Unit 5 (Waste Water Management)

Advance treatments
Tertiary or advanced treatment pertains to the unit operations and chemical unit processes which
are used to further remove BOD, nutrients, pathogens, parasites and sometimes toxic substances.
These include both physical and chemical processes, like filteration using sand, coal or activated
carbon filters or chemical oxidation processes which utilizes chlorination, H2O2 fentons reagent,
ozone and permanganate.

The physical oxidation processes which include

 UV oxidation

 Sonication

 Wet air oxidation

 Supercritical water oxidation (SCWO)

The effluent from a typical secondary treatment plant still contains 20-40 mg/L BOD which may
be objectionable in some streams. Suspended solids, in addition to contributing to BOD, may settle
on the stream bed and inhibit certain forms of aquatic life. The BOD if discharged into a stream
with low flow, can cause damage to aquatic life by reducing the dissolved oxygen content. In
addition the secondary effluent contains significant amounts of plant nutrients and dissolved solids.
If the waste water is of industrial origin, it may also contain traces of organic chemicals, heavy
metals and other contaminants. Different methods are used in advanced waste treatment to satisfy
any of the several specific goals, which include the removal of (1) suspended solids (2) BOD (3)
plant nutrients (4) dissolved solids and (5) toxic substances. These methods may be introduced at
any stage of the total treatment process as in the case of industrial waterways or may be used for
complete removal of pollutants after secondary treatment.
Removal Of Suspended Solids:
This treatment implies the removal of those materials that have been carried over from a secondary
treatment settler. Many methods were proposed of which two methods were commonly used. The
two methods are microstaining and chemical coagulation followed by settling and mixed media
filtration.
Microstraining:
It is a special type of filtration procedure which makes use of filters oven from stainless steel wires
with opening only 60-70 μm across to remove very small particles. High flow rates and low back
pressures are normally achieved.
Coagulation and flocculation:
The object of coagulation is to alter these particles in such a way as to allow them to adhere
to each other. Most colloids of interest in water treatment remain suspended in solution because
they have a net negative surface charge that causes the particles to repel each other. The intended
action of the coagulant is to neutralise that charge, allowing the particles to come together to form
larger particles that can be more easily removed from the raw water.
The usual coagulant is alum [Al2(SO4)2• 18H2O ], though FeCl3, FeSO4 and other coagulants, such
as polyelectrolytes, can be used. Alum when added to water, the aluminium in this salt hydrolyses
by reactions that consume alkalinity in the water such as:

The gelatinous hydroxide thus formed carries suspended material with it as it settles. In addition,
however, it is likely that positively charged hydroxyl-bridged dimers such as

and higher polymers are formed which interact specifically with colloidal particles, bringing about
coagulation. Metal ions in coagulants also react with virus proteins and destroy upto 99% of the
virus in water.
Anhydrous ion (III) sulphate can also act as effective coagulant similar to aluminium sulfate. An
advantage with iron (III) sulfate it that it works over a wide range of pH.

Removal of dissolved solids:

The dissolved solids are of both organic and inorganic types. A number of methods have been
investigated for the removal of inorganic constituents from waste water. Three methods which are
finding wide application in advanced waste treatment are ion-exchange, electrodialysis and reverse
osmosis. For the removal of soluble organics from waste water the most commonly used method
is adsorption on activated carbon. Solvent extraction is also used to recover certain organic
chemicals like phenol an d amines from industrial waste waters.
Removal of nitrogen:
Nitrogen compounds may be removed in waste water in two ways. Even after secondary treatment,
most of nitrogen exists as ammonia. Increasing the pH produces the reaction,

Much of the dissolved ammonia gas may then be expelled from the water into the atmosphere. The
ammonium ion in the waste water may also be oxidised to nitrate by bacteria like nitrobacter and
nitrosomonas, in a process called nitrification.

These reactions are slow and require long retention times in the aeration tank as well as
sufficient DO. If the flow rate is too high, the slow-growing microorganisms are washed out of the
aeration tank.
Once the ammonia has been oxidised to nitrate, it may be reduced by anaerobic bacteria like
pseudomonas. This denitrification requires a source of carbon and methanol is often used for that
purpose.

