4. Water treatment processes
• Preliminary treatment is any physical, chemical or mechanical process used
on water before it undergoes the main treatment process.
• The purpose of preliminary treatment processes is to remove any materials
which will interfere with further treatment.
• Pretreatment may include screening, presedimentation, chemical
addition, flow measurement, and aeration.
5. Preliminary Treatment / Screens
• The screens are used to remove
rocks, sticks, leaves, and other debris.
• Very small screens can be used to screen out algae
in the water.
• All objects are removed by physical size separation
• Screens on the outside of intakes are often cleaned by
flushing water from the treatment plant backwards
• There are two primary types of screens - bar screens
and wire-mesh screens.
• A bar screen is used to remove large debris. The
spaces between the bars are two to four inches wide.
• A wire-mesh screen is used to remove smaller
debris. The gaps are about half an inch wide.
• Water must be flowing slowly in order to pass
through a wire-mesh screen - velocities should be no
greater than 3.5 inches per second.
A wire-mesh screen
A bar screen
6. Preliminary Treatment / Presedimentation - Aeration
Presedimentation is to settle out sand, grit, and gravel which will settle rapidly out of the
water without the addition of chemicals at the beginning of the treatment process.
Presedimentation depends on gravity and includes no coagulation and flocculation.
Presedimentation will reduce the load on the coagulation/flocculation basin and on the
sedimentation chamber, as well as reducing the volume of coagulant chemicals required to
treat the water.
Presedimentation basins are useful because raw water entering the plant from a reservoir is
usually more uniform in quality than water entering the plant without such a holding basin
Here in pretreatment, the purpose of sedimentation is to make the chemical treatment phase
of the water treatment process more efficient by removing sediment from the raw water.
In presedimentation basin, activated carbon may be added to the basin for taste, odor, and
color problems, and some chemicals to control the growth of algae.
Aeration removes carbon dioxide and hydrogen sulfide from the water. It also oxidizes
the iron and manganese.
7. Preliminary Treatment / Monitoring
• Flow Measurement : to adjust chemical feed rates, calculate detention
times, and monitor the amount of water being treated.
• It is also monitored for a variety of characteristics including
pH, turbidity, total alkalinity, temperature, and coliform bacteria.
• The pH and total alkalinity of the water will influence the amount of alkali to
be added and can also influence the flocculation conditions
• The level of turbidity will influence the amount of polymer (coagulant) added
to the water.
• Temperature is also measured since cold water does not floc as well as warm
water and requires the addition of more polymer
8. Primary Sedimentation
• sedimentation may not be necessary in
low turbidity water of less than 10 NTU
• In this case, coagulation and flocculation
are used to produce pinpoint (very
small) floc which is removed from the
water in the filters
• Sedimentation is a treatment process in which the velocity of the water is
lowered below the suspension velocity and the suspended particles settle
out of the water due to gravity.
• The process is also known as settling or clarification
• Settled solids are removed as sludge, and floating solids are removed as scum
• The efficiency or performance of the process is controlled by: detention
time, temperature, tank design, and condition of the equipment.
9. Primary Sedimentation / Location in the
• The most common form of sedimentation follows coagulation and flocculation
and precedes filtration.
• This type of sedimentation requires chemical addition (in the
coagulation/flocculation step) and removes the resulting floc from the water.
• sedimentation following coagulation/flocculation is meant to remove most of
the suspended particles in the water before the water reaches the filters,
• Sedimentation at this stage in the treatment process should remove 90% of the
suspended particles from the water, including bacteria.
• The purpose of sedimentation here is to decrease the concentration of
suspended particles in the water, reducing the load on the filters.
• Sedimentation can also occur as part of the pretreatment process, where it is
known as presedimentation.
10. Types of
Rectangular basins: have a variety of advantages -
predictability, cost-effectiveness, and low
maintenance. In addition, rectangular basins are
the least likely to short-circuit, especially if the
length is at least twice the width. A disadvantage
of rectangular basins is the large amount of land
Double-deck rectangular basins: This type of basin
conserves land area - has higher operation and
Square or circular sedimentation basins with
horizontal flow are known as clarifiers. This type
of basin is likely to have short-circuiting problems.
