Membrane technology

Membrane technology covers all engineering approaches for the transport of substances
between two fractions with the help of permeable membranes. In general, mechanical
separation processes for separating gaseous or liquid streams use membrane technology.

Applications:
Membrane separation processes operate without heating and therefore use less
energy than conventional thermal separation processes such
as distillation,sublimation or crystallization. The separation process is purely physical and both
fractions (permeate and retentate) can be used. Cold separation using membrane technology is
widely used in the food technology, biotechnology and pharmaceuticalindustries. Furthermore,
using membranes enables separations to take place that would be impossible using thermal
separation methods. For example, it is impossible to separate the constituents
of azeotropics liquids or solutes which form isomorphicscrystals by distillation
or recrystallization but such separations can be achieved using membrane technology.
Depending on the type of membrane, the selective separation of certain individual substances
or substance mixtures is possible. Important technical applications include the production of
drinking water by reverse osmosis (worldwide approximately 7 million cubic metres annually),
filtrations in thefood industry, the recovery of organic vapours such as petro-chemical vapour
recovery and the electrolysis for chlorine production.
In waste water treatment, membrane technology is becoming
increasingly important. With the help of UF and MF (Ultra/Microfiltration) it is possible to
remove particles, colloids and macromolecules, so that waste-water can be disinfected in this
way. This is needed if waste-water is discharged into sensitive waters especially those
designated for contact water-sports and recreation.
About half of the market is in medical applications such as use in
artificial kidneys to remove toxic substances byhemodialysis and as artificial lung for bubble-
free supply of oxygen in the blood.
The importance of membrane technology is growing in the field of
environmental protection (NanoMemPro IPPC Database). Even in modern energy recovery
techniques membranes are increasingly used, for example in fuel cells and in osmotic power
plants.


Current market and forecast :

The global demand for membrane modules was estimated at
approximately 15.6 billion USD in 2012. Driven by new developments and innovations in
material science and process technologies, global increasing demands, new applications, and
others, the market is expected to grow around 8% annually in the next years. It is forecast to
increase to 21.22 billion USD in 2016 and reach 25 billion in 2018.


Membrane operations
According to driving force of the operation it is possible to distinguish:
pressure driven operations
microfiltration
ultrafiltration
nanofiltration
reverse osmosis
concentration driven operations
dialysis
pervaporation
forward osmosis
artificial lung
gas separation
operations in electric potential gradient
electrodialysis
membrane electrolysis e.g. chloralkali process
electrodeionization
electrofiltration
fuel cell
operations in temperature gradient
membrane distillation
Membrane separation processes:
Membrane separation processes have very important role in separation
industry. Nevertheless, they were not considered technically important until mid-1970.
Membrane separation processes differ based on separation mechanisms and size of the
separated particles. The widely used membrane processes
include microfiltration, ultrafiltration, nanofiltration, reverse
osmosis, electrolysis, dialysis, electrodialysis, gas separation, vapor permeation, pervaporation,
membrane distillation, and membrane contactors. All processes except for pervaporation
involve no phase change. All processes except (electro)dialysis are pressure driven.
Microfltration and ultrafiltration is widely used in food and beverage processing (beer
microfiltration, apple juice ultrafiltration), biotechnological applications and pharmaceutical
industry (antibiotic production, protein purification), water purification and wastewater
treatment, microelectronics industry, and others. Nanofiltration and reverse osmosis
membranes are mainly used for water purification purposes. Dense membranes are utilized for
gas separations (removal of CO2 from natural gas, separating N2 from air, organic vapor
removal from air or nitrogen stream) and sometimes in membrane distillation. The later
process helps in separating of azeotropic compositions reducing the costs of distillation
processes.

Pore size and selectivity
The pore sizes of technical membranes are specified differently depending on the
manufacturer. One common distinction is by nominal pore size. It describes the maximum pore size
distribution and gives only vague information about the retention capacity of a membrane. The
exclusion limit or "cut-off" of the membrane is usually specified in the form of NMWC (nominal
molecular weight cut-off, or MWCO,Molecular Weight Cut Off, with units in Dalton). It is defined as the
minimum molecular weight of a globular molecule that is retained to 90% by the membrane. The cut-
off, depending on the method, can by converted to so-called D
90
, which is then expressed in a metric
unit. In practice the MWCO of the membrane should be at least 20% lower than the molecular weight of
the molecule that is to be separated.
Filter membranes are divided into four classes according to pore size:
Pore size
Molecular
mass
Process Filtration Removal of
> 10

"Classic" filter

> 0.1 m > 5000 kDa microfiltration < 2 bar larger bacteria, yeast, particles
100-
2 nm
5-5000 kDa ultrafiltration 1-10 bar
bacteria, macromolecules, proteins, larger
viruses
2-1 nm 0.1-5 kDa nanofiltration 3-20 bar viruses, 2- valent ions
[5]