Phosphate removal (chemical treatment):

Phosphate may be removed chemically or biologically. The most popular chemical methods use
lime, Ca(OH)2 and alum, Al2(SO4)3.Under alkaline conditions, the calcium will combine with
phosphate to form calcium hydroxyapatite, a white insoluble precipitate that is settled out and
removed from waste water. Insoluble calcium carbonate is also formed and removed.

The aluminium ion from alum precipitates as very slightly soluble aluminium phosphate,

and also forms aluminium hydroxide.

which forms sticky flocs that help to settle out phosphates.
Phosphate removal (biological treatment)
Biological phosphorous removal does not require the addition of chemicals. In this process, the
aeration tank in the activated sludge system is subdivided into zones, some of which are not
aerated. In these zones, the aerobic microorganisms become solely stressed because of the lack of
oxygen. If these microorganisms are then transferred to an aerated zone, they try to make up for
lost time and assimilate organic matter (as well as phosphorous) at a rate much higher than they
ordinarily would. Once the microorganisms have adsorbed the phosphorous, they are removed as
waste activated sludge, thus carrying with them high concentrations of phosphorous. Using such
sequencing of nonaerated and aerated zones, it is possible to remove as much as 90% of the
phosphorous.
Removal of dissolved organic compounds:

Adsorption: One of the most commonly used techniques for removing organics involves the
process of adsorption, which is the physical adhesion of chemicals on to the surface of the solid.
The effectiveness of the adsorbent is directly related to the amount of surface area available to
attract the particles of contaminant. The most commonly used adsorbent is a very porous matrix
2
of granular activated carbon, which has an enormous surface area (~ 1000 m /g). Adsorption on
activated carbon is perhaps the most economical and technically attractive method available for
removing soluble organics such as phenols, chlorinated hydrocarbons, surfactants, and colour and
odour producing substances from waste water.

Granular activated carbon treatment systems consist of a series of large vessels partially
filled with adsorbent. Contaminated water enters the top of each vessel, trickles down through
granulated activated carbon, and is released at the bottom. After a period of time, the carbon filter
becomes clogged with adsorbed contaminants and must be either replaced or regenerated.
o
Regeneration of the carbon is accomplished by heating it to 950 C in a steam air atmosphere. This
process oxidises surface, with an approximately 10% loss of carbon.
Synthetic organic polymers such as Amberlite XAD-4 have hydrophobic surfaces and are quite
useful in removing relatively insoluble organic compounds such as chlorinated pesticides. These
absorbents are readily regenerated by solvents such as isopropanol and acetone.
Filteration
Filteration is defined as the process of allowing waste water to pass through a thick layer of sand
or other filtering media. Filters may be classified as slow sand filters and rapid sand filters
depending upon the rate of filteration. The phenomena of filteration is quite complex, but generally
four function are performed.

1. Mechanical straining: which removes large suspended matterwhich cannot pass through
interstics between sand grains.
 2. Sedimentation and adsorption: accounts for the removal of colloids, suspended and
bacterial particles. The interstices between sand grains act as minute sedimentation basins.

3. Biological metabolism: it is the growth and life process of the living cells. The surface
layer gets coated with a zoogleal film in which bacterial activities are highest.

4. Electrolyte action: a certain amount of dissolved and suspended matter in H2O is ionized
which interacts with particles of sand which are also ionized. These neutralize each other
and while doing so, change the chemical character of water.

The selected filter sand should be free from clay, loam, vegetable or organic matter. It should also
be of uniform and of proper size. If the sand is too fine, it tends to quickly clog which causes a
greater loss of head in the filter.

If the sand is too coarse, it will permit suspended solids and bacteria to pass through voids between
the sand grains. Effective size of the sand is defined as the sieve size in mm which permits 10%
of the sand by weight to pass or in other worlds, as the size of the grain that is larger than 10% by
weight of all the particles comprising the sand.