Solids-contact clarifiers , also known as upflow
solids-contact clarifiers or upflow sludge-
blanket clarifiers combine coagulation,
flocculation, and sedimentation within a single
basin. found in packaged plants and in cold
climates where sedimentation must occur indoors
11. Sedimentation and flotation zones
• All sedimentation basins have four zones -
the inlet zone, the settling zone, the
sludge zone, and the outlet zone.
• In a clarifier, water typically enters the
basin from the center rather than from one
end and flows out to outlets located around
the edges of the basin. But the four zones
can still be found within the clarifier
A rectangular sedimentation basin
12. Sedimentation and flotation zones/Inlet Zone
Purposes of the inlet zone of a sedimentation basin are
• to distribute the water and to control the water's velocity as it
enters the basin.
• inlet devices act to prevent turbulence of the water.
• The incoming flow must be evenly distributed across the width of
the basin to prevent short-circuiting.
• Short-circuiting is a problematic circumstance in which water
bypasses the normal flow path through the basin and reaches the
outlet in less than the normal detention time.
• If the water velocity is greater than 0.5 ft/sec, then floc in the
water will break up due to agitation ) of the water.
13. Sedimentation and flotation zones/Inlet Zone
Two types of inlets.
1. The stilling ( ) wall, also known as a perforated
baffle wall , spans the entire basin from top to bottom
and from side to side. Water leaves the inlet and enters
the settling zone of the sedimentation basin by flowing
through the holes evenly spaced across the stilling wall.
2. The second type of inlet allows water to enter the
basin by first flowing through the holes evenly spaced
across the bottom of the channel and then by flowing
under the baffle in front of the channel.
The combination of channel and baffle serves to evenly
distribute the incoming water
14. Sedimentation and flotation / Settling Zone
• water enters the settling zone where water velocity is
• the bulk of floc settling occurs and this zone will
make up the largest volume of the sedimentation
• For optimal performance, the settling zone requires a
slow, even flow of water.
• The settling zone may be simply a large expanse of
open water. But in some cases, tube settlers and
lamella plates, such as those shown below, are
included in the settling zone.
• Tube settlers and lamella plates
• Water flows up through slanted tubes or along
slanted plates. Floc settles out in the tubes or plates
and drifts back down into the lower portions of the
• Clarified water passes through the tubes or between
the plates and then flows out of the basin.
Actual Area vs.
15. Sedimentation and flotation / Settling Zone
Why Tube settlers and lamella plates:
To increase the settling efficiency and speed in sedimentation basins. Each tube or plate
functions as a miniature sedimentation basin, greatly increasing the settling area. Tube
settlers and lamella plates are very useful in plants where site area is limited, or to increase
the capacity of shallow basins.
Adding inclined settling surface technology to an existing clarifier can increase water
treatment flow by as much as 75%.
20. Sedimentation and flotation / Outlet Zone
Outlet Zone is designed to:
• prevent short-circuiting of water in the basin.
• ensure that only well-settled water leaves the basin and enters the filter.
• control the water level in the basin.
• ensure that the water flowing out of the sedimentation basin has the minimum
amount of floc suspended in it.
• A typical outlet zone begins with a baffle in front of the effluent.
• This baffle prevents floating material from escaping the sedimentation basin and
clogging the filters.
• The weirs serve to skim the water evenly off the tank
21. Sedimentation and flotation / Sludge Zone
• The sludge zone is found across the bottom of the sedimentation basin.
• Velocity should be very slow to prevent resuspension of sludge.
• The tank bottom should slope toward the drains
• Sludge removal by ( automated equipment or manually at least twice per year).
• The best time of cleaning when water demand is low, (April and October).
• Many plants have at least two sedimentation basins so that water can continue
to be treated while one basin is being cleaned, maintained, and inspected.
• If sludge is not removed from enough, the effective volume of the tank will
decrease, reducing the efficiency of sedimentation.
• Sludge built up on the bottom of the tank may become septic (anaerobically).
• Septic sludge may result in taste and odor problems or may float to the top of
the water and become scum or resuspended to be carried over to the filters.