< 1 nm < 100 Da
reverse
osmosis
10-
80 bar
salts, small organic molecules
The form and shape of the membrane pores are highly dependent on the manufacturing process and
are often difficult to specify. Therefore, for characterization, test filtrations are carried out and the pore
diameter refers to the diameter of the smallest particles which could not pass through the membrane.
The rejection can be determined in various ways and provides an indirect measurement of the
pore size. One possibility is the filtration of macromolecules (often Dextran, polyethylene
glycol or albumin), another is measurement of the cut-off by gel permeation chromatography. These
methods are used mainly to measure membranes for ultrafiltration applications. Another
testing method is the filtration of particles with defined size and their measurement with a
particle sizer or by laser induced breakdown detection (LIBD). A vivid characterization is to
measure the rejection of Dextran blue or other colored molecules. The retention
of bacteriophage and bacteria, the so-called "bacteriachallenge test", can also provide
information about the pore size.
Nominal pore size micro-organism ATCC root number
0.1 m Acholeplasma laidlawii 23206
0.3 m Bacillus subtilis spores 82
0.5 m Pseudomonas diminuta 19146
0.45 m Serratia marcescens 14756
0.65 m Lactobacillus brevis

To determine the pore diameter, physical methods such as porosimetry (mercury,
liquid-liquid porosimetry and Bubble Point Test) are also used, but a certain form of the pores
(such as cylindrically or concatenated spherical holes) is assumed. Such methods are used for
membranes whose pore geometry does not match the ideals, we get "nominal" pore diameter,
which characterize the membrane, but does not necessarily reflect their actual filtration
behavior and selectivity.
The selectivity is highly dependent on the separation process, the composition
of the membrane and their electrochemical properties in addition to the pore size. By a high
selectivity, isotopes can be enriched (uranium enrichment) in nuclear engineering or industrial
gaseous like nitrogen be recovered (gas separation). Ideally, can be enriched with a suitable
membrane even racemics.
In the selection of the membrane selectivity has priority over a high
permeability, as can low flows easily offset by increasing the filter surface with a modular
structure. For the gas phase is to be noted that, in a filtration process different deposition
mechanisms act, so that particles having sizes below the pore size of the membrane can be
retained as well.




Microfiltration:
Microfiltration (commonly abbreviated to MF) is a type of physical filtration process where a
contaminated fluid is passed through a special pore-sized membrane to
separate microorganisms and suspended particles from process liquid. It is commonly used in
conjunction with various other separation processes such as ultrafiltration and reverse
osmosis to provide a product stream which is free of undesired contaminants.

General Principles:
Microfiltration usually serves as a pre-treatment for other separation
processes such as ultrafiltration, and a post-treatment for granular media filtration. The typical
particle size used for microfiltration ranges from about 0.1 to 10 m. In terms of approximate
molecular weight these membranes can separate macromolecules generally less than 100,000
g/mol.The filters used in the microfiltration process are specially designed to prevent particles
such as, sediment, algae, protozoa or large bacteria from passing through a specially designed
filter. More microscopic, atomic or ionic materials such as water (H2O), monovalent species
such as Sodium (Na+) or Chloride (Cl-) ions, dissolved or natural organic matter, and small
colloids and viruses will still be able to pass through the filter.
The suspended liquid is passed though at a relatively high velocity of
around 13 m/s and at low to moderate pressures (around 100-400 kPa) parallel or tangential
to the semi-permeable membrane in a sheet or tubular form.

A pump is commonly fitted onto
the processing equipment to allow the liquid to pass through the membrane filter. There are
also two pump configurations, either pressure driven or vacuum. A differential or
regular pressure gauge is commonly attached to measure the pressure drop between the outlet
and inlet streams. See Figure 1 for a general setup.


The most abundant use of microfiltration membranes are in the water, beverage andbio-
processing industries (see below). The exit process stream after treatment using a micro-filter
has a recovery rate which generally ranges to about 90-98 %.
Range of Applications:
Water Treatment:
Perhaps the most prominent use of microfiltration membranes pertains to the
treatment of potable water supplies. The membranes are a key step in the primary disinfection
of the uptake water stream. Such a stream might contain pathogenssuch as the
protozoa Cryptosporidium and Giardia lamblia which are responsible for numerous disease
outbreaks. Both species show a gradual resistance to traditional disinfectants (i.e. chlorine). The
use of MF membranes presents a physical means of separation (a barrier) as opposed to a
chemical alternative. In this sense, both filtration and disinfection take place in a single step,
negating the extra cost of chemical dosage and the corresponding equipment (needed for
handling and storage).
Similarly, the MF membranes are used in secondary wastewater effluents to
remove turbidity but also to provide treatment for disinfection. At this
stage, coagulants (iron or aluminum) may potentially be added to precipitate species such
asphosphorus and arsenic which would otherwise have been soluble.

