INTERUNIVERSITY PROGRAMME FOR MASTER OF SCIENCE IN WATER

RESOURCE ENGINEERING
Katholieke Universiteit Leuven
Vrije Universiteit Brussel

Mixed matrix composite membrane fabricated with

steel residue for heavy metals removal
By Mayank Bhatia

Promoter:
Prof. Dr. Ir. Bart Van der Bruggen

Supervisor:
Ir. Julieta García Chirino

i
Acknowledgment

The successful completion of the master’s thesis is attributed to the direction and support
provided by many individuals, for which I am extremely thankful. During this endeavor, their
assistance has been crucial, and I am honored to recognize their help and support. First of
all, I express my appreciation to the almighty for empowering me with the power, wisdom,
and determination to undertake and complete this study project. Without the bestowed
benefits and afforded possibilities, this achievement would have remained unattainable .
I wish to express my sincere respect to my promoter Prof. dr. ir. Bart Van der Bruggen and my
daily supervisor Julieta García Chirino who helped me all along, till the completion of my
thesis. I also sincerely thank all the teaching faculty members of the IUPWARE program, KU
Leuven, and VUB for the valuable knowledge they shared. I would also like to thank all non-
teaching faculty members, research scholars, and other staff of Leuven Chem & Tech
Laboratory for their timely guidance and support.
Finally, I wish to convey my gratitude towards my parents, friends, and well-wishers for their
unalloyed support.

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Table of Contents
Lists of Symbols ................................................................................................................................. iv
List of Tables ....................................................................................................................................... v
List of Figures ..................................................................................................................................... vi
Abstract ............................................................................................................................................. vi
Introduction and Literature Review .................................................................................................... 1
Materials and Methods .....................................................................................................................12
Results and Discussions.....................................................................................................................20
Analysis of Real Wastewater .............................................................................................................40
Conclusion ........................................................................................................................................48
References ........................................................................................................................................50

iii
Lists of Symbols
CA Cellulose Acetate
PA Polyamide
PSF Polysulfone
PES Polyether Sulfone
PVDF Polyvinylidene Fluoride
PI Polyimide
PE Polyethylene
PP Polypropylene
PAN Polyacrylonitrile
PET Polyethylene terephthalate
PDMS Polydimethylsiloxane
PEI Polyetherimide
MF Microfiltration
UF Ultrafiltration
NF Nanofiltration
RO Reverse Osmosis
MMM Mixed Matrix Membrane
CA Contact Angle
SEM Scanning Electron Microscope
MWCO Molecular Weight Cut-off
Fourier Transform Infrared
FTIR
Spectroscopy
CFF Cross Flow Filtration
DMAc N, N dimethylacetamide
PVP Polyvinylpyrrolidone
XRD X-ray Diffraction
PEG Polyethylene Glycol
AgNPs Silver Nanoparticles
rGO Reduced Graphene Oxide
HNTs Halloysite Nanotubes
ICP Inductively coupled plasma
FRR Fouling Recovery Ratio
TFR Total Fouling Ratio
RFR Reversible Fouling Ratio
IFR Irreversible Fouling Ratio

iv
List of Tables

Table 1 Comparison of different technologies for heavy metal removal (Abdullah et al., 2019) ......... 2
Table 2 Different Flux governed by different equations and laws ........................................................ 4
Table 3 : Common polymers in manufacturing different types of membranes (Abdel-Fatah et al.,
2021), (Zahid et al., 2018) .................................................................................................................. 5
Table 4 Membrane Application Matrix (Saleh & Gupta, 2016) ............................................................. 6
Table 5 XRD of oxycut powder (García-Chirino et al., 2023)................................................................. 9
Table 6 Different composition of the casting solution. .......................................................................15
Table 7 Pore size in nm for M 0.05, M 0.5, M 1, and M 3 ....................................................................21
Table 8 Summary of spectrum with corresponding peak assignment .................................................25
Table 9 Summary of research demonstrating reduction of the contact angle by incorporating
nanoparticles into the pristine polymeric membrane. .......................................................................27
Table 10 Percentage (%) rejection of Cr(III) by different membranes with varying pressure at 2, 3, 5,
and 7 bars .........................................................................................................................................31
Table 11 Percentage (%) rejection of Pb(II) by different membranes with varying pressure at 2, 3, 5,
and 7 bars .........................................................................................................................................32
Table 12 Initial Concentrations of the heavy metals. ..........................................................................40
Table 13 Concentration of the heavy metals during adsorption with stainless steel slag. ...................41
Table 14 Adsorption Capacity of heavy metals ...................................................................................43
Table 15 Concentration of the heavy metal from the overnight solution treated with membrane M 1
at pressure 2,3,5, and 7 bars .............................................................................................................43
Table 16 The table shows the final rejection percentage from adsorption and the membrane with
different pressures. ...........................................................................................................................45
Table 17 Comparison of the concentration of a few treated heavy metals from WHO regulatory limits
.........................................................................................................................................................46

v
List of Figures

Figure 1 Wastewater production share by EU (Procházková et al., 2023) ............................................ 2

Figure 2 Classification of membranes based on solute and Molecular Weight Cut-off (Jang, 2023) ..... 6
Figure 3 Number of publications per year on MMM related to water treatment application(García-
Ivars et al., 2019). ............................................................................................................................... 7
Figure 4 Selectivity of NF membranes ...............................................................................................10
Figure 5 XRD of oxycut powder (García-Chirino et al., 2023). .............................................................13
Figure 6 SEM of oxycut powder .........................................................................................................13
Figure 7 Schematic diagram of membrane preparation by phase inversion method. ..........................14
Figure 8 (a) The casting knife (b) The casting solution over magnetic stirrer .......................................15
Figure 9 Components of FTIR (Mohamed et al., 2017) ......................................................................16
Figure 10 Contact Angle Device .........................................................................................................17
Figure 11 Cross-flow Setup ................................................................................................................19
Figure 12 PEG retention percentage vs molecular weight in Daltons for (a) M 0.05, (b) M 0.5, (c) M 1
and (d) M 3 ......................................................................................................................................20
Figure 13 shows SEM images of the surface at 50 microns, 5 microns, and crossectional 200 microns
respectively for (a) PES (b) M 0.05 (c) M 0.5 (d) M 1 (e) M3 (f) M 5 ..........................................23
Figure 14 FTIR spectrum of all membranes from wavenumber 600 to 1800 cm-1. .............................24
Figure 15 Contact angle measurement in degrees for different membranes ......................................26
Figure 16 Pure Water Permeabilities of PES, M 0.05, M 0.5, M 1, M 3, and M 5 in L.m-2.h-1.bar-1 ........28
Figure 17 Percent Rejection of Sodium Sulphate and Magnesium Chloride by PES, M 0.05, M 0.5, M 1,
M 3 and M 5 .....................................................................................................................................29
Figure 18 Percentage (%) Rejection variation of Cr(III) with different pressures in bars ......................31
Figure 19 Percentage (%) Rejection variation of Pb(II) with different pressures in bars .......................32
Figure 20 The fouling propensity of the membrane at the different time intervals .............................34
Figure 21 Summary of anti-fouling parameters ..................................................................................36
Figure 22 Heavy metals rejection percentage vs time in minutes .......................................................37
Figure 23 The total resistance of the membrane at the different time intervals. ................................39
Figure 24 Concentration profile of (a) Fe (b) Mg (c) Al, (d) Cr,and (e) Zn during adsorption with
stainless-steel slag.............................................................................................................................41
Figure 25 Overnight concentrations of heavy metals .........................................................................42
Figure 26 The concentration of overnight adsorbed solution vs pressures 2,3,5, and 7 bars (a) Fe (b)
Mg (c) Al (d) Cr, and (e) Zn .................................................................................................................44

vi
Abstract

The excessive growth over the last decades of industries such as textile, electrochemical,
petrochemical, and others, have increased the presence of heavy metals in the environment
posing a serious threat. Conventional treatments to mitigate contaminants in industrial
effluents are typically expensive, insufficient, and non-sustainable. In this study, membrane
technology is evaluated for the removal of Cr(III) and Pb(II) with the fabrication of a
sustainable mixed matrix membrane (MMM). An unexplored steel residue, oxycut powder,
was incorporated into the polymeric matrix to assess its potential as a substitute for
commercial iron oxides, moving toward a circular economy approach. Six different
membranes were prepared via phase inversion with different oxycut loads and characterized
by scanning electron microscope (SEM), molecular weight cut-off (MWCO), Fourier transform
infrared spectroscopy (FTIR), and contact angle. The mixed matrix membrane's performance
and heavy metal rejection were determined in a crossflow setup. Membrane M 1
demonstrated high salt and heavy metal rejection rates achieving 97.40% of Cr(III) and
91.88% of Pb(II). The anti-fouling test of membrane M 1 exhibited a flux recovery ratio of
81.82% indicating its robustness against fouling. Finally, M 1 was tested as a second-stage
treatment for wastewater from electroplating, showcasing more than 98% removal efficiency
in a real case scenario, proving the suitability of waste valorization within membrane
fabrication.

vii
Chapter 1
Introduction and Literature Review

1. Introduction

1.1 State of the Problem

The Industrial, while important in advancing modern civilization, also introduced significant
environmental challenges, notably in the form of water pollution. Among these, the
industrial wastewater with heavy metals like lead and chromium is alarming. These
contaminants pose severe risks to environmental and human health, which necessitates
effective solutions.