24. Aeration• Aeration is the process of bringing water
and air into close contact.
• Aeration is the process to remove
dissolved gases, such as carbon
dioxide, hydrogen sulfide, and to oxidize
dissolved metals such as iron. It can also be
used to remove volatile organic chemicals
It happened by:
• Exposing drops or thin sheets of water to
the air or
• introducing small bubbles of air and letting
them rise through the water.
the aeration is accomplished the desired
• Sweeping ) or scrubbing action
caused by the turbulence of water and air
• Oxidizing certain metals and gases
25. CHEMICAL SUBSTANCES AFFECTED BY
The constituents that are commonly affected by aeration are:
• Volatile organic chemicals, such as benzene, found in
gasoline, or trichloroethylene, dichloroethylene, and
perchloroethylene, examples of solvents are used in dry cleaning
or industrial processes.
• Carbon dioxide
• Hydrogen sulfide (rotten-egg odor)
• Methane (flammable)
• Iron (will stain clothes and fixtures)
• Manganese (black stains)
• Various chemicals causing taste and odor
26. CHEMICAL SUBSTANCES AFFECTED BY
AERATION / CARBON DIOXIDE
• Surface waters have a low CO2 content ( 0 to 2 mg/l).
• Deep lake or reservoir can have high CO2 content due to the respiration of
microscopic animals and lack of abundant plant growth at the lake bottom.
• aerators remove CO2 by the physical scrubbing or sweeping action caused by
• aeration can reduce the CO2 content to 4.5 mg CO2 /l
• Concentration of CO2 in groundwater are usually higher than in surface
• Water from a deep well normally contains less than 50 mg/l, but a shallow well
can have a much higher level, up to 50 to 300 mg/l.
27. CARBON DIOXIDE REMOVAL
• The most appropriate treatment for carbon dioxide may be aeration, addition
of an alkali, or a combination of the two
• CO2 gas dissolves easily in water, resulting in carbonic acid:
• H2O + CO2 <===> H2CO3
• CO2 is neutralized through the addition of an alkali (basic, ionic salt), such as
lime (Ca(OH)2) or soda ash (Na2CO3).
• Lime reacts with carbon dioxide, removing the carbon dioxide from the water
as shown below:
• CO2 + Ca(OH)2 <===> CaCO3 + H2O
CO2 above 5 to 15 mg/l in raw water can cause three operating problems:
• It increases the acidity of the water, making it corrosive by forming a “weak”
• It tends to keep iron in solution, thus making iron removal more difficult.
• It reacts with lime added to soften water, causing an increase in the amount of
lime needed for the softening reaction.
28. HYDROGEN SULFIDE
• A poisonous gas (Brief exposures--less than 30 minutes in concentrations as low
as 0.03 percent by volume in the air) - rotten-egg odor
• H2S occurs mainly in groundwater supplies.
• It may be caused by the action of iron or sulphur reducing bacteria in the well.
• Occasional disinfection of the well can reduce the bacteria producing the H2S
• H2S in a water supply will disagreeably alter the taste of coffee, tea, and ice.
• H2S is corrosive to piping, tanks, water heaters, and copper alloys that it contacts.
• Disinfection of the water can become less effective because of the chlorine
demand exerted by the hydrogen sulfide.
– H2S + Cl2 + O2- → S + H2O + 2Cl-
– H2S + 4Cl2 + 4 H2O → H2SO4 + 8 HCl
• There could be corrosion of the piping systems and the water tanks.
29. H2S Removal by Aeration method
• Hydrogen sulfide is physically removed by agitating ) the water via
bubbling or cascading ) and then separating or "stripping )" the
hydrogen sulfide in a container. H2S + O2 = water (H2O) + elemental sulfur
• Aeration is most effective when hydrogen H2S are lower than 2.0 mg/l.
• At higher concentrations, this method may not remove all of the offensive odor
unless the air is used to oxidize hydrogen sulfide chemically into solid
sulfur, which is then filtered.
• In a typical aeration system, ambient air is introduced into the water using an air
compressor or blower.
• Well-designed aeration tanks maintain a pocket of air in the upper third or upper
half of the tank.
• If the tank does not maintain an air pocket, sulfur odor may return.
