, 2007), vegetable fibres (Annunciado et al., 2005), sawdust (Banerjee et al., 2006),
cotton fibres (Deschamps et al., 2003), rice husks (Kumagai et al., 2007), populus seed fibres
(Likon et al., 2013), and sugar cane bagasse (Said et aI., 2009; Sun et al., 2003; Hussein et al.,
2008) are the examples of natural organic sorbents. Natural organic sorbents are the best oil
sorbents material in tenns of abundance, eco-friendly, comparatively low cost, sustainable and
biodegradable compared to other sorbents.
2
Despite of their advantages, many natural sorbents might be submerged after saturation due to
its ability to absorb/adsorb both oil and water (Li et ai., 2012). Lack of hydrophobicity and
low buoyancy of the sorbent will reduce the effectiveness of oil sorption in aqueous system.
Therefore, several approaches have been made to improve oil sorption capacity of natural
sorbent material through chemical modification. Among the approaches are solvent treatment
(Wang et ai., 2012, Abdullah et ai., 2010), esterification (Banerjee et ai., 2006; Said et ai.,
2009), and acetylation (Adebajo and Frost, 2004; Sun et ai., 2003; Sun et ai., 2004).
Sago bark, a type of waste from metroxyion sagu, has potential to be used as natural fibre for
oil removal. It is because sago bark comprises of cellulose and lignin with large amount of
hydroxyl functional groups (-OH), which prone to chemical modification and used for oil
sorption. Metroxyion sagu also known as sago comes from genus metroxyion and belongs to
Palmae family (Singhal et ai., 2008). In the production of sago starch, large quantity of waste
which contains both solid and liquid materials is produced. In Sarawak, about 20,000 tons of
sago barks were produced annually from sago mill industries (Wahi et ai., 2014). Most people
use the barks of the trunk as timber fuel, temporary walls, ceilings and fences (Rahman, 2008).
Due to its chemical composition, raw sago bark has the potential to be utilised as oil sorbent.
The raw sago bark generally has good sorption capacity, comparable density with synthetic
sorbent, chemical free and highly degradable. Therefore, the utilisation of agricultural waste
such as sago bark into value added products is good to be used for global environmental
conservation and sustainable development (Rahman and Sundin, 2008).
3
1.2 Problem statement
In Malaysia, oil pollution is one of the mam prob~ems affecting the marine coastal
environment. Oil pollution in coastal area occurs from t!xploitation, extraction, transportation
and/or disposal activities (Rengasamy et aI., 2011). Oil spills are serious environmental
disasters, often leading to significant, long-term impacts on the environment, ecology and
sosio-economic activities of an area. Mortality and damage to marine life, disrupting the food
chain, affecting community health and many others are examples of oil spill effects. Safe and
environmentally oil spill management has become an increasing problem worldwide. Thus, oil
spills should be handled systematically and effectively to reduce environmental pollution
especially in lake, river and marine environment. Most published works on the oil spill
remediation has dealt with advanced recovery technology. Wahi et al. (2013) claimed that
removal ofoil particles in oily water by advanced technologies have certain limitations such as
expensive and difficult to maintain. Biomass such as agricultural wastes is the most potential
natural resource of oil spill remediation. Sago starch production industry generated significant
amount of wastes sago bark annually, which is about 20,000 tons (Wahi et aI., 2014). The high
production of sago bark in sago processing industries could be the alternative way to recovery
oil spill. However, the major drawbacks of this waste are low hydrophobicity and low
buoyancy that could lead to low oil removal efficiency and low oil sorption capacity. One of
the chemical modification techniques to increase oil removal efficiency of natural sorbent is
esterification. Modification of natural sorbent via esterification has been proven to contain
lower water uptake and higher oil sorption capacity in comparison with untreated fibre
(Banerjee et aI., 2006; Said et al., 2009). This study has directed on improving and deploying
natural sorbent which are not only low cost but also safest resources of oil spill control.
4
I,...
1.3 Justification of study
The present research examines a chemical modification of sago bark using esterification with
fatty acid derivative for the preparation of oil sorption materials. So far, only few studies on
esterification of natural fibre for oil sorption were conducted and no studies on esterification
of sago bark have been published. Therefore, this study provides information regarding the
usefulness of modified sago bark via esterification with fatty acid derivative for oil spilled
treatment in water bodies. This study also provides information on the characteristic of
untreated sago bark and modified sago bark as oil sorbents. The modification of sago bark
could be used effectively to recover oil spilled in water bodies for instance, heavy industrial
wastewater or ecosystem.
1.4 Research objectives
The objectives of this study are:
1. To prepare the modified sago bark (MSB) via esterification with fatty acid
derivative for oil sorption.
11. To characterise the untreated sago bark (SB) and MSB as oil sorbent that are
applicable to clean up oil spill.
111. To investigate and compare the capability of untreated SB and MSB to adsorb used
engine oil (UEO) in deionized water and seawater system
IV. To study the reusability of untreated SB and MSB.
5
I.S Scope of study
In this study, modification of SB with stearic acid and calcium oxide as a catalyst was
perfonned via esterification process. The scope of this study involved measuring the
behaviours of untreated SB and MSB as oil sorbent. The untreated SB and MSB were
characterised by proximate analysis, FTIR analysis and SEM analysis. The physical properties
such as hydrophobicity, buoyancy, surface area and pore size of untreated SB and MSB were
also investigated. In tenns of application, untreated SB and MSB were exposed in oily water
containing UEO. Oil sorption in water system was studied in non-turbulent (wet static system)
and turbulent (wet dynamic system) environment. In addition, oil sorption behaviour of
untreated SB and MSB in oily seawater were also examined. Water sorption capacity was
perfonned to evaluate the potential of untreated SB and MSB to adsorb water. The reusability
test of MSB was conducted and the results were compared to the untreated SB.
6
CHAPTER 2
LITERATURE REVIEW
2.1 Nature of oil and its toxicity
Oil is a complex substance containing hundreds of different compounds mainly consist of
carbon and hydrogen which is immiscible with water but soluble in organic solvents. There
are many different types of oil ranging from very light oils to heavy crude oils depending on
the number of carbon atoms in the hydrocarbon chain (Boyd et al., 2001 ). It includes 284
crude oils varying in proportion, and refined oils such as diesel oil, heavy fuel oil, lubricating
oil, kerosene and gasoline (Enache and Zagan, 2009). Oil is a viscous liquid having density
less than water. In addition, oil is immiscible in water thus emulsion will form between oil and
water or floating film that can caused water pollution (Karan et al., 2011).
Water pollution caused by oil spillage is very dangerous to ecosystem due to its toxicity.
Different oil types have different toxicity and can be divided into different groups based on the
properties of spilled oil. Enache and Zagan (2009) stated there are three main groups of oil
which are light refined, heavy refined and crude oils. !hey can be distinguished according to
their appearance on the water surface. Light refined oils such as petrol, gasoline and kerosene
are very volatile and will evaporate quickly after spill, often disappear within two to three
days. Heavy refined oils such as diesel and fuel oil are very viscous and do not disappear
naturally. Characteristics and behaviours of crude oils can be classified according to their
types and origins. Most crude oils will form emulsion with seawater within 24 to 48 h. This
7