CHAPTER 1

INTRODUCTION

1.1 Research background

Nowadays, water contamination by heavy metals remains a major environmental concern

as heavy metals persistently present in water subjected by their non-degradable properties (Li et
al., 2003). At trace level, heavy metals play vital roles in biochemical processes. However, over
accumulation of heavy metals into body will causes negatively effects to public health (Kumar,
Isloor, & Ismail, 2014b; Meybeck, Kuusisto, Mkel, & Mlkki, 1996; K. Saeed, Park, & Oh,
2011). . By the aforementioned statement, hence, an effective measure needs to be taken to
control the emission of heavy metals into water.

Among the common heavy metals that present in water, lead (Pb) and cadmium (Cd) has
attract great attention for their studies of removal as both metals are proved to pose adverse
effects on human health even at minimum level (Vila et.al, 2012; Zhang & Jiao, 2013). The
emission of Pb and Cd may occur naturally or anthrophogenically. Cd is normally appear in the
form of Cd2+ and naturally emitted by volcanic eruption and anthrophogenically emitted via
metal mining and refining industries (Wu et.al., 2010). On the other hand, Pb normally exists in
the state of 2+ in water. Naturally, Pb is released by volcanic eruption while the anthrophogenic
sources of Pb are from battery storage, paint and ceramic and pipework industries (Flora et.al.,
2012). Both metals have been reported to cause severe defects to body system. To date,
maximum contaminants level set by World Health Organization for Cd and Pb is 0.003 mg/L and
0.015 mg/L respectively (Khairy et.al., 2014)

Various methods have been implied upon removal of lead and cadmium laden in water
streams such as ion exchange (Ahmed et.al, 1998; Islam & Patel, 2009; Street et.al, 2002; Trgo
et.al ,2006), precipitation (Eren, 2009; Esalah et.al, 1999; Lee et.al, 1997; Matlock et.al, 2002;
Rojas, 2014), coagulation-flocculation (Chu, 1999; Debora et.al, 2013; Pang et.al, 2011), and
flotation (Drzymala et.al, 2003; Ghazy et.al, 2008; Ghazy & Ragab, 2007; Yuan et.al, 2008)
where each of this method possesses their own limitations more likely to be incomplete removal,
generation of secondary waste, and inefficient removal efficacies (Barakat, 2011a; Fu & Wang,
2011). Adsorption is another technique that is frequently applied for removal of heavy metals
laden in water. There are wide range of adsorbents are available, one good example is nano-
scaled metal oxides (NMOs) such as titanium oxides, manganese oxides, ferric oxides, cerium
oxides and magnesium oxides. Among the previously mentioned NMOs, hydrous ferric oxides
(HFO) are classified to be as a promising adsorbent during adsorption process of heavy metals,
mainly attributed by their high specific surface area of surface to volume ratio, fast kinetic rate
and cost effective (Sarkar et.al, 2012; Arsuaga et.al, 2012;(Deliyanni, Lazaridis, Peleka, &
Matis, 2004).

Nevertheless, HFO adsorption performance is often hindered by their poor stability as

their sizes are reduced into nanoscale whereby impregnation of HFO into porous support as a
composite adsorbent may serve as a good approach (Pan et.al, 2009). To this date, HFO has been
co-supported with different kind of porous support such as cation exchange resin (Cumbal &
Sengupta, 2005; Jang et.al,2006; Wang et.al, 2011), diatomite (Jang et al., 2006), bentonite
(Eren, 2009), and zeolite (Han et al., 2009). Compared to other host materials, incorporating
HFO into porous polymeric membrane host seems to an attractive option as their pore size can be
controlled as well as possess excellent mechanical strength and surface chemistry for long-term
use.

In general, polymeric membranes can be divided into four different types which are
microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) which
the first two membranes types are porous membranes while the latter are non-porous membranes.
Among them, UF is a preferable method as because of its simple operation, economically
feasible due to low energy requirement in comparison to NF and RO (Kumar et.al, 2014;
Farahbakhsh et.al, 2004). However, the large pores size of UF membrane often omits its
efficacies to remove small metallic ions. Impregnation of HFO into UF porous membrane may
solve the major limitation of large pores UF membrane upon removal of heavy metals. Besides,
development of UF mixed matrix membrane impregnated with metal oxides provide dual-
functions, selective adsorption of heavy metallic ions and separating water at the same time. In
addition, the membrane can be regenerated via simple washing with acidic solution, as well as it
skips the post treatment process of adsorption because the adsorbents are retained in the
membrane (Gohari et.al, 2013).