• When sulfur levels exceed 10 mg/l, larger aeration tanks, repressurization
systems, chlorination systems, or a combination may be needed.
• Methane gas can be found in groundwater.
• It may be formed by the decomposition of organic matter.
• It can be found in water from aquifers that are near natural-gas deposits.
• Methane is a colorless gas that is highly flammable and explosive.
• When mixed with water, methane will make the water taste like garlic.
• The gas is only slightly soluble in water and therefore is easily removed by
the aeration of the water.
31. IRON AND MANGANESE
• Iron and manganese minerals are found in soil and rock.
• Iron and manganese can dissolve into groundwater as it percolates through the
soil and rock.
• Iron in the ferrous form and manganese in the manganous form are
• more than 0.3 mg/l of iron will cause yellow to reddish-brown stains of
plumbing fixtures or almost anything that it contacts.
• If the concentration exceeds 1 mg/l, the taste of the water will be metallic and
the water may be turbid.
• Manganese even at levels as low as 0.1 mg/l, will cause blackish staining of
fixtures and anything else it contacts.
• If the water contains both iron and manganese, staining could vary from dark
brown to black.
• Consumer complaints are laundry is stained and that the water is red or dirty.
• iron and manganese should not be aerated unless filtration is provided.
32. Iron and Manganese Removal
• Iron and manganese in well waters occur as soluble ferrous and manganous
• In the aeration process, the water is saturated with oxygen to promote the
• The oxidation products, ferric hydroxide and manganese dioxide, are insoluble.
• After aeration, they are removed by clarification or filtration
• Occasionally, strong chemical oxidants such as chlorine (Cl2 or potassium
permanganate (KMnO4 may be used following aeration to ensure complete
4Fe(HCO3)2 + O2 + 2H2O = 4Fe(OH)3
ferrous bicarbonate oxygen water ferric hydroxide carbon dioxide
2Mn(HCO3)2 + O2 = 2MnO2 + 4CO2
33. TASTE AND ODOR & DISSOLVED OXYGEN
TASTE AND ODOR
• Aeration is effective in removing tastes and odors that are caused by volatile
• Volatile materials (e.g Methane and hydrogen sulfide) have low boiling point
and will vaporize very easily.
• Many taste and odor problems in surface water could be caused by oils and by-
products that algae produce.
• Since oils are much less volatile than gases, aeration is only partially effective.
• Oxygen is injected into water through aeration to remove the flat taste.
• The amount of oxygen that the water can hold is dependent on the temp.
• The colder the water, the more oxygen the water can hold.
• Water that contains excessive amounts of oxygen can become very corrosive.
• Excessive oxygen can cause air binding of filters.
34. TYPES OF AERATORS
Aerators fall into two general categories.
• introduce air into the water or water into the air.
• The water-to-air method is designed to produce small drops of
water that fall through the air
• The air-to-water method creates small bubbles of air that are
injected into the water stream.
• All aerators are designed to create a greater amount of contact
between the air and water to enhance the transfer of the gases.
35. WATER INTO AIRCascade Aerators
• consists of a series of steps that the water
• aeration is accomplished in the splash
• The aeration action is similar to a
• Splash areas are created by placing
blocks across the incline.
• Cascade aerators used to oxidize iron and
to partially reduce dissolved gases.
• the oldest and most common type of
• are used primarily to oxidize iron and
manganese prior to filtration.
• the water pumped to the top of the cones
and then allowed to cascade down
through the aerator.
36. WATER INTO AIR
Slat ( ) and Coke Aerators
• similar to the cascade and cone types.
• They usually consist of three-to-five stacked trays, which have spaced
wooden slats in them.
• The trays are filled with fist-sized ( pieces of coke, rock, ceramic
balls, limestone, or other materials.
• The primary purpose of the materials is provide additional surface contact
area between the air and water.
spray aeration is successful in
oxidizing iron and manganese and
is successful in increasing the
dissolved oxygen of the water.
37. WATER INTO AIR
Draft Aerators: the air is
induced by a blower.
• external blowers mounted at
the bottom of the tower to
induce air from the bottom of
• Water is pumped to the top
and allowed to cascade down
through the rising air.
