universiti putra malaysia preparation and characterization of

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


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


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


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


(Internal Examiner)

Zulkarnain b Zainal, PhD

Prof.Dr.

Faculty of Science


(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


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


(Chairman)

Md. Jelas Bin Haron, PhD

Professor

Faculty of Science


(Member)

Mohd. Zobir Bin Hussein, PhD

Professor

Faculty of Science


(Member)

____________________________

BUJANG BIN KIM HUAT, PhD Professor and Dean

School of Graduate Studies


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.

_________________________


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


3.6.2 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


4.4.2 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

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