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UNIVERSITI PUTRA MALAYSIA
SYNTHESIS AND CHARACTERIZATION OF NEW CHELATING RESINS CONTAINING THIOUREA AS THE FUNCTIONAL GROUP
MOHO SHABERI BIN MOHD AMIN
FSAS 2002 62
SYNTHESIS AND CHARACTERIZATION OF NEW CHELATING RESINS CONTAINING THIOUREA AS THE FUNCTIONAL GROUP
MOHO SHABERI BIN MOHD AMIN
MASTER OF SCIENCE
UNlVERSITI PUTRA MALAYSIA
2002
SYNTHESIS AND CHARACTERIZATION OF NEW CHELATING RESINS CONTAINING THIOUREA AS THE FUNCTIONAL GROUP
By
MOHD SHABERI BIN MOHD AMIN
Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia, in Fulfilment of the Requirements for tbe Degree of Master of Science
October 2002
Abstract of thesis presented to the Senate of Uruversiti Putra Malaysia in the fulfilment of requirement for the degree of Master of Science
SYNTHESIS AND CHARACTERIZATION OF NEW CHELATING RESINS CONTAINING THIOUREA AS THE FUNCTIONAL GROUP
By
MOHD SHABERI BIN MOHD AMIN
October 2002
Chairman: Sidik bin Silong, Ph.D.
Faculty: Science and Environmental Studies
11
A senes of chelating resins, derived from a macroreticular styrene-
divinylbenzene (2%) copolymer beads grafted with various spacer from propylene
groups (-CfiJ-CfiJ-CH2k (n=1, 2, 4) and containing thiourea as chelating function,
have been synthesized in a four-step reaction sequence. The steps began by the
reaction of diethyl malonate with a spacer (ethylene groups), followed with the
attachment of the arm group to the polymer. The polymer was then hydrolyzed and
converted to its polychloride acid derivatives and followed by the attachment of the
thiourea functional group to produce the new chelating resins.
The reaction of diethyl malonate with the spacer has been monitored by using
nuclear magnetic. resonance analysis. Meanwhile, the presence of all the functional
1II
groups has been deduced by infrared spectroscopy. Due to the insolubility of the
backbone resin, the presence or absence of certain bands expected for particular
functional groups in their infrared spectra was used to monitor the success of the
grafting process. The e, H, Nand S elemental analyses data were used to estimate
the degree of conversion in each and every step of the reactions and the surface
morphology was studied by using scanning electron microscopy.
The complexation behavior of these resins was investigated towards Hg(II),
eu(II) and Pb(II) ions in aqueous solutions by the batch equilibration technique. The
influence of pH on adsorption capacity was also examined. The adsorption values for
metal ions' intake followed the order Hg(n) > eu(n) > Pb(II). Polymers can be
regenerated by washing with the mixture solution of hydrochloric acid and an
aqueous solution of thiourea by using the column method.
Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai memenuhi keperluan untuk ijazah Master Sains
PENYEDIAAN DAN PENCIRIAN RESIN PENGKELAT BARU YANG MENGANDUNGI KUMPULAN BERFUNGSI TIOUREA
Oleh
MOHD SHABERI BIN MOHD AMIN
Oktober 2002
Pengerusi: Sidik bin Silong, Ph.D.
Fakulti: Sains dan Pengajian Alam Sekitar
IV
Satu siri resin pengkelatan diterbitkan dari manik-manik rangkaian makro ko-
polimer stirena-divinilbenzena (2 %) yang tercangkuk dengan bahagian lengan
mengandungi kumpulan berfungsi tiourea menerusi beberapa peruang propilena (-
CHrCH2-CHZ)n (n = 1, 2, 4), telah disediakan melalui empat langkah tindak balas.
Dimulai dengan tindak balas dietilmalanot dengan peruang (kumpulan etilena) yang
kemudiannya dirangkaikan kepada polimer. Seterusoya polimer terubahsuai itu
dihidrolisis dan ditukarkan menjadi asid poliklorida terbitan, serta diikuti deogan
memasukkan kumpulan berfungsi tiourea bagi mendapatkan resin pengkelat barn.
