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UNIVERSITI PUTRA MALAYSIA
KOAY YIN SHIN
FK 2013 22
ADSORPTION OF REACTIVE DYES FROM AQUEOUS SOLUTIONS BY QUATERNIZED PALM KERNEL SHELL
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ADSORPTION OF REACTIVE DYES FROM AQUEOUS SOLUTIONS BY QUATERNIZED
PALM KERNEL SHELL
KOAY YIN SHIN
MASTER OF SCIENCE
UNIVERSITI PUTRA MALAYSIA
2013
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ADSORPTION OF REACTIVE DYES FROM AQUEOUS SOLUTIONS BY
QUATERNIZED PALM KERNEL SHELL
By
KOAY YIN SHIN
Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia,
in Fulfilment of the Requirements for the Degree of Master of Science
May 2013
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COPYRIGHT
All material contained within the thesis, including without limitation text, logos,
icons, photographs and all other artwork, is copyright material of Universiti Putra
Malaysia unless otherwise stated. Use may ne made of any material contained within
the thesis for non-commercial purposes from the copyright holder. Commercial use
of material may only be made with the express, prior, written permission of
Universiti Putra Malaysia.
Copyright © Universiti Putra Malaysia
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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.
ADSORPTION OF REACTIVE DYES FROM AQUEOUS SOLUTIONS BY
QUATERNIZED PALM KERNEL SHELL
By
KOAY YIN SHIN
May 2013
Chairman: Intan Salwani Binti Ahamad, PhD
Faculty: Engineering
Quaternized biomass serves as substitution to activated carbon as adsorbent to solve
the issue on activated carbon such as cost, environment impact and sustainability.
However, there is lack of research on reactive dyes adsorption by quaternized
lignocellulosic fibers and none of research on quaternized PKS as adsorbent been
reported up to date. Therefore, an attempt was made to chemically quaternized palm
kernel shell (QPKS) as adsorbent to increase adsorption affinity towards two reactive
dyes namely Reactive Black 5 (RB5) and Reactive Red E (RRE). Palm kernel shell
(PKS) was quaternized successfully by treating with N-(3-chloro-2-
hydroxypropyl)trimethylammonium chloride under basic condition. The QPKS was
characterized by CHN elemental analysis, Fourier Transform Infrared Spectroscopy
(FTIR), Scanning Electron Microscope (SEM), Energy Dispersive X-Ray (EDX),
Brunauer, Emmett and Teller (BET) analysis, Thermalgravimetric analysis (TGA)
and X-Ray Diffraction analysis (XRD). Result from CHN and EDX elemental
analysis demonstrated an increase of nitrogen percentage after treatment further
support the success of the reaction. Surface characterization of QPKS by SEM and
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BET analysis confirmed the surface pore enlargement from mesopores to macropores
after quaternization. Furthermore, chemical properties such as point zero charge,
surface chemistry and chemical composition were determined. Point of zero charge
of QPKS measured at 25 ˚C was at pH 2.2.
Adsorption experiment was carried out to investigate the effect of pH, dosage of
QPKS, initial concentration, contact time and temperature in single batch system
with constant shaking rate of 160 rpm for both dyes. The optimum pH for removal of
RB5 and RRE by QPKS was at pH4. 1.0 g/L of QPKS was chosen as the appropriate
dosage for both dyes adsorption. Four analytical isotherm equations, Langmuir,
Freundlich, Sips and Redlich-Peterson models were fitted to the equilibrium
adsorption data. The Redlich-Peterson model is best fitted to the data. The maximum
adsorption capacity of QPKS was found to be 191.2 mg/g for RB5 and 182.8 mg/g
for RRE. The rate of adsorption in single system was found to agree with pseudo-
second-order kinetics model. The adsorption of both dyes onto QPKS is spontaneous
process and exothermic in nature. Hence increase in adsorption temperature does not
favor the process. For binary system, an artificial neural network (ANN) model was
developed to stimulate the adsorption of RB5 and RRE by QPKS under varying
parameters such as pH, dosage and dye concentration.
