UNIVERSITI PUTRA MALAYSIA
KINETICS AND MECHANISM OF AMMONIUM ION ADSORPTION USING NATURAL ZEOLITE - MORDENITE
NORMALA BT HALIMOON
FSMB 2001 32
KINETICS AND MECHANISM OF AMMONIUM ION ADSORPTION USING NATURAL ZEOLITE - MORDENITE
By NORMALA BT HALIMOON
Thesis Submitted in Fulfilment of the Requirement for the Degree of Master of Science in the Faculty of Food Science and Biotechnology University Putra Malaysia February 2001
DEDICATION
Bismillahirrahmannirahim,
Alhamdullillah.
Specially dedicated to:
Q4ty 9Y�#1N;'M' @ mol P.O?'. glfolta»wd oYmtaii rein Q91tdal dYCu0n oily 9/O'mmdke CJllem6tmJ @ pp� � P.O�. � rein � (0) pp� olladya P.O?'. oIw�, rein �M(pn
flitpMp?, ({jJ 97falimoo1'l rein QYtl1md oily ?noMp?, @ 'mahamah ??i3t oltohd
Q
- Qx/IImll J(:b/in:J4 - cs;1;;my/--/('1u/ - c£ind Q4{'Zf .;fu'evd?((m4 @ QYOuu'T(I/ 0YC,Mli QYCl4na,rad4r.·# Thanks for your loving support during the difficult time.
Amin.
ii
Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfilment of the requirement for the degree of Master of Science KINETICS AND MECHANISM OF AMMONIUM ION ADSORPTION USING NATURAL ZEOLITE- MORDENITE By NORMALA BT HALIMOON February 2001 Chairman: Faculty:
Professor Dr . Mohamed Ismail Bin Abdul Karim Food Science and Biotechnology
Mordenite , one of the natural zeolites , has the capacity to remove ammonium ion from wastewaters through adsorption phenomenon. This study is a preliminary work of using mordenite to remove ammonium in effluent for tertiary treatment. The feasibility of using mordenite to remove ammonium ion in aqueous solution was carried out using shake flask , stirred tank batch reactor and packed-bed
column experiments.
The effect of mordenite particle
size,
ammonium concentration, mordenite concentration, pH, temperature and degree of agitation on the efficiency of adsorption were investigated. The kinetics of ammonium ion sorption was determined using Langmuir and Scatchard sorption isotherm models . The mechanism of ammonium adsorption was investigated using FTIR and electron microscope.
In shake flask experiment under equilibrium conditions , the efficiency of ammonium ion removal was optimum at resident time of 6 hours , for granules of
iii
75 J.tm size, in water containing less than 6 mg/L ammonium ion, in mordenite concentration of 3 giL, at room temperature, with agitation of 200 rpm and near neutral initial pH (6. 5-7.5). Ammonium ion removal of 94 % (2 .49 mg/g uptake) was achieved when 50 giL mordenite was used to remove 1 00 mg/L ammonium concentration under optimum conditions . The sorption isotherm kinetic data of ammonium ion by mordenite fitted well to Langmuir model but did not fit well to Scatchard plot. SEM and FTIR data indicated that ammonium ion was adsorbed on the mordenite particle. When 2 L stirred tank: reactor was used as a contactor, the ammonium uptake capacity ranging from 85-96 % was obtained at agitation speed of 200 rpm, concentration of mordenite of 2 . 67 gIL and 6 mg/L ammonium concentration. Absolute removal of ammonium from solution was achieved when fixed packed-bed column was used as a contactor at low flowrate (2 mLimin) and increased weight of mordenite in the column (48 g), which show less than 5 mglL ammonium in the effluent before breakthrough was achieved when 1 00 mg/L ammonium concentration was used . Desorption experiments showed that 37 % ammonium recovery in the shake flask and 80-98 % in the column contactor . From the study, the result indicated that mordenite has a potential to be promoted as adsorbent that could be used to removed ammonium from solution and can be apply for wastewater treatment.
iv
Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai memenuhi keperluan Ijazah Master Sains KINETIK DAN MEKANISMA PENJERAPAN ION AMMONIUM OLEH ZEOLITE SEMULAJADI- MORDENITE Oleh NORMALA BT HALIMOON Februari 2001 Pengerusi:
Profesor Dr. Mohamed Ismail Bin Abdul Karim
Fakulti:
Sains Makanan dan Bioteknologi
Mordenite adalah satu daripada zeolite semulajadi yang mempunyai keupayaan untuk memindahkan ion ammonium dari air sisa secara penjerapan. Kajian ini adalah asas untuk memindahkan ammonium menggunakan mordenite dalam merawat air sisa peringkat ketiga . Kebolehan mordenite memindahkan ion ammonium dalam larntan akuas telah dijalankan dalam kelalang pengoncang , reaktor pengaduk dan turns 'packed-bed' . Kesan kecekapan penjerapan telah dijalankan ke atas saiz partikal , kepekatan ammonium, kepekatan mordenite, pH larutan, suhu dan darjah pengacauan pada keseimbangan. Kinetik jerapan ion ammonium ditentukan menggunakan model isotherma jerapan seperti Langmuir dan Scatchard . Manakala mekanisma
penjerapan ditentukan menggunakan
FTIR
dan mikroskop elektron.
