MEMBRANE APPLICATION IN THE RECOVERY OF GAHARU …
Transcript of MEMBRANE APPLICATION IN THE RECOVERY OF GAHARU …
MEMBRANE APPLICATION IN THE RECOVERY OF GAHARU ACTIVE
MARKER COMPOUND FROM WATER MIXTURE
CHIN WENG FOO
Thesis submitted in partial fulfilment
of the requirements for the award of the degree of
Bachelor of Chemical Engineering
Faculty of Chemical & Natural Resources Engineering
UNIVERSITI MALAYSIA PAHANG
FEBRUARY 2013
TABLE OF CONTENTS
PAGE
TITLE PAGE i
ACKNOWLEDGEMENT ii
TABLE OF CONTENTS iii
LIST OF TABLES vi
LIST OF FIGURES vii
LIST OF SYMBOLS xi
LIST OF ABBREVIATIONS xii
ABSTRACT xiii
ABSTRAK xiv
CHAPER 1 INTRODUCTION
1.1 Background of Study 1
1.2 Problem Statement 1
1.3 Objectives of Study 2
1.4 Scope of Study 2
CHAPTER 2 LITERATURE REVIEW
2.1 Introduction 4
2.2 History of Gaharu 5
2.3 Gaharu Marker Compound 6
2.3.1 Agarospirol 7
2.3.2 Jinkohol II 8
2.3.3 α-guaiene 9
2.3.4 Seline-3,11-dien-9-al 10
2.4 Membrane Separation 11
2.4.1 Introduction 11
2.4.2 Advantage of Membrane Separation 11
2.4.3 Nanofiltration 13
2.4.4 Ultrafiltration 14
2.4.5 Microfiltration 15
2.4.6 Factors that Affect the Membrane Performance 16
2.5 Mass Transfer in Membrane 18
2.5.1 Diffusion 18
2.5.2 Permeability and Selectivity 20
CHAPTER 3 Methodology
3.1 Membrane Selection 22
3.2 Milipore Stirred Ultrafiltration Cell Model 8200 23
3.3 Field Emission Scanning Electron Microscope 26
3.4 Preparative HPLC 26
3.5 Permeability Calculation 28
3.6 Experimental Procedure 28
3.6.1 List of Equipments 28
3.6.2 Experimental Procedure 29
CHAPTER 4 RESULT AND DISCUSSION
4.1 Results 33
4.2 Results for Membrane Filtration Experiment 34
4.3 Field Emission Scanning Electron Microscope Testing 39
4.3.1 SEM Image of TS40 Membrane Before Experiment 39
4.3.2 SEM Image of SB90 Membrane Before Experiment 42
4.3.3 SEM Image of TS40 after the Experiment for Run 1 44
4.3.4 SEM Image of TS40 after the Experiment for Run 2 48
4.4 Preparative HPLC Testing 52
CHAPTER 5 CONCLUSION AND RECOMMENDATION
5.1 Conclusion 59
5.2 Recommendation 60
REFERENCES 62
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LIST OF TABLES
PAGE
Table 2.1 Properties of Agarospirol 7
Table 2.2 Properties of Jinkohol II 8
Table 2.3 Properties of α-guainene 9
Table 2.4 Properties of Selina-3,11-dien-9-al 10
Table 2.5 Properties of Nanofiltration, Ultrafiltration and 16
Microfiltration Membrane
Table 3.1 Parts List for AMICON 8200 25
Table 4.1 Results for TS40 Run 1 34
Table 4.2 Results for TS40 Run 2 34
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LIST OF FIGURES
PAGE
Figure 2.1 Aquilaria Malaccensis Tree 6
Figure 2.2 Molecular Structure of Agarospirol 7
Figure 2.3 Molecular Structure of Jinkohol II 8
Figure 2.4 Molecular Structure of α-guainene 9
Figure 2.5 Molecular Structure of selina-3,11-dien-9-al 10
Figure 3.1 Molecular Structure of polypiperazine amide 23
Figure 3.2 Molecular Structure of cellulose acetate 23
Figure 3.3 AMICON 8200 Model 24
Figure 3.4 Parts List for AMICON 8200 25
Figure 3.5 Methodology for Preparative HPLC 27
Figure 3.6 Flow of Experimental Procedure 29
Figure 3.7 Experimental Set Up of Membrane Separation 32