• The other, an induced-draft
aerator, has a top-mounted
blower forcing air from
bottom vents up through the
unit to the top.
• Both types are effective in
oxidizing iron and manganese
38. AIR INTO WATER
• These are not common types used in water treatment.
• The air is injected into the water through a series of nozzles submerged in
• It is more commonly used in wastewater treatment for the aeration of
• Draft tube
39. AIR INTO WATER
• Uses a pressure vessel.
• The water to be treated is sprayed into the
high-pressure air, allowing the water to
quickly pick up dissolved oxygen.
• A pressure aerator commonly used in pressure
filtration is a porous stone installed in a
pipeline before filtration.
• The air is injected into the stone and allowed
to stream into the water as a fine
bubble, causing the iron to be readily oxidized.
• The higher the pressure, the more readily the
transfer of the oxygen to the water.
• more O2 is available, more readily the
oxidation of the Fe or Mn.
40. AIR STRIPPING
• can be quite effective in removing volatile
organic chemicals (VOCs) from water.
• A major concern is that VOCs may be
• Air stripping capable of removing up to 90
percent of the most highly volatile VOCs.
• water flow over cascade aerators or in
specially designed air-stripping towers.
• water is allowed to flow down over a
support medium or packing contained in the
tower, while air is being pumped into the
bottom of the tower.
43. COMMON OPERATING PROBLEMS
• Aeration raises the dissolved oxygen content of the water.
• If too much oxygen is injected into the water, the water becomes supersaturated
• Supersaturation may cause corrosion whenever water and oxygen come into
contact with metallic surfaces
• False Clogging Of Filters-Air Binding (the spaces between the filter media
particles begin to fill with bubbles).
• Air binding causes the filter to plugged and in need of backwashing.
• Slow removal of the hydrogen sulfide from the towers, algae
production, clogged filters, and overuse of energy.
• Hydrogen sulfide is most efficiently removed, not by oxidation, but by the
physical scrubbing action of aeration.
• This removal is dependent on the pH of the water. At a pH of 6 or less, the
hydrogen sulfide is easily removed.
• high pH, the hydrogen sulfide will ionize, preventing removal by aeration.
44. OPERATIONAL TESTING
Three basic control tests are involved in the operation of the aeration process:
• Dissolved oxygen (to estimate whether the process is over or under aerated)
• pH (give an indication of the amount of carbon dioxide removal. pH increases
as the carbon dioxide is removed. pH can also be used to monitor the effective
range for hydrogen sulfide, iron, and manganese removal)
• Temperature (is important as the saturation point of oxygen increases as the
• As water temperature drops, the operator must adjust the aeration process to
maintain the correct DO level.
• Adsorption: is the adhesion of atoms, ions, biomolecules or molecules of
gas, liquid, or dissolved solids to surface
• This process creates a film of the adsorbate (the molecules or atoms being
accumulated) on the surface of the adsorbent.
• It differs from absorption, in which a fluid permeates or is dissolved by a liquid
• The term sorption encompasses both processes, while desorption is the reverse
of adsorption. It is a surface phenomenon.
48. Types of Adsorption
• Types of Adsorption: Depending on the nature of the forces
between adsorbate & adsorbent, Adsorption is of two types.
• 1. Physical Adsorption or physisorption: Forces of attraction
between adsorbate and adsorbent are Van der Waal‟s forces,
they are weak.
• 2. Chemical Adsorption or chemisorption: Forces of
attraction between adsorbate and adsorbent are as strong as
chemical bonds, they are strong. This type of adsorption
cannot be easily reversed.
• Adsorption, is sorption processes in which certain adsorbates are selectively
transferred from the fluid phase to the surface of insoluble, rigid particles
suspended in a vessel or packed in a column.
• Adsorption systems treat water by adding a substance, such as activated carbon
or alumina, to the water supply.
• Adsorbents attract contaminants by chemical and physical processes that cause
them to „stick‟ to their surfaces for later disposal.
• the most commonly-used adsorbent is activated carbon
• Powdered activated carbon is often used when temporary quality
problems arise; it can simply be added to the water and discarded with
• Granular activated carbon is often arranged in a bed through which
source water is slowly passed or percolated.