Tindak balas diantara dietilmalanot dengan peruang telah ditentukan
menggunakan analisis resonan magnetik nuklear. Manakala kehadiran semua
v
kumpulan berfungsi ditentukan melalui spektroskopi infra-merah kerana ketidak
larutan rangka asas resin. Kejayaan setiap langkah tindak balas penyangkukan
ditentukan berdasarkan kepada kehadiran atau ketidakhadiran jalur-jalur serapan
tertentu bagi kumpulan-kumpulan berfungsi berkaitan. Analisis unsur e, H, N dan S
dilakukan bagi menganggarkan kadar pengubahan bagi setiap langkah tindak balas,
manakala morfologi permukaan dikaji menggunakan mikroskopi pengimbasan
elektron.
Pembentukan komplek resin ini terhadap ion-ion Hg(II), eU(Il) dan Pb(ll)
telah dikaji dalam larutan akuas menggunakan teknik keseimbangan pukal. Kesan
pH terhadap kapasiti penjerapan resin juga dikaji. Nilai jerapan resin ini terhadap ion
logam adalah mengikut urutan Hg(II) > eu(II) > Pb(II). Polimer ini boleh dijana
semula selepas dibilas menggunakan campuran Iarutan asid hidroklorida dan larutan
akuas tiourea melalui keadah turus.
VI
ACKNOWLEDGEMENTS
All praise to Allah S. W. T. who has showered me with kindness and affection
during the course of my study that I cannot adequately thank for. His endless grace
and love have provided me with the strength to finish this study.
I would like also to express my deepest and warmest sense of thanks and
appreciation to my honorable project supervisor, Dr. Sidik bin Silong for his
invaluable assistance, constructive criticisms and inspiring guidance. But most of all
for his most understanding and patience which has been a great favour on my behalf,
I am also grateful to other members of the supervisory committee (Assoc. Prof Dr.
Md. lelas bin Haron, Prof Dr. Wan Md. lin bin Wan Yunus and Assoc. Prof. Dr.
Mohd. laki bin Abd. Rahman).
My sincere thanks also go to all lecturers in Department of Chemistry and I
would like to acknowledge the assistance provided by the Department of Chemistry
and staff of this department, especially to Mr. lainal Zahari, Mr. Zainal Kassim, Mr.
Kamal Margona and Mrs. Rosnani for their favourable help_ Thank also go to the
Ministry of Science, Technology and Environment, Government of Malaysia for
financial assistant. This research was funded by an IRPA Grant No: 09-02-04-0057.
vii
Finally, I would like to express my deepest gratitude to my family and friends
for their endless encouragement, patience and sacrifices, which had helped me in
understanding and completing this research project.
VI11
I certify that an Examination Committee met on 28th October 2002 to conduct the final examination of Mohd Shaberi bin Mohd Amin on his Master of Science thesis entitled "Synthesis and Characterization of New Chelating Resins Containing Thiourea as the Functional Group" in accordance with Universiti Pertanian Malaysia (Higher Degree) Act 1980 and Universiti Pertanian Malaysia (Higher Degree) Regulations 1981. The Committee recommends that the candidate be awarded the relevant degree. The members of the Examination Committee are as follows:
MANSOR BIN AHMAD, Ph.D.
Associate Professor Faculty of Science and Environmental Studies, Universiti Putra Malaysia (Chairman)
SIDIK BIN SILONG, Ph.D.
Faculty of Science and Environmental Studies, Universiti Putra Malaysia. (Member)
MD. JELAS BIN HARON, Ph.D.
Associate Professor Faculty of Science and Environmental Studies, Universiti Putra Malaysia. (Member)
WAN MD. ZIN BIN WAN YUNUS, Ph.D.
Professor Faculty of Science and Environmental Studies, Universiti Putra Malaysia. (Member)
MOHD. ZAKI BIN ADD. RAHMAN, Ph.D.
Associate Professor Faculty of Science and Environmental Studies, Universiti Putra Malaysia. (Member)
_�J ..... SHER MOHAMAD RAMADILI, Ph.D. Professor/ Deputy Dean School of Graduate Studies, Universiti Putra Malaysia Date: ·2 4 S�:: 2002
IX
This thesis submitted to the Senate of Universiti Putra Malaysia has been accepted as partial fulfilment of the requirement for the degree of Master of Science. The members of the Supervisory Committee are as follows:
SIDIK BIN SILONG, Ph.D.