Sterilisation
Petroleum Refining
Dairy Processing


Other Applications:
Other common applications utilising microfiltration as a major separation process
include
Clarification and purification of cell broths where macromolecules are to be separated
from other large molecules, proteins, or cell debris.
Other biochemical and bio-processing applications such as clarification of dextrose.
Production of Paints and Adhesives

Comparison with Similar Processes:
Membrane microfiltration is fundamentally the same as other filtration techniques utilising
a pore size distribution to physically separate particles. It is analogous to other technologies such as
ultra/nanofiltration and reverse osmosis, however, the only difference exists in the size of the particles
retained, and also the osmotic pressure. The main of which are described in general below:
Ultrafiltration (UF)
Ultrafiltration membranes have pore sizes ranging from 0.1 m to 0.01 m and are able
to retain proteins, endotoxins, viruses and silica. UF has diverse applications which span from waste
water treatment to pharmaceutical applications.

Nanofiltration (NF)
Nanofiltration membranes have pores sized from 0.001 m to 0.01 m and filters
multivalent ions, synthetic dyes, sugars and specific salts. As the pore size drops from MF to NF, the
osmotic pressure requirement increases.

Reverse Osmosis (RO)
Reverse Osmosis is the finest separation membrane process available, pore sizes range
from 0.0001 m to 0.001 m. RO is able to retain mostly all molecules except for water and due to
the size of the pores, the required osmotic pressure is significantly greater than that for MF. Both
reverse osmosis and nanofiltration are fundamentally different since the flow goes against the
concentration gradient, because those systems use pressure as a means of forcing water to go from
low pressure to high pressure.

Recent Developments:
Recent advances in MF have focused on manufacturing processes for the
construction of membranes and additives to promote coagulation and therefore the fouling of
the membrane. Since MF, UF, NF and RO are closely related, these advances are applicable to
multiple processes and not MF alone.
Recently studies have shown dilute KMnO4 preoxidation combined FeCl3 is able to
promote coagulation, leading to decreased fouling, in specific the KMnO4 preoxidation
exhibited an effect which decreased irreversible membrane fouling.
Similar research has been done into the construction high flux poly(trimethylene
terephthalate) (PTT) nanofiber membranes, focusing on increased throughput. Specialised heat
treatment and manufacturing processes of the membranes internal structure exhibited results
indicating a 99.6% rejection rate of TiO2 particles under high flux. The results indicate that this
technology may be applied to existing applications to increase their efficiency via high flux
membranes.
Ultrafiltration:
Ultrafiltration (UF) is a variety of membrane filtration in which forces
like pressure or concentration gradients leads to a separation through a semipermeable
membrane. Suspended solids and solutes of high molecular weight are retained in the so-called
retentate, while water and low molecular weight solutes pass through the membrane in
the permeate. Thisseparation process is used in industry and research for purifying and
concentrating macromolecular (10
3
- 10
6
Da) solutions, especially protein solutions.
Ultrafiltration is not fundamentally different from microfiltration, nanofiltration ormembrane
gas separation, except in terms of the size of the molecules it retains - it is defined by
the Molecular Weight Cut Off (MWCO) of the membrane used. Ultrafiltration is applied in
cross-flow or dead-end mode.

Applications:
Industries such as chemical and pharmaceutical manufacturing, food and beverage processing,
and waste water treatment, employ ultrafiltration in order to recycle flow or add value to later
products. But also blood dialysis belongs to ultrafiltration.

Drinking Water :
UF can be used for the removal of particulates and macromolecules from raw water to produce
potable water. They have been used to either replace existing secondary (coagulation,
flocculation, sedimentation) and tertiary filtration (sand filtration and chlorination) systems
employed in water treatment plants or as standalone systems in isolated regions with growing
populations. When treating water with high suspended solids, UF is often integrated into the
process, utilising primary (screening, flotation, filtration) and some secondary treatments as
pre-treatment stages.

UF processes are currently preferred over traditional treatment methods
for the following reasons:
No chemicals required (aside from cleaning).
Constant product quality regardless of feed quality.
Compact plant size.
Capable of exceeding regulatory standards of water quality, achieving 90-100%
pathogen removal.
UF processes are currently limited by the high cost incurred due to membrane fouling and
replacement. Additional pretreatment of feed water is required to prevent excessive
damage to the membrane units.
In many cases UF is used for pre filtration in reverse osmosis plants to protect the RO.