Dalam ujikaji kelalang
penggoncang pada keseimbangan, kecekapan
penjerapan adalah optima pada masa 6 jam , partikal size 75 pm, kepekatan ion ammonium < 6 mg/L, kepekatan mordenite 3 gIL, pada suhu bilik 3 0°C,
v
pengacauan 200 rpm dan pH awal hampir natural (6 . 5-7 .5). Pemindahan ion ammonium mencapai 94 % (2 .49 mg/g) menggunakan 50 giL mordenite untuk memindahkan 1 00 mg/L ammonium pada keadaan optima.
Data kinetik
penjerapan isoterma ion ammonium oleh mordenite dari ujikaji menepati model Langmuir tetapi tidak menepati model Scatchard .
Data SEM dan FtiR
menunjukkan ammonium terjerap di atas partikal mordenite . Apabila tangki pengaduk 2 L digunakan sebagai kontaktor, pengambilan ammonium paling baik dalam julat 85-96 % diperolehi pada kelajuan pengacauan 200 rpm, kepekatan mordenite 2 . 67 giL dan kepekatan ammonium 6 mg/L. Pemindahan ammonium dalam larutan paling berkesan dicapai apabila turus 'packed bed' digunakan sebagai kontaktor pada kadar alir yang rendah (2 mLimin) dan pada berat mordenite yang paling tinggi dalam turus (48 g), yang menunjukkan kurang daripada 5 mg/L ammonium dalam larutan akhir sebelum 'breakthrough' dicapai pada kepekatan awal 1 00 mg/L. Ujikaji nyah-jerapan menunjukkan 37 % ammonium diperolehi dalam kelalang penggoncang dan 80-98 % dalam turus . Dari ujikaji ini , menunjukkan mordenite berpotensi sebagai bahan penjerap untuk memindahkan ammonium dalam larutan dan boleh diagihkan untuk merawat air sisa.
vi
ACKNOWLEDGEMENTS
B ismillahirrahmannirahim, Firstly I would like to express my sincere appreciation and thanks to my chairman, Prof. Dr. Mohamed Ismail Bin Abdul Karim and members of supervisory committee Assoc . Prof. Dr Arbakadya Bin Ariff and Assoc. Prof. Dr. Mohd Ali Bin Hassan for their suggestions , advice, support and guidance throughout my study .
I give thanks to merciful Allah for giving me the strengths to complete this study. My appreciation and gratitude go to my father , Haj i Halimoon Bin Hamid and my mother, Hajjah Rahamah Bt Mohd for their constant support, love and for being so patient throughout my graduate study . My heartfelt thanks to Khairul Husni bin Kamaruddin (Abg) for his supports , wonderful patience and care . Thank you very much .
Sincere thanks and gratitude are also extended to all staff of Fermentation Technology Laboratory especially to Mr. Rosli Aslim, Mrs . Aluyah Marzuki, Mrs . Renuga alp Panjamurti and Mrs Latifah Husin for their help during to using instrument and glassware for my lab work study . Also to all my postgraduate friends : Miss Anisah Hasan, Miss Norrizan Abdul Wahab, Miss Noranizam Azali, Miss Julia, Miss Suhaila, Miss Azlian, Miss Madihah, Miss Nor'aini, Miss Jameah and Mr. Khaw Teik Seong of the Department of Biotechnology-UPM for their help towards the success of this project.
vii
I certify that an Examination Committee met on 1 3 th February 2001 to conduct the final examination of Normala Bt Halimoon on her Master of Science thesis entitled "Kinetics and Mechanism of Ammonium ion Adsorption Using Natural Zeolite - Mordenite" in accordance with Universiti Pertanian Malaysia (Higher Degree) Act 1 980 and Universiti Pertanian Malaysia (Higher Degree) Regulations 1 98 1 . The committee recommends that the candidate be awarded the relevant degree. Members of the Examination Committee are as follows:
BADLISHAH SHAM BAHARIN , P . Eng . Associate Professor Department of Food Technology , Faculty of Food Science and Biotechnology , Universiti Putra Malaysia. (Chairman) MOHAMED ISMAIL ABDUL KARIM , Ph. D . Professor/ Head Department of Biotechnology, Faculty of Food Science and Biotechnology , Universiti Putra Malaysia . (Member) ARBAKARIYA ARIFF, Ph. D . Associate Professor Fermentation Technology Center, B ioscience Institute , Universiti Putra Malaysia. (Member) MOHD ALI HASSAN , Ph . D . Associate Professor Department of Biotechnology , Faculty of Food Science and Biotechnology , Universiti Putra Malaysia . (Member)
. GHAZALI MOHAYIDIN, Ph. D , Professor/Deputy Dean o f Graduate School , Universiti Putra Malaysia Date: 2 7 MAR 2001,
viii
This thesis submitted to the Senate of Universiti Putra Malaysia has been accepted as fulfilment of the requirement for the degree of Master of Science .