Key contributors of heavy metals in wastewater are mining operations, manufacturing

sectors, chemical production facilities, and textile industries. Lead contamination in water
sources, especially from industrial activities, is an emerging concern due to neurotoxic effects
that lead to cognitive impairments and developmental delays (Bouida et al., 2022). Similarly,
during certain leather tanning procedures, a variety of chemicals, salts, and auxiliaries are
used at multiple stages. The effluent produced by this procedure contains organic
substances, particulate debris, and notably chromium. Chromium also poses significant
health risks, such as stomach ailments, and lungs cancer, when it contaminates water bodies
(Nur-E-Alam et al., 2020).

In Europe, sustainable practices are marked to approach industrial wastewater treatment

and its reuse. A substantial volume of wastewater, accounting for approximately 25,500
million m3, is generated annually, leading to the adoption of advanced treatment
technologies that aim to treat wastewater and maximize its reuse. So, the European
approach emphasizes reuse, which is particularly significant in water-intensive sectors, as it
is an environmental necessity and a cost-saving measure. Figure 1 illustrates the distribution

1
of wastewater generation in different sectors of the European Union (Procházková et al.,
2023).

Figure 1 Wastewater production share by EU (Procházková et

al., 2023)

1.2 Technologies used in heavy metal removal

Several techniques employed for the elimination of heavy metals include coagulation,
membrane filtration, adsorption, precipitation, and ion exchange (Carolin et al., 2017). Table
1 presents a brief overview of the benefits and drawbacks of different technologies.

Table 1 Comparison of different technologies for heavy metal removal (Abdullah et al., 2019)

Methods Description Advantages Disadvantages

Precipitation Conversions of metal Simple & and high Ineffective in high

ions into insoluble degree of selectivity concentrations of
precipitates either metal ions
hydroxides,
sulphides, etc.
Adsorption Adsorptive materials Wide selections of Desorption
entrap the metal adsorbents
ions by
physical/chemically
interactions
Ion Exchange H+ released from Fast Kinetic Low concentration &
functional groups and highly sensitive
allows the to pH
complexation of
metals with free
functional groups.
Membrane Species transport The high percentage Membrane Fouling
Separation through the driving removal of heavy
force metals

2
2 Membrane Technology

Membrane technology offers results in higher-quality treated water, with better control over
removing contaminants and lower energy consumption. Traditional water treatment often
requires harsh chemicals for coagulation, but in membrane-based separation, chemicals are
reduced or sometimes eliminated, making them environmentally friendly. Although
membrane-based separation is often adopted over other methods for heavy metal removal,
it can effectively remove a wide range of contaminants like microorganisms, particulates, etc
(Madhura et al., 2018).

The advantages offered by membrane technology are numerous over other wastewater
treatments. Membrane separation processes are highly selective in nature based on pore
size, charge, and other properties for different kinds of contaminants (Obotey Ezugbe &
Rathilal, 2020). The scalability of the membrane is also one of the factors that enhance their
versatility and suitability for small and large-scale treatment (Siagian et al., 2023). However,
in contrast to the adsorption and ion exchange, the minimum use of chemicals is there and
hence supports less secondary waste generation (Tilebon et al., 2024) (Van Der Bruggen et
al., 2003).

2.1 Membrane Separation Process

The membrane separation process is controlled by the transportation of different species

over the membrane, which is caused by the driving force. The driving force is determined by
the gradient of chemical potential. The majority of membrane-based processes are
controlled by the rate. In general, the chemical potential can be categorized as –

1. Concentration Gradient
2. Temperature Gradient
3. Pressure Gradient
4. Electrochemical Potential Gradient.

The term "chemical potential" refers to the availability of free energy during a reaction. It can
be very challenging to quantify the chemical potential, however, it is typically expressed to

3
easily measurable characteristics such as concentration, pressure, temperature, or the
electrochemical potential gradient. If the purpose of the membrane process is to increase
the concentration of a substance, then the retentate is the resulting product stream.
However, in most purification procedures, the desired product stream is the permeate
(Conidi et al., 2023). Characterization of a specific membrane depends upon its affinity to
accomplish a particular type of separation. Transport through a membrane is due to the
driving force and the permeation rate through the membrane is proportional to the driving
force. A phenomenological equation describes the relationship between flux and force which
is a linear equation (Chae & Kim, 2021).

𝑑𝑌
𝐽 = −𝐾 Equation 1
𝑑𝑦

𝑑𝑌
where, 𝐾 is the phenomenological coefficient, and, 𝑑𝑦 is the potential gradient where, 𝑌 can

be temperature, concentration or pressure, etc. The above equation can be expressed and
used for mass transfer, heat flux, volume flux, momentum flux, etc. Table 2 below describes
different transport phenomena (Gratz, 2002),

Table 2 Different Flux governed by different equations and laws

Flux Equation Law

Mass Flux 𝑑𝑐 (Fick)
𝐽𝑚 = −𝐷
𝑑𝑥
Heat Flux 𝑑𝑇 (Fourier)
𝐽ℎ = −𝜆
𝑑𝑥
Volume Flux 𝑑𝑃 (Darcy)
𝐽𝑣 = −𝐿𝑝
𝑑𝑥
Electric Flux 𝑑𝐸 (Ohm)
𝐽ℎ = −𝐼/𝑅
𝑑𝑥

2.2 Membrane Classification and its Application

The membrane performance is primarily determined by two factors: the chemical

composition of the membrane and its physical properties. The membrane's relative
permeability to a specific feed solution is crucial for achieving the necessary separation.
Several important characteristics of membranes include porosity, surface chemistry, pore

4
size distribution, and chemical and physical compatibility. Membranes can consist of a
diverse range of materials, including polymers, metals, and ceramics. Inorganic membranes,
specifically metallic and ceramic membranes, are preferred for applications that involve
extreme environments due to their durability and resilience. Polymeric membranes are the
most preferred for separating heavy metals from wastewater, as they are comparatively
more cost-effective to produce. They are commonly referred to as organic membranes. The
membranes employ several polymers such as Polyamide, Cellulose Acetate (CA), Polysulfone
(PS), Polyether Sulfone (PES), Polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), and
others (Abdel-Fatah et al., 2021) as mentioned in Table 3.

Table 3 : Common polymers in manufacturing different types of membranes (Abdel-Fatah et al., 2021), (Zahid et al., 2018)

Separation Process Polymer

Reverse Osmosis (RO), Microfiltration (MF), Polyamide (PA), Cellulose acetate (CA),
Polysulfone (PSF), Polyether sulfone (PES),
Ultrafiltration (UF) and Nanofiltration (NF)
Polyvinylidene fluoride (PVDF), Polyimide
(PI), Polyethylene (PE), Polypropylene (PP),
Polyacrylonitrile (PAN), Polyethylene
terephthalate (PET), Polydimethylsiloxane
(PDMS), Polyetherimide (PEI)

Gas Separation and Pervaporation (PV) Polyacrylonitrile (PAN),

Polydimethylsiloxane (PDMS)

Pressure-driven membrane processes can be categorized into four basic types: microfiltration
(MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO). The four pressure-
driven processes described below the graphic rely on the pore size of the membranes and
the type of solute to be removed as mentioned in Figure 2.

5
 Figure 2 Classification of membranes based on solute and Molecular Weight Cut-off (Jang, 2023)

The primary advantage of membrane separation is its minimal energy consumption, as it

does not require the expenditure of latent heat during phase shift. The MF membrane has
the highest pore size, while the pore size of the RO membrane is significantly reduced.
Various membrane pore diameters with varying pressures are utilized based on the presence
of distinct unnecessary solutes shown in Table 4 (Saleh & Gupta, 2016).

Table 4 Membrane Application Matrix (Saleh & Gupta, 2016)

Application Microfiltration Ultrafiltration Nanofiltration Reverse

(MF) (UF) (NF) Osmosis (RO)
Water Reuse    
Desalination  
Softening 
Colour  
Organic  
Removal
Heavy Metals  
Clarification  

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2.3 Mixed Matrix Membrane (MMM) in water treatment
A mixed matrix membrane (MMM) is a type of membrane in which an inorganic filler is
evenly distributed inside a continuous polymer media. Historically, polymeric membranes
have been cost-effective and versatile, serving a wide range of purposes. However, their
intrinsic constraints, such as the trade-offs between permeability and selectivity, make them
less suitable for some separation processes. Inorganic membranes provide enhanced
separation characteristics compared to polymeric membranes due to their precisely defined
pore structures and selectivity. However, their brittleness and challenges in fabrication
contribute to their high processing costs on a wide scale. The concept of mixed matrix
membranes (MMM) was developed to overcome the limitations of both polymeric and
inorganic membranes (Klaysom & Shahid, 2019). The selection of membrane material is crucial
in determining the occurrence of fouling phenomena. In general, polymers containing
hydrophobic elements tend to exhibit more fouling and, as a result, experience a decrease in
permeability. The inclusion of hydrophilic nanoparticles not only enhances water
permeability but also effectively rejects heavy metals without sacrificing mechanical
integrity. The incorporation of fillers increases the ratio of surface area to volume, hence
generating a greater number of active sites for adsorption and filtration (García-Ivars et al.,
2019). Figure 3 below shows the growing development of MMM in water purification.