Other Applications:
Filtration of effluent from paper pulp mill
Cheese manufacture, see ultrafiltered milk
Removal of pathogens from milk
Process and waste water treatment
Enzyme recovery
Fruit juice concentration and clarification
Dialysis and other blood treatments
Desalting and solvent-exchange of proteins (via diafiltration)
Laboratory grade manufacturing

New Developments:
In order to increase the life-cycle of membrane filtration systems, energy
efficient membranes are being developed in membrane bioreactor systems. Technology has
been introduced which allows the power required to aerate the membrane for cleaning to be
reduced whilst still maintaining a high flux level. Mechanical cleaning processes have also been
adopted using granulates as an alternative to conventional forms of cleaning; this reduces
energy consumption and also reduces the area required for filtration tanks.
Membrane properties have also been enhanced to reduce fouling tendencies
by modifying surface properties. This can be noted in the biotechnology industry where
membrane surfaces have been altered in order to reduce the amount of protein
binding. Ultrafiltration modules have also been improved to allow for more membrane for a
given area without increasing its risk of fouling by designing more efficient module internals.
The current pre-treatment of seawater desulphination uses ultrafiltration
modules that have been designed to withstand high temperatures and pressures whilst
occupying a smaller footprint. Each module vessel is self supported and resistant to corrosion
and accommodates easy removal and replacement of the module without the cost of replacing
the vessel itself.

Nanofiltration:
Nanofiltration is a relatively recent membrane filtration process used most often with low total
dissolved solids water such as surface water and fresh groundwater, with the purpose of
softening (polyvalent cation removal) and removal of disinfection by-product precursors such as
natural organic matter and synthetic organic matter.
Nanofiltration is also becoming more widely used in food
processing applications such as dairy, for simultaneous concentration and partial
(monovalent ion) demineralisation.
Nanofiltration is a membrane filtration based method that
uses nanometer sized cylindrical through-pores that pass through the membrane at a 90.
Nanofiltration membranes have pore sizes from 1-10 Angstrom, smaller than that used in
microfiltration and ultrafiltration, but just larger than that in reverse osmosis. Membranes used
are predominantly created from polymer thin films. Materials that are commonly used
include polyethylene terephthalate or metals such as aluminum.Pore dimensions are controlled
by pH, temperature and time during development with pore densities ranging from 1 to 106
pores per cm
2
. Membranes made from polyethylene terephthalate and other similar materials,
are referred to as track-etch membranes, named after the way the pores on the membranes
are made.Tracking involves bombarding the polymer thin film with high energy particles. This
results in making tracks that are chemically developed into the membrane, or etched into the
membrane, which are the pores. Membranes created from metal such as alumina membranes,
are made by electrochemically growing a thin layer of aluminum oxide from aluminum metal in
an acidic medium.

Range of applications:
Historically, nanofiltration and other membrane technology used for molecular separation was
applied entirely on aqueoussystems. The original uses for nanofiltration were water treatment
and in particular water softening. Nanofilters can soften water by retaining scale-forming,
hydrated divalent ions (e.g. Ca
2+
, Mg
2+
) while passing smaller hydrated monovalent ions .
In recent years, the use of nanofiltration has been extended into other industries such as milk
and juice production. Research and development in solvent-stable membranes has allowed the
application for nanofiltration membranes to extend into new areas such as pharmaceuticals,
fine chemicals, and flavour and fragrance industries. Development in organic solvent
nanofiltration technology and commercialization of membranes used has extended possibilities
for applications in a variety of organic solvents ranging from non-polar through polar to polar
aprotic.
Industry Uses
Fine chemistry and Pharmaceuticals
Non-thermal solvent recovery and management
Room temperature solvent exchange
Oil and Petroleum chemistry
Removal of tar components in feed
Purification of gas condensates
Bulk Chemistry
Product Polishing
Continuous recovery of homogeneous catalysts
Natural Essential Oils and similar
products
Fractionation of crude extracts
Enrichment of natural compounds Gentle Separations
Medicine
Able to extract amino acids and lipids from blood and other cell
culture.

New Developments:
Contemporary research in the area of Nanofiltration (NF) technology is primarily concerned
with improving the performance of NF membranes, minimising membrane fouling and reducing
energy requirements of already existing processes. One way in which researchers are
attempting to improve NF performance more specifically increase permeate flux and lower
membrane resistance is through experimentation with different membrane materials and
configurations. thin film composite membranes (TFC), which consist of a number of extremely
thin selective layersinterfaciallypolymerized over a microporous substrate, have had the most
commercial success in industrial membrane applications due to the capability of optimizing the
selectivity and permeability of each individual layer. Recent research has shown that the
addition of nanotechnology materials such as electrospunnanofibrous membrane layers (ENMs)
to conventional TFC membranes results in an enhanced permeate flux. This has been attributed
to inherent properties of ENMs that favour flux, namely their interconnected pore structure,
high porosity and low transmembrane pressure. A recently developed membrane configuration
which offers a more energy efficient alternative to the commonly used spiral wound
arrangement is the hollow fibre membrane. This format has the advantage of requiring
significantly less pre-treatment than spiral wound membranes, as solids introduced in the feed
are displaced effectively during backwash or flushing. As a result, membrane fouling and pre-
treatment energy costs are reduced. Extensive research has also been conducted on the
potential use of Titanium Dioxide (TiO2, titania) nanoparticles for membrane fouling reduction.
This method involves applying a nonporous coating of titania onto the membrane surface.
Internal fouling/pore blockage of the membrane is resisted due to the nonporosity of the
coating, whilst the superhydrophilic nature of titania provides resistance to surface fouling by
reducing adhesion of emulsified oil on the membrane surface.

