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A REPORT

Submitted by

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in partial fulfillment of the requirements for the degree of

B. TECH CHEMICAL ENGINEERING

ON THE SUJECT

ENVIRONMENTAL SCIENCE AND ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

KPR INSTITUTE OF ENGINEERING AND
TECHNOLOGY
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ABSTRACT

The development of India into a modern country is slow but the

population growth is rapid. Air, water and food are the three important things
for day-to-day life. Pure form of these three is must. Nowadays many water
resources and air in the environment are polluted due to massive increase in
population growth, industrialization, and modern Urbanization. The discharge
of heavy metals, dyes, pesticides etc., are mainly polluting the water bodies.
In current scenario the world is in the urge of treating the water bodies,
wastewater, and sea water to reduce the water scarcity level. Everywhere
wastewater and water treatment processes possess at least one separation
process in the treatment units. In this work, conventional treatment methods
and advanced treatment methods are discussed. Membrane separation process
is playing a main role in the treatment processes. The performance of
polymeric membrane and the inorganic membrane is discussed based on the
literature. In this work the detailed review is carried out about the membrane
processes, materials, fabrication methods, advantages and disadvantages. To
overcome the drawbacks of both membranes, the new innovative idea called
mixed matrix membrane is derived and discussed.
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TABLE OF CONTENTS

CHAPTER NO. TITLE PAGE NO.

ABSTRACT v
LIST OF TABLES xv
LIST OF FIGURES xviii

1 INTRODUCTION 1
2 LITERATURE REVIEW 20
3 METHODOLOGY 32
4 DISCUSSION 117
5 CONCLUSION 133
REFERENCES 137
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LIST OF TABLES

TABLE NO. TITLE PAGE NO.

1 Drinking water regulations and health effects 2

2 Types of filtration and its particle capture sizes 7
3 Composition of PES with SiO2 34
4 Composition of PES with ZrO2 35
5 Composition of PES with ZrSiO4 35
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LIST OF FIGURES

FIGURE NO. TITLE PAGE NO.

1 Average pore size of the membranes 6

2 Schematic diagram of the membrane systems 7
for the separation of different sized molecules
3 Pot mill (wet grinding) 33
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1. INTRODUCTION

Food, water, clothing and shelter are the basic requirements of

human beings. According to the UN population statistics, the world growth
rate has increased by 30% between 1990 and 2010. The world population has
been reported as 3.4 billion in 2009. Eventually, there is a possibility of an
increase in the population upto 6.3 billion around 2050 (Bruinsma et al.
2009). India holds the highest growth rate (350 million) in the world. Parallel
to the population growth, the world is also heading towards rapid
industrialization and urbanization. Due to this rapid growth, now-a-days,
human being lack pure air, water and soil.

Deriving pure water from surface water sources, sea water and from
domestic and industrial effluents becomes an important parameter to
overcome the water scarcity. The wastewater is now being discharged into
land or river or sea. Checking the quality of wastewater also plays an
important role while discharging the wastewater into water bodies. Table 1.1
shows the disposal standards for disposing the wastewater in land and water.
Water and wastewater treatment are very important to dispose the water after
usage and also to derive the water for drinking, cooking, washing and other
industrial and commercial purposes.
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Table 1 Drinking water regulations and health effects (IS2490(Part I))

Disposal standards
Permissible Into inland
Parameter Into public On land for Into marine
value surface
sewer irrigation coastal
water
Chloride 250- 1000 mg/L 1000 mg/L 600 mg/L -
1000mg/L
Color 5-15 colour Appreciable Appreciable Appreciable Appreciable
units
Dissolved 3-5mg/L - - - -
oxygen
Biochemical - 30mg/L 350 mg/L 100 mg/L 100 mg/L
oxygen demand
Chemical - 250mg/L - - 250mg/L
Oxygen
demand
Fluoride 2.0 mg/L 2 mg/L 15 mg/L - -
Iron 0.3 mg/L
Managanese 0.05 mg/L
pH 6.5-8.5 5.5-9.0 5.5-9.0 5.5-9.0 5.5-9.0
Sulfate 250 mg/L 1000 mg/L 1000 mg/L 1000 mg/L
Total Dissolved 500 mg/L 2100mg/L 2100mg/L 2100mg/L -
Solids
Suspended 700mg/L 100mg/L 600mg/L 200mg/L 1000mg/L
solids
Zinc 5 mg/L 5 mg/L 15 mg/L - 16 mg/L
Alkalinity 600 mg/L 1000mg/L 1000mg/L - 1000mg/L
Hardness 600 mg/L 1000mg/L 1000mg/L - 1000mg/L
Calcium 200 mg/L 200 mg/L 300 mg/L - 300mg/L
Magnesium 100 mg/L 100 mg/L 150 mg/L - 150 mg/L
Nitrate 100 mg/L 100 mg/L 150 mg/L - 150 mg/L
Arsenic 0.05 mg/L 0.2 mg/L 0.2 mg/L 0.2 mg/L 0.2 mg/L
Mercury 0.001 mg/L - - - -
Lead 0.05 mg/L 0.1mg/L 1 mg/L - 1 mg/L
Chromium 0.05 mg/L 2mg/L 2mg/L - 2mg/L
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2. WATER AND WASTEWATER TREATMENT