Figure 3 Number of publications per year on MMM related to water treatment application(García-Ivars et al.,
2019).

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2.4 Relevance of Oxycut in MMM Preparation
Inorganic fillers are of significant importance in enhancing the performance of Mixed Matrix
Membrane (MMMs). These inorganic fillers have high ion exchange capacity and selection
adsorption properties which enhance the effectiveness of the membrane.

2.4.1 Overview of metal oxides in MMM Preparation

The numerous comparative studies of metal oxides demonstrate that they possess varying
degrees of strengths and limitations, in enhancing the performance of polymeric
membranes. Some of these metal oxides are titanium dioxide (TiO2), zinc oxide (ZnO), iron
oxide (Fe2O3), and silicon dioxide (SiO2), etc. Titanium dioxide (TiO2) and zinc oxide (ZnO) are
known for their photocatalytic and antibacterial properties, which improve the antifouling
capabilities of the membranes and result in the efficient removal of metals like lead (Pb(II))
and cadmium (Cd(II)). Nevertheless, these nanoparticles may sometimes experience
agglomeration resulting in a decrease in their effective surface area (Chen et al.,
2020)(Maqbool et al., 2023) On the other hand, silicon dioxide (SiO2) is the best filler for
providing mechanical strength and thermal stability which contribute durability and
longevity of the polymeric membrane. SiO2-dispersed membranes exhibit improved
performance in (Cu(II)) and (Zn(II)) removal (Wang et al., 2013). Conversely, Iron oxide
nanoparticles have magnetic properties, which help in easy membrane recovery. The
chromium Cr((III)) and arsenic (Ar(V)) removal are facilitated due to the magnetic properties
efficiently. But despite their advantages, iron oxide nanoparticles pose issues with potential
oxidation (Adam et al., 2019).
In summary, metal oxide fillers demonstrated the potential removal of heavy metals with
improved performance of the membrane. However, it is important to note that each filler
has its own set of limitations. By exploring more alternative fillers, it is possible to develop
more sustainable and efficient membrane technologies for better water treatment
applications.

8
2.4.2 Oxycut Powder as MMM Filler
The oxycut powder is a residual substance generated during the process of cutting scrap
metal in the carbon steel sector. Primary conformed of iron oxides (71.90%, Fe 2O3). It can
serve as a substitute for commercially available iron oxides (García-Chirino et al., 2023).
Table 5 shows the chemical composition of oxycut powder (weight %).
Table 5 XRD of oxycut powder (García-Chirino et al., 2023).

Chemical Fe2O3 ZnO MnO SO3 NiO CaO P 2O5 Cr2O3 CuO MoO3
Composition
Weight (%) 71.90 26.20 0.28 0.23 0.23 0.21 0.12 0.10 0.10 0.10

The iron-based nanoparticles provide a wide spectrum of contaminant removal through

diverse mechanisms, including adsorption, ion exchange, redox reactions, etc (Aragaw et al.,
2021). The adaptability and high efficiency demonstrated by these nanoparticles, make them
suitable candidates for integration into MMMs. By incorporating the oxycut as an industrial
residue into the polymeric membrane, we can understand the unique merits of oxycut as a
novel and potential material by comparing the properties and application of other fillers. The
use of residues is crucial for transitioning towards a circular economy, as it enables, waste
valorization for the fabrication, and preparation of material and sustainable solutions for
water treatment technologies.

2.5 Mixed Matrix NF membrane

Nanofiltration is a membrane filtration process that selectively blocks dissolved solutes with
diameters around 1 nanometer (10 Angstroms), positioned between the cutoffs of reverse
osmosis (RO) and ultrafiltration (UF). Nanofiltration (NF) membranes are highly efficient in
removing various substances such as organics, insecticides/pesticides, herbicides, sugars,
and pyrogens. The extraction of monovalent ions from salts such as sodium, potassium, and
chlorides is rather mild. The NF membrane incorporates the characteristics of both RO and
UF membranes, since it effectively separates ions based on their size and electrical
properties, taking advantage of the ion interaction principles of RO. Figure 4 shows the
selectivity of NF membranes based on different solutes (Kamcev & Freeman, 2014).

9
 Monovalent Multivalent Bacteria/Viruses Suspended
Water
Ions Ions Solids

Figure 4 Selectivity of NF membranes

2.5.1 Transport mechanism in NF membranes

Most NF membranes possess hydrophilic properties. When it comes to uncharged solutes,
particularly organic molecules in an aqueous solution, separation primarily occurs through
the sieving effect. There is minimal contact between the solutes and the membranes.
As the mechanism operates based on pressure, the equation that governs the transport of
solvent flux is the Hagen-Poiseuille equation. This equation is derived from the Navier-Stokes
equation, considering certain boundary conditions, the control volume, and membrane
pores as cylindrical (Nagy, 2019).

Solution-Diffusion Theory
The membrane functions as the porous layer where the solvent and solute (ion) dissolve.
The movement of water is driven by hydraulic pressure, while the transportation of solute is
influenced by concentration gradient forces. Convection, diffusion, and electromigration are
the fundamental mechanisms by which solutes are transported across the membrane
module. Diffusion occurs as a result of the concentration potential gradient, while
convection is generated by the movement of the solvent. Electromigration, on the other
hand, is the result of the attraction or repulsion of charges within the thickness of the
membrane module (Nagy, 2019).

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Donnan Exclusion
The phenomenon of decreasing the concentration of mobile ions in an ion exchange
membrane as a result of the presence of fixed charges. The NF membrane possesses a small
charge, resulting in the repulsion of solutes with comparable charges and the attraction of
solutes with opposing charges. The counter ions are drawn towards the immobile charges of
the membrane, resulting in an elevated concentration relative to the surrounding bulk
solution and the creation of a potential difference at the interface between the membrane
and the bulk solution. This phenomenon occurs because of the repulsion of similarly charged
counterions, resulting in their rejection. On the other hand, the co-ions can pass through
(Teow et al., 2021).

3 Objective
This study aims to examine the potential and effectiveness of oxycut powder as an
alternative filler to prepare sustainable Mixed Matrix Membranes (MMMs) to remove heavy
metals, specifically chromium (Cr(III)) and lead (Pb(II)) from industrial wastewater.

The specific objectives are as follows:–

1) Membrane Development - Mixed Matrix Membranes (MMM) preparation by adding
oxycut powder in different weight percentages into the polymer matrix.
2) Characterization of the Membranes - Physiochemical analysis of all the prepared
membranes to ascertain their inherent characteristics.
3) Performance - Evaluation of the fabricated membranes in terms of their permeability and
heavy metals retention. Determining the most efficient configuration of oxycut-polymer
membranes.

11
Chapter - 2
Materials and Methods
This chapter describes the fabrication of mixed matrix membrane (MMM) and the
methodology used to employ MMM in the heavy metal removal experiment. The chapter
also gives an overview of materials utilized in membrane fabrication. The phase inversion
method was used to cast the membranes, and Fourier Transform Infrared Spectroscopy
(FTIR), Contact Angle (CA), Molecular Weight Cut-Off (MWCO), and Scanning Electron
Microscope (SEM) were employed to characterize their physiochemical properties. The
performance of the membranes was assessed using a Cross Flow Filtration (CFF) setup.

1 Chemicals
The chemicals used for preparing the casting solution were Polyether sulfone (PES, BASF CO.
Ltd., Germany), N, N – Dimethylacetamide (DMAc, VWR Chemicals BDH),
Poly(vinylpyrrolidone) (PVP, MW 40,000, AMRESCO) and oxycut powder an industrial residue
produced in Monterrey, Mexico. For supporting the membrane a non–woven polypropylene
fabric (Novatex - 2471) with a thickness of 0.18 mm (Freudenberg Group, Germany) was
used. For calculating Molecular Weight Cut-off (MWCO), the neutral solute used was
Polyethylene glycol (PEG, MW 400, 600, 1000, 2000, and 3000 Sigma-Aldrich) (PEG, MW 200,
ACROS Organics) (PEG MW 8000, Alfa Aesar). The heavy metals solutions were prepared
with Lead (II) Chloride (PbCl2 98 %, Sigma-Aldrich), Zinc Chloride (ZnCl2, 98 %, AnalaR BDH),
and Chromium (III) sulfate hydrate (Cr2(SO4)3 98 %, Sigma-Aldrich). Deionized water (DI) was
used in all experiments.

1.1 Oxycut Powder

The sample used in this work was produced in Mexico. Figure 5 shows the X-ray diffraction
pattern (XRD) of oxycut (M = magnetite and Z = zincite) demonstrating that this residue was
composed primarily of magnetite, owing to its capacity to remove heavy metals.

12
The morphology of the raw oxycut powder (Figure 6) was characterized by its non-porous,
coarse surfaces and variable particle sizes (García-Chirino et al., 2023).

Figure 5 XRD of oxycut powder (García-Chirino et al., 2023).