• Activated alumina treatment is used to attract and remove
contaminants, like arsenic and fluoride, which have negatively charged
51. Physical adsorption (Physisorption)
• In physical adsorption, the forces of attraction between the molecules of the
adsorbate and the adsorbent are of the weak van der Waals' type.
• van der Waals forces is the sum of the attractive or repulsive forces
between molecules (or between parts of the same molecule) other than those
due to covalent bonds or to the electrostatic interaction of ions with one another
or with neutral molecules
• A van der Waals bonding already illustrates the difference in bonding between
two molecules and one molecule with a solid.
• A van der Waals bonding between two molecules can be described as the
interaction between two point dipoles.
• Since the forces of attraction are weak, the process of physisorption can be
easily reversed by heating or decreasing the pressure of the adsorbate (as in the
case of gases). The attraction is not fixed to a specific site and the adsorbate is
relatively free to move on the surface
52. Chemical adsorption (Chemisorption)
• In chemisorption, the forces of attraction between the adsorbate and the
adsorbent are very strong;
• the molecules of adsorbate form chemical bonds with the molecules of the
adsorbent present in the surface.
• Adsorption is generally accompanied by release of energy, that is, most
adsorption processes are exothermic in nature.
• Enthalpy is a measure of the total energy of a thermodynamic system.
• It includes the internal energy, which is the energy required to create a
system, and the amount of energy required to make room for it by displacing
its environment and establishing its volume and pressure.
• Enthalpy of Physisorption, which is the enthalpy change for the adsorption of
one mole of an adsorbate on an adsorbent surface, is in the range of 20 kJ/mole
• Enthalpy values for chemisorption, are an order of magnitude high, that is, 200
kJ/mole to 400 kJ/mole
53. Comparison between Physisorption and
Forces of attraction are vander Waals‟ forces
Forces of attraction are chemical
Low enthalpy of adsorption (20 - 40
High enthalpy of adsorption (200 -
This process is observed under conditions of
This process takes place at high
It is not specific It is highly specific
Multi-molecular layers may be formed
Generally, monomolecular layer is
This process is reversible This process is irreversible
54. Adsorption Equillibria
• Adsorption equilibrium is a dynamic concept achieved when the
rate at which molecules adsorb onto a surface is equal to the rate at
which they desorb.
• Most of the adsorption theories have been developed for gas solid
systems because the gaseous state is better understood than the
• Till now the statistical theories developed for gas – solid systems
were applied for liquid solid systems with little confidence for
designing of the equipment.
• The most commonly used equilibrium models to understand the
adsorption systems was Freundlich and Langmuir isotherm
55. ADSORPTION EQUILIBRIA / Isotherm
• Adsorption is usually described through isotherms
• If the adsorbent and adsorbate are contacted long
enough an equilibrium will be established between
the amount of adsorbate adsorbed and the amount of
adsorbate in solution. The equilibrium relationship
is described by isotherms.
• isotherms is the amount of adsorbate on the
adsorbent as a function of its pressure (if gas) or
concentration (if liquid) at constant temperature.
• The quantity adsorbed is nearly always normalized
by the mass of the adsorbent to allow comparison of
58. Freundlich: K Freundlich isotherm coefficient and n
• The amount of adsorbate adsorbed is a function of the liquid-phase
concentration and called adsorption equilibrium isotherm.
• Different functions can be used to describe the adsorption
• Freundlich isotherm data can be used.
• This adsorption isotherm empirical equation is.
• in which:
• qmax = loading capacity (g/kg)
• cs = equilibrium concentration (g/m3)
• x = adsorbed amount of compound (g)
• m = mass of activated carbon (kg)
• K = Freundlich constant ((g/kg).(m3/g)n)
• n = Freundlich constant (-)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
n = 0.5
n = 0.2
n = 2
n = 1
n = 5
n = 0.1
59. Freundlich: K Freundlich isotherm coefficient and n
• The Freundlich constants K and n are influenced by water temperature, pH,
type of carbon and the concentration of other organic compounds.
