universiti putra malaysia preparation and characterization of
TRANSCRIPT
UNIVERSITI PUTRA MALAYSIA
PREPARATION AND CHARACTERIZATION OF MONTMORILLONITE MEMBRANE FOR REMOVAL OF LEAD AND CHROMIUM
IONS FROM AQUEOUS SOLUTIONS
NURUL AIN BINTI A. TALIB
FS 2013 7
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PREPARATION AND CHARACTERIZATION OF MONTMORILLONITE
MEMBRANE FOR REMOVAL OF LEAD AND CHROMIUM IONS FROM
AQUEOUS SOLUTIONS
By
NURUL AIN BINTI A. TALIB
Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia, in
Fulfilment of the Requirements for the Degree of Master of Science
April 2013
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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
PREPARATION AND CHARACTERIZATION OF MONTMORILLONITE
MEMBRANE FOR REMOVAL OF LEAD AND CHROMIUM IONS FROM
AQUEOUS SOLUTIONS
By
NURUL AIN BINTI A. TALIB
April 2013
Chairman : Associate Professor Mansor Bin Ahmad, PhD
Faculty : Science
Fabrication of membrane from montmorillonite was carried out for removal of metal
ions from aqueous solutions. The formation of membrane was optimized based on
materials compositions, sintering time and sintering temperature. Montmorillonite KSF
(MMT) was used as replacement for the usually expensive materials in membrane
fabrication to reduce the cost of production. Each membrane was prepared by suspension
of powder materials method. The paste casting was done with different compositions of
MMT along with other relatively inexpensive materials which were sand quartz, calcium
carbonate, sodium carbonate and boric acid. All membranes were characterized by
Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA),
differential thermal analysis (DTA), scanning electron microscopy (SEM), X-ray
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diffraction (XRD), nitrogen adsorption-desorption (BET analyzer) and hardness test.
Metal ions concentration in solutions was determined by inductively coupled plasma
optical emission spectrometry (ICP-OES).
Compared to usually high sintering temperature needed in regular preparation of ceramic
membrane, this membrane was fabricated at temperature below 1000 °C, which was
considered low for inorganic membrane preparation. TGA and DTA results showed that
as the sintering time and temperature increased, the thermal stability of membrane also
increased. No more degradation of samples was identified after 5 h sintering. By
incorporating higher percentages of MMT, the stability of the membranes increased. For
samples containing 35% MMT and above, 850 °C sintering temperature was sufficient to
produce membranes stable for application up to 1000 °C.
The porosity of membrane also increased with sintering temperature. However, as the
MMT composition in membrane increased, the porosity decreased due to consolidation
of materials at high temperature. Sample 35% MMT sintered at 900 °C was identified as
suitable microfiltration membrane based on its maximum pore size 2013 Å (201.3 nm),
while main pore distribution was centered at 34.3 Å (3.4 nm) as determined by nitrogen
adsorption-desorption analysis.
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Lead ions were successfully removed from aqueous solution up to 98% by hybridization
of adsorption-microfiltration technique at pH 6.1 with 0.8 wt% (w/v) ferric oxide, Fe2O3,
as the adsorbent. 92% of chromium ion was also successfully removed at pH 6.0 using
the same technique. Other than above metal ions removal, there are also possibilities for
separation between metal ion such as Pb2+
ion and Cu2+
ion, and Cr2+
ion and Cu2+
ion.
The relatively low cost MMT membrane with sufficient membrane properties is a good
material for metal ions removal from aqueous solutions. The hybridization of
adsorption-microfiltration technique has high potential application for toxic metal ions
removal from wastewater system containing metal waste such as electroplating industrial
waste.
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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai
memenuhi keperluan untuk ijazah Master Sains
PENYEDIAAN DAN PENCIRIAN MEMBRAN MONTMORILONIT UNTUK
PENYINGKIRAN ION PLUMBUM DAN ION KROMIUM DARIPADA
LARUTAN AKUEUS
Oleh
NURUL AIN BINTI A. TALIB
April 2013
Pengerusi : Profesor Madya Mansor Bin Ahmad, PhD
Fakulti : Sains
Fabrikasi membran daripada montmorillonit telah dilakukan untuk digunakan dalam
penyingkiran ion logam daripada larutan akueus. Pembentukkan membran telah
dioptimumkan berdasarkan komposisi bahan, tempoh sinter dan suhu sinter.