Figure 4.1 Graph of Permeate Flux vs Pressure for TS40 Run 1 34
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Figure 4.2 Graph of Permeate Flux vs Pressure for TS40 Run 2 35
Figure 4.3 Water flux for unmodified and modified membranes 36
Figure 4.4 Molecular Structure of Cellulose Acetate 37
Figure 4.5 Circular stain on SB90 Membrane 37
Figure 4.6 Yellowish Stain on SB90 Membrane 38
Figure 4.7 Two Yellowish Stain on SB90 Membrane 38
Figure 4.8 Upper Coating of TS40 at 60x 40
Figure 4.9 Upper Coating of TS40 at 7000x 40
Figure 4.10 Rough Surface of TS40 at 200x 41
Figure 4.11 Rough Surface of TS40 at 500x 41
Figure 4.12 Rough Surface of TS40 at 1000x 42
Figure 4.13 Rough Surface of SB90 at 200x 43
Figure 4.14 Rough Surface of SB90 at 500x 43
Figure 4.15 Rough Surface of SB90 at 1000x 44
Figure 4.16 Gaharu Extract on the Surface of TS40 at 100x 45
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Figure 4.17 Gaharu Extract on the Surface of TS40 200x 45
Figure 4.18 Gaharu extract on the surface of TS40 750x 46
Figure 4.19 Gaharu extract on the surface of TS40 5000x 47
Figure 4.20 Gaharu Extract on the Surface of TS40 at 10000x 47
Figure 4.21 Gaharu Extract on the Surface of TS40 at 30000x 48
Figure 4.22 Gaharu Extract on the Surface of TS40 1000x 49
Figure 4.23 Gaharu Extract on the Surface of TS40 5000x 49
Figure 4.24 Gaharu Extract on the Surface of TS40 10000x 50
Figure 4.25 Gaharu Extract on the Surface of TS40 20000x 50
Figure 4.26 Gaharu extract on the surface of TS40 30000x 51
Figure 4.27 HPLC Result for Gaharu Water Mixture from Industry 53
Figure 4.28 HPLC Result for TS40 1 Bar Run 1 Permeate 54
Figure 4.29 HPLC Result for TS40 3 Bar Run 1 Permeate 54
Figure 4.30 HPLC Result for TS40 4 Bar Run 1 Permeate 55
Figure 4.31 HPLC Result for TS40 2 Bar Run 2 Permeate 55
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Figure 4.32 HPLC Result for TS40 3 Bar Run 2 Permeate 56
Figure 4.33 HPLC Result for TS40 4 Bar Run 2 Permeate 56
Figure 4.34 HPLC Result for TS40 2 Bar Run 1 Permeate 57
Figure 4.35 HPLC Result for TS40 1 Bar Run 2 Permeate 58
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LIST OF SYMBOLS
V Volume of permate
A Effective area of membrane
P Pressure of nitrogen gas
t Time to collect permeate
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LIST OF ABBREVIATIONS
FESEM - Field Emission Scanning Electron Microscope
HPLC - High Performance Liquid Chromatography
MF - Microfiltration
NF - Nanofiltration
UF - Ultrafiltration
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MEMBRANE APPLICATION IN THE RECOVERY OF GAHARU ACTIVE
MARKER COMPOUND FROM WATER MIXTURE
ABSTRACT
This study focuses the membrane application in the recovery of gaharu active
marker compound from water mixture. The objective of this study is to design the
separator process using membrane technique to recover gaharu active marker
compound from water mixture and to analyse the recovered gaharu marker
compound using membrane separation. The gaharu marker compounds that needed
to be separated are agarospirol, jinkohol, α-guainene and selina-3,11-dien-9-al.
