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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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Page 1: UNIVERSITI PUTRA MALAYSIApsasir.upm.edu.my/47862/1/FK 2013 22R.pdf · UNIVERSITI PUTRA MALAYSIA KOAY YIN SHIN FK 2013 22 ADSORPTION OF REACTIVE DYES FROM AQUEOUS SOLUTIONS ... masa

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