Montmorilonit KSF (MMT) telah dipilih sebagai pengganti kepada bahan yang biasanya
mahal dalam pembikinan membran untuk mengurangkan kos pengeluaran. Setiap
membran dihasilkan menggunakan kaedah suspensi bahan serbuk. Pembentukan pes
dilakukan dengan komposisi MMT yang berbeza bersama-sama bahan kos rendah yang
lain iaitu pasir quartz, kalsium karbonat, natrium karbonat dan asid borik. Pencirian
semua membran dilakukan menggunakan spektroskopi inframerah transformasi Fourier
(FT-IR), analisis termogravimetri (TGA), analisis pembezaan terma (DTA), mikroskopi
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pengimbasan elektron (SEM), pembelauan sinar-X (XRD), analisis luas permukaan dan
keliangan (analisis BET) dan ujian kekerasan. Kepekatan ion logam dalam larutan
akueus ditentukan menggunakan spektrometri pemancaran optik plasma berganding aruh
(ICP-OES).
Berbanding dengan kebiasaan suhu sinter yang tinggi diperlukan untuk penyediaan
membran seramik, membran ini dihasilkan pada suhu kurang daripada 1000 °C, yang
mana dianggap rendah untuk penyediaan membran bukan organik. Pencirian melalui
TGA and DTA menunjukkan bahawa apabila tempoh dan suhu sinter ditingkatkan,
kestabilan terma membran meningkat. Tiada lagi proses degradasi dikenalpasti selepas
sampel disinter selama 5 jam. Peratusan MMT yang tinggi turut meningkatkan
kestabilan membran. Bagi membran yang mengandungi 35% MMT dan ke atas, suhu
sinter 850 °C sudah mencukupi untuk menghasilkan membran yang stabil untuk aplikasi
sehingga 1000 °C.
Bilangan keliangan membran turut bertambah dengan pertambahan suhu sinter. Walau
bagaimana pun, apabila komposisi MMT dalam membran bertambah, bilangan
keliangannya berkurangan disebabkan oleh penggabungan bahan pada suhu tinggi.
Sampel 35% MMT yang disinter pada 900 °C telah dikenalpasti sesuai sebagai membran
mikropenurasan berdasarkan saiz liang maksimumnya iaitu 2013 Å (201.3 nm),
manakala taburan liang utamanya berpusat pada 34.3 Å (3.4 nm) seperti yang ditentukan
dengan menggunakan analisis penjerapan-penyahjerapan nitrogen.
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Ion-ion plumbum telah berjaya disingkirkan dari larutan akues sehingga 98%
menggunakan teknik hibrid penjerapan-mikropenurasan pada pH 6.1 dengan 0.8 wt%
(w/v) ferik oksida, Fe2O3, sebagai penjerap. Sebanyak 92% ion kromium turut berjaya
disingkirkan pada pH 6.0 menggunakan teknik yang sama. Selain daripada penyingkiran
ion logam tersebut di atas, terdapat juga kebarangkalian untuk pemisahan antara ion,
seperti pemisahan antara ion Pb2+
dengan ion Cu2+
, dan antara ion Cr2+
dengan ion Cu2+
.
Membran MMT berkos rendah yang cukup dengan sifat membran ini merupakan bahan
yang sesuai untuk penyingkiran ion logam daripada larutan akueus. Teknik hibrid ini
mempunyai potensi aplikasi yang tinggi untuk penyingkiran logam toksik daripada
sistem air buangan yang mengandungi buangan logam seperti bahan buangan industri
penyaduran.
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ACKNOWLEDGEMENTS
I would like to express my sincere gratitude to my supervisor Assoc. Prof. Dr. Mansor
Bin Ahmad for his supervision, valuable advices, idea, guidance, support and
encouragement throughout this study. Also thanks to Prof. Dr. Md. Jelas Bin Haron and
Prof. Dr. Mohd. Zobir Bin Hussein.
Special thanks must go to my friends, labmates, and members of Polymer Group for
their help, consideration, knowledge sharing and support during my study period. Not
forgotten to all Faculty of Science staff that had given me their best technical expertise
and help. Thanks to everyone who had helped me directly or indirectly in completion of
this project.
Last but not least, I also would like to express my uncountable thanks to my parents,
family and bestfriends for their endless pray, support, patients, faith, encouragement and
understanding that give me strength throughout this study.
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I certify that an Examination Committee has meet on date of viva voce to conduct the
final examination of Nurul Ain Binti A. Talib on her Master of Science thesis entitled
“Preparation and Characterization of Montmorillonite Membrane for Removal of Lead
and Chromium Ions from Aqueous Solutions” in accordance with Universiti Pertanian
Malaysia (Higher Degree) Act 1980 and Universiti Pertanian Malaysia (Higher Degree)
Regulations 1981. The Committee recommends that the student be awarded the relevant
degree.
Members of the Examination Committee were as follows:
Mahiran bt Basri, PhD
Prof. Dr.
Faculty of Science
Universiti Putra Malaysia
(Chairman)
Nor Azowa bt Ibrahim, PhD
Dr.
Faculty of Science
Universiti Putra Malaysia
(Internal Examiner)
Zulkarnain b Zainal, PhD
Prof.Dr.