Preparative High Performance Liquid Chromatography was used as the qualitative
analysis of the gaharu active marker compound in the mixture. The membrane was
applied to separate the marker compound from the water mixture. Milipore Stirred
Ultrafiltration Cell Model 8200 was used as the membrane separation proces unit.
Field Emission Scanning Electron Microscopy was used to capture microscope
image of the TS40 and SB90 nanofiltration membrane used in the experiment. At the
end of the experiment, TS40 nanofiltration membrane was able to separate the
gaharu marker compounds at the average flux value of 0.45 ml/cm2.h to 2.00
ml/cm2.h with varying pressure from 1 bar to 4 bar.
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APLIKASI MEMBRAN DALAM PEMULIHAN SEBATIAN KIMIA
GAHARU YANG TERDAPAT DALAM CAMPURAN AIR
ABSTRAK
Kajian ini berfokus pada aplikasi membran untuk pemulihan sebatian kimia
gaharu yang terdapat dalam campuran air gaharu. Objektif kajian ini adalah untuk
mereka bentuk satu proses pemisahan menggunakan teknik membran untuk
pemulihan sebatian kimia gaharu dalam campuran air and juga untuk menganalisis
sebatian kimia gaharu yang telah melalui proses pemulihan menggunakan proses
pemulihan membran. Sebatian kimia gaharu yang ingin dipisahkan adalah
agarospirol, jinkohol, α-guainene dan selina-3,11-dien-9-al. Kromatografi Cecair
Berprestasi Tinggin telah digunakan kualiti analisis untuk sebatian kimia gaharu
dalam campuran air. Membran telah digunakan untuk memisahkan sebatian kimia
gaharu dalam campuran air. "Milipore Stirred Ultrafiltration Cell Model" telah
digunakan sebagai proses unit untuk pemisahan membran. "Field Emission Scanning
Electron Microscopy" digunakan untuk menangkap imej mikroskop membran TS40
dan membran SB90. Di akhir experimen ini, membran TS40 dapat memisahkan
sebatian kimia gaharu dengan nilai fluks purata dari 0.45 ml/cm2.h hingga 2.00
ml/cm2.h dengan tekanan dari 1 bar hingga 4 bar.
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CHAPTER 1
INTRODUCTION
1.1 Background of Study
Gaharu or agarwood is one of the most famous incenses in the East. Gaharu
are mainly produced by trees of Aquilaria and Gyrinops. The most popular species of
Aquilaria in Peninsular Malaysia is Aquilaria Malaccensis. Gaharu oil is formed by
mixtures of sesqiuternes, sesquiternes alcohol, chromone derivatives and resin
(Adam et al. 2011). The important key components that contribute the aroma of
gaharu are agarospirol, jinkohol-eremol, jinkohol and kusenol.
1.2 Problem Statement
Nowadays, membrane separation is one of the most popular methods of
separation because of its capability. The use of membrane for separation is becoming
increasingly important in the process industries. In this study, membrane is applied to
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separate the gaharu marker compound from the gaharu water mixture. A suitable set
of membrane are needed to separate these marker compounds. The membranes are
selected based on their pore size, permeability and selectivity.
The selected membrane to be used must be made up of compound that can
have molecular interaction with the marker compounds that present inside the gaharu
marker compounds. By using the correct compound, the membrane can pull the
marker compounds into its surface and thus separating them from the gaharu water
mixture.
1.3 Objective of Study
In this study, the objectives which aims to be achieved are :
1. To design the separator process using membrane technique to recover gaharu
active marker compound from water mixture
2. To analyse the recovered gaharu marker compound using membrane separation
3. To make comparison between membranes that were used
1.4 Scope of Study
In this study, there are a few parameters that are needed to be controlled. The
parameters include permeability and selectivity of the membrane, permeate flux and
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the pressure where these parameters will affect the membrane's performance in the
separation process.