Construction of slow sand filter

It consists of a water tank, 2.5-3.5m in depth, having a sand bed 0.6-0.9m thick, supported on a
bed of gravel 0.3-0.45m thick laid in 5-6 layers, beneath with the under drainage system is laid
over a concrete bed sloping towards a central longitudinal drain. The underground system consists
of open-jointed drains of baked clay or concerete pipe in length of 30-40m which a maximum
spacing of lateral of 2m.
The raw mater is led gently on the filter bed, percolating downwards passes through the
underdrains iinto an outlet chamber.

Construction of rapid sand filter (Gravity type)

It consist of an oper water-tight tank 3-3.5m deep of masonry or concrete with a concrete floor
having coarse sand 0.6-0.75m thick, laid on the top with a layer of grated gravel 0.6-0.75m thick,
laid on the top with a layer of grated gravel 0.45m thick supporting below. The gravel is underlain
by an underdrainge system consisting of cast iron, central longitudinal conduct or manifold with
strainers mounted on top and pipes of smaller diameter called lateral branching off at right angle
to the manifold. The laterals are fixed 15-30cm centres and carry perforations on sides and bottom.
About 1.75-2.5m of water depth may be allowed on the filter bed.

Comparative characteristics of slow sand filter and Rapid Sand filters

Rapid Sand Filter

Characteristic Slow Sand Filter

Area Require more area Require less area

 Sand grains are finer.
Sand grains slightly coarser.
Effective size lies
Size of sand or
between 0.3-0.35mm Effective size lies between 0.45-0.70mm
filtering media
Uniformly coefficient is Uniformly coefficient is 1.70 maximum.
2.

Low 100 to 200

Rate of filteration High 2000 to 6000 litres/m2/hr.
litres/m2/hr.

It is very small. Only

Loss of head It is more -2.5 to 3m.
0.6-0.9m

Simple to operate.

Supervision Does not require Requires skilled operators.

Skilled operators

Does not require

Requires the addition of a coagulant in order to
Coagulation premliminary coagulant
get satisfactory filteration.
mixing.

Washing is done by reversing the flow of

Washing is done by water, taking the help of compressed air and a
Method of
scrapping a thin layer of high pressure of wash water. Washing is
cleaning
sand from the surface. completed in a few minutes, say 15-30
minutes.

Period of cleaning Once every 2-3 months 24-48 hr

Amount of wash 0.2-0.6% of filtered

2-4% of filtered water.
water water.

Remove bacteria Remove bacteria only partially. It is more

Efficiency completely because the efficient in the removal of colour. because the
rate of filteration is slow rate of filteration is slow
 Operating cost per
Operating Cost thousand litres of water It is more
treated is less.

More because of maintenance of pumps for

Maintenance cost Small pumping up wash-water and a compressor unit
for obtaining compressed air.

Drawbacks of rapid sand fillers

Due to filetration on graded sand the majority of impurities are removed and stored in the limited
space available in top sand layers. As the filters gets stratified after back washing it leads to surface
clogging with quicker build up of head loss at higher velocity of filteration. Therefore the rapid
sand filter has to be operated at somewhat lower filteration rates with shorter filter runs. The fine
to coarse gradation of filter medium often results in poor filterate quality due to non-removal of
finer-floc particles which may lodge in the region below the top sand layers.

To offset these drawbacks, indepth filteration is done where impurities laden water first passed
through a medium having maximum pore space for arresting impurities. After this, the resulting
water travels deeper into filter beds come in contact with the layers having smaller pore size. This
enables the smaller sized particles to be detained and finally removed along with the finer floc
particles.

This leads to higher quality filterates and greater utilization of the lower filter bed layers and
consequently increased filter runs. This concept of indepth filteration uses the following filters:

1. Dual media filters

A dual media filter consists of a fine sand layer topped with a bed of anthraute coal each generally
30cm deep. The coarser an thracite top layer has intustices about 20% larger than the sand media.
These openings are capable of adsorbing and trapping particles so that the flocs carried once in
clarifier does not accumulate on the filter surface and sand bed forematurily. Because of the
different specific gravity f the two materials (Coal 1.4 and sand 2.65), the coal of proper size in
relation to the sand remains on top of sand during back washing.they have high rate of filteration
of about 12000-15000 litres/m2/h with the produce of high quality water. However, due to low
total surface area of media particles they have a low resistance to turbidity break-through with
changing flow rates.