Figure 6 SEM of oxycut powder

2 Membrane Preparation
The phase inversion method is used to prepare the polymer solution (casting solution) for
casting the membrane. The composition of the casting solution included PES, DMAc, PVP,
and an oxycut at different concentrations (Figure 7). Table 6 details the variation in the

13
percentages of oxycut and DMAc utilized in fabricating various membranes. Stirring the
solution over a magnetic stirrer (Figure 8 (b)) at ambient temperature for twenty-four
hours. With the assistance of a casting knife (Figure 8 (a)) with a 200 µm gap, the casting
solution is cast on a non-woven polypropylene/polyester fabric supporting layer.
Immediately after that, it is submerged in a coagulation bath, also known as a gelation bath
containing deionized water. There will be an exchange in the solvent (DMAc) from the
polymer matrix and the deionized water from the coagulation bath because of the
concentration gradient which results in pore formation. The process of exchange of the
solvent and the DI water is known as demixing. The pore size of the polymeric membranes
can be controlled by controlling the extent of demixing. If the demixing is quick, precipitation
occurs fast and results in the formation of a dense polymer matrix. However, if the demixing
is delayed, finger-like pores or macrovoids are formed which are less uniform but more
interconnected (Rahimpour et al., 2024). After two hours in the water immersion, allow it to
air dry for two hours. The membranes are subsequently submerged in DI water until the
residual solvent has been completely leached.

Polymer (PES)
+
Solvent (DMAc)
+
Coagulation Bath
Additives Flat-Sheet
Casting Solution (DI Water)
(PVP)
Demixing membrane
+
Metal oxides
/Nanoparticles
(Oxycut)

Figure 7 Schematic diagram of membrane preparation by phase inversion method.

14
Table 6 Different composition of the casting solution.

Membrane PES (%) PVP (%) Oxycut (%) DMAc (%)

PES 20 1 0 79
M 0.05 20 1 0.05 78.95
M 0.5 20 1 0.5 78.50
M1 20 1 1 78
M3 20 1 3 76
M5 20 1 5 74

(a)

(b)
Figure 8 (a) The casting knife (b) The casting solution over magnetic stirrer

15
3 Membrane Characterization
3.1 Fourier Transform Infrared Spectroscopy
In the FT-IR setup, infrared radiation is passed through the sample, and the IR absorption
band in the spectrum to the wave numbers is used to identify the different chemical
components. Based on the specific peaks in the spectrum, we can observe various types of
bonds absorbed in the region as shown in Figure 9.

Figure 9 Components of FTIR (Mohamed et al., 2017)

3.2 Contact Angle (CA) Measurement

The measurement of contact angle on membrane surfaces is crucial for understanding their
wetting properties, it’s a direct indicator of its wettability or hydrophilicity. A lower contact
angle suggests a hydrophilic nature and a higher angle indicates hydrophobicity, where
water interaction is minimal. Figure 10 shows the contact angle device.

16
 Figure 10 Contact Angle Device

3.3 Scanning Electron Microscope

Scanning electron microscopes (SEMs) employ a focused beam of electrons to generate
highly detailed images of samples, thereby revealing the surface features, composition, and
internal structure of materials.

3.4 Molecular Weight Cut-Off

Molecular weight cut-off (MWCO) also known as nominal weight cut-off is the minimum
molecular weight when 90% of the solute is retained by the membrane. It is a gross
interpretation of the pore size of the membrane. For MWCO testing, charged solutes are
generally avoided and neutral solutes like (Polyethylene glycol) PEG, dextral, etc. of different
molecular weights are used (Drioli et al., 2016).
The pore size can be calculated based on Stokes diameter Equation 2,

17
 𝑑𝑠 = 33.46 × 10−3 × 𝑀0.557 Equation 2

where, 𝑑𝑠 is the stokes diameter in nm and M is the molecular weight cut-off (Y. Guo et al.,
2022).

4 Membrane Performance

The performance of the membrane is determined by two crucial factors: (a) Flux or
penetration rate, and (b) Selectivity of the membrane. The flux is commonly described as the
rate at which volume flows across the membrane per unit area.

The volume flow is measured in 𝐿. 𝑚−2 . ℎ−1 . 𝑏𝑎𝑟 −1 The conversion of volume flux to mass
flux can be achieved by multiplying it by the density ρ. Similarly, to obtain the molar flux rate,
the volume flux should be multiplied by the density ρ and divided by the molecular weight
M. Figure 11 shows the cross-flow setup used in the experiment,

The membrane's selectivity is quantified by the retention factor. It is the retention rate,
denoted by "R".

The retention is given by Equation 3 –

𝑐
𝑅 = 1 − 𝑐𝑝 Equation 3
𝑓

where 𝑐𝑝 and 𝑐𝑓 are the solute concentration in permeate and feed respectively and 𝑅, is the
dimensionless parameter. The value of retention varies from 0% (complete retention) to 100
% (no retention and the component passes through the membrane freely) (Lewis, 2023).

4.1 Heavy metals and salt rejection

The heavy metal solutions were prepared using chromium (III) sulphate (Cr2(SO4)3) and lead
(II) chloride PbCl2 of concentrations 10mg/L, 30mg/L, 70mg/L, and 100mg/L. Each
membrane is then subjected to pressure tests at 2, 3, 5, and 7 bars. Na 2SO4 and MgCl2
solutions, with an initial concentration of 1000mg/L, were tested for salt rejection and
measured with a conductivity meter. The concentration of heavy metals in the permeate was
determined by Inductive Coupled Plasma Optical Emission Spectrometry (ICP-OES).

18
4.2 Antifouling tests

The test was performed for 6 hours at 5 bars on the best-selected membrane using a mixture
of heavy metals Cr(III), Pb(II), and Zn(II) at an initial concentration of 115mg/L, 40mg/L and
115mg/L respectively. The solution's flux is determined for a time interval of 20 minutes,
along with the corresponding rejection percentages. The flux recovery rate is determined by
calculating the clean water flux both before and after the heavy metal rejections. 𝑃𝑊𝐹𝑖 and
𝑃𝑊𝐹𝑓 are the pure water flux before and after the heavy anti-fouling test. The flux recovery
ratio is given by equation 4, (Nadig et al., 2021)

𝑃𝑊𝐹𝑓
Flux Recovery Ratio = Equation 4
𝑃𝑊𝐹𝑖

Figure 11 Cross-flow Setup

19
 Chapter-3
Results and Discussions
1. Membrane Characterization

1.1 Molecular Weight Cut-off (MWCO)

The membranes M 0.05, M 0.5, M 1, and M3 exhibited variations in MWCO values as shown
in Table 7 which can be attributed to the different percentages of the oxycut, influencing the
interaction with the polymer. Regarding the PES membrane, 90% retention was not
reached, so the calculation was not determined, due to the dense structure of the pristine
PES membrane which does not possess enough porosity to reject PEG molecules effectively.
The MWCO is positively related to the average pore size. However, in some studies, MWCO
can vary with different morphologies of the PES, from 1000 to 50,000 daltons (Du et al.,
2022). Figure 12 below shows the graph between the molecular weight and the retention
percentage of the other four membranes.

(a) (b)

(c)
(d)

Figure 12 PEG retention percentage vs molecular weight in Daltons for (a) M

0.05, (b) M 0.5, (c) M 1 and (d) M 3

20
Table 7 Pore size in nm for M 0.05, M 0.5, M 1, and M 3

MWCO in
Membrane Type Pore size in (nm)
(Daltons)

M 0.05 6494.5 4
M 0.5 1133 1.68
M1 596 1.17
M3 5486 4.04

The concentration of oxycut increases from M 0.05 to M 1, and MWCO decreases, resulting
in a reduction in the membrane's pore size. The increase in nanoparticle loading affects the
membrane structure by inhibiting the formation of macro-voids, leading to a denser
membrane structure (Panda et al., 2015). The M 0.05 can be classified as an ultrafiltration
membrane (UF) membrane based on its MWCO which falls within the range of 6-8 kDa for UF
membranes (V, 2017).

Nevertheless, MWCO increases once more for M 3, as little alterations could be attributed to
the operational circumstances encountered during the membrane preparation (Chung et al.,
2022). The inability of the M 5 membrane to achieve 90% rejections underscores that at very
large concentrations of the oxycut, the effective surface area reduces drastically resulting in
the strength and stability of the membrane (García-Ivars et al., 2019).

Typical NF membranes have MWCO ranging between 200 to 2000 Da (Koyuncu et al., 2015).
The membranes M 1 and M 0.5 mentioned in Table 7 have pore sizes in the order of 1 nm,
comparable to the conventional NF membrane, which has a pore size ranging from 0.5 nm to
2nm (Siddique, 2023). Membrane M 1 with a MWCO less than 500 Da can be referred to as a
tight NF membrane. Numerous studies show that these membranes are widely used
commercially and exhibit outstanding performance (Chakrabarty et al., 2022).

21
1.2 Scanning Electron Microscope (SEM)

(a)

(b)

(c)

(d)

(e)

22
 (f)
Figure 13 shows SEM images of the surface at 50 microns, 5 microns, and crossectional
200 microns respectively for (a) PES (b) M 0.05 (c) M 0.5 (d) M 1 (e) M3 (f) M 5

The SEM images of the different membranes are depicted in the above figures. The pristine
membrane in Figure 13 (a) reveals a uniform and smooth surface morphology, showing a
consistent matrix and the baseline texture is important for comparing the effects of
incorporating the fillers. The cross-sectional view indicates a tight polymeric matrix with a
dense and homogenous structure. However, from Figure 13 (b) the addition of filler in M
0.05 reflects minor heterogeneities whereas the large finger-size pores can be observed in
the cross-sectional image. This shows that by adding a specific percentage of fillers the
small-sized pores are transformed into finger-like micropores (Mondal et al., 2017).

