UNIVERSITI PUTRA MALAYSIA ADSORPTION OF REACTIVE DYES FROM AQUEOUS SOLUTIONS BY QUATERNIZED PALM KERNEL SHELL KOAY YIN SHIN FK 2013 22
ADSORPTION OF REACTIVE DYES FROM AQUEOUS SOLUTIONS BY QUATERNIZED PALM KERNEL SHELL KOAY YIN SHIN MASTER OF SCIENCE UNIVERSITI PUTRA MALAYSIA 2013
ADSORPTION OF REACTIVE DYES FROM AQUEOUS SOLUTIONS BY QUATERNIZED PALM KERNEL SHELL By KOAY YIN SHIN Thesis Submitted to the School of Graduate Studies,, in Fulfilment of the Requirements for the Degree of Master of Science May 2013
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. Copyright
Abstract of thesis presented to the Senate of in fulfilment of the requirement for the degree of Master of Science. ADSORPTION OF REACTIVE DYES FROM AQUEOUS SOLUTIONS BY QUATERNIZED PALM KERNEL SHELL Chairman: Faculty: By KOAY YIN SHIN May 2013 Intan Salwani Binti Ahamad, PhD 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 ii
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 pseudosecond-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. iii
Abstrak tesis yang dikemukakan kepada Senat sebagai memenuhi keperluan untuk ijazah Master Sains. PENJERAPAN PEWARNA REAKTIF DARIPADA LARUTAN AKUES DENGAN MENGGUNAKAN CENGKERANG ISIRONG KELAPA SAWIT YANG TELAH DIKUATERNISASI Pengerusi: Fakulti: Oleh KOAY YIN SHIN Mei 2013 Intan Salwani Binti Ahamad, PhD 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 iv
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. v
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. vi
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 [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 (Chairman) Mohd Halim Shah bin Ismail, PhD Associate Professor Faculty of Engineering (Internal Examiner) Shafreeza binti Sobri, PhD Senior Lecturer Faculty of Engineering (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 Date: vii
This thesis submitted to the Senate of 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 (Chairman) Luqman Chuah Abdullah, PhD Professor Faculty of Engineering (Member) Thomas Choong Shean Yaw, PhD, IR Professor Faculty of Engineering (Member) BUJANG BIN KIM HUAT, PhD Professor and Dean School of Graduate Studies Date: viii
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 or other institution. KOAY YIN SHIN Date: 20 May 2013 ix
TABLE OF CONTENTS ABSTRACT ABSTRAK ACKNOWLEDGEMENTS APPROVAL DECLARATION LIST OF TABLES LIST OF FIGURES LIST OF NOTATIONS / SYMBOLS LIST OF APPENDICES CHAPTER Page ii iv vi vii ix xiii xv xvii xviii 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 2.19 2.8.2 Freundlich Isotherm 2.20 2.8.3 Sips Isotherm 2.21 2.8.4 Redlich-Peterson Isotherm 2.22 2.8.5 Error Analysis 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 x
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 3.3 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 4.1.2 BET Analysis 4.2 4.1.3 CHN Elemental Analyzer 4.3 4.1.4 Energy Dispersive X-Ray (EDX) 4.4 4.1.5 Fourier Transform Infrared Spectroscopy (FTIR) 4.6 4.1.6 Thermogravimetric Analysis (TGA) 4.7 4.1.7 X-Ray Diffraction Analysis (XRD) 4.8 4.1.8 Point Zero Charge (ph pzc ) of QPKS 4.9 4.1.9 Surface Chemistry 4.10 4.1.10 Chemical Composition 4.11 4.2 Single System 4.12 4.2.1 Effect of Mercerization 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 4.28 4.3.1 Effect of Parameters 4.31 4.3.2 Effect of Initial Dye Concentration 4.32 4.3.3 Effect of Initial ph 4.33 3.5 3.5 3.6 3.6 3.6 3.7 3.7 xi
4.4 4.3.4 Effect of Adsorbent Dosage Regeneration 4.34 4.35 5 CONCLUSIONS AND SUGGESTIONS 5.1 5.1 Conclusions 5.1 5.2 Recommendations 5.3 REFERENCES R.1 APPENDICES A1.1 BIODATA OF STUDENT C.1 LIST OF PUBLICATION C.2 xii