2. Mixed media filter

A mixed media filter is a three layer filter of three properly graded materials: Coal (sp. gr.1.4),
sand (sp.gr.2.65) and garnet (sp.gr.4.2) in the proporation of 60, 30 and 10% resp. the particle sizes
range from 1.0mm to 0.12mm from top to bottom of filter bed. After back washing, the three
materials are mixed thoroughly through out the depth of the bed. However, at each level in the bed
particles of coarse coal, medium sand and fine garnet are present.

Particles of turbidity in the influent to the mixed filter first pass through large pores and encounter
the coarse media then reach smaller pores resulting from the mixing of finer media with coarser
occur. Materials are removed and sorted throughout the full depth of the bed.

 The vast storage capacity of the mixed media filters greatly inceases the length of
filter runs.

 The total surface area of the grains is much more resistant to break-through and
more tolerant to increases in filter rates.

 It is thus possible to achieve filter rates of 1500litres/m2/hr.

Activated Carbon filters is based on liquid to solid adsorption process which remove a solute from
water via a selective solid resin. Physical adsorption involves weak Vanderwaal’s forces. Chemical
adsorption involves stronger interactions (e.g ion excahange or hydrogen banding between the
solid and the solute).The solids may be

 Activated carbon

 Activated alumina

 Organoclays etc.
Adsorption can occur in fluidized, move or fixed bed as wll as in upflow pressure or gravity contact
systems (in which the adsorbant is dropped through a column of water). The fixed resin bed is
typically used in waste water treatment, it involves passing waste water down through a paxked
column of resin.

Activated carbon is the most popular adsorbant because it is

 Relatively inexpensive

 Adsorbs wide range of organic and inorganic substances.

 Can be made from several materials e.g wood, sawdust, fruit pits, coconut shells,
coal lignite and petroleum residues.
To make activated carbon the chosen material is carbonized and then activated with hot air or
steam. The extensive pore structure provides an extensive adsorption surface, which can range
from 600-1100m2/g of active carbon.

In waste water treatment systems, multiple solutes often complete for adsorption sites on the
activated carbon. Differences in carbon source, temperature swings and other systemspecific
variances require that the pilot tests should be conducted before designing an activated carbon
process.
Activated carbon is thought to remove a solute from solvent in 3 steps:-

 Transfer across a liquid boundry

 Sorption to the outer surface

 Migration into deep pores.

Many full-scale designs incorporate two or three columns. In two column design, one column
regenerates, while the other is on-line. In three-column design, two columns operate in series while
the third regenerates.

Disinfection of water
None of the previous methods used for treatment of waste water either singly or in combination
can be relied upon to remove the bacteria present in water especially pathogenic one. Therefore it
is necessary to disinfect or kill the bacteria. The methods employed to disinfect water depends
upon the disinfecting materials used for the purpose. The general requirement is

1. It should be harmless and unobjectionable to the consumer

2. It should retain a residual disinfecting effect for a long time.

Principle methods used for disinfection are

1. Chlorination

2. Ozonization

3. Ultraviolet ray method

4. Excess lime method

5. Iodine and bromine methods

1) Chlorination

It is the application of small quantity of chlorine or chlorine compounds in water. The dose applied
is generally less than 1mg/l so as to produce residual chlorine of trace quantity i.e 0.05-0.20mg/l.
Chlorine hydrolysis in water to form hypochlorous acid (HoCl) which further dissociates to
produce hypochlorite ion (ocl-). HoCl and oCl- together are known as free available chlorine. The
reaction is as follows:

Chlorine is generally applied after all other treatments to the water has been given. This may be
termed as post chlorination and is the standard treatment for all water works. There are however,
other special methods of chlorination depending upon particular purpose.
i) Pre-chlorination: It is the application of chlorine preceding filteration. It reduces bacterial load
on filters resulting in increased filter runs and oxidizes excessive organic mater thus removing
taste and odour.

ii) Double chlorinaton: Application of chlorine at two points i.e prechlorination and to the final
effluent.

Advantages are:

 Decreases in load of filters.