Many polymers can be used for preparation of polymeric UF membrane namely

polytetrafluoroethylene (PTFE), polivinylidenefluoride (PVDF), polypropylene (PP),
polysulfone (PSF) and polyethersulfone (PES). Out the aforementioned polymers, PSf is an
excellent polymer selection because of its outstanding properties which are easy-handling, high
strength of mechanical, high chemical resistances well as favourable selectivity-permeability
characteristics. PSf can be dissolved by using common solvent such as NMP and DMAC, hence
it serves as a great polymeric material for preparation of asymmetric flat sheet membranes by
phase inversion by using water as coagulant.
 Eventhough UF MMMs is an excellent technique to be selected; one major problem that
frequently arising is fouling. Fouling has been found to decrease the flux rate of water and it
negatively affects the overall performance of a membrane. Fouling can be classified into several
types which are biofouling, colloidal fouling, scaling and and organic fouling. Hence, selecting a
proper additive may increase the antifouling properties of a membrane.

1.2 Problem statement

Membrane technology is versatile technique upon removing various unwanted constituents,

including metallic ions from wastewater. When compared to NF and RO, UF membrane is more
favorable method for water treatment attributed by its low energy requirement, easy operation
and economically feasible. However, upon removing metallic ions, the use of neat UF membrane
will not efficiently remove heavy metal ions due to its relatively bigger pore size that allow small
size ions to pass through.

In addition, preparation of PSf polymeric UF membrane offer advantages in term its

mechanical, chemical, and thermal properties. One major issue when using polymeric membrane
is its hydrophobicity that omit the passage of water and elevate the impact of fouling that result
to significant reduction of overall performance of the membrane. The formation of fouling is
usually induced by pore blocking in membrane and cake layer on membrane surface attributed
by colloid, microorganism and organic matters. Membrane morphology and hydrophilicity of
membrane are found to be closely related to membrane fouling where it can be enhanced by
addition of inorganic nanoparticles into membrane that can improve membrane characteristics
and at same time have excellent adsorption capacity towards metallic ions. Among many metal
oxides, hydrous ferric oxides (HFO) have been found to high hydrophilicity, excellent fouling
resistance and high permselectivity, (Yang et.al.,2005; Bae and Tak, 2005; Cao et.al.,2006; Li
et.al., 2009). Apart of that, HFO have excellent adsorption capacity towards metallic ions;
nevertheless, their adsorption performance is hindered by their poor stability as their sizes are
reduced into nanoscale.

Incorporation of HFO into UF membrane may boost the limitation of large pore size and
fouling of while UF porous membrane serve as excellent host to enhance the stability of both
metal oxides as an adsorbents. For further improvement of finely dispersed HFO in polymer
matrix, selection of appropriate doping of filler and are the most addressed efforts. Hence, in this
proposed research study, attempts will be made to construct mixed matrix membrane of PSf
embedded with HFO.

1.3 Objectives of study

The aim of this project is to study the removal of heavy metals (lead and cadmium) by
adsorptive ultrafiltration mixed matrix membrane of PSf/HFO. The objectives of this study are
stated as below:

1. To fabricate flat sheet PSf/HFO membrane using different loading of HFO and study its
effects towards structural and physical properties of membrane.

2. To evaluate the performance and regeneration of fabricated membrane on removal of lead

and cadmium.

3. To study the antifouling properties of fabricated adsorptive membrane by using bovine

albumin serum (BSA) as model protein.
1.4 Scopes of study

In order to achieve the aforementioned objectives, the following scopes of study are outlined:

1. Synthesizing HFO by chemical precipitation process and morphological

characterizations of HFO by SEM, TEM, XRD, BET and FTIR.

2. Preparing and fabricating dope solution of PSf/HFO/NMP/PVP with different loading

ratio of HFO using phase inversion technique.

3. Characterizing the fabricated membrane in terms of structural and physical properties.

4. Evaluating the performance of adsorption of fabricated membrane via batch adsorption

studies and kinetic studies.

5. Evaluating the continuous performance membrane in term of rejection and regeneration

by using flat sheet commercial ultrafiltration membrane system via measurement
permeability of membrane as function of time and rejection for Pb and Cd.

6. Investigating the antifouling properties of fabricated membrane by using bovine serum

albumin (BSA) as model protein and calculation of fouling resistance ration (FRR).

1.5 Significance of study

 The application of UF MMMs for removal of heavy metals will serve as an alternative
measure apart of current methods that available nowadays as it requires less energy, feasible and
cost effective. Production of an adsorptive UF mixed matrix imbedded with HFO membranes
will resolve the problem of UF membrane that not viable to separate heavy metals due to its big
size exclusion.

As there are only few studies have been conducted of aforementioned technique, this
proposed study may provide better understanding in production of mixed matrix membrane
incorporated with adsorbents as additive and determining parameters that give major impacts of
the method. As result of that, the application of UF MMMs will reduce , the threat of heavy
metals pollution towards surrounding environment and human health