Faculty of Science and Environmental Studies, Universiti Putra Malaysia. (Chairman)
MD. JELAS BIN HARON, Ph.D.
Associate Professor Faculty of Science and Environmental Studies, Universiti Putra Malaysia. (Member)
WAN MD. ZIN BIN WAN YUNUS, Ph.D. Professor Faculty of Science and Environmental Studies, Universiti Putra Malaysia. (Member)
MOHD. ZAKI BIN ABD. RAHMAN, Ph.D.
Associate Professor Faculty of Science and Environmental Studies, Universiti Putra Malaysia. (Member)
AINI IDERIS, Ph.D. ProfessorlDean School of Graduate Studies, Universiti Putra Malaysia
Date: 1:3 FEB 2nm
x
DECLARA TION
I hereby declare that the thesis is based on my original work expect 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.
MOUD SlfABERI BIN MOHD AM IN
Date: �� / J � / �oo'.t
Xl
TABLE OF CONTENTS
Page
ABSTRACT Il ABSTRAK ACKNOWLEDGEMffiNTS APPROVAL SHEETS DECLARATION
iv VI Vl1l X
TABLE OF CONTENTS LIST OF TABLES
Xl XIV XV XVlll
LIST OF FIGURES LIST OF ABBREVATIONS AND SYMBOLS
CHAPTER
I INTRODUCTION 1.1 Heavy Metal 1 1.2 Toxicity 4
1.2.1 Copper 4 1.2.2 Lead 5 1.2.3 Mercury 8
1.3 Chelating Resin 11 1.4 Objectives 12
n L ITERATURE REVIEW
2.1 Cation Exchangers 13 2.2 Anion Exchangers 16 2.3 Crosslinked Polystyrene Resins 17
2.3.1 Physical Nature of the Crosslinked Polymers 18 2.3.2 Solvent Swellable Resin Beads 18 2.3.3 Rigid Macroporous or Macroreticular Beads 20 2.3.4 Popcorn Polymers 21
2.4 Synthesis of Complexing and Chelating Ion-exchange Resins 21 2.5 Types and Synthesis of Polymeric Matrices 22 2.6 Synthesis of Chelating Resins based from Styrene-divinylbenzene 26 2.7 Thiourea 33
ill EXPERIMENTAL
xii
3.1 Materials 35 3.2 General Approach 36 3.3 Purification of Die thy 1 Malonate 4 1 3.4 Preparation of the Reagents 41 3.5 Synthesis of the Resins 42
3.5.1 Preparation of Alkylmalonic Ester. [Diethy12-(3-hydroxypropyl) malonate ( n = 1), DiethyI2-(6-hydroxyhexyl) malonate ( n = 2) and Diethyl 2-(12-hydroxydodecyl) malonate ( n = 4)] 42
3.5.2 Preparation of Alkylmalonic Ester Grafted Chloromethylated Polystyrene Beads ( PSR-ET) 43
3.5.3 Hydrolysis of Alkylmalonic Ester Grafted Chloromethylated Polystyrene Beads (PSR-OH) 44
3.5.4 Modification of the Polycarboxylic Acid to the New Polymeric Resin (PSR-SH) 44
3.6 Characterization of Reaction Products 45 3.7 Resin Characterization 46
3.7.1 Stability of the Resins 46 3.7.2 Water Regain 46
3.8 Batch Method 47 3.8.1 Resins Capacity for Metal Ions 47 3.8.2 Isotherm Study 48
3.9 Column Method 48 3.9. 1 Extraction and Elution of Metallons 48 3.9.2 Separation of Metal Ions 49 3.9.3 Breakthrough Experiment 49
IV RESULTS AND DISCUSSION
4. 1 Synthesis of the Resin 4.2 Characterization of the Reaction Products
4.2.1 Nuclear Magnetic Resonance 4.2.2 Infrared Spectroscopy 4.2.3 Elemental Analysis 4.2.4 Scanning Electron Microscopy
4.3 Resins Characterization 4.3.1 Stability of the Resins 4.3.2 Water Regain
4.4 Batch Method Study 4.4.1 Sorption of Metal Ion
50 52 52 60 71 74 78 78 78 79 79
4.4.2 Isothenn Study 4.5 Column Method Study
4.5.1 Extraction 4.5.2 Elution of Metal Ions 4.5.3 Separation of Metal Ions 5.3.5 Breakthrough Study
V CONCLUSION AND RECOMM ENDAT ION
5.1 Conclusion 5.2 Recommendation for Future Study
REFERENCES
APPENDICES
Appendix A Appendix B AppendixC
BIODATA OF THE AUTHOR
Xlll
86 88 88 90 95 100
102 104
106
115 123 128
133
XlV
L IST OF TABLES
Table Page