MOHD. GHAZALI MOHAYIDIN, Ph.D
Professor Deputy Dean of Graduate School Universiti Putra Malaysia
Date:
1 4 JUN
2001
ix
DECLARATION
I hereby declare that the thesis is based on my original work except for quotations and citations, which have been duly acknowledged. I also declare that it has not been previously or concurrently submitted for any other degree at UPM or other institutions .
NORMALA BT HALIMOON Date : 2 7 MAR 2001
x
TABLE OF CONTENTS Page ii
DEDICATION... ... ... ... ... . , . ... ... ... ... ... '" ........ .. , ... ... ..... , '" .... ABSTRACT ..... , ... ... ... . ,. '" ... ... '" '" '" ... ... ... ... ..... ... ... ... ... ....
iii
ABSTRAK... ... ... ... ...... ... ... ... ...... ... ... ...... ........... ......... ......
v
ACKNOWLEDGEMENTS... ............ ... ... ... ... ... ... ..... ... ...... . ..
vii
APPROVAL SHEETS . .. '" ... . , . ........ , .. , .. , ..... , " . ... ... ... ....... .. ' .
viii
DECLARATION FORM.. ... ... ... .. .. . . .. ...
x
.
.
.
.
LIST OF TABLES... .. , ...... ... ... ...... '" LIST OF FIGURES... .. ,
.
0 0 .
0 0 .
. . .
. . .
. . .
. . .
. . .
.
.. ..
XlV
... ... ... ... ...... .......... ,. '"
xv
......... ... ... ......... ... ... .... ... " ..... , .. , ... ..
LIST OF ABBREVIATIONS... ... ... ... ... ... ... ... ... ... ... ... ... ... .....
xvii
CHAPTER
2
INTRODUCTION ... .. , ... ... ... ... ... ... ... '" ... .............. , .. ,
1
LITERATURE REVIEW.. . ... .. . ... .. , ... ... ...... '" ... .. , '" .. , . 2.1 Water Pollution and Wastewater... ...... ...... ... ...... .....
5 5
Characteristic of the Wastewater .... " ....... .. , ...
6
2.2
Treatment of Wastewater... ... ......... ... ... ... ... ... .......
8
2.3
Ammonium Pollution in the Wastewater . . .. ... ... .. , ....
11
2.1.1
.
2.3.1 The Characteristic of Ammonium... ...... ... ... .....
15
Utilizing of Ammonium-Nitrification....... ,' .. , ...
16
2.3.2
2.4
.
2.3.3
Application of Ammonium in Industry... ... ... ....
19
2.3.4
Hazardous and Toxicity of Ammonium .. ... .. , ...
20
2.3.5
Method of Ammonium Removal from Wastewater
22
.
Zeolite .. . ..
...... ... ... '" ... ...
25
2.4.1
The History of Zeolite... .. . ... ... ... '" '" '" ... .....
26
2.4.2
Hydrothermal Zeolite Synthesis�Zeo1ite Formation
27
2.4.3
Hydrolysis... ... ...... ...... ...... ... ... ...... ... .......
28
2.4.4
Physical Structure of Zeolite ... ..
29
2.4.5
Structural Chemical Aspects of Zeolite... ... ... ....
31
Intracrystalline Diffusion... ... ... ...... ... ... ... ... ... 2.4.7 Nature of the Active Site... .... .. ... ... ... ... ...
33
,
. . .
. . .
. . .
.
.
.
.
.
.
. . .
. . .
. . .
. . .
.
.
.
0 0
,
. . .
"'
0 0 '
... '" .....
2.4.6
0 0 '
2.5
0 0 .
Mordenite... ......... ... ...... ... ... ... ... ... ... ... ... ... ... ..... 2.5.1 Properties of Mordenite...... ... .. , ... ... ... ... ... .... 2.5.2 Structure of Mordenite... ... ... ... ... ......... ... .....
33 36 36 40
2.5.3 Hydrogen Zeolite... ... ... ... ......... ... ... ... ... ... ... Adsorption of Adsorbates Using Zeolite... '" ... ... ... ..... ..
41
2.6
Carbon Adsorption... . ,. '" ... ... . ,.. ,. ... ... ... ........
45
2.7
Mechanism...... '" ... '" '" '" ......... ... ... ... ... ... .... ... ....
46
2.7.1 Adsorption... .................. ......... ......... ........
46
2.6.1
Ion-exchange...... ......... ...... ... ...... ......... ......
51
Kinetics of Adsorption Isotherm Parameter Estimation. . ,.