 Greater removal of bacteria –higher bacterial efficiency
 Greater factor of safety due to maintenance of 2 chlorinating plants.
 Control of algae and slimy growths in coagulating basins and filters.
iii) Superchlorination: It is the application of water with excess amount of chlorine i.e < 1mg/l
to 2 mg/l this method is effective in destroying high concentratation of tastis and odours in water.
Bacteria removal is also high.

iv) Breakpoint chlorination: It is also termed as free-residual chlorination which involves the
addition of sufficient chlorine so as to oxidize a organic matter, reducing substances and free
ammonia in raw water leaving behind mainly free available cl2 which possess strong disinfecting
action against pathogens.

2) Ozonization

It is a highly oxidizing agent containing 3 atoms of oxygen (O3) which changes to O2 and releases
nascent oxygen (O). the nascent oxygen reduces organic matter present in water without
production of objectionable tastes and odours as with chlorine.

The ozone dose is 2-3mg/l to give a trace to 0.1 mg/l residual after 10 minutes contact. It is regarded
as a natural means of disinfecting water having bacterial spores. However, it is costly to
manufacture, it has very little residuals presents, not quite suitable for highly turbid waters.

3) Ultraviolet rays

It is an effective method of disinfecting clear water which kills all type of bacteria, cysts and
spores. Water is passed over a uv lamp as the effective penetration of rays in water is only for a
depth of 30cm or so.

Advantages

 No taste and no odour

 Presenting no danger of overdose

Disadvantages
  High cost

 Absence of any residual action.

 Use in restricted normally to small installations like swimming pools.

4) Excess lime method

Excess lime method involves application of sufficient lime for the combined objectives of
softening and disinfecting of water coliform reduction may be as high as 99%

 Dose given is between 10-20mg/l

 It frequently becomes necessary to remove excess lime after the process

through recarbonation.
5) Iodine and Bromine methods

Their use is restricted to small water supplies such as army camps and swimming pools. Water
which is muddy or colored needs to be filtered before disinfection. These are cheaply available in
the form of pellets. Dosage is about 8-10mg/l. for heavily polluted water, it may be doubled only
objection is the resulting medical taste.

The Basics of Membrane Filtration

Cross flow membrane filtration is an alternative process for separating solids from a liquid phase.
The process uses a membrane, rather than a granular medium, to prevent the passage of solids to
the effluent stream. When wastewater under pressure is applied to a membrane filter, water
permeates through the membrane as the wastewater containing solids passes along the length of
the membrane. Consequently, the concentration of solids increases as the wastewater flows along
the length of the membrane. One possible membrane filtration schematic is shown in the following
figure:
Figure--- Typical Ultrafiltration Wastewater Treatment Flow Schematic
The membrane provides a physical barrier to the passage of solids, and even to the passage of
large molecules. The size of the molecules that are able to cross the membrane can be selected
based on the characteristics of the membrane.

Types of Membrane Filters

Membranes can be constructed of various materials and with various characteristics. A simple
distinction is to differentiate membranes based on the size of the molecules they pass. On this basis
there are a few significant membrane processes: microfiltration, ultrafiltration, nano-filtration, and
reverse osmosis.
These processes are gaining favor for industrial wastewater pretreatment applications. Highlights
of these processes are presented below.
Microfiltration
 Microfiltration membranes have pores that range in size from 0.1 to 2.0 microns (which is
relatively large).
A micron is one-millionth of a meter.
 Because of the relatively large pore size, this process is more suitable for production
processes
rather than for wastewater treatment processes. The large pores let too much wastewater
 contamination through the membrane.
Ultrafiltration
 Ultrafiltration is the most commonly used membrane for wastewater treatment
applications. It uses a membrane with pore sizes ranging from 0.005 to 0.1 micron.
Emulsified oils, metal hydroxides, proteins, and starches are larger than the pore size and
will not pass through the membrane.
Nano filtration
 The pores for a nanofilter are so small that they will allow only small molecules, such as
salts, to pass, but will retain larger molecules, such as sugars and nitrogen molecules. These
larger molecules create BOD and COD in wastewaters, and therefore nanofiltration is
effective in reducing the BOD of wastewater by removing these molecules.
 There is a trade-off between small pore size and solids handling capacity. Nanofilters may
not be efficient for many wastewaters because the amount of solids present may require a
disproportionately long time for cleaning.
Reverse Osmosis
The tightest membranes are used in reverse osmosis, which only allows very small molecules
such as water to pass. Most solids, even salts, are retained on the membrane. Because of the
small size of the pores, reverse osmosis has limited solids handling capability, so the process
is most often used following a coarser filtration process, such as ultrafiltration and only when
very high quality water is required.