Due to water scarcity and pollution, there is a need for treatment of

water and wastewater and to be reused. The following conventional treatment
methods (Manisha Vidyavathy et al. 2015) are usually carried out namely

1. Primary and Secondary Treatment

2. Tertiary treatment

Different stages of primary and secondary treatment are

1. Mixing.

2. Equalization.

3. Screening.

4. Clarification.

5. Clariflocculation.

6. Filtration.

The advanced treatment methods like adsorption, Ion exchange,

and membrane filtration are recently being followed.

Tertiary treatment is the final cleaning process inorder to improve

the water quality (nitrogen and phosphorous removal, disinfection, etc.,)

Initially the wastewater is mixed and equalized to obtain a

homogeneous solution. The water from the equalizer is then fed to the screen
chamber to remove the large size materials followed by oil trap for removing
oil, fat, and grease. The water is then subjected into the flash mixing chamber
with addition of coagulants such as lime, alum, ferrous sulphate, ferric
chloride and polyelectrolyte and then it is processed through Clariflocculator
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or flocculator. This treated water is further sent to a settling tank for the
impurities to settle. The water from the settling tank is then fed into the
filtration tank. Sand, stone, filter cloth, plastic beads are used as a filter media
in the filtration tank. In a recent research, membranes are prepared and used
as a filter media. The treated water from the filtration tank can be supplied for
other applications or can be discharged into the water resources. The treated
water can also be disinfected and supplied for drinking purposes.

Most of the processes in the chemical industry involve at least one

separation or purification process in order to remove or to recover the desired
products (Ahuja et al. 2003). The separation process is generally classified
into two categories namely equilibrium governed process and rate governed
process. Equilibrium governed process includes distillation, absorption,
adsorption, drying etc., Most of the membrane-based processes are rate
governed process. It includes Osmosis, Reverse Osmosis, Dialysis, etc., These
processes are carried out by establishing a gradient of chemical potential (i.e.,
concentration gradient, pressure gradient, temperature gradient and
electrochemical potential gradient).

3. MEMBRANE FILTRATION

Nowadays, novel separation processes are the growing research

field. Membrane based separation processes, chromatographic separation
processes, electric field assisted separation processes and ion exchange
processes fall under this category.

Initially the membrane separation processes was started as a

laboratory scale. Later it was established as an industrial pilot plant with
proper technical and commercial installations.
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The choice of the membrane technology is based on the following two

reasons namely

1. Fast process with short residence time

2. Less component specific.

The basic principle of membrane processes involves the mechanism

of impaction, diffusion, electrostatic interaction, hydrophobic property and
adsorption.

The transport selectivity of the membrane, high efficiency, low

capital cost and operating cost, ease of operation lower energy requirement
and low time for the completion of processes are also the main advantages of
the membrane separation processes when compared with the conventional
processes. In the current scenario, the gas and liquid separation by membranes
is also the field which is growing extremely fast (Walther et al. 1998).

Membrane technology covers all the approaches related to the

transport of substances between two fractions. In general, the mechanical
separation processes for separating gaseous or liquid streams use the
membrane technology. The application of membrane science has been in prior
use since the late nineties. The wide spectrum is now a subject of continuous
modulation and improvement in search of development of a better prototype
for various types of filtration in various fields of effluent management. In near
future, the emergence of new types of membrane materials and simple
fabrication techniques may lead to the development of low-cost membranes.