54
Langmuir Model... ... ... ... ... ... ... ... ... ... ... ... .....
55
2.7.2 2.8
42
.
2.8.1
xi
2.9
2.8.2 Scatchard Model...
2.9.1 2.9.2 2.9.3 3
......... ... ... ...... '" ... ... ..... 57
"
Regeneration... ... ... ... ...... ... ... .., .. , ...... '" .. , '"
Forward and Reverse�f1ow Regeneration... ... ... ... Other Uses of Zeolite ... .. , '" ... .., ... ... ... ... ... .....
58 60 63 64
GENERAL MATERIALS AND METHODS... '" '" ... '" ... '"
Preparation of Mordenite Particles. . . ... ... .. . ... ... ....., .....
66
3.1
66
Nessler Method...... ... . , . ... ... ... ... '" ........... , ...... ... . ,.
67
3.2 3.3 3.4 4
'
The Advantages of Using Zeolite... ... . . . ... ... ......... ... ...
Preparation of Ammonium Stock Solution... ... ... ... ... ..... 67 Experimental Design... '" ... ... '" ... ... ... ... ... ... ... ... .. , ...
68
KINETICS AND MECHANISM OF AMMONIUM ADSORPTION BY MORDENITE ... ... '" ... ... ... '" '" ... . ,. ... ... ... ... ... ..... .....
69
4.1
69
4.2
Introduction... '" ... .., ., .............. , . ... '" ... ... ... ... ... ..... Materials and Methods ......... .. , '" .... .. , ... '" .. , ., . ... ... " 4.2.1 SEM... ... ... ... . . . ... ... ... ... ........... . ... ...... ... ... 4.2.2 4.2.3
4.3
FTIR... .
.
... . ,. ... ... ... ... ... ... ... ... ... ... ... ... ... ...
Equilibrium removal of ammonium ion ... ... ... .....
Results and Discussions... . .... ... . . . . ... ... ... .. . . ... . ,. ... .
4.3.1
.
.
.
Effect on Ammonium Adsorption... . . ... ... ... ..... .
4.3.1.1 4.3.1.2
Time Course of Ammonium Adsorption..
Effect of Mordenjte Particle Size ... ... ....
Effect of Ammonium Concentration... .. . . 4.3.1.4 Effect of Mordenite Concentration.. . ... .. . 4.3.1.3
4.3.1.5
Effect of Temperature... ... ... ... '" ... ... ...
70 72 73 74 75 75 75 77 78 80 81
Effect of Agitation Speed... ... ... ... '" ... ... 83 4.3.l.7 Effect of Initial pH. .. ... . . . ... .. ... ..... . ... 84
4.3.l.6
.
4.3.1.8 Application of Optimum Condition... .. ...
88
Concentrations... ... . . .., .,. ... ...... ... ... ... ... . ,. ...
88
.
4.3.2 The Ratio oflnitial AmmoniumIMordenite .
Adsorption of Other Ions by Mordenite . . .. , ... . ,. . 4.3.4 Adsorption of Ammonium Other Adsorbent... ..... 4.3.3
4.3.5
4.3.6
.
Adsorption Kinetics. . . .. , ... ... ... ... ...... .. , ... ... ...
Langmuir Model... .. ... ...... ... ... ... ... ... ... ... .... Scatchard Model.. . ... ... .., '" ... ... '" ... ...... ... ... 4.3.8 SEM .. . ... ... ... ... ... ... ... ... ... ... ... ... .. , ... ... ... ... 4.3.9 FTIR... '" ... ... ... ... ... '" ....., ...... '" ... .., ... ... ... Conclusion ... ....... . . . . ... ... ... ... ... ... .. ... '" ... ... ... ... ... .
4.3.7
4.4
5
.
90 90
91
93 96 97 97 101
ADSORPTION OF AMMONIDM BY MORDENITE USING STIRRED TANK BATCH REACTOR . ..... .. , .,. ... ....... .....
5.1 5.2
Introduction...... ... . . ... . ,. ... ... . .. ... ... ... ... ... ... ... ... ... .
103
103
Materials and Methods ... ... '" ... ... '" ... ... ... ... ... ... ... ..
106
5.2.1
106
5.2.2
Effect of Agitation Speed ... ... . . ...... ... ... ... ... ... .
Effect of Mordenite and Ammonium Concentrations 106
xii
5.2.3 Adsorption with Sequential Feeding... ..... ...... ... ... 5.3
107
Results and Discussions... ." ... ... ... ... ... ... ... ... ... ... .....
108
5.3.1 Effect of Agitation Speed...... ... ... " ... ... ... ......
108
.
110 Effect of Ammonium Concentration ......, ... '" ..... 111 113 5.3.4 Final pH of Ammonium Adsorption... ... ... ... ..... 5.3.5 Ammonium Adsorption using Sequential Feeding 114 Reactor .. . ... ... .,. '" ... ...... ...... ... '" ... ... ... ... ... Conclusion... ... ... ...... .. , ... ... '" ...... ... ... ... ... ... ... ... ... 117 5.3.2 Effect of Mordenite Concentration... ... ... ... ... .... 5.3.3
5.4
6
REMOVAL OF AMMONIUM FROM SOLUTION USING PACKED-BED COLUMN...... ......... ... ... ..... ..... .............