Regeneration of QPKS was carried out by shaking the used QPKS in 0.1M NaOH
solution. Regeneration of QPKS for adsorption of RB5 was valid but not for RRE.
In conclusion, the QPKS synthesized was proven able in removing RB5 and RRE
dye in aqueous solution.
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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai
memenuhi keperluan untuk ijazah Master Sains.
PENJERAPAN PEWARNA REAKTIF DARIPADA LARUTAN AKUES
DENGAN MENGGUNAKAN CENGKERANG ISIRONG KELAPA SAWIT
YANG TELAH DIKUATERNISASI
Oleh
KOAY YIN SHIN
Mei 2013
Pengerusi: Intan Salwani Binti Ahamad, PhD
Fakulti: Kejuruteraan
Kuartenisasi atas product sampingan industri pertanian mempunyai potensi tinggi
untuk menggantikan karbon teraktif sebagai penjerap. Kekurangan penyelidikan
terhadap penjerapan pewarna reaktif atas serat kuartenisasi cengkerang isirong
kelapa sawit (QPKS) sebagai penjerap sehingga kini. Oleh itu, percubaan telah
dilaksanakan untuk mensistesis QPKS sebagai penjerap dengan kaedah kimia,
dengan tujuan untuk meningkatkan penjerapan afiniti dua pewarna reaktif, iaitu
Reaktif Hitam 5 (RB5) dan Reaktif Merah E (RRE). Cengkerang isirong kelapa sawit
(PKS) telah berjaya dikuartenisasi dengan menindak balas dengan N-(3-chloro-2-
hydroxypropyl)trimethylammonium chloride dalam keadaan alkali. QPKS telah
diciri dengan menggunakan analisai unsur CHN, Spektroskopi Inframerah
Transformasi Fourier (FTIR), Pengimbas Mikroskop Elektron (SEM), Penyebar
Tenaga X-Ray (EDX), analisasi Brunauer, Emmett dan Teller
(BET),Thermogravimetrik analisasi (TGA), dan analisasi X-Ray Pembelauan
(XRD). Di samping itu, analisis unsur CHN dan EDX menunjukkan peningkatan
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peratusan nitrogen pada QPKS selepas ditindak balas menjadi sokongan yang kukuh
bahawa tindak balas kuartenisasi telah berjaya. Selain itu, pencirian permukaan
QPKS oleh SEM dan BET analisasi mengesahkan pembesaran liang permukaan dari
meso kepada macro selepas pengubahsuaian. Tambahan pula, sifat-sifat kimia seperti
titik caj kosong, kimia permukaan, dan komposisi kimia telah ditentukan. Titik caj
sifar QPKS yang diambil bacaan pada suhu 25 ˚C adalah di pH 2.2.
Kajian penjerapan telah dijalankan untuk mengaji kesan pH, dos QPKS, kepekatan
awal pewarna reaktif, masa reaksi, dan kesan suhu dalam sistem kelompok dengan
kadar goncangan 160 rpm. pH optima untuk penyingkiran RB5 dan RRE oleh QPKS
adalah pada pH 4. 1.0 g/L dos QPKS telah ditentukan sebagai jumlah mínimum yang
diperlukan dengan menunjukkan penyingkiran yang terbaik untuk kedua-dua
pewarna. Equilibria isoterm dianalisis oleh model Langmuir, Freundlich, Sips, dan
Redlich-Peterson dan Redlich-Peterson model paling menghampiri data-data kajian.
Kapasiti maximum penjerapan MPKS didapati ialah 191 mg/g untuk RB5 dan 182
mg/g untuk RRE. Kadar penjerapan dalam sistem tunggal didapati setuju dengan
kinetik pseudo-tertib kedua. Untuk sistem binari, model penjerapan RB5 dan RRE
oleh MPKS bawah parameter yang berbeza seperti pH, dos MPKS, dan kepekatan
pewarna telah mensimulasikan dengan menggunakan rangkaian neural tiruan (ANN).