Reverse osmosis:
Reverse osmosis (RO) is a water purification technology that uses a semipermeable membrane.
This membrane technology is not properly a filtration method. In reverse osmosis, an applied
pressure is used to overcome osmotic pressure, a colligative property, that is driven by
chemical potential, a thermodynamic parameter. Reverse osmosis can remove many types
of molecules and ions from solutions, and is used in both industrial processes and the
production of potable water. The result is that the solute is retained on the pressurized side of
the membrane and the pure solvent is allowed to pass to the other side. To be "selective", this
membrane should not allow large molecules or ions through the pores (holes), but should allow
smaller components of the solution (such as the solvent) to pass freely.
In the normal osmosis process, the solvent naturally moves from
an area of low solute concentration (high water potential), through a membrane, to an area of
high solute concentration (low water potential). The movement of a pure solvent is driven to
reduce the free energy of the system by equalizing solute concentrations on each side of a
membrane, generating osmotic pressure. Applying an external pressure to reverse the natural
flow of pure solvent, thus, is reverse osmosis. The process is similar to other membrane
technology applications. However, key differences are found between reverse osmosis and
filtration. The predominant removal mechanism in membrane filtration is straining, or size
exclusion, so the process can theoretically achieve perfect exclusion of particles regardless of
operational parameters such as influent pressure and concentration. Moreover, reverse
osmosis involves a diffusive mechanism, so that separation efficiency is dependent on solute
concentration, pressure, and water flux rate. Reverse osmosis is most commonly known for its
use in drinking water purification from seawater, removing the salt and other effluent materials
from the water molecules.

Process:
Osmosis is a natural process. When two liquids with different concentrations of a solute are separated
by a semipermeable membrane, the fluid has a tendency to move from low to high solute
concentrations for chemical potential equilibrium.
Formally, reverse osmosis is the process of forcing a solvent from a region of high solute concentration
through a semipermeable membrane to a region of low solute concentration by applying a pressure in
excess of the osmotic pressure. The largest and most important application of reverse osmosis is the
separation of pure water from seawater and brackish waters; seawater or brackish water is pressurized
against one surface of the membrane, causing transport of salt-depleted water across the membrane
and emergence of potable drinking water from the low-pressure side.
The membranes used for reverse osmosis have a dense layer in the polymer matrixeither the
skin of an asymmetric membrane or an inter facially polymerized layer within a thin-film-
composite membranewhere the separation occurs. In most cases, the membrane is designed
to allow only water to pass through this dense layer, while preventing the passage of solutes
(such as salt ions). This process requires that a high pressure be exerted on the high
concentration side of the membrane, usually 217 bar (30250 psi) for fresh and brackish
water, and 4082 bar (6001200 psi) for seawater, which has around 27 bar (390 psi)
.
natural
osmotic pressure that must be overcome. This process is best known for its use
in desalination (removing the salt and other minerals from sea water to get fresh water), but
since the early 1970s, it has also been used to purify fresh water for medical, industrial, and
domestic applications.



















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6yr
Innovative Water Technologies,
Hyderabad


6-629/C, Vimamanapuri Colony, Quthbullapur Road ,
Hyderabad - 500055, Andhra Pradesh, Indiawww.innovativewatertechnologies.co.in
08588873644

Membrane Filter System

Membrane Filter System
For filtration of sterile liquid Models: 142mm dia, 292mm dia with Bubble testmore...
11yr
Vihar Engineering, Mumbai,
Mumbai


9, Kembros Industrial Estate, Sonapur Lane Behind Asian Paints, Bhandup West,
Mumbai - 400078, Maharashtra, Indiawww.viharengineering.com
09953352827





Advanced oxidation process:
Advanced oxidation processes (abbreviation: AOPs), in a broad sense, refers to a set of
chemical treatment procedures designed to remove organic (and sometimes inorganic)
materials in water and waste water by oxidation through reactions with hydroxyl
radicals (OH).[1] In real-world applications of wastewater treatment, however, this term
usually refers more specifically to a subset of such chemical processes that
employ ozone (O3), hydrogen peroxide (H2O2) and/or UV light.[2]One such type of process is
called in situ chemical oxidation.