118
6.1
Introduction ...... ... ... ... ... . . ... ... ........ .., ... ... . ,. ... .... .
118
6.2
Materials and Methods... ... .,. ....., .,. ..........., ... ...... ...
121
6.3
Results and Discussions .. ......... .. ... .. .. '" ... ... ... .. ,
122
6.3.1 Effect of Flow Rate .. ... ... ... ... ....... ... ... ... ... ....
122
.
.
.
.
.
.
.
.
.
.
6.4
7
6.3.2 Effect of Weight of Mordenite in the Column.......
125
6.3.3 Final pH of Ammonium Adsorption in the Column..
127
Conclusion... ... ... ... ... ... ... ... ... ... ... ... ... ...... ... ... ... ...
129
DESORPTION IN THE SHAKE FLASK AND FIXED PACKED-BED COLUMN... ...... ...... ... ...... ...... ...... ... ... ... ... ..... ... . . ... ...... 130 7.1 Introduction...... ... .... ... ... ... ...... '" .., ... ... ... ... ... ... ... .. , 130 .
7.2
Materials and Methods ... ... ... ... ... '" ... ... ... .., ... ... ... '" ... 7.2.1 Shake Flask Desorption. . .. .... ......... ... ... ... ..... ... ,
13 1
7.2.2
Column Desorption... . . ... ...... ... ... ... '" ... ... ... ....
131
7.2.3 Percent Recoveries........ , ...... ... ... ... ... '" ...... '" ..
132
.
8
131
.
7.3
Results and Discussions... '" ...... ... ... ... ... ... ... ... ... ... ....
132
7.4
Conclusion... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ....
135
GENERAL DISCUSSIONS, CONCLUSIONS AND RECOMMENDATIONS...... ... ... ... ... ...... ... ... ... ...... ... ... . 8.1 General Discussions... ... ... '" ... ... '" ... '" ... ... ... .., ... .... 8.2 General Conclusions... . . .. . '" ... ... ... .............. ... ... .. , ... 8.3 Recomendations .. .. . . ... ...... .. .. .. .... .. , ... ... ... ... .
.
.
. .
. .
. . .
.
.
.
136 136 137
138
BffiLIOGRAPHY... ............ ... ... ... ... ...... ... ...... ...... ......... ... ...
139
APPENDIXES......... ..... , ... ... ... ... ... ... ... ... ... ... .. , ... ... ... ....... .....
150
VITA... ...... ...... ... ... ... ...... ... ...... ... ...... ... ... ... ... ... ... ... .. .... ..... 151 .
xiii
LIST OF TABLES Page
Table 1
The Characteristic of Typical Domestic Sewage at Five Countries.
2
Typical Removal Efficiencies of Total Nitrogen...
........ .....
11
3
Peninsular Malaysia: Rate of Change of Index of Ammoniacal Nitrogen ........................ ,
13
Proposed Interim National for Malaysia and DOE of Ammoniacal Nitrogen. . , . ... ...... ... ... ... .. , ............ ............ ... .. ,
14
5
Status of River Content Ammoniacal Nitrogen in Malaysia . . ,.. ,
14
6
The Other Used of Ammonium
'" '" .. , ... .. , ... ... .... ...
20
7
Elemental Composition of Natural Mordenite . . , ...... .........
38
8
The Characteristic of the Mordenite... ... ... ... ...... ... ... ...... .....
38
9
The Typical Characteristic of the Mordenite .
39
. . .
4
. .
10
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. .
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. ,
.
.
. . .
. . .. .
.
.
.
. . .
. .
.
.
. .
. . .
.
.
. .
,.... ... ... ......
6
Comparison of Ammonium Adsorption by Certain Zeolite With Other Adsorbates in Different Contactor... . ... ... ...... ... ... ..... ... ...
43
11
The Characteristic of Physical and Chemical Adsorption... ... ...
50
12
Parameter of Ammonium Adsorption Using Mordenite
. .......
72
13
The Stretching Mode of Ammonium with the Location of Adsorption . , ... ... '" '" ......... '" '" ... ...... ... ... .... ,.
.
. . .
. . .
. . .
. .
. .
.
. .
98
xiv
LIST OF FIGURES Figure
Page
1
Wastewater Nitrogen Cycles... ... ... ...... ... ... .. .... .. . .. . , . ... .. , .....
17
2
Diagram of the "Surface" of a Zeolite Framework. .. .. , ... ... ... ... ...
35
3
Schematic Representation of the Mordenite Structure... ... ... ... .....
37
4
Sheet Projection of Mordenite Showing 12- and 8- Member Rings..