Penjerapan kedua-dua pewarna pada QPKS adalah reaksi spontan dan eksotermik.
Penjanaan QPKS telah dilaksanakan dengan mengoncang QPKS yang terpakai dalam
0.1M NaOH. MPKS gagal dijana semula untuk penjerapan RRE tetapi boleh diguna
pakai semula untuk penjerapan RB5. Kesimpulannya, penjerap QPKS yang disintisis
dibuktikan cekap dalam menjerap RB5 dan RRE pewarna.
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ACKNOWLEDGEMENTS
I would like to express my utmost gratitude to my supervisor Dr.Intan Salwani Binti
Ahamad and co-supervisors Prof. Luqman Chuah Abdullah Prof. Thomas Choong
Shean Yaw and Dr. Mohsen for their valuable guidance, support and constructive
comments throughout this project. I would like to gratefully acknowledge the
technicians in the Department of Chemical and Environmental Engineering and my
colleagues for their willingness in helping me. A Loving thanks to my family and
friends who give me encouragement and support throughout this journey. From the
deepest of my heart, I am very grateful and appreciate to all individual who had
contributed in my work. Sincere apologies to any individual I had unintentionally left
off.
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I certify that a Thesis Examination Committee has met on May 2013 to conduct the
final examination of Koay Yin Shin on her Master of Science thesis entitled
“Adsorption of Reactive Dyes from Aqueous Solutions by Modified Palm Kernel
Shell” in accordance with the Universities and University Colleges Act 1971 and the
Constitution of the Universiti Putra Malaysia [P.U.(A) 106] 15 March 1998. The
Committee recommends that the student be awarded the degree of Master of Science.
Members of the Thesis Examination Committee were as follows:
Salmiaton binti Ali, PhD
Associate Professor
Faculty of Engineering
Universiti Putra Malaysia
(Chairman)
Mohd Halim Shah bin Ismail, PhD
Associate Professor
Faculty of Engineering
Universiti Putra Malaysia
(Internal Examiner)
Shafreeza binti Sobri, PhD
Senior Lecturer
Faculty of Engineering
Universiti Putra Malaysia
(Internal Examiner)
Abdul Latif Ahmad, PhD
Professor
School of Chemical Engineering
Universiti Sains Malaysia
(External Examiner)
________________________________
SEOW HENG FONG, PhD
Professor/Deputy Dean
School of Graduate Studies
Universiti Putra Malaysia
Date:
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This thesis submitted to the Senate of Universiti Putra Malaysia and has been
accepted as fulfilment of the requirement for the degree of Master of Science. The
members of the Supervisory Committee were as follows:
Intan Salwani binti Ahamad, PhD
Senior Lecturer
Faculty of Engineering
Universiti Putra Malaysia
(Chairman)
Luqman Chuah Abdullah, PhD
Professor
Faculty of Engineering
Universiti Putra Malaysia
(Member)
Thomas Choong Shean Yaw, PhD, IR
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 other
institution.