Description:
AOPs rely on in-situ production of highly reactive hydroxyl radicals (OH).
These reactive species are the strongest oxidants that can be applied in water and can virtually
oxidize any compound present in the water matrix, often at a diffusion controlled reaction
speed. Consequently, OH reacts unselectively once formed and contaminants will be quickly
and efficiently fragmented and converted into small inorganic molecules. Hydroxyl radicals are
produced with the help of one or more primary oxidants (e.g. ozone, hydrogen
peroxide, oxygen) and/or energy sources (e.g. ultraviolet light) or catalysts (e.g. titanium
dioxide). Precise, pre-programmed dosages, sequences and combinations of these reagents are
applied in order to obtain a maximum OH yield. In general, when applied in properly tuned
conditions, AOPs can reduce the concentration of contaminants from several-hundreds ppm to
less than 5 ppb and therefore significantly bring COD andTOC down, which earned it the credit
of water treatment processes of the 21st century.[3]

The AOP procedure is particularly useful for cleaning biologically toxic or non-
degradable materials such as aromatics,pesticides, petroleum constituents, and volatile organic
compounds in waste water.[4] Additionally, AOPs can be used to treat effluent of secondary
treated wastewater which is then called tertiary treatment.[5] The contaminant materials are
converted to a large extent into stable inorganic compounds such as water, carbon dioxide and
salts, i.e. they undergomineralization. A goal of the waste water purification by means of AOP
procedures is the reduction of the chemical contaminants and the toxicity to such an extent
that the cleaned waste water may be reintroduced into receiving streams or, at least, into a
conventional sewage treatment.

Although oxidation processes involving OH have been in use since late 19th
century (such as in Fenton reagent, which, however, was an analytical reagent at that time), the
utilization of such oxidative species in water treatment did not receive adequate attention until
Glaze et al. suggested the possible generation of OH in sufficient quantity to affect water
purification and defined the term Advanced Oxidation Processes for the first time in 1987.
AOPs still have not been put into commercial use on a large scale (especially in developing
countries) even up to today mostly because of the relatively high costs. Nevertheless, its high
oxidative capability and efficiency make AOPs a popular technique in tertiary treatment in
which the most recalcitrant organic and inorganic contaminants are to be eliminated. The
increasing interest in water reuse and more stringent regulations regarding water pollution are
currently accelerating the implementation of AOPs at full-scale. There are roughly 500
commercialized AOPs installations around the world at present, mostly in Europe and the
United States. Other countries like China are showing increasing interests in AOPs.

Chemical principles:
Generally speaking, chemistry in AOPs could be essentially divided into three parts:
1. Formation of OH;
2. Initial attacks on target molecules by OH and their breakdown to fragments;
3. Subsequent attacks by OH until ultimate mineralization.
The mechanism of OH production (Part 1) highly depends on the sort of AOP technique that is
used. For example, ozonation, UV/H
2
O
2
and photocatalytic oxidation rely on different mechanisms of
OH generation:
UV/H
2
O
2
:
H
2
O
2
+ UV 2OH (homolytic bond cleavage of the O-O bond of H
2
O
2
leads to formation of
2OH radicals)
Ozone based AOP:
O
3
+ HO
-
HO
2
-
+ O
2
(reaction between O
3
and a hydroxyl ion leads to the formation of
H
2
O
2
(in charged form))
O
3
+ HO
2
-
HO
2
+ O
3
-
(a second O
3
molecule reacts with the HO
2
-
to produce the ozonide
radical)
O
3
-
+ H
+
HO
3
(this radical gives to OH upon protonation)
HO
3
OH + O
2

the reaction steps presented here are just a part of the reaction sequence, see reference for
more details
Photocatalytic oxidation with TiO
2
:
TiO
2
+ UV e
-
+ h
+
(irradiation of the photocatalytic surface leads to an excited electron (e
-
)
and electron gap (h
+
)
Ti(IV) + H
2
O Ti(IV)-H
2
O (water absorbs onto the catalyst surface)
Ti(IV)-H
2
O + h
+
Ti(IV)-OH + H
+
the highly reactive electron gap will react with water
the reaction steps presented here are just a part of the reaction sequence, see reference for
more details

Currently there is no consensus on the detailed mechanisms in Part 3, but researchers have cast
light on the processes of initial attacks in Part 2. In essence, OH is a radical species and should
behave like a highly reactive electrophile. Thus two type of initial attacks are supposed to
be Hydrogen Abstraction and Addition. The following scheme, adopted from a technical handbook
and later refined, describes a possible mechanism of the oxidation of benzene by OH.