37
5
The Adsorption of Ammonium on the Surface of Mordenite... ... ...
48
6
Mechanism of Ion Exchange of Zeolite in the Solution... ... ... ... ...
53
7
Experimental Design of Ammonium Adsorption at Different Parameter...... ... " .... ...... '" ... ... . , . ... ... ... ... ... ............... ... . , .
68
8
Effect of Time Course of Ammonium Adsorption in Shake Flask...
76
9
Effect of Particle Size of Mordenite .. . ... '" ...... '" ... ....... ... .. , ...
76
10
Effect of Ammonium Concentration ... ... ... ... ....... ... ...... ... .....
79
11
Effect of Mordenite Concentration... ... ......... ... ... ... ... ... ......
79
12
Effect of Temperature of Solution ... ... .. ...... ........ ... ... ... ... ...
82
13
Effect of Agitation Speed Ranges from 50-250 rpm of Ammonium Ion Adsorption using 3 gIL Mordenite ... ... ... ... .. , ." '" ... ... ... .. , ... .. 82
14
Ammonium Adsorption by Mordenite at Different of Initial pH....
15
Final pH of Ammonium Solution When Initial pH was Fixed at 6.5.. 86
16
The Ratio of Initial Ammonium 1M0rdenite Concentration on Ammonium Ion Uptake... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... .....
.
.
86
89
17
Adsorption of Various Ions (Ammonium, Phosphorus And sulfate) by Mordenite... ... ...... ... ... ... ... ... '" .. , ... ...... ..... , ." ... .. , ... ......... 89
18
Comparison Adsorption of Ammonium ion Using Other Adsorbent.
92
19
Linear Isotherm of Langmuir Adsorption of Ammonium ion Removal by Mordenite at Different Initial Concentration... .. .. , .,.
92
.
xv
20 Non linear Isothenn of Langmuir Adsorption of Ammonium Removal By Mordenite at Different Initial Concentrations , . . . . . . .. . . . . . .. 95 -
. . .
21
22
Non-linear Isotherm of Scatchard Model Adsorption Removal by Mordenite at Different Initial Concentrations... . . . ... ... . . . . . . ... ...
95
Typical SEM Micrographs of Natural (A) and Ammonium Exposed Mordenite (B)... ... ... ... ............ . . . . . . . . . .. . . . . . .. . . . . . . . . . . . . . . .
99
Photoacoutic FTIR of the Natural Mordenite (Bottom line) and Ammonium Exposed Mordenite (Top line) .. . . ... .. . .. ,.
1 00
.
23
.
.
.
24
26
.
29
. .
.
.
.
.
Ammonium Adsorption by Mordenite at Different Degree of Agitations using 2 L Stirred Tank Batch Reactor... .. ...
1 09
Different Mordenite Concentrations on Ammonium Uptake in the Stirred Tank Batch Reactor... . .. . . . . . . ... . . . . . . . . . . . . . . . . . . ... . . . ... . . . ... . . . 1 09 . .
Graph Different Concentrations of Ammonium Ion in the 2 L Stirred Tank Batch Reactor . . . . . . . ,. '" . " . . . ... . . . . . . . , . ... ...
1 12
Graph Adsorption of Ammonium by Mordenite with obtained the Final pH of Solution in the Stirred Tank Batch Reactor......
1 12
.
28
. .
. .
.
27
. .
The Mechanism of Ammonium Adsorption in the Stirred Tank Batch Reactor . . '" ... ... . ,. . .. . .. ... .. . ... " . . . , '" ..... . . . . . . . . , .... ... . " . . . 103 .
25
. .
.
.
.
. . .
. .
Adsorption of Ammonium using Mordenite in the Sequential Feeding 1 16 Reactor , . . .... ... . . . . . . . .. . , . ..... . . . .. '" '" ... . . . .. , '" . . . .. . . ,. ... ... . .
30
Graph Adsorption of Ammonium Using Mordenite in the Sequential Feeding Reactor. , '" . .. ... . .. . . . ... 1 16 . .
31
32
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. . . . . . . .
. . .
. . .
. .
Effect of Different Flow rates of Ammonium Solution in the Down-flow of Ammonium by Mordenite... 1 24
Packed-bed Column on Adsorption
Graph Different Weights and Heights ofMordenite in the Packed Bed Column. . . . .. . .. , .. . .. , . . . '" ...... .. , ... '" ... .. ...... , . . ... 124 . .
. .
. . .
.
.
. .
. . .
.
. .
33
Final pH of Ammonium Adsorption in the Packed-Bed Column...
1 28
34
Desorption of Loaded Mordenite using Na+ pH 1 2 in the Shake Flask Experiment... . . . . .. ... . .. . . . .. . .. . . . . .. . . .. .. , '" ... . .. ... . . .