During the experiment, the membrane performance can affect how the marker
compounds of gaharu are being separated and filter out. Therefore, it is important to
know the concept of permeability, selectivity, mass transfer and diffusion process in
a membrane system.
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CHAPTER 2
LITERATURE REVIEW
2.1 Introduction
One of the objectives of this chapter is to explain the gaharu and its marker
compound. Explanation on gaharu will be more detailed in the Aquilaria Malaccensis
species which are found in Peninsular Malaysia. Then this chapter will explain the
types of membrane that can be used in membrane separation.
The literature review is done based on the journals that are related Aquilaria
Malaccensis species of gaharu. The literature review will cover the origins, types and
characteristics of Aquilaria Malaccensis. This chapter will also cover the gaharu
marker compound in its essential oils
The membrane application will also be covered in the scope of this chapter.
Types of membranes, properties and their application will be explained in this
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chapter. There are three types of membrane that will be discussed here which are
ultrafiltration, microfiltration and nanofiltration.
This chapter will let the reader to know the importance of gaharu and its
marker compound. The concept of membrane separation will be explained to the
reader.
2.2 History of Gaharu
Gaharu is a fragnant wood that is derived from the diseased timber of the
genus Aquilaria. It is often occurs as dark coloured patches or streaks in the tree.
Gaharu oil is greatly valued as perfume ingredient and incense because of its strong,
unique scent and medical properties (Nor Azah et al. 2008).
Aquilaria genus is an aromatic plant that is commonly known as “Gaharu
Wood” in South East Asia. The Aquilaria species is found mostly in Malaysia,
Indonesia, India, Iran, Singapore, Bangladesh, Myanmar, Philippines and Thailand.
One of the species, Aquilaria Malaccensis produces valuable resin marinate in the
heartwood (Ibrahim et al. 2011).
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Figure 2.1 Aquilaria Malaccensis Tree
Gaharu are classified into various grades such as Grade A, Grade B, Grade C
and Grade D. Gaharu is graded according to their physical properties, formation and
their unique scent (Nor Azah et al. 2008). Aquilaria Malaccensis produces valuable
resin marinate in the heartwood which originates as a consequences of natural
immune response towards fungal attack. One of the fungus, endophyte lives inside
healthy plant tissues. Some of these endophytes have found to have anticancer and
antidiabetic properties. Essential oils of Aquilaria Malaccensis is safe and simple to
use. It is produced and commonly used in traditional medicine to relieve pain, fever,
rheumatism, and asthma (Ibrahim et al. 2011).
2.3 Gaharu Marker Compound
The lower grades of gaharu such as Grade C are often distilled to get gaharu
oil (Nor Azah, 2008). In an extraction process, the presence of main components
such as agarospirol, jingkohol-eremol, jingkohol and eremol are found in gaharu
essential oils. In this study, it is desired to separate four compounds from the gaharu
water mixture using membrane separation. The four compounds are agarospirol,
jinkohol, guainene and selina.
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2.3.1 Agarospirol
Agarospirol is a chemical compound that consists of fifteen carbon atoms,
twenty six hydrogen atoms and one oxygen atom. The molecular weight and volume
are 222.366 and 183.5 respectively. This compound has five methyl groups and a
functional group of hydroxyl.
Agarospirol is reported as one of the main marker compound that contribute
to the scent of gaharu. Figure 2.2 represent the molecular structure of agospirol.
Table 2.1 shows the chemical formula and molecular weight of agarospirol.