Scheme 1. Proposed mechanism of the oxidation of benzene by hydroxyl radicals
The first and second steps are electrophilic addition that breaks the aromatic ring in benzene
(A) and forms two hydroxyl groups (OH) in intermediate C. Later an OH grabs a hydrogen
atom in one of the hydroxyl groups, producing a radical species (D) that is prone to undergo
rearrangement to form a more stable radical (E). E, on the other hand, is readily attacked by
OH and eventually forms 2,4-hexadiene-1,6-dione (F). As long as there are sufficient OH
radicals, subsequent attacks on compound F will continue until the fragments are all converted
into small and stable molecules like H
2
O and CO
2
in the end, but such processes may still be
subject to a myriad of possible and partially unknown mechanisms.

Advantages
AOPs hold several advantages that are unparalleled in the field of water treatment:
It could effectively eliminate organic compounds in aqueous phase, rather than
collecting or transferring pollutants into another phase.
Due to the remarkable reactivity of OH, it virtuallyreacts with almost every aqueous
pollutants without much discrimination. AOPs could therefore be applicable in many, if
not all, scenarios where many organic contaminants are expected to be removed at the
same time.
Some heavy metals could also be removed in forms of precipitated M(OH)
x
.
In some AOPs designs, disinfection could also be achieved, leading AOPs to an
integrated solution to some of the water quality problems.
Since the complete reduction product of OH is H
2
O, AOPs theoretically do not introduce
any new hazardous substances into the water.

Current shortcomings:
It should also be aware that AOPs are not perfect and have several drawbacks.
Most prominently, costs of AOPs are too high, since a continuous input of expensive chemical
reagents are required to maintain the operation of most AOPs system.
Some techniques require pre-treatment of wastewater to ensure reliable performance, which
could be potentially costly and technically demanding. For instance, presence of bicarbonate ion
(HCO3-) can appreciably reduce the concentration of OH due to scavenging processes that yield H
2
O
and a much less reactive species, CO
3
-
. As a result bicarbonate must be wiped out from the
system or AOPs are compromised otherwise.
Given the potential costs, AOPs may not individually handle a large amount of wastewater;
instead, AOPs should be deployed in the final stage after primary and secondary treatment have
successfully removed a large proportion of contaminants.
Future perspectives:
Since Glaze first proposed the definition of AOPs in 1987, this realm has witnessed a rapid
development both in theory and in application. So far, TiO
2
/UV system, H
2
O
2
/UV system and
Fenton system have received extensive scrutiny. Yet there are still many research needs to
address the shortcomings of existing AOPs techniques mentioned above.
Another way to fix the shortcomings is the development of new, modified AOPs that are
efficient and economical. In fact, there has been some studies that offer constructive solutions.
For instance, doping TiO2 with non-metallic elements could possibly enhance
the photocatalytic activity; and implementation of ultrasonic treatment could promote the
production of hydroxyl radicals
As the need for safe and clean water increases globally, there is certainly a growing demand for
technologies that could fulfill such tasks. A promising future for AOPs awaits.

















Physicochemical wastewater treatment

Industrial wastewaters from certain industries don't meet the standards (eg. Vlarem in
Flanders) for discharge, and certainly not for reuse as processwater. First of all, the toxic
components have to be removed from the wastewater flow. Physicochemical wastewater
treatment is a frequently used technique in the area of wastewater treatment. Physicochemical
wastewater treatment techniques are applied for the removal of heavy metals, oils and
greases, suspended matter and emulgating organic substances, organic and anorganic
components, difficult to decompose, non polar organic substances, toxic pollutants or high salt
concentrations, phosphorus,... The physicochemical wastewater treatment techniques are used
as pretreatment, final treatment as well as specific treatment for wastewater reuse as
processwater.

Physicochemical wastewater treatment : used techniques
(flocculation,coagulation, flotation, neutralization, electroflotation, membrane
technology-membrane filtration, NH3 stripper-absorbers, sludge treatment)

General overview

The treatment method selected depends in the first place on the size of the particles
present in the wastewater. Solids, visible to the naked eye, can be removed by filtration,
or can be settled by sedimentation, or they can be separated by means of flotation
techniques, this in function of the density of the solids. The major problem however
comes from fine suspended solids (particle size < 1 m). These are very stable and they
all have an electrostatic laden surface (usualy negative), which means that they repell
each other, and will not clot together nor settle. This kind of fine suspended solids can
only be removed by means of physicochemical techniques. For this purpose chemicals
are added (coagulants or floculants) to accomplish the clotting together or coagulation
of the suspended solids, allowing to finally settle. Preliminar laboratory tests with
wastewater samples (Jar tests), will allow in advance a rather accurate view on the
estimated result of the proposed wastewater treatment technique in practice.

Flotation : separation of suspended solids, oils, greases and undissolved particles. This
technique can be used as a preliminary treatment method for further purification, but at
the same time the wastewater treatment can be limited to the flotation technique only.
The most used flotation technique is D.A.F. (Dissolved Air Flotation), by which
compressed air is dissolved in the waste water, to be treated. The released air forms
tiny bubbles, adhering to the suspended matter (flakes) in the water (to which
coagulants and/or flocculants have been added previously - see above), this tiny bubbles
and suspended solids flakes can now float to the surface, because of their now reduced
density (by the dissolved air). The float layer formed that way is skimmed and collected
in a container, installed next to the DAF-unit. The sludge can be further thickened
and/or dewatered. This kind of installations can be fully automated and as a result, they
are most maintenance friendly.