On the other hand, as the concentration of the filler increases, notably to 0.5 % to 3%, more
white patches become evident, indicating aggregation of the particles, which suggests the
incompatibility between the polymer matrix and nanomaterial (van den Berg & Ulbricht,
2020) Figure 13 (c). The M 1 and M 3 membranes in Figure 13 (d) and Figure 13 (e) exhibit
more rough and dense filler distributions compared to M 0.05 and M 0.5 which affects the
effective porosity and connectivity. This is because strong van der Waals forces influence the
increased nanoparticle interaction, reducing the membrane’s effective area and impacting
its performance (Lavagna et al., 2020). Finally, M 5 displays contrasting results in Figure 13
(f) huge pores and uneven mixing, highlighting difficulties in integrating higher filler
concentrations with the polymeric membrane. We can conclude from the above observation
that a pristine PES membrane may show the least permeability due to its dense structure.
Conversely, membranes with the oxycut may demonstrate high permeability because of the

23
formation of macro-voids which facilitate fluid flows by creating pathways through the
membranes.

1.3 FTIR Analysis

The range between (1665 -1675 cm-1 )for the assigned peak 1665 cm-1 is characterized by
C=C stretching of alkenes. A second notable peak at 1579 cm -1 (1475-1600 cm-1) indicates
aromatic stretching between carbon atoms. Around 1487 cm -1, the C-H alkane methylene
group was observed. Furthermore, the peak at 1404 cm -1 (1330-1420 cm-1) corresponds to
the bending of O-H bonds in alcohols. The sulfone groups (1120-1160 cm-1) exhibited S=O
stretching, as indicated by the peak at 1151 cm-1, while the C-O alkyl aryl ether group was
detected at 1238 (1200-1275 cm-1). C-O stretching aliphatic ethers were identified at 1105
cm-1 (1085-1150 cm-1), followed by C=C bending alkenes at 835 cm-1 (790-840 cm-1). Table 8
shows the classification of different functional groups.

Figure 14 FTIR spectrum of all membranes from wavenumber 600 to 1800 cm-1.

24
Table 8 Summary of spectrum with corresponding peak assignment

Peak Assignment (cm-1) Peak Range (cm-1) Functional Group

1665 (1665-1675) C=C stretching alkene
1579 (1475-1600) C=C aromatic
1487 ~ 1465 C-H alkane methylene group
1404 (1330-1420) O-H bending alcohol
1238 (1200-1275) C-O Alkyl aryl ether
1151 (1120-1160) S=O stretching sulfone
1105 (1085-1150) C-O stretching aliphatic ether
835 (790-840) C=C bending alkene

The above functional groups are common with the pristine PES membrane and other
membranes with fillers (“Infrared Spectroscopy Absorption Table,” 2014) (Arahman et al.,
2022)(Mohamed et al., 2017). Whereas, the membranes M 3 and M 5, which contain the
most significant proportions of oxycut fillers and are evident in most peaks exhibit the largest
peaks compared to other membranes at various wavenumbers among all membranes, with
PES following suit. However, specific peaks detected at 1665 cm -1, 1404 cm-1, 1073 cm-1, and
1011 cm-1 might indicate the oxycut, predominantly composed of iron oxides. The hydroxyl
group (OH) can also be linked to the presence of oxycut fillers. It can create strong complexes
with heavy metals and enhance the adsorption of heavy metal ions onto the membrane
surface, successfully eliminating them from wastewater. Comparing it to studies concerning
the characterization of iron oxides reveals that certain peaks observed at 1060 cm-1, 1026
cm-1, and within the range of 1641-1665 cm-1 are similar to the spectrum depicted in Figure
14, (Murtaza & Zaheeruddin, 2019).

25
1.4 Contact Angle (CA) measurement

Figure 15 Contact angle measurement in degrees for different membranes

Figure 15 shows the contact angles of all the membranes. The PES membrane has an angle of
approximately 80.31o. Typically, a contact angle less than 90o is classified as hydrophilic. In
addition, dispersing nanoparticles reduces the contact angle further, leading to an increase in
hydrophilicity and improving permeation. However, for M 0.05, the contact angle decreases
to 48.35o. Similarly, in several research, the addition of a nanocomposite consisting of silver
nanoparticles (AgNPs), halloysite nanotubes (HNTs), and reduced graphene oxide (rGO) into
the PES matrix resulted in a decrease in contact angle (Zhao et al., 2015). The high exposure
of these particles on the membrane surface reduces interface energy. However, as a load of
oxycut increases, the contact angle also increases as indicated from the chart, membrane M
0.05 (48.35o) to M 0.5 (55.25o) and continuously increases from M 0.5 (55.25o), M 1 (62.42o)
and the highest with M 3 (70.65o). This high concentration results in a higher surface energy,
making the particles more likely to agglomerate and seek more thermodynamic stability.

26
Consequently, this affects the hydrophilicity and selectivity of the membrane (García-Ivars et
al., 2019) (Moradi et al., 2022). At last, membrane M 5 showed the lowest contact angle of
45.80o indicating the highest hydrophilicity, which is probably due to very large macropores
caused by uneven dispersion of oxycut. Table 9 provides a summary of various research from
several studies that demonstrate a reduction in contact angle by adding nanoparticles.

Table 9 Summary of research demonstrating reduction of the contact angle by incorporating nanoparticles into the pristine
polymeric membrane.

Polymer Filler Contact Angle Contact Angle Sources/References

of pristine of the
membrane membrane with
(in degrees) nanoparticles
(in degrees)

PES Hydrous 69.50 16.40 (Jamshidi Gohari et

Manganese al., 2014)
dioxide (HMO)

PES Titanium 73.00 20.28 (Shruti Singh,

dioxide (TiO2) 2018)

Halloysite 81.39 50.30 (Wan Ikhsan et al.,

nanotube – 2018)
PES
hydrous ferric
dioxide (HNT-
HFO)

PES - CA Silver Oxide 73.00 60.25 (Gul et al., 2017)

(Ag2O)

27
In summary, it is essential to consider the relationship between the membrane's contact
angles and its permeability. Membranes M 0.05 and M 5 have lower contact angles and are
more hydrophilic, facilitating increased permeability. Conversely, membranes M 1 and M 3,
which have higher contact angles, may demonstrate lesser permeability. Hence, the
correlation indicates that variations in the contact angle can arise due to changes in the filler
concentration, which directly impacts the membrane's permeability.

2 Membrane Performance

The membrane's performance was assessed based on its permeability and quality, which are
determined by the concentration of the permeate or the retention of solutes. The
experiment involved the use of two heavy metals, namely trivalent chromium (Cr (III)) and
lead (Pb (II)) along with two salts, Na2SO4 and MgCl2. The heavy metals were tested at varying
concentrations and operating pressures.

2.1 Membrane Permeability / Pure Water Permeability

Figure 16 Pure Water Permeabilities of PES, M 0.05, M 0.5, M 1, M 3, and M 5 in L.m-2.h-

1.bar-1

28
The pure water permeability of the six membranes is displayed in Figure 16. It was
determined to be 8.91, 36.08, 21.65, 16.84, 13.78, and 44.57 L.m -2.h-1.bar-1 for PES, M 0.05,
M0.5, M 1, M 3, and M 5 respectively at 2 bars. The increased permeability of the
membrane is due to enhancement in membrane porosity, which is the consequence of the
increased exchange rate between solvent and non-solvent that occurs during immersion
precipitation (Birsan et al., 2021). The lowest load of oxycut (0.05%) exhibited a permeability
around 4 times higher than the pristine PES membrane. This behavior may be due to the
addition of the nanomaterial filler to the casting solution enhancing thermodynamic
instability, resulting in an accelerated solvent-non-solvent exchange, known as demixing ,
and the creation of macro voids (Idris et al., 2017).
Nevertheless, the permeability reduces when the concentration of oxycut filler surpasses
0.05 %, i.e., for 0.5 %, 1 %, and 3 % because the viscosity of the casting solution is increased
by adding more filler, resulting in a delay in demixing and the development of a dense layer
(Dutta et al., 2021) (Tshindane et al., 2023). Also, the accumulation of fillers results in a
reduction in the effective area of the particles and further reduces the flux (Tembhare et al.,
2021). Finally, M 5 presented the highest permeability which may be attributed to the
extremely large defective pore size of the membrane.