• Using laboratory experiments the Freundlich constants can be determined
for a single substance with a specific type of activated carbon.
• Taking logs and rearranging:
log q = log K + n log Cs.
• When these graphs are plotted on a logarithmic scale the Freundlich
constant K can be determined from the intersection of the graph with the y-
• The slope of the line is equal to the Freundlich constant n.
• The higher the K-value, the better the adsorption.
• In 1916, Irving Langmuir published a new model isotherm for gases
adsorbed to solids. It is a semi-empirical isotherm derived from a proposed
It is based on four assumptions:
– The surface of the adsorbent is uniform, that is, all the adsorption sites are
– Adsorbed molecules do not interact.
– All adsorption occurs through the same mechanism.
– At the maximum adsorption, only a monolayer is formed: molecules of
adsorbate do not deposit on other, already adsorbed, molecules of
adsorbate, only on the free surface of the adsorbent.
• These four assumptions are seldom all true
• Langmuir suggested that adsorption takes place through this mechanism:
where Ag is a gas molecule and S is an adsorption site.
• Letting xo represent the total concentration of available sites on a given amount
of fresh solid substrate, we can define a fractional coverage (θ) as
where x is the concentration of occupied sites.
• The rate of adsorption va will be proportional to the concentration of gas or
liquid (c) above the surface and the fraction of the surface that is not covered (1-
θ), yielding a rate equation
where ka is the rate constant for adsorption.
• The rate of desorption is simply proportional to the fraction of the surface that is
already occupied, so the rate equation is
• and kd is the rate constant for desorption. Setting equations (2) and (3) equal
yields an equilibrium statement that can be written as
The ratio of rate constants in equation (4) is equal to an equilibrium constant
(K = ka/kd).
• Upon substitution and further rearrangement, the fractional coverage is given by
• Equation (5) is plotted for an arbitrary value of K, (is often called a Langmuir
• The surface sites becomes saturated as the concentration rises.
• The magnitude of K quantifies the relative affinity that a given solute has for
• Like all equilibrium constants, K is temperature dependent.
65. BET Isotherm
• Often molecules do form multilayers, that is, some are adsorbed on already
adsorbed molecules and the Langmuir isotherm is not valid.
• In 1938 Stephen Brunauer, Paul Emmett, and Edward Teller developed a
model isotherm that takes that possibility into account. Their theory is
called BET theory, after the initials in their last names.
• They modified Langmuir's mechanism as follows:
• A(g) + S ⇌ AS
• A(g) + AS ⇌ A2S
• A(g) + A2S ⇌ A3S and so on
66. Characteristics and general requirements
• Adsorbents are used in the form of spherical pellets, rods, moldings ), or
monoliths ( ) with hydrodynamic diameters between 0.5 and 10 mm.
• They must have high abrasion resistance ), high thermal stability and
small pore diameters, which results in higher exposed surface area and hence
high surface capacity for adsorption.
• The adsorbents must also have a distinct pore structure which enables fast
transport of the gaseous vapors.
Most industrial adsorbents fall into one of three classes:
• Oxygen-containing compounds – Are typically hydrophilic and polar, including
materials such as silica gel and zeolites.
• Carbon-based compounds – Are typically hydrophobic and non-polar, including
materials such as activated carbon and graphite.
• Polymer-based compounds - Are polar or non-polar functional groups in a
porous polymer matrix.
67. Silica gel
• a chemically inert, nontoxic, polar and dimensionally stable (< 400 C)
amorphous form of SiO2.
• Prepared by the reaction between sodium silicate and acetic acid, which is
followed by a series of after-treatment processes such as aging, pickling.
• After treatment methods results in various pore size distributions.
• Silica is used for drying of process air (e.g. oxygen, natural gas) and adsorption
of heavy (polar) hydrocarbons from natural gas
• silica gel is a solid
• it has an average pore size of 2.4 nanometers and has a strong affinity for water
• Natural or synthetic crystalline aluminosilicates.
• Havin a repeating pore network and release water at high temperature.
• Zeolites are polar in nature. They are manufactured by hydrothermal synthesis of sodium
aluminosilicate or another silica source in an autoclave followed by ion exchange with
certain cations (Na+, Li+, Ca2+, K+, NH4+).