133
Graph Desorption of Loaded Mordenite in Different Weights ofMordenite using Na+ pH 12 in the Packed-Bed Column... '"
133
35
...
xvi
LIST OF ABBREVIATIONS Ca
Calcium
Ceq
Adsorbate concentration at equilibrium (mgIL)
CI
Chlorine
Co
Initial adsorbate concentration (mg/L)
COD
Ch e mical oxygen demand
Cs
Cesium
DOE EC
Development of Environment
H
Hydrogen
H30
Hydrosonium ion
Environmental Center
�
Standard enthalpy
INWQS
The Interim National Water Quality Standard
K
Potassium Magnesium S odiu m
Mg Na NH3
...
NHt+
Nif
Ammonia gas
Ammonium ion nitrogen fixation
O&G
oil and grease
OR
Hydroxyl ion
pH
Hydrogen potential
Q
Experimental maximum ammonium ion adsorption (mg/g)
q qo
Amount of adsorbate adsorbed at time t (mg/g) Amount of adsorbate adsorbed per unit weight of adsorbent
at the beginning of adsorption process (mg/g) Amount of adsorbate adsorbed per unit weight of adsorbent at equilibrium (mg/g)
Rb SEM
Rubidium Surface Electron Microscope
t TMA
Time (minute) Tetramethylammonium
TOC
Total or gani c carbon
TSS
Total Suspended solid United S t ate
US Vo WHO
WQI
Volume of solution in the contactor (L) The World Health Organization Water Quality Index
Wt
Weight
Xo Zeo
Amount or weight of adsorbent in the contactor (g)
Zeolite
xvii
CHAPTER 1
INTRODUCTION
Nowadays our environments are exposed to polluted water such as domestic sewage, industrial and animal wastewaters . The basic component of municipal wastewater is a mixture of domestic wastewater with small amounts of industrial , agro-zoo-technical and housing wastewater (Negulescu, 1986) and its composition varies from town to town. This type of wastewater is harmful to the environment if discharged at high concentrations because it contains solids , heavy metals and other organic compounds . One of the compounds in municipal wastewater is ammonium, which is present in wastewater streams including municipal , industrial and animal wastewaters . The concentration of ammoniacal nitrogen in raw domestic wastewater ranged from 12 to 50 mg/L (Long , 1990) .
Generally, un-ionized ammonium enters water system as a pollutant and may become toxic to fish if nitrification does not convert the reduced form to nitrite and ultimately to nitrate (Thurston et aI . , 1 978). High amounts of ammonia in water supply also
increases the chlorine dosage required achieving free residual
chlorine in disinfection . When ammonia is present in the raw water at concentration higher than 0.3 mg/L, it can cause an unpleasant taste and odor when it is allowed to degrade anaerobically during treatment (Long, 1 990) . For this reason, ammonia in wastewater has to be reduced to concentration lower than
0 . 2 mg/L before discharging to the river . The DOE Standard A show that the level of ammoniacal nitrogen in water supply and fishery uses is < 0. 1 mg/L (Ministry of Agriculture, 1995 ) . Out of 53 rivers monitored in Malaysia, as analyzed based on ammonical nitrogen index (Environmental Quality Report, 1990) (42 %) was seriously polluted, 1 8 rivers (34 % ) were slightly polluted and 1 3 rivers (24 % ) were clean.
Activated carbon is known to effectively remove organic chemicals from water but ineffective for removing ammonia (Dawson et al. , 1 976) . Nitrification method, which has been used for treatment of wastewater is complicated and expensive . The usage of alum in the tap water treatment may end up as aluminium sulfate, which could endanger our health . Aluminium poisoning giving rise to tremors , loss of memory and jerking has first been reported in 192 1 and there is evidence that aluminium can be a neurotoxin (Albery , 1996) . Therefore, new alternative method to solve this problem of water treatment is urgently needed. There were some reports on the utilization of zeolite in wastewater treatment (Gottardi and Galli, 1 985). Zeolite can be used as adsorbent to remove ammonium from solution. The first commercial application of zeolites , based on adsorption phenomenon was for the removal of ammonia from the effluent as the secondary step in the treatment of domestic wastewater (Gottardi and Galli, 1985) .
Zeolites are inorganic aluminosilicate mineral containing exchangeable 2 2 alkali and alkaline earth metal cations (Ca + , Na + , K+ and Mg + ), that can be found
2
in cavities in basaltic rocks. It is a sedimentary rock that was formed from hydrothermal alteration of volcanic rock, which is widely found in Indonesia. Having a high selectivity for ammonium, mordenite were considered to be the optimal zeolite for the removal of ammonium. It is also considered as a molecular sieve due to the pores roughly from 3·10 A in the internal and external surface (Barrer, 1978). Zeolite is widely used in wastewater treatment because of its commercial factors such as 1) low cost, 2) good structural chemistry, 3) availability and 4) stability in a wide pH range 4-12. In 1970s, natural zeolites have became more significant to scientists who discover specifically their valuable chemical and physical properties, their large mineable deposits, and their potential application in industry and agricultural technology (Ouki
e/
al., 1994).