Neutralisation : too acid or too alkaline wastewater flows are neutralized until a pH
value of approx 7 is reached. The main reason to neutralize wastewater is to prepare it
for further treatment in a biological wastewater treatment station or to meet the
standards for discharge (eg. too acid wastewater can damage the sewer system and
wastewater treatment plants). The most important objectives of this technology are the
following : part from neutralization, the pH of the wastewater can be altered for several
reasons : eg. a better control of the speed of chemical reactions, breaking down
emulsions, conditioning, stabilization of raw wastewater, etc. For neutralization
techniques, chemicals are added to the wastewater. Some examples ofneutralisation
units are to be found in the pictures above : neutralization units are compact units,
composed of storage- and reaction tanks, completed with the necessary dosing- and
mixing equipment. The chemicals added to obtain a higher pH-value are lye (NaOH) or
limemilk (Ca(OH)
2
), to obtain a lower pH-value sulphuric acid (H
2
SO
4
), hydrochloric acid
(HCl) or carbon dioxide (CO
2
) are used. Neutralization techniques can be used for a wide
range of wastewaters coming from almost any kind of industrial activities. This kind of
installation is uncomplicated, can be fully automated and are thus maintenance friendly.
The simple construction allows for a reduced investment cost.

Membrane technology-membrane filtration : deferrization, water softening,
demineralization by means of membranes, also water recycling and reuse (see the
corresponding page for more details).

Stripping: removal of volatile substances with an NH
3
stripper (stripping tower) -
absorber (see corresponding page for more details).

Sludge treatment : in many cases sludge will be the residue in the final stage of the
physicochemical wastewater treatment process. Many companies have opted for
removal of this sludge by third parties (waste collection and waste treatment
companies), hence the importance of reducing the volume of this sludge as much as
possible. Seen the strong reduction of the sludge collecting and treatment cost by
investing in sludge volume reduction equipment, the payback time for this part of the
physicochemical wastewater treatment process will be rather short. One of the
methods to dewater sludge is the chamber filter press. The sludge is dewatered by
pumping it into a confined space or chamber under increasing pressure (to 10 15 bar).
These chambers are formed by pressing opposite square plates against each other,
under high pressure. Each filter plate is on both sides covered with filter cloth. The filter
cloths retains the sludge, while the water is drained away by the ribbed surface of the
filter plates. After the pressing stage, the chambers open and the filter cakes, in normal
circumstances, fall off automatically. The filter presses can optionally be equipped with
a high pressure spraying system for automatic cleaning of the filter cloths every cycle or
after a certain number of cycles. The dewatered sludge residue can now be collected
periodically for further treatment.

Applications :
Physico-chemical treatment may constitute a single stage in the wastewater treatment process
or be added as an additional treatment process during pre-treatment (to improve the
biodegradation of wastewater in the biological process and secondary treatment (such as
polishing).
Physico-chemical processes have been implemented for over 100 years (45). However in 1930,
these processes were replaced by biological processes due to the high costs incurred by the
treatment of large quantities of sludge (46). Recently, they have been reintroduced for various
purposes: the elimination of phosphorus (17, 44, 45 and 47) for effluent being discharged to the
sea, obtaining average quality effluent at lower cost than conventional treatments and for
water used for agricultural irrigation (9, 20, 33 and 34), for potabilization (10 and 49), industrial
water treatment (24 and 50) conditioning of sludge (primary and/or secondary) (23, 26, 27, 51
and 52). The resurgence of these processes is also due to increased recognition that the cost of
treatment should be consistent with the desired efficiency, as progress in the synthesis of
flocculation polymers with high efficiencies has been achieved at a lower cost (33).
Using this type of process it is feasible to remove 80 to 90% of total suspended solids (TSS), 40
to 70% of BOD
5
, 30 to 40% of COD and 17 to 100% of nutrients (N and P), depending on the
dose and type of coagulant used (2, 7, 9, 17, 26, 33, 34, 47, 53 and 54). Heavy metals may also
be removed by these processes, but the removal efficiency depends on the metal type and
concentration (17, 33 and 55). Recently, these processes have been used to remove pathogens
such as helminth eggs and have proven to be capable of removing up to 2 log
concentration (20, 33, 34 and 48). In addition they are very efficient when used to remove
bacteria (0-1 log unit), viruses and protozoa (1-3 log units in each case) (33 and 48). Current
studies are focusing on their use for the removal of emerging contaminants (50, 56 and 57).