In the reverse osmosis process, demineralisation water is produced by forcing water

through semipermeable membranes at high pressure. In ordinary osmosis, if a vessel is divided by
a semipermeable membrane (one that is permeable to water but not the dissolved material), and
one compartment is filled with water and other with concentrated salt solution, water diffused
through the membrane towards the compartment containing salt solution until the difference in
water levels on the two sides of the membrane creates a sufficient pressure to counteract the
original water flow. The difference in levels represents the osmotic pressure of the solution
 The process can be reversed by applying sufficient pressure to the concentrated solution to
overcome the osmotic pressure force the net flow of water through the membrane towards the
dilute phase. The solute concentration (impurity) builds up on one side of the membrane while
relatively pure water passes through the membrane . In order to obtain adequate solvent (water)
2
flux through the membrane, pressures of the order of 4000 to 7000 kN/m are required.
Fig.(below) represents the principle of operation of the reverse osmosis unit.

Operational Considerations
Membrane filtration systems require proper pretreatment of the feed to prevent fouling or
plugging of the system. In addition, several process parameters are important to the proper
functioning of a membrane filter and are worthy of discussion.
Temperature
  Temperature affects membrane filtration because the viscosity of fluids is inversely
related to temperature (the higher the temperature the smaller the viscosity). Therefore,
operating at the upper end of the allowable temperature range will optimize the
performance of a membrane filtration system.
 However, temperatures exceeding the design range will likely damage and may destroy
the membrane. Consult the manufacturer’s instructions to determine the appropriate
operating temperature for the specific membrane used.
Flux
 Membrane filtration systems are generally designed to achieve a specified flux rate. This
design takes into account the variables that affect the flux of a system (as discussed above).
 Deviation from the design flux generally indicates a problem with the system or a change
in the influent characteristics from the design values. The problems could entail a drop in
transmembrane pressure or a reduction in the recirculation flow rate (due to potential pump
problems), or fouling or plugging of the membrane surface (indicating that cleaning is
required).
Transmembrane Pressure
 For ultrafiltration, the transmembrane pressure is typically in the range of 20 to 80
pounds per square inch (PSI) and for reverse osmosis is in the range of 400 to 1,000
PSI.
 Flux is a function of transmembrane pressure up to a point where the wastewater
concentration becomes great enough to negate the effect of transmembrane pressure on
flux.
Differential Pressure of the Recirculation Flow
 The differential pressure of the recirculation flow is a measure of the pressure drop from
the inlet of the membrane system (at the pump discharge) to the outlet of the membrane
system (where therecirculation flow leaves the system). This pressure drop is generally
related directly to the recirculation flow rate through the membrane system and is a simple
pipe flow head loss relationship.
 Changes in the influent characteristics or build-up of solids on the membrane can cause
changes in the differential pressure. Deviations from the normal differential pressure
should be investigated immediately as an indication of potential major problems with the
system.
Membrane Fouling
Fouling is a molecular attraction between contaminants in the feed with the membrane material.
 Reversible fouling is expected for all membrane and can be managed with routine cleaning.
 Irreversible fouling, though rare, can also occur. In this case, contaminants that are not
compatible with the membrane material react with the membrane so that they cannot be
 cleaned off or removed. Consult manufacturer’s literature for the specific membrane
material to identify potential irreversible fouling contaminants.
Cleaning Options
• Cleaning of membranes is a routine procedure that may need to be performed on a weekly
or semi-weekly basis, depending on the process characteristics. A cleaning cycle typically
takes approximately two to four hours to complete.