Zeolites are used to adsorb a variety of materials such as inorganic compound, heavy metal (Pb, Ni, Zn), radioactive and others compound in the wastewater.
In this study, the effectiveness of ammonium removal by mordenite, one of the zeolite
was
determined. In this case, mordenite is used as the adsorbent and
ammonium solution is the adsorbate. The kinetics of adsorption was studied using shake flask experiment. Experiments were undertaken to characterize the mordenite in terms of its rate of ammonium ion adsorption under various conditions. Equilibrium data from the uptake capacity of ammonium ions was analyzed using Langmuir and Scatchard adsorption isotherm modeL The mechanism of �+ adsorption in the mordenite was also studied usi ng electron microscope and FTIR technique. The adsorption of ammonium using reactor and
3
packed-bed column was investigated. Desorption of loaded mordenite using Na + pH 12 was also investigated. This parameter can be applied in wastewater treatment to remove ammonium in solution form.
The objectives of this study are: 1) To study the kinetics and mechanism of ammonium adsorption by mordenite using shake flask experiment. 2) To study the effect of different adsorption conditions especially particle size of mordenite, ammonium concentration, mordenite concentration, pH, temperature and agitation speed on the efficiency of ammonium adsorption by mordenite. 3) To compare the performance of ammonium adsorption by mordenite in different contactors (shake flask, batch stirred tank reactor, sequential feeding reactor and fixed packed-bed column).
4
CHAPTER 2
LITERATURE REVIEW
2. 1 Water Pollution and Wastewater
A supply of clean water is an essential requirement for the establishment and maintenance of a healthy community . Its acts not only as a source of potable water, but also provides valuable food supplements through supporting the growth of aquatic life, and also by its usage for irrigation in agriculture. Water, which has been utilized and discharged from domestic dwellings ,
institutions and
commercial establishments , leachates from solid waste disposal sites , together with water discharged from manufacturing industries , contains a large number of potentially harmful compounds . Consequently , if it is discharged directly into a watercourse, serious damage might result to the many forms of life which inhabit this water. To ensure that such problems are avoided or minimized, attention should be paid to the management of our aquatic resources and also of the pollutants which enter them (Horan, 1 990) .
The organic and inorganic components of wastewater are present in both soluble and insoluble form. Watercourses receive pollution from many different sources, which vary both in strength and volume. Identification of the major sources of these pollutants is important, as they can be controlled most easily at the source (Long, 1990) . The main source of both chemical and biological
5
pollution in domestic sewage resulted from human excreta with a smaller contribution from wastewater resulting from laundry , food preparation and bath (Horan, 1990) . The characteristic of typical domestic sewage at five countries is illustrated in Table 1 below :
Table 1: The Characteristic of Typical Domestic Sewage at Five Countries (Horan, 1990) . Determinant
Manchester (UK)
BOD (mg 0 2/L) 240 COD (mg02/L) 520 PV (mg02/L) 210 Suspended solids (mg/L) -
Ammonia N (mg/L) PH
Temperature COC)
(as 22
7.4 14
Mafraq Campina (Abu Dhabi Grande town) (NE Brazil) 228 240 600 570 75 198 3 92
Amman (Jordan)
Nairobi (Kenya)
770 1830
520 520
-
-
900
520
35.2
38
1 00
33
7.6
7 .8 2.6
-
-
-
22
7.0 24
2. 1 . 1 Characteristics of the Wastewater
In general , wastewater can be characterized based on its bulk organic parameters , physical characteristics and specific contaminants . The bulk organic wastewater quality parameters measure the amount of organic matter present in a waste stream (Belhateche, 1 995) . Typical parameters are total organic carbon (TOC) , chemical oxygen demand (COD) and oil and grease (O&G) . All these parameters measurements indicate the amount of organic matter present in a
6
waste stream that require stabilization or oxidation stream (Belhateche, 1 995) . These parameters are useful for measuring the organic quality of wastewater only when such compounds are expected to be present in large qualities , such as in refinery wastewater as shown below :
1 ) Physical characteristics - The physical characteristics of wastewater include total suspended solids (TSS) , temperature , pH, color , odour , turbidity , flow variability , conductivity , settleability and sometimes oxidation/reduction (redox) potential (Long , 1 990) .
2) Biological characteristics - Bacteriological testing determines the presence of pathogenic (disease causing) organisms or indicator bacteria for such organisms in the raw wastewater, processed streams , and treated effluent (Long , 1990) .
3) Chemical
composition
- chemical
testing
provides
information
on
the
concentrations of the specific substances for which the tests are designed . The determination composition of wastewater include pH, alkalinity , solids , BOD (Biological oxygen demand) , COD (Chemical Oxygen Demand) , Nitrogen organic nitrogen, ammonia, nitrite and nitrate, phosphorus , chlorine , sulfide, fat oils-greases and priority pollutants (Long, 1 990) .
7