Faculty of Science
Universiti Putra Malaysia
(Internal Examiner)
Mohd. Asri Nawi, PhD
Assoc.Prof.Dr
Universiti Sains Malaysia
(External Examiner)
_____________________________
NORITAH OMAR, PhD
Assoc. Professor and Deputy Dean
School of Graduate Studies
Universiti Putra Malaysia
Date: 2 August 2013
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This thesis was submitted to the Senate of Universiti Putra Malaysia and has been
accepted as fulfillment of the requirement for the degree of Master of Science. The
members of the Supervisory Committee were as follows:
Mansor Bin Ahmad, PhD
Associate Professor
Faculty of Science
Universiti Putra Malaysia
(Chairman)
Md. Jelas Bin Haron, PhD
Professor
Faculty of Science
Universiti Putra Malaysia
(Member)
Mohd. Zobir Bin Hussein, PhD
Professor
Faculty of Science
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 acknowledge. I also declare that it has not been previously, and is not
concurrently, submitted for any other degree at Universiti Putra Malaysia or at any other
institutions.
_________________________
NURUL AIN BINTI A. TALIB
Date: 23 April 2013
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TABLE OF CONTENTS
Page
ABSTRACT ii
ABSTRAK v
ACKNOWLEDGEMENTS viii
APPROVAL ix
DECLARATION xi
LIST OF TABLES xv
LIST OF FIGURES xvi
LIST OF ABBREVIATIONS xix
CHAPTER
1 INTRODUCTION
1.1 Background of study 1
1.2 Statement of problems 5
1.3 Scope of Study 6
1.4 Objectives of studies 7
2 LITERATURE REVIEW
2.1 Membrane 8
2.2 Membrane technology 11
2.3 Inorganic polymer membrane/Ceramic membrane 14
2.4 Materials in ceramic membrane 15
2.4.1 Clay membrane 15
2.4.2 Montmorillonite 16
2.4.3 Quartz 17
2.4.4 Calcium carbonate 18
2.4.5 Boric acid 18
2.4.6 Sodium carbonate 19
2.5 Method for Preparation of Ceramic Membrane 20
2.5.1 Effect of Montmorillonite 22
2.5.2 Effect of Sintering Temperature 23
2.5.3 Effect of Sintering Time 25
2.6 Microfiltration Ceramic Membrane and its Application 25
2.7 Hybrid Adsorption and Microfiltration 27
2.7.1 Ferric oxide as adsorbent 29
2.7.2 Effect of pH 30
2.7.3 Effect of Amount of Adsorbent 31
2.7.4 Effect of Contact Time 32
2.7.5 Effect of Temperature 32
2.7.6 Kinetic study model 33
2.8 Separation of lead by adsorption and microfiltration 34
membrane
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2.9 Separation of chromium by adsorption and 35
microfiltration membrane
3 MATERIALS AND METHODS
3.1 Materials 37
3.2 Preparation of Membrane 39
3.3 Optimization study of membrane preparation 40
3.3.1 Effect of paste composition 40
3.3.2 Effect of sintering time 42
3.3.3 Effect of sintering temperature 42
3.4 Characterization techniques of membrane 43
3.4.1 Fourier Transform Infrared Spectroscopy 43
3.4.2 Thermogravimetric Analysis 43
3.4.3 Differential Thermal Analysis 43
3.4.4 X-ray Diffraction 44
3.4.5 Scanning Electron Microscopy 44
3.4.6 Nitrogen adsorption-desorption analysis 45
3.4.7 Hardness test 45
3.5 Screening of removal of metal ions by membrane 45
3.6 Evaluation of membrane for separation of lead and 47
chromium ions
3.6.1 Effect of pH 47
3.6.2 Effect of time 48
3.6.3 Effect of amount of adsorbent 48
3.6.4 Effect of temperature 49
3.7 Analysis of metal solution 49
3.7.1 Inductively Coupled Plasma-Optical 49
Emission Spectrometer
3.7.2 pH determination 49
4 RESULTS AND DISCUSSION
4.1 Preparation of Membrane 50
4.2 Characterization of membrane 52
4.2.1 Fourier Transform Infrared Spectroscopy 52
4.2.2 Thermogravimetric Analysis 59
4.2.3 Differential Thermal Analysis 73
4.2.4 X-ray Diffraction 83
4.2.5 Scanning Electron Microscopy 88
4.2.6 Nitrogen adsorption-desorption analysis 93
4.2.7 Hardness test 100
4.3 Screening of removal of metal ions by membrane 102
4.4 Evaluation of membrane for separation of lead and 104
chromium ion
4.4.1 Effect of pH 104
4.4.2 Effect of amount of adsorbent 106
4.4.3 Effect of time 106
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4.4.4 Kinetics Model 109
4.4.5 Effect of temperature 111
5 CONCLUSION AND RECOMMENDATIONS 113
REFERENCES 116
APPENDICES 124
BIODATA OF STUDENT 127