• The channel diameter of zeolite cages usually ranges from 2 to 9 Å.
• The ion exchange process is followed by drying of the crystals, which can be pelletized
with a binder to form macroporous pellets.
• Zeolites are applied in drying of process air, CO2 removal from natural gas, CO removal
from reforming gas, air separation…
• Non-polar (siliceous) zeolites are synthesized from aluminum-free silica sources or by
dealumination of aluminum-containing zeolites.
• The dealumination process is done by treating the zeolite with steam at elevated
temperatures, typically greater than 500 C.
• This high temperature heat treatment breaks the aluminum-oxygen bonds and the aluminum
atom is expelled from the zeolite framework.
69. Activated carbon
• non-polar and cheap, highly porous, amorphous solid consisting of
microcrystallites with a graphite lattice
• Usually prepared in small pellets or a powder.
• Its main drawbacks (it is reacts with oxygen at moderate temp. (over 300 C).
• manufactured from carbonaceous material, including coal, peat, wood, or
nutshells (e.g., coconut).
• The manufacturing process consists of two phases, carbonization and
• The carbonization process includes drying and then heating to separate by-
products, including tars and other hydrocarbons from the raw material, as well
as to drive off any gases generated.
• The process is completed by heating the material over 400 C in an oxygen-free
atmosphere that cannot support combustion.
70. Activated carbon
• The carbonized particles are then "activated" by exposing them to an
oxidizing agent, usually steam or carbon dioxide at high temperature.
• This agent burns off the pore blocking structures created during the
carbonization phase and so, they develop a porous, three-dimensional graphite
• The size of the pores developed during activation is a function of the time that
they spend in this stage.
• Longer exposure times result in larger pore sizes.
• The most popular aqueous phase carbons are bituminous based
because of their hardness, abrasion resistance, pore size distribution, low cost
• Activated carbon is used for adsorption of organic substances and non-polar
adsorbates and it is also usually used for waste gas (and waste water) treatment.
• It is the most widely used adsorbent??? most of its chemical (eg. surface
groups) and physical properties (eg. pore size distribution and surface area) can
be tuned according to what is needed.
73. Characteristics of Different
Table. Characteristics of Different Adsorbents
Removal of organic
organics over water
Drying gas streamsHigh capacity,
Drying gas streamsHigh capacity,
74. Factors Affecting the Rate of Adsorption
1. Surface area of the adsorbent:
• The rate of adsorption increases with increase in surface area of the adsorbent
• Rate of adsorption ά 1/ Diameter of adsorbent for powdered activated carbon
2. Nature of solute (adsorbate):
• Solubility of solute: Adsorption ά (1/Solubility of solute in solvent)
• Chain length of molecules: Adsorption ά chain length of molecule
• Molecular size of solute: Increase in molecular size of solute favors adsorption
• Geometry of the molecule: Branched- lesser tendency to get removed, Coiled-
more easily removed because easily entrapped in the interstices.
• Degree of ionization: Adsorption ά (1/ Dissociation constant) this is the reason
why salts are not much removed by activated carbon
3. Surface tension of the solvent:
• Those substances which lower the surface tension of solvent in which they are
dissolved become concentrated in surface layer (eg: organic substances), while
those substances which raise the surface tension are less concentrated in the
surface than in the bulk of solution. (eg.inorganic ions)
75. Ion Exchange
• The ion exchange process percolates water through bead-like spherical resin
materials (ion-exchange resins).
• Ions in the water are exchanged for other ions fixed to the beads.
• The two most common ion-exchange methods are softening and deionization.
• Ion exchange materials are insoluble substances containing loosely held ions
which are able to be exchanged with other ions in solutions which come in
contact with them.
• Exchanges take place without any physical alteration to the ion exchange
• Ion exchangers are insoluble acids or bases which have salts which are also
insoluble, and this enables them to exchange either positively charged ions
(cation exchangers) or negatively charged ones (anion exchangers).
• Many natural substances such as proteins, cellulose, living cells and soil
particles exhibit ion exchange properties which play an important role in the
way the function in nature.
76. Ion Exchange
• Ion exchange uses