Figure 2.2 Molecular Structures of Agarospirol
Table 2.1 Properties of Agarospirol
Chemical Formula Molecular Weight
C15H26O 222.366
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2.3.2 Jinkohol II
Jinkohol II is a chemical compound that consists of fifteen carbon atoms,
twenty six hydrogen atoms and one oxygen atom. The molecular weight and volume
are 222.366 and 176.64 respectively. It has three methyl group and the functional
group of one hydroxyl group.
Similar with agarospirol, jinkohol II is classified as the main marker
compound in gaharu. Jinkohol II also contributes to the characteristic aroma of
gaharu. Figure 2.3 represent the molecular structure of jinkohol II. Table 2.2 lists the
chemical formula and molecular weight of the compound.
Figure 2.3 Molecular Structure of Jinkohol II
Table 2.2 Properties of Jinkohol II
Chemical Formula Molecular Weight
C15H26O 222.366
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2.3.3 α-guaiene
α-guaiene is a chemical compound that consists of five carbon atoms, five
hydrogen atoms, five nitrogen atoms and an oxygen atom. The molecular weight and
volume are 151.126 and 83. It has three double bonds.
α-guaiene is one of the main marker compound in the gaharu water mixture.
Therefore it is one of the most important compound that present in the gaharu water
mixture. Figure 2.4 represent the molecular structure of α-guaiene. Table 2.3 lists the
chemical formula and molecular weight of α-guaiene.
Figure 2.4 Molecular Structures of α-guaiene
Table 2.3 Properties of α-guaiene
Chemical Formula Molecular Weight
C5H5N5O 151.126
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2.3.4 Selina-3,11-dien-9-al
Selina-3,11-dien-9-al is a chemical compound consists of hydrogen bonds
and methyl groups. Similarly with other compounds that were explained above,
selina-3,11-dien-9-al is also one of the main marker compound that present inside the
gaharu.
The molecular structure of selina-3,11-dien-9-al has the functional group of
hydroxyl. Figure 2.5 represent the molecular structure of selina-3,11-dien-9-al. Table
2.4 lists the chemical formula and molecular weight of selina-3,11-dien-9-al.
Figure 2.5 Molecular Structure of Selina-3,11-dien-9-al
Table 2.4 Properties of Selina-3,11-dien-9-al
Chemical Formula Molecular Weight
C15H24O 220.35
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2.4 Membrane Separation
2.4.1 Introduction
Membrane separation is becoming increasingly important in process
industries. In this process, the membrane acts as a semi permeable barrier. The
separation process occurs by the membrane controlling the rate of the movement of
various molecules between two liquid phases, two gas phases, or a liquid or a gas
phase (Geankoplis et al. 2003)
In this study, three types of membrane separation process will be discussed
which are ultrafiltration, nanofiltration and microfiltration.
2.4.2 Advantage of Membrane Separation
Membrane separation can be used in a number of applications. One of the
them is the separation of two chemical compounds in a mixture that have narrow
boiling points. In the field of hydrocarbon separations, the separation of condensed
olefin from corresponding paraffins is complicated process. Separation of paraffin
and olefin by conventional distillation is expensive and difficult as the two
substances has a narrow temperature ranges.
Therefore, membrane separation can be offered as an alternative for the
separation process. In the polymeric matrix membranes, the introduction of
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chemically active sites can offer increase membrane selectivity and permeability.
This can therefore improve in the efficiency of olefin and paraffin separations
(Bessarabov et al. 1999).
Besides that, membrane separation can also be applied in the water and waste
water treatment plant. A number of advantages can be offered by membrane
processes over conventional water and waste water treatment processes. The
advantages include reduced environmental impact of effluents, land requirement
reduce, higher standards of final product and the potential of the mobile treatment
units of membrane process.
In the water and waste water treatment, membranes can used in a few
applications. The applications include removal of colour, trihalomethanes and other
disinfection by product removal and also iron removal.
Membrane processes are also reported to be cost effective in a few situations
and applications. It can be used as an alternative to conventional softening plant and
as a pretreatment plant for reverse osmosis (Owen et al. 1995).