1.1 Substances Present in Industrial Effluents (Lester, 1987) 2
2.1 Cation and Anion Exchangers 17
4.1 IR Characteristic Bands ( em-I) of Resins 70
4.2 Elemental Analysis Data 71
4.3a The capacity of Cu( II) adsorbed at different pH values using resins with different length of spacer 84
4.3b The capacity ofPb( II) adsorbed at different pH values using resins with different length of spacer 8S
4.3c The capacity of Hg(U) adsorbed at different pH values using resins with different length of spacer 8S
4.4 Maximum recovery of metal ions using resins with different length of spacers 95
xv
LIST OF FIGURES
Figure Page
2.1 Condensation Polymers 24
2.2 Addition Polymers 25
2.3 Chemical Structure of Resin Synthesized by Lezzi et at. (1994) 27
2.4 Chemical Structure of Resin Synthesized by Akerkar et at. (1998) 28
2.5 Chemical Structure of Resin Synthesized by Kapil and Rao (1996) 29
2.6 Chemical Structure of Resin Synthesized by Ahuja et at. (1996) 30
2.7 Chemical Structure of Resin Synthesized by Suzuki and Yokoyama (1983 )31
2.8 Chemical Structure of Resin Synthesized of Drago et al. (1980) 32
2.9 Chemical Structure of Resin Synthesized of Kumar et al. (2000) 32
4.1 Synthesis Pathway 51
4.2a IH NMR Spectrum of Die thy I Malonate 53
4.2b IH NMR Spectrum ofDiethyI2-(3-Hydroxypropyl) Malonate 54
4.2c IH NMR Spectrum ofDiethyI2-(6-Hydroxyhexyl) Malonate 57
4.2d IH NMR Spectrum ofDiethyI2-(12-Hydroxydodecyl) Malonate 58
4.3a Chemical Structure ofDiethyI2-(3-Hydroxypropyl) Malonate 55
4.3b Chemical Structure ofDiethyI2-(6-Hydroxyhexyl) Malonate 56
4.3c Chemical Structure ofDiethyI2-(12-Hydroxydodecyl) Malonate 59
4.4a IR Spectrum of Diethyl Malonate Using NaCI Window 61
xvi
4.4b IR Spectrum ofDiethyI2-(3-Hydroxypropyl) Malonate Using NaCI Window 62
4.4c IR Spectrum ofChloromethylated Polystyrene Beads (PSR-CL) in KBr Pellet 65
4.4d IR Spectrum ofDiethyI2-(3-Hydroxypropyl) Malonate Grafted Chloromethylated Polystyrene Beads (PSR-ET) in KBr Pellet 66
4.4e IR Spectrum of Hydrolysis Diethyl 2-(3-Hydroxypropyl) Malonate Grafted Chloromethylated Polystyrene Beads (PSR-OH) in KBr Pellet 67
4.4f IR Spectrum of New Polymeric Resin (PSR-SH) in KBr Pellet 68
4.5 Schematic Diagram of Suggested Beads Structure 73
4.6a Scanning Electron Microscopy Image of Chloromethylated Polystyrene Beads (PSR-CL) 76
4.6b Scanning Electron Microscopy Image ofDiethyI2-(3-Hydroxypropyl) Malonate Grafted Chloromethylated Polystyrene Beads (PSR-ET) 76
4.6c Scanning Electron Microscopy Image of Hydrolysis Diethyl 2-(3-Hydroxypropyl) Malonate Grafted Chloromethylated
Polystyrene Beads (PSR-OH) 77
4.6d Scanning Electron Microscopy Image of New Polymeric Resin 77
4.7a Percentage sorption of Cu(II) ion at various pH using resin with different length of spacers 80
4.7b Percentage sorption ofPb( II) ion at various pH using resin with different length of spacers 81
4.7c Percentage sorption ofHg(ll) ion at various pH using resin with different length of spacers 82
4.8a Equilibrium Isotherm for the Sorption of Cu(n) Ion 87
4.8b Langmuir Isotherm for the Sorption of Cu(n) Ion 88
4.9 Suggested Complex Formation 89
XVIi
4.10a Elution of Cu(II) ion with PSR-SH ( n=l) 92
4.10b Elution ofPb(II) ion with PSR-SH ( n=l) 93
4.10c Elution of Hg( II) ion with PSR-SH ( n=l) 94
4.1 1a Separation of Cu(II) - Hg(II) by resin n = 1 97
4. 11b Separation ofPb(II) - Hg( II) by resin n = 1 98