2.2 Salt Rejections

Figure 17 Percent Rejection of Sodium Sulphate and Magnesium Chloride by PES, M 0.05, M 0.5, M 1, 29
M 3 and M 5
Figure 17 displays the salt rejection performance of all the synthesized membranes when
exposed to two salts, MgCl2 and Na2SO4. The order of salt rejections was as follows: MgCl2 >
Na2SO4. This is because the Mg2+ ion possesses a greater and more tightly bound hydrated
radius than Na+, due to having a higher charge. As a result, Mg2+ experiences a stronger
repulsive force from the membrane compared to Na+ which facilitates greater rejection from
the membranes (Gholami et al., 2022) (Tansel et al., 2006). Reverse osmosis (RO) membranes
effectively eliminate all dissolved salts from water with a high efficiency ranging from 95% to
99%. On the other hand, nanofiltration (NF) membranes have a lower effectiveness of
approximately 80% to 85% in removing bi- or tri-valent ions (such as Ca2+, Mg2+, and Al3+) and
an even lower efficiency of up to 40% in removing monovalent ions (such as Na +, K (Brandt et
al., 2017). Consequently, the pristine PES membrane exhibited the lowest rejection rate for
Na2SO4, which is 46.21%. However, when membranes are enhanced with fillers, in the case
of oxycut, the rejection rate varies from 67% to 91% due to the Donnan effect, which causes
the counter ions to be rejected (Gholami et al., 2022).
The incorporation of oxycut in the mixed matrix membranes fabrication showed encouraging
outcomes in eliminating salts from water. Selectively rejecting the divalent ions while
allowing the passage of monovalent ions, contributes to the advancement of sustainable
water treatment of different wastewaters to facilitate water reuse applications.

2.3 Heavy Metal Rejection

The study shows the rejections of heavy metal Cr and Pb with an initial concentration of 100
mg/L with varying pressure in the order of Cr(III) > Pb(II).

Table 10 and Figure 18 show a consistency pattern of higher rejection rates for chromium (III)
as the pressure increases across all types of membranes. The rejection percentages varied
from 89.15% to 95.14% when the pressure was at 2 bars, then subsequently increased to
89.68% to 97.86% when the pressure was at 7 bars. Among the membranes, the M 3
membrane exhibited the highest rejection rates at elevated pressures, reaching a maximum
of 97.86% at 7 bars, with a final concentration of 2.19 mg/L of Cr(III).

30
 Figure 18 Percentage (%) Rejection variation of Cr(III) with different pressures in bars

Table 10 Percentage (%) rejection of Cr(III) by different membranes with varying pressure at 2, 3, 5, and 7 bars

Pressure PES M 0.05 M 0.5 M1 M3 M5

(bars)
2 89.15 89.83 90.29 93.39 95.14 92.75
3 89.24 89.81 93.03 93.86 96.26 91.86
5 89.62 91.00 93.40 94.46 96.47 90.77
7 89.68 95.73 96.05 97.40 97.86 90.04

In contrast, the rejection of lead exhibited a more diverse pattern in Figure 19 and Table 11.
The rejection percentages varied greatly between 9.64% and 90.79% at 2 bars of pressure,
with a significant rejection rate of 90.79% found in the M 1 membrane. The pattern of
experiencing high rejection rates with the M 1 membrane persisted at all pressures, reaching
its highest point at 91.88% when the pressure was set at 7 bars. Nevertheless, all other
membranes did not exhibit a consistent pattern in rejection rates with rising pressure, with
specific membranes displaying an increase, while others like M 0.5 and M 5 indicate
an overall decline in rejection percentages with increasing pressure likely due to fast

31
membrane fouling. Membrane M 1 has proved better suitable for effective lead removal due
to its high and consistent rejection rates across all pressures.

Figure 19 Percentage (%) Rejection variation of Pb(II) with different pressures in bars

Table 11 Percentage (%) rejection of Pb(II) by different membranes with varying pressure at 2, 3, 5, and 7 bars

Pressure PES M 0.05 M 0.5 M1 M3 M5

(bars)
2 9.64 12.47 79.50 90.79 80.48 51.97
3 9.22 11.12 55.79 90.86 80.42 52.25
5 11.11 15.06 55.59 90.92 80.74 52.94
7 10.62 15.97 55.42 91.88 81.02 48.75

Treatment of Cr(III) by M 1 and M 3 exhibited the highest rejection percentages, however,

the highest Pb(II) was given by M1 at 7 bars. The final concentrations of Cr(III) and Pb(II) are
2.60 mg/L and 8.12 mg/L respectively. The presence of oxycut as a source of iron oxides
contributes to the enhancement of surface charge density and hydrophilicity of the
membrane. The trivalent state of Cr(III) has a higher positive charge and has more tendency
to get adsorbed by oxycut due to strong electrostatic interactions. Additionally, Cr(III) has a
smaller ionic radius than Pb(II), and the affinity to get blocked or adsorbed is higher, being
consistent with the results. In summary, Cr(III) with a higher charge and a smaller size has

32
more hydration energy than Pb(II) leading to more resistance to the diffusion of Cr(III)
resulting in a slowdown of its permeation (Bai et al., 2020; Jumina et al., 2011).

The maximum allowable concentration of total Cr in surface water is 5 mg/L, while the limit
for hexavalent chromium is 1 mg/L (Vaiopoulou & Gikas, 2020). In contrast, the
Environmental Quality Standard (EQS) sets a more stringent limit for Pb(II) compared to Cr
which is 0.0072 mg/L on the inland surface (European Union, 2008).

M 1 emerges as the most suitable membrane based on the performance of heavy metal
removal, demonstrating high rejections for lead across all pressures with the best removal at
7 bars achieving 91.88% removal, and for Cr(III) 97.4% at the same pressure. This makes M 1
an ideal choice for the subsequent antifouling test. For long-term operations and
maintenance, the antifouling properties are very crucial.

2.4 Anti-fouling Test

To investigate the performance over time of M 1 when exposed to contaminants, an

antifouling test was performed as indicated in section 2.4. Figure 20 includes a detailed
analysis of the antifouling properties of membrane M 1, focusing on flux behavior under
different conditions. To explore further the antifouling properties of the membrane, zinc (II)
was also included, together with chromium (III) and lead (II). Zinc was selected since it is a
typical heavy metal contaminant present in various industrial wastewater, and its presence
aids in the assessment of the membrane’s antifouling properties more precisely. This
approach ensures a more realistic approach to evaluating the flux recovery and anti-fouling
parameters, where multiple heavy metals are present.

Initially, the membrane was subjected to compaction at 5 bars with deionized water, leading
to flux stabilization. This stability is an indication of the baseline performance of the
membrane, represented in section A in Figure 20. Following the initial compaction and
stabilization with DI water, the feed is replaced with a solution containing approximately 115
mg/L of Zn(II) and Cr(III), and 40 mg/L of Pb. Section B shows the variation of the flux from
minute 80 to minute 400, where it is observed a gradual flux decrease due to membrane

33
fouling. The fouling occurs due to the accumulation of the solute on the upstream surface of
the membrane. This results in a concentration gradient and the process is called
concentration polarization (Matthiasson & Sivik, 1980).

Figure 20 The fouling propensity of the membrane at the different time intervals

Section C (Figure 20) depicts a constant flux, indicating a state of equilibrium between the
fouling process and the membrane’s rejection capacity. The equilibrium demonstrates that
the membrane can afford to resist further fouling with prolonged exposure to heavy metals.
Section C also provides insights into the membrane’s long-term stability without undergoing
significant flux degradation enabling us to identify the threshold limit to the membrane
filtration ability. Moreover, the threshold limits can aid in membrane optimization with
enhanced antifouling properties.
In section D, the heavy metal solution is replaced with DI water again to study the
membrane’s flux recovery ability, and no flux change is observed. The fouling layer over the
membrane does not allow flux to change immediately. However, in section E, a gradual
increase in flux is observed, explaining the beginning of the recovery from fouling. Assessing

34
the membrane’s self-cleaning ability at stage E is crucial since it demonstrates how the flux
begins to recover.
Finally, section F showcases the constant flux value, indicating the recovery from the initial
heavy metal-induced fouling.
Based on the experimental antifouling test, the flux recovery ratio (FRR) is calculated by
comparing the final constant flux of 68.88 L/m2-h with the initial baseline flux of 84.18 L/m 2-
h. The recovery ratio percentage is 81.82% which is the quantitative measure of the
membrane’s ability to recover its original flux. The relatively high value of the recovery ratio
indicates effective mitigation of fouling and can be reused without significant loss in flux.
The total fouling ratio (TFR) compares the change in flux from baseline flux to post-fouling
constant flux with the initial baseline flux. The total fouling ratio is 30.77%, indicating the
overall fouling of the membrane. The total fouling represents the reversible and irreversible
fouling. Reversible Fouling Ratio (RFR) and Irreversible Fouling Ratio (IFR) explain the
reversible and irreversible fouling phenomenon of the membrane. The reversible fouling
occurs mainly due to the concentration polarization, and mitigation from reversible fouling
can be achieved from backwashing. The RFR percentage is 12.59% obtained by comparing
the recovered flux between post-fouling and recovered flux with the initial baseline flux.
However, the irreversible fouling ratio (IFR) is calculated as 18.18% comparing the initial and
final DI water flux with the initial baseline flux, indicating the interaction of the heavy metals
(solutes) with the membrane surface or the dead-end pores present in the membrane which
also signifies the casting defects. The IFR, or irreversible fouling ratio, of 18.18% denotes the
permanent loss of flux resulting in a reduction in the life span of the membrane. The
irreversible fouling ratio (IFR) exceeds the reversible Fouling Ratio (RFR) suggesting a larger
portion of the fouling that cannot be reduced through physical methods and necessitates
intensive chemical cleaning.
Chemical cleaning of the membrane can reduce the irreversible fouling to some extent as
physical methods like backwashing hardly mitigate irreversible fouling (Kimura et al., 2005)
(Ariono et al., 2017). Various literature shows addition of the nanoparticles to the polymer
matrix enhances the anti-fouling capacity of the membrane by reducing the effective