The cleaning cycle includes:

 Displacement of wastewater from the system with clean water.
 Circulation of a warm, caustic surfactant solution through the system.
 Flushing the system with warm water after the wash cycle is completed.
 Washing the system with a warm, dilute acid cleaner to remove accumulated salts.
 Flushing again with warm water.
 Checking and recording flux rate using clean water.

• Exposure of membranes to aggressive cleaning solutions contributes significantly to their

degradation, so cleaning solutions should be carefully prepared to minimize damage to the
membrane while still completing the necessary cleaning function.
• Tubular systems can be mechanically cleaned as well as chemically cleaned. To perform a
mechanical cleaning, sponge balls sized for the tube diameter are flushed through the
system.
• Hollow fiber systems can be mechanically cleaned by backwashing the membrane with
clean water. However, most tubular and spiral membrane systems cannot be backwashed
do to delamination of the membrane from the support.
Ion exchange:
This technique has been used extensively to remove hardness, and iron and manganese
salts in drinking water supplies. It has also been used selectively to remove specific impurities and
to recover valuable trace metals like chromium, nickel, copper, lead and cadmium from industrial
waste discharges. The process takes advantage of the ability of certain natural and synthetic
materials to exchange one of their ions.
A number of naturally occuring minerals have ion exchange properties. Among them the notable
ones are aluminium silicate minerals, which are called zeolites. Synthetic zeolites have been
prepared using solutions of sodium silicate and sodium aluminate. Alternatively synthetic ion-
exchange resins composed of organic polymer with attached functional groups such as –SO--3 H+
- +
(strongly acidic cation exchange resins), or – COO- H (weakly acidic cation exchange resins or
+ -
-N (CH3)3OH (strongly basic anion exchange resins) can be used.

In the water softening process, the hardness producing elements such as calcium and magnesium
are replaced by sodium ions. A cation exchange resin in sodium form is normally used. The water-
softening capability of cation exchange can be seen when sodium ion in the resin is exchanged for
calcium ion in solution.

(where “Res” represents resin phase)

The product water thus has high sodium content, which is not likely to be troublesome unless the
original water is very hard. When the exchanger is saturated, it has to be regenerated to allow reuse
2+
of expensive resin. Regeneration can be achieved by sodium chloride solution which removes Ca
2+
and Mg ions from the resin.

Since for regeneration large amounts of NaCl has to be used, appreciable amounts of sodium
chloride can be introduced into sewage by this route. This problem can be overcome by using
- +
weakly acidic cation exchange resin such ResCOO H . These cation exchangers having -COOH
as functional group are useful for removing alkalinity along with hardness. Alkalinity is generally
manifested by bicarbonate ion. This ion is sufficiently basic to neutralise the acid of weak cation
exchange. Another advantage with these resins is that these can be regenerated almost
stoichiometrically with dilute strong acid, thus avoiding pollution problem caused by excess NaCl.
This technique has also been successfully applied to the recovery of chromate from waste water in
pigment manufacturing.
The removal of inorganic solute is essential for complete water recycling. The effluent from
secondary waste treatment contains 300-400 mg/L more dissolved inorganic material than does
municipal water. The removal of these bulk inorganics can be efficiently done by reverse osmosis
and electrodialysis .

Electrodialysis:
Electrodialysis uses ion-selective membranes and an electrical potential difference to separate
anions and cations in solution.

In the past electrodialysis was most often used for purifying brackish water, but it is now finding
a role in hazardous waste treatment. Metal salts from plating rinses are sometimes removed in this
way.
Fig(above) shows a simple dialysis cell in which waste water may be deionised. As shown
in the figure two types of membranes (anionic and cationic) are arranged alternatively to form
many compartments between the electrodes placed at the two ends. When the voltage is applied
across the cell containing mineralised water, the anions migrate to the positive electrode and the
cations migrate to the negative electrode. This causes solution in alternate compartments to
become more concentrated while that in the remaining becomes more dilute. The electric power
requirement is proportional to the number of ions removed from the water.
In the electrodialysis process, organic molecules are not removed and they can collect on and clog
the membranes. Another disadvantage of this method is that it still leaves concentrated waste water
to be disposed of by some appropriate scheme. The process does not require any chemical additives
and has low energy requirements and as such it can be an economically feasible means of
demineralisation.