4. 1 1c Separation of Cu(II) - Pb(II) by resin n = 1 99
4.12 Breakthrough Curves 100
xviii
LIST OF SYMBOLS AND ABBREVIATIONS
ppm Part per million
DVB Divinylbenzene
PSR Polystyrene resin
v Stretching vibration
8 Bending vibration
Os Scissor vibration
op Rocking vibration
Ot Twisting vibration
Ow Wagging vibration
Co Initial concentration
C Equilibrium concentrations
WR Weight of dry resin
Q Capacity
V-- Polymeric chain
1 .1 Heavy Metal
CHAPTER I
INTRODUCTION
The problem of heavy metal contamination in waterbodies is widespread
and becoming more acute, threatening an ever increasing portion of global
population. Such an environmental pollution is mainly due to rapid
industrialization together with the increase in modem method of agriculture
especially in the developing countries.
Water pollution is mainly caused by untreated released of effluent by
industries such as plating, electroplating, leather, textile and battery manufacturer.
(Some of the sources where heavy metals could be found are listed in Table 1.1).
Among the most common heavy metals found in industrial wastewater are ell, Ni,
Zn, Cr, Hg and Pb. Accumulation of these metal ions in trace quantity in human
body cause physiological and neurological disorder. However, at a higher
concentration they are very toxic and cause severe health problem, which may
cause death. Therefore, heavy metal ion concentration in wastewater must be
controlled and reduce to a low level.
2
Chemical precipitation, ion exchange, reverse osmosis, solvent extraction
and ultrafiltration could achieve removal of metal ions from wastewater.
Table 1.1: Substances Present in Industrial Effiuents (Lester, 1987).
Substances Usage in Industries
Arsenic Semi-conductors & photoconductors, agrochemical such as insecticides.
Aluminum Construction of building and transport, aluminum foils.
Cadmium Electroplating & coating industry pigment for paint.
Chromium Machinery-construction industry alloys in transport & heater elements.
Copper Electronics, plating, brass & other alloys, fertilizer, rayon manufacture.
Lead Battery manufacture, anti-knock additions for gasoline, piping.
Mercury Instrumentation for measurement and control, amalgam in dentistry.
Nickel Alloys, electroplating, pigments, catalysts, electrical contacts & batteries.
Silver Photographic products plated silverware, jewelry & battery manufacture.
Zinc Brass & bronze alloys for galvanizatio� cosmetics & pharmaceuticals.
Shkinev et al. (1989) reported a new method for determination of trace
heavy metal in water by atomic absorption spectrometry after preconcentration by
liquid-phase polymer-based retention The method has been applied to the
determination of NL Cu, Zn, Hg and Cd in drinking and river water with
poly(ethyleneimine) and its thiourea derivative as complexing polymer. The
metals were determined in aqueous concentrate after a 250-fold preconcentration
by 2% polymer solution at pH 7.
3
laporozhets et al. (1999) obtained the modified sorbents with dithizone
and zinc thizonate adsorbed on the silica surface. Adsorption of heavy metal ions
from aqueous solutions onto loaded silica was studied. Color scales for Ag(I),
Hg(II) and Pb(U) visual test detection were developed. The modified silica gels
were established to be applicable to the quantitative determination of these metal
ions in buttermilk, natural, mineral and wastewater.