35
adhesion sites in the membrane. The improved anti-fouling property of the membrane can
also be correlated with an increase in the membrane’s hydrophilicity (lower contact angle)
and lower surface roughness leading to fewer deposits and preventing the clogging of pores
(Eslami et al., 2024; Maraddi et al., 2024; Nadig et al., 2021; Sherugar et al., 2021).
Figure 21 shows the ratio of these fouling recovery metrics (Nadig et al., 2021).
𝐽𝑤2
𝐹𝑙𝑢𝑥 𝑅𝑒𝑐𝑜𝑣𝑒𝑟𝑦 𝑅𝑎𝑡𝑖𝑜 (𝐹𝑅𝑅) = × 100
𝐽𝑤1
𝐽𝑤1 − 𝐽𝑝
𝑇𝑜𝑡𝑎𝑙 𝐹𝑜𝑢𝑙𝑖𝑛𝑔 𝑅𝑎𝑡𝑖𝑜 (𝑇𝐹𝑅) = × 100
𝐽𝑤1
𝐽𝑤2 − 𝐽𝑝
𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝐹𝑜𝑢𝑙𝑖𝑛𝑔 𝑅𝑎𝑡𝑖𝑜 (𝑅𝐹𝑅) = × 100
𝐽𝑤1
𝐽𝑤1 − 𝐽𝑤2
𝐼𝑟𝑟𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝐹𝑜𝑢𝑙𝑖𝑛𝑔 𝑅𝑎𝑡𝑖𝑜 (𝐼𝐹𝑅) = × 100
𝐽𝑤1
where, 𝐽𝑤1 is the initial baseline DI water flux (section A), 𝐽𝑤2 is the final DI water flux
(section F, Figure 20) and 𝐽𝑝 is the constant flux achieved after fouling (section C, Figure 20)
𝐿 𝐿 𝐿
So, 𝐽𝑤1 = 84.18 𝑚2 −ℎ , 𝐽𝑤2 = 68.88 𝑎𝑛𝑑 𝐽𝑝 = 58.28 𝑚2 −ℎ
𝑚 2 −ℎ

Figure 21 Summary of anti-fouling parameters

36
Figure 22 shows a detailed combination of both flux and rejection data over time since it is
essential for understanding the membrane’s capabilities. The rejection percentage versus
time graph is also divided into sections B and C, corresponding to the flux versus time graph.
In section B, as the flux reduces gradually over time, the rejection percentage decreases
rapidly within the first 20 minutes (from 80 to 100 min), from 90.66% to 53.03%. This rapid
decline in rejection percentage indicates that the initial strong interaction between heavy
metals and membrane leads to a quick saturation or blockage of the active sites. After the
sharp decline, the rejection percentage stabilizes and remains almost steady throughout the
rest of Section B and Section C due to to equilibrium between the rate of fouling and the
flux.
When the rejection percentage versus time graph is compared to the flux versus time graph,
it is observed that the membrane’s capacity to reject heavy metals is not solely dependent
on the flux rate. The initial rapid decline in the rejection percentage with time when the flux
decreases gradually indicates the complexity of the fouling process.

Figure 22 Heavy metals rejection percentage vs time in minutes

37
The reduction of the flux due to fouling can be attributed to the total resistance of the
membrane since the permeability of the membrane is inversely proportional to the
resistance of the membrane. Figure 23 illustrates the variation of the resistance with time,
where the constant resistance observed in section A, represents the intrinsic resistance (Rm)
offered by the membrane after achieving the baseline constant flux with DI water before
being exposed to the heavy metal. The resistance offered by the fouling heavy metals is
denoted by (Rs), whereas the total resistance (Rt) is a result of Rm and Rs.

Darcy’s equation below describes the relation between flux and total resistance (Aouni et al.,
2011).

𝛥𝑃−𝛥𝜋
𝐽= Equation 5 Darcy's Relation between flux and pressure difference
𝜇(𝑅𝑚 + 𝑅𝑠 )

Δ𝑃 is the transmembrane pressure difference in bars, Δ𝜋 is the osmotic pressure in bars, 𝜇

is the dynamic viscosity of the solution in kg m-1s-1, Rm, and Rs in m-1.

The osmotic pressure of the DI water is zero and for the heavy metal solution, it is calculated
by Van’t Hoff Equation (Ma et al., 2023),

𝜋(𝑏𝑎𝑟) = 𝑖𝑐𝑅𝑇 Equation 6 Van't Hoff Equation

i = Number of dissociated ions, R is the universal gas constant (0.083144 bar/K mol), T is the
absolute temperature (K) 298.15 K, and c is the molar concentration of the solution (M).

The molar concentration of PbCl2, ZnCl2 and Cr2(SO4)3 for preparing 40 mg/L of Pb(II), 115
mg/L of Zn(II) and 115 mg/L of Cr(III) is 1.93×10-4 M , 1.75×10-3 M , and 1.10×10-3 M
respectively.

The osmotic pressure of the heavy metal solution is 0.2795 bars which is considerably
smaller than the working pressure of 5 bars. However, the solution’s overall molar
concentration is 0.003 M indicating a lower value. Therefore, the dynamic viscosity of the
solution can be considered similar to water (Brunner, 2014).

38
 Figure 23 The total resistance of the membrane at the different time intervals.

The total resistance of the membrane determined from Darcy’s equation is in the order of
magnitude of 1010. However, it is important to note that the total resistance of the
membrane is also affected by an additional factor of adsorption (Koutake et al., 1992). The
mixed matrix membrane M 1 utilized for the test is an adsorptive membrane, therefore, the
resistance offered by the adsorption must be considered. The adsorption of the heavy
metals on the membrane surface which may alter the surface charge of the membrane can
be the reason for the rapid decline in the rejection percentage compared to the flux. The
alteration in the membrane’s surface charge results in a change in the membrane’s
properties leading to the passage of more heavy metal ions quickly while only reducing the
flux partially (Abdulkarem et al., 2021). However, in addition to the filtration and
adsorption, sometimes the electrostatic repulsion can also partially contribute to the heavy
metal reduction. The reduction in the repulsion of the heavy metal due to a change in the
membrane’s surface charge may result in a rejection percentage more rapidly than the flux
(Kanagaraj et al., 2015).

39
Chapter-4
Analysis of Real Wastewater
1 Introduction

This chapter outlines the analysis of wastewater treatment from an electroplating industry,
which focuses on heavy metal removal in a two-step process of adsorption and membrane
filtration. Based on the findings from the previous chapter, the best membrane M 1 has been
chosen for the secondary treatment of wastewater.

First, adsorption was used as a pretreatment of the real wastewater to ensure a significant
reduction of heavy metal concentration hence, making membrane filtration more effective.
250ml of wastewater was treated with a dose of 60 g/L of stainless-steel slag with periodical
withdrawals over 24 h. After the adsorption process, the wastewater was decanted before
entering the second treatment step.

The second step was performed in a crossflow setup through the oxycut mixed matrix
membrane namely M 1%. The membrane’s performance was evaluated at different
pressures (2, 3, 5, and 7 bars). The membrane filtration is used to reduce further metal
concentrations after adsorption, in an attempt to demonstrate the effectiveness of
technology integration with the sustainable use of industrial residues.

2 First step removal: Adsorption of heavy metals

The initial concentrations of metals from the electroplating wastewater sample are
mentioned in Table 12. Al, Fe, and Mg were analyzed together since concentrations are
relatively close. Cr and Zn exceeded 1000 mg/L and were examined separately, as for Ni, Cu,
Pb, Ti, Cd, and Ba their concentrations are already less than 0.5 mg/L.

Table 12 Initial Concentrations of the heavy metals.

Fe Mg Cr Ni Cu Pb Zn Al Ti Cd Ba
(mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
9.28 13.36 1207.50 0.19 0.13 0.18 1141.25 5.45 0.28 0.04 0.07

40
Table 13 Concentration of the heavy metals during adsorption with stainless steel slag.

Time Fe Mg Al Cr Zn
(min) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
0 9.28 13.36 5.45 1207.50 1141.25
15 0.98 4.67 0.96 126.20 125.06
30 0.76 4.01 1.03 97.34 96.37
60 0.69 3.84 0.68 88.58 87.83
120 0.61 3.70 0.71 78.77 77.95
240 0.54 3.28 0.54 67.42 69.65

(a) (b)

(c) (d)

(e)
41
Figure 24 Concentration profile of (a) Fe (b) Mg (c) Al, (d) Cr,and
(e) Zn during adsorption with stainless-steel slag.
Figure 24 illustrates the concentration profile of Fe, Mg, Al, Cr, and Zn during the four-hour
adsorption process, while Table 13 shows the final concentration of each contamination at a
given time. A rapid decrease in concentration is observed for all the pollutants within the
first 15 minutes of contact with the stainless steel, demonstrating the effectiveness of the
residue. At 240 minutes, their concentrations reach their lowest values of 0.18 mg/L for Fe,
2.06 mg/L for Mg, 1.04 mg/L for Al, 18.50 mg/L for Cr, and 18.46 mg/L. The column chart
Figure 25 illustrates the final concentration after overnight adsorption.

Figure 25 Overnight concentrations of heavy metals

The adsorption capacity (mg/g) of the of the adsorbent is given by: (L. Guo et al., 2024)

𝐶0 −𝐶𝑒
𝑉 Equation 7
𝑚

Where C0 and Ce are the initial and overnight concentrations of heavy metals respectively, V
is the volume of sample (L) and m is the dosage of stainless-steel slag (g).

The adsorption capacity of the stainless–steel slag for the different metals is given below in
Table 14,

42
Table 14 Adsorption Capacity of heavy metals

Metals Adsorption Capacity (mg/g)

Fe 0.15
Mg 0.18
Al 0.07
Cr 19.81
Zn 18.71

One advantage of utilizing stainless-steel slag is the low cost and availability since it is an
industrial solid residue widely produced by different metallurgical industries. Research
indicates that given the higher surface area, high porous structure, and ion exchange
capacity, slags exhibit a significant adsorption capacity (Abd El-Azim et al., 2019; Huy et al.,
2020). even under acidic environments (pH 3.5), removal efficiency is more than 95%
ensuring strong interaction between heavy metals and slag.

3 Second step removal: Oxycut mixed matrix membrane

Table 15 Concentration of the heavy metal from the overnight solution treated with membrane M 1 at pressure 2,3,5, and 7
bars

Pressure Fe Mg Al Cr Zn
(bars) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
0 0.18 2.06 1.04 18.50 18.46
2 0.05 0.24 0.29 5.33 5.36
3 0.05 0.18 0.27 4.85 4.93
5 0.05 0.09 0.25 3.92 3.99
7 0.01 0.00 0.09 1.04 1.07

The membrane M 1 was employed to treat the remaining solution post overnight adsorption
in a cross-flow setup to make the heavy metal removal process more efficient. In Figure 26,
the concentration changes are shown under varying pressure(2,3,5, and 7 bars). In particular,
at 7 bars the concentration of Cr and Zn reduced to approximately 1 mg/L while, the

43
concentration drop of Fe, Al, and Mg was reduced to less than 0.5 mg/L as depicted in Table
15.

(a) (b)

(c) (d)

(e)

Figure 26 The concentration of overnight adsorbed solution vs pressures

2,3,5, and 7 bars (a) Fe (b) Mg (c) Al (d) Cr, and (e) Zn

44
Hybrid systems involving adsorption and membrane filtration offer enhanced removal
efficiency in wastewater treatment as proven in this work. The adsorption process, as a
preliminary treatment removes a wide range of highly concentrated heavy metals, resulting
in less polluted water. Additionally, the integration of membrane separation demonstrated
further purification by removing the remaining heavy metals and producing permeate that
complies with water discharge regulations. This is because the dissolved ions which surpass
the adsorption stage are effectively removed. The combined efficiency of this hybrid system
is more than 98% at 7 bars for all the metals as shown in Table 16.

Table 16 The table shows the final rejection percentage from adsorption and the membrane with different pressures.

Pressure in bars Fe Mg Al Cr Zn
2 99.47 98.18 94.68 99.56 99.53
3 99.45 98.68 95.09 99.60 99.57
5 99.42 99.36 95.39 99.68 99.65
7 99.87 100.00 98.34 99.91 99.91

In membrane separation, the fouling and the flux reduction take place because of the
concentration polarization which affects the efficiency of the process. The permeability
calculated at 2 bars after treatment was 15.50 L. m-2. h-1.bar-1 which is close to the baseline
permeability of the M1 membrane 16.84 L. m-2. h-1.bar-1. This shows that the flux didn’t
decline. The adsorption reduced the heavy metal concentration responsible which prevented
the membrane from choking and fouling, increasing usable life span and reducing membrane
cleaning frequency. In this way, the adsorption-membrane hybrid became the best system to
attain high-quality effluent water (Nure & Nkambule, 2023). However, the most important
aspect of this study is that the pressure-driven method proves to be more effective than
other processes in treating the contaminated water. Nevertheless, to enhance the efficiency
of the wastewater treatment plants, it is important to alleviate the membrane’s fouling
hence improving the membrane’s capacity for subsequent use. To mitigate the membrane’s
fouling, harsh chemicals are employed resulting in a decrease in the membrane’s life and
increasing the operational cost.

45
By comparing the results of heavy metal rejections in Chapter 3, we can conclude that a
hybrid system enables the membrane to operate more efficiently. With 100 mg/L of initial
concentration of Cr(III) and Pb(III) each, the final concentration at 7 bars reduced to 2.60
mg/L and 8.12 mg/L respectively. However, despite both Cr(III) and Zn(II) having an initial
concentration of more than 1000 mg/L in real wastewater, the final concentration following
treatment using the combined adsorption-membrane system is 1.04 mg/L and 1.07 mg/L.
Table 17 mentions a comparison of a few heavy metals from regulatory limits by WHO.

Table 17 Comparison of the concentration of a few treated heavy metals from WHO regulatory limits

Heavy Metal Concentration After Regulatory Limit Source/Reference

Treatment (mg/L) (mg/L)
Fe 0.01 0.30 (HISTORIES OF
GUIDELINE
DEVELOPMENT FOR
THE FOURTH EDITION
(IRON), n.d.)
Cr 1.04 0.05 (FAO/WHO (2000)
Pesticide Residues in
Food—1999
Evaluations WHO
(2003) Chlorpyrifos in
Drinking-Water, n.d.)
Zn 1.07 3.00 (HISTORIES OF
GUIDELINE
DEVELOPMENT FOR
THE FOURTH EDITION
Zn, n.d.)
Al 0.09 0.10 (Aluminium in
Drinking-Water
Background Document

46
 for Development of
WHO Guidelines for
Drinking-Water Quality
Al, n.d.)

47
Chapter - 5
Conclusion

This work demonstrates the preparation of 5 mixed matrix membranes (MMM) using the
phase inversion technique. This method enables the control of the pore size of the
membrane by controlling the demixing rate, with the kinetics of the demixing process
influenced by relative weight percentages of the oxycut used in all five membranes. The
membrane characterization provides insights into the presence of a specific fraction of
oxycut, responsible for the proper pore formation. The M 0.05 has the highest molecular
weight cutoff (MWCO) indicating the presence of the macrovoids, which can be correlated
by its cross-section image from SEM, revealing the finger-like pores. However, membranes
M 0.05 (1.68 nm) and M 1 (1.17 nm) exhibited a smaller pore size and can be classified as
nanofiltration (NF) membranes. Both membranes can be operated at pressure below reverse
osmosis (RO) and above ultrafiltration (UF), making them suitable for divalent and
multivalent ions. They also partially allow some monovalent ions to pass making them
acceptable for applications where moderate energy consumptions are required. This ensures
that with the partial rejection of the smaller solutes, these membranes may exhibit certain
characteristics of reverse osmosis (RO).
The membrane M 0.05 has excellent pore formation and displays the lowest contact angle
indicating around 40% reduction compared to the pristine membrane. Conversely, the
hydrophilicity decreases when oxycut concentration increases from M 0.5 to M 3. The M 5
membrane exhibits wider defective pores indicating that a higher concentration of filler
causes uneven mixing, despite having the highest pure water permeability. These
observations indicate that maintaining a balance between the hydrophilicity and the
membrane’s structural integrity is crucial with variations in the concentration of the filler.
Improved hydrophilicity of the membrane improves the permeability of the membrane and
the desired flux is obtained with less pressure resulting in low energy consumption.

48
At a pressure of 7 bars, M 3 and M 1 exhibited almost similar rejection percentages for Cr(III)
97.40% and 97.86% respectively. Nevertheless, M 1 displays consistent and the highest
rejection for the Pb(II) achieving 91.88 at 7 bars which can be attributed to its optimal pore
size and surface charge. The flux recovery ratio, in the anti-fouling test for the M 1
membrane is 81.22% which reveals the membrane’s ability to recover its flux after fouling.
The enhanced hydrophilicity in comparison to the pristine PES, promotes effortless adhesion
of the heavy metals foulant which facilitates more convenient recovery of the flux. The easy
flux recovery is crucial for long-term operational stability and minimizing the need for
frequent membrane replacement. The decline of flux over time did not follow similar to the
pattern as a percentage of rejection over time. The resistance Rs offered by fouling heavy
metals is primarily affected by the membrane’s surface charge, which enhances the heavy
metal diffusion and enables their passage through the membrane.
The analysis of the real wastewater treatment from the hybrid adsorption-membrane
system reveals that pretreatment with adsorption using stainless-steel slag enhanced the
efficiency of the membrane, resulting in a 98% rejection of the tested metals. Chromium and
Zinc having an initial concentration of more than 1000 mg/L reduced to 1.04 mg/L and 1.07
mg/L respectively. The real wastewater treatment study ensures that improved
effectiveness of pressure-driven systems, through pretreatment, results in the production of
high-quality clean water. Finally, membrane separation is capable of treating a wide range of
pollutants from the wastewater. Starting from microfiltration used for removing the
macromolecules to reverse osmosis capable of rejecting 95-100% of inorganic salts and
charged organics, ensures the best solutions for water reuse and reclamation helping to
preserve the ecosystem.

49
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