__________________________
KOAY YIN SHIN
Date: 20 May 2013
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TABLE OF CONTENTS
Page
ABSTRACT ii
ABSTRAK iv
ACKNOWLEDGEMENTS vi
APPROVAL vii
DECLARATION ix
LIST OF TABLES xiii
LIST OF FIGURES xv
LIST OF NOTATIONS / SYMBOLS xvii
LIST OF APPENDICES xviii
CHAPTER
1 INTRODUCTION
1.1 Palm Oil Biomass in Malaysia 1.1
1.2 Dye Effluent 1.1
1.3
1.4
1.5
Problem Statement
Objectives Of The Study
Scope of Study
1.2
1.3
1.3
1.6 Thesis Layout 1.5
2 LITERATURE REVIEW
2.1 Reactive Dyes 2.1
2.2 Environmental and Health Effect of Dye Effluent 2.3
2.3 Dye Effluent Treatment 2.5
2.4
2.5
Low-cost Biomass as Adsorbent
Quaternization on Lignocellulosic Fiber
2.7
2.10
2.6 Palm Kernel Shell (PKS) 2.13
2.7 Factors Effecting Adsorption Capacity and Rate 2.16
2.8 Adsorption Isotherm 2.19
2.8.1 Langmuir Isotherm
2.8.2 Freundlich Isotherm
2.19
2.20
2.8.3 Sips Isotherm
2.8.4 Redlich-Peterson Isotherm
2.8.5 Error Analysis
2.21
2.22
2.22
2.9 Kinetics of Adsorption 2.25
2.10
2.11
2.12
Thermodynamic of Adsorption
Artificial Neural Network (ANN)
Summary
2.26
2.29
2.31
3 MATERIALS AND METHODOLOGYS
3.1 Materials
3.1.1 Reagents and Chemicals 3.1
3.1.2
3.1.3
Adsorbent
Adsorbate
3.2
3.2
3.2 Characterization
3.2.1 CHN Elemental Analysis
3.4
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3.2.2 Fourier Transform Infrared Spectroscopy (FTIR)
3.2.3 Scanning Electron Microscope (SEM) and Energy
Dispersive X-Ray (EDX)
3.2.4 BET Analysis
3.2.5 Thermogravimetric Analysis (TGA)
3.2.6 X-Ray Diffraction Analysis (XRD)
3.2.7 Point Zero Charge
3.2.8 Surface Chemistry
3.2.9 Chemical Composition
3.5
3.5
3.6
3.6
3.6
3.7
3.7
3.3 Adsorption Experiment 3.10
3.3.1
3.3.2
3.3.3
3.3.4
3.3.5
3.3.6
Flow Chart of Adsorption Experiments
Effect of Mercerization
Effect of NaOH Ratio on Quaternization Reaction
Effect of Particle Size
Effect of Initial pH
Effect of Dosage
3.11
3.12
3.12
3.12
3.13
3.13
3.3.7
3.3.8
3.3.9
Single System Equilibrium Studies
Single System Kinetic Studies
Single System Thermodynamic Studies
3.13
3.14
3.15
3.3.10
3.3.11
Binary Equilibrium Studies
Artificial Neural Network (ANN)
3.15
3.15
3.4
3.5
Regeneration
Duplication and Control
3.17
3.18
4 RESULTS AND DISCUSSION
4.1 Characterization
4.1.1 Scanning Electron Microscope (SEM)
4.1.2 BET Analysis
4.1.3 CHN Elemental Analyzer
4.1.4 Energy Dispersive X-Ray (EDX)
4.1.5 Fourier Transform Infrared Spectroscopy (FTIR)
4.1.6 Thermogravimetric Analysis (TGA)
4.1.7 X-Ray Diffraction Analysis (XRD)
4.1.8 Point Zero Charge (pHpzc) of QPKS
4.1.9 Surface Chemistry
4.1.10 Chemical Composition
4.1
4.2
4.3
4.4
4.6
4.7
4.8
4.9
4.10
4.11
4.2 Single System
4.2.1 Effect of Mercerization
4.12
4.13
4.2.2 Effect of NaOH in Quaternization Reaction 4.14
4.2.3 Effect of Particle Size 4.14
4.2.4 Effect of Initial pH 4.16
4.2.5
4.2.6
Effect of Dosage
Equilibrium Studies
4.17
4.18
4.2.7 Kinetic Studies 4.21
4.2.8 Thermodynamic Studies 4.26
4.3
Artificial Neural Network (ANN) Modeling on Binary System
4.3.1 Effect of Parameters
4.3.2 Effect of Initial Dye Concentration
4.3.3 Effect of Initial pH
4.28
4.31
4.32
4.33
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4.4
4.3.4 Effect of Adsorbent Dosage
Regeneration
4.34
4.35
5 CONCLUSIONS AND SUGGESTIONS 5.1
5.1 Conclusions
5.2 Recommendations
REFERENCES
5.1
5.3
R.1
APPENDICES A1.1
BIODATA OF STUDENT
LIST OF PUBLICATION
C.1
C.2