A method for the determination of Cu, In, Fe, Ni and Cd by flame atomic
absorption spectrophotometry (F-AAS) after preconcentrating on a column
containing Escherichia coli immobilized on sepiolite has been developed by Bag
et al. (2000). Optimum pH values, amount of adsorbent, elution solution and flow
rate have been obtained for the elements studied. The effect of interfering ions on
the recovery of the analytes has also been investigated. Recoveries ofCu, Zn, Fe,
Ni and Cd by E. coli immobilized on sepiolite were 99.1 ± 0.6, 98.2 ± 0.6, 98.1 ±
0.5, 97.2 ± 0.8 and 98.2 ± 0.4 % (at 95 % confidence level), respectively. The
adsorption capacity of E. coli immobilized on sepiolite was found to be 0.148,
0.064,0.098,0.134 and 0.088 mmol/g for Cu, In, Fe, Ni and Cd, respectively.
Tiravanti et al. (1997) investigated the conservative technologies to utilize
natural and synthetic reactive polymers for selective metal removal, recovery and
reuse. Examples refer to the treatment of industrial wastes containing silver,
cadmium, mercury, chromium, iron and aluminum by different innovative
processes. A precipitation process was described, namely Metals Extration by
Xanthate Insolubilization and Chemical Oxidation (MEXICO), using agricultural
4
raw materials to prepare starch or cellulose xanthates as precipitating agents for
metals.
1.2 Toxicity
1.2.1 Copper
Copper is an essential element used in process of blood formation and iron
utilization, with a human daily requirement of 0.03 mglkg for adults. The main
intake is normally through the diet and water consumption. Copper occurs in
aqueous solution in oxidation states of (I) and (II), but former is unstable above
equilibrium concentration of 10-2 M and in aerated natural waters it is generally
oxidized to Cu(II).
Copper is absorbed through the intestinal tract (40 to 70 %) and absorption
varies with intake. Its half-life in human is 80 days and total body burden is 75 to
150 mg. Once absorbed, copper is transported in the blood and stored normally in
muscle, liver and brain tissue. In cases of acute toxicity, copper is found in the
brain, liver, stomach, hair roots and urine. Symptoms of acute toxicity are gastric
ulcers, hemolysis, jaundice, hepatic necrosis and renal damage. Chronic toxicity
in man is found infrequently but has been reported to cause "pink disease" in
infant ingesting copper-contaminated water at concentrations of 0.8 mg/I.
Elevated levels of copper are associated with disorders such as biliary atresia and
cirrhosis in children, Hoadkin's disease, leukemia and atherosclerosis.
5
Microamount of copper takes part in oxidization inside the human body
and is relative to some illnesses of the body, so it is important to determine
microamount of copper. Ma et al. (1999) synthesized a new sensitive reagent
based on the new long-chain saturated fatty hydrocarbon substituting group
compound, N-undecyl-N -(sodium p-aminobenzenesulfonate)-thiourea (UPT).
According to the studies on its analytical performance, it is found that this reagent
can be used to identify Cu2+ and determine microamounts of copper (E300A nm =
2.39 X 105 I morl em-I) in aqueous solution. These new methods are simple and
convenient and can provide satisfactory results on samples.
Ferreira et al. (2000) proposed a procedure for the separation and
preconcentration of trace amounts of copper in natural water samples. It is based
on the adsorption of copper(ll) ions onto a column of Amberlite XAD-2 resin
loaded with calmagite reagent. This way amounts of copper within the range
from 0.0125 to 25.0 J,lg, in a sample volume of 25 to 250 ml, and pH from 3.7 to
10.0 was concentrated as camagite complex in a column of 0.50 g of Amberlite
XAD-2 resin. Detection and determination limits of the proposed procedure for
250 ml sample volume were 0.15 and O. 50 J,lg r\ respectively.
1.2.2 Lead
Lead (Pb) is one of the oldest metals known to man and, since medieval
times, has been used in piping, building materials, soldering, paints, ammunition
and castings. More recently, lead has been used mainly in storage batteries (35