The main part or heart of the membrane process is the membrane

only. In order to obtain better removal efficiency, process identification of the
new membrane materials with the desired requirements is strongly growing in
the current research field. Generally, the criteria for selecting materials for
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membrane separation are found to be difficult. The material selection and

pore size of the membranes depends on the application for which it would be
used (Boor Singh Lalia et al. 2013).

There are four main types of membrane system commonly used in

industries (Aptel et al. 1996) based on the pore size: (a) Microfiltration (MF)
is widely applied in particulate removal process and maintains degreasing.
(b) Ultra filtration (UF) is generally used for oil, water and emulsion
separations, paint recovery and the separation of fats, oils or greases in the
food industry. (c) Reverse osmosis (RO) and nanofiltration (NF) are
extensively used for water purification, desalination and disinfection. UF and
MF are
well-developed techniques used for water treatment, whereas RO is widely
used for water desalination and purification. MD is a new developing
technique and it has the potential for desalinating highly saline water (Khayet
et al. 2011, Alkhudhiri et al. 2012). Figure 1.1 shows the average pore size
requirement for the membranes and Figure 1.2 shows the schematic diagram
of the membrane system for the separation of different sized molecules.

Nano filtration
Microfiltration

Ultrafiltration

Membrane
Reverse osmosis distillation

0.1 nm 1 nm 10 nm 100 nm 1µm 10 µm

Figure 1 Average pore size of the membranes

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Figure 2 Schematic diagram of the membrane systems for the separation

of different sized molecules

4. CONCLUSION

 Many of the basic dyes are non- degradable and toxic pollutants
in textile industrial wastewater. The colorant that is often used
in the textile industry is Methylene blue (MB), a cationic dye
that exists at a large scale in the textile wastewater which is
discharged into the nearby environment without proper
management, particularly in developing countries. Therefore,
MB is chosen in this study.

 The PES Ultrafiltration (UF) technique consists of the addition

of a high molecular weight water-soluble polymer. The
objective of this UF is separating low molecular weight species
such as heavy metals, dyes, dissolved organic compounds, etc.
[Huang et al. (2015)]. The technique is based on the polymer
interaction with the dissolved solute present in Methylene Blue
(MB) solution, increasing in size, and being able to be retained
by a membrane that can separate molecules of sizes in the order
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of 100 nm. The binding behavior between the dye and the
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polymer depends entirely on the chemical structure of the

polymer and dye, so it cannot be generalized. The polymer–dye
interaction is hydrophobic and energetic, and involves
electrostatic interactions, chemical interactions, and hydrogen
bonding.
 Addition of nano porous or microporous inorganic material
with rigid and glassy polymers by phase inversion method
can increase free volume. Rezakazemi et al., (2014)
concluded that nano porous or microporous inorganic
material can be used for the mixed matrix membrane
preparation. Macrporous > 50 nm (UF, MF) Mesoporous =
2-50 nm (UF, UF) Microporous <2nm. (GS) So, in this
work, the average particle size of the inorganic material
chosen was around 1µm.

 Pure PES provides smooth surface and organo inorganic

membrane increases the number of pores on the surface. If
the percentage of inorganic material increases, it will
provide the clearly visible surface. The pore density also will
be increased. Higher inorganic material addition with PES
membrane induces the aggregate phenomenon on the
surface. This provides interfacial stresses between polymer
and silica which forms interfacial pores due to the shrinkage
of organic phase during the demixing process. The thickness
of the skin layer increases with the addition of inorganic
material with the polymer. Similar observations were made
by Lin et al. (2003), Lv et al. (2007) and Arthanareeswaran
et al.(2008). This shows the distribution of the inorganic
material on the membrane surface that forms finger like
pores linked by the sponge walls which confirmed that many
micropores allow the finger like pores to communicate with
each other.
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 The effect of phase inversion method on mixed matrix

membrane morphology was investigated. Experimental trials
were carried out with three different materials namely: SiO 2,
ZrO2, ZrSiO4 which were low cost and with the aim of
minimising membrane production costs.

 It was proposed that the phase inversion method modifies

the pore size and structural formation of the membranes. The
t-zirconia was formed in PES/ZrSiO4 membrane. Due to this
formation, the sieving and diffusion mechanism also gave a
big impact on filtration.

 The results from TGA analysis, contact angle, water uptake

and tensile strength tests for the PES/ZrSiO4, PES/ZrO2 and
PES/SiO2 membranes shows the high thermal stability, less
contact angle, high water uptake and high tensile strength
respectively when compared with the PES membrane.

 The porosity is controlled by inter-particle void, which is a

function of the particle size. These results therefore strongly
suggests that the inorganic material played an important role
in changing the pore size of the membrane, which in turn
altered the inter-particle voids and thus influenced the
membrane mass resistance to water transport. As the voids
of the membrane increased, the water flux of the membranes
increases.

 The membranes were also able to achieve high rejections

close to 90-95% for COD with PES/ZrSiO4 membrane when
compared to the PES membrane.

 Part of this work was also devoted to environmental effluent

treatment, as an environmental concern around the world.
The membranes showed the ability to separate water with
COD concentration (780 ppm). High COD rejection values
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of 63.84% for PES/ZrSiO4 membranes whilst PES/ZrO2 and

PES/SiO2 membranes should rejection values as low as 56.5
and 53.58% respectively. The results showed that all the
membranes can be fouled by effluent after some trials. The
results show that the fouling of the membrane can be
controlled with the re arrangement of the membrane and do
back washing with distilled water.

 Backwater flush, air flush and chemical cleaning for the

membrane regeneration. Materials like bleaching powder,
hydrogen peroxide and hydrochloric acid can be used as
solvents for chemical cleaning.

 In summary, based on the experimental trials and the results

obtained, PES/ZrSiO4 mixed matrix membranes are found to
be a suitable membrane for textile effluent treatment.

5. SUGGESTIONS

1. Other parameters (composition variation, material variation,

rotational speed, temperature, etc.,) for the preparation of
membranes should be considered. For instance,
incorporating inorganic materials which can be derived from
the wastes or from other different processes can be used.
This will tend to further understand on the cost reduction.

2. Membrane testing should be considered using high Reynolds

numbers to increase turbulence and to reduce fouling.

3. Finally, there are several industrial wastewater emissions

around the world so the membranes prepared in this work
could be used in nano-filtration or micro-filtration in
industries such as food, tannery and pharmaceuticals etc.,
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REFERENCES

1. Ahmad Kayvani Fard, Gordon McKay, Anita Buekenhoudt, Huda Al

Sulaiti, Filip Motmans, Marwan Khraisheh & Muataz Atieh 2018,
‘Inorganic Membranes: Preparation and Application for Water
Treatment and Desalination’, Materials, vol. 11, p. 74.

2. Ahuja 2003, ‘Ferromagnetism above room temperature in bulk and

transparent thin films of Mn-doped ZnO’, Sep. Sci. Tech, vol. 4,
pp. 17-35.

3. Alkhudhiri, A, Darwish, N & Hilal, N 2012, ‘Membrane distillation: A

comprehensive review’, Desalination, vol. 287, pp. 2-18.

4. Amin, SK, Abdallah, HAM, Roushdy, MH & El-Sherbiny, SA 2016,

‘Investigation of polyvinylchloride and cellulose acetate blend
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5. API 2000, in ‘Overview of Exploration and Production Waste

Volumes and Waste Management Practices in the United States,’
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6. Aptel, P & Buckley, CA 1996, in ‘Water Treatment membrane

processes’ McGraw-Hill, New York, p. 26.

7. Athayde, DD, Souza, DF, Silva, AMA, Vasconcelos, D, Nunes, EHM,

Costa, JCD & Vasconcelos, WL 2016, ‘Review of perovskite ceramic
synthesis and membrane preparation methods’, Ceramics International,
vol. 42, pp. 6555-6571.

8. Azadeh Ghaee, Mojtaba Shariaty-Niassar, Jalal Barzin, Takeshi

Matsuura & Ahmad Fauzi Ismail 2015, ‘Electrospinning of
PVA/chitosan nanocomposite nanofibers containing gelatin
nanoparticles as a dual drug delivery system’, Desalination and Water
Treatment, vol. 57, no. 31, pp. 1-8.

9. Ballinas, L, Torras, C, Fierro, V & Garcia-Valls, R 2004, ‘Arsenic(V)

Removal with Polymer Inclusion Membranes from Sulfuric Acid
Media using DBBP as Carrier’, J. Phys. Chem. Solids, vol. 65, no. 2-3,
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pp. 633-637.
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10. Benfer, S, Popp, U, Richter, H, Siewert, C & Tomandl, G 2001,

‘Optimization of the operational parameters for a 50 nm ZrO2 ceramic
membrane as applied to the ultrafiltration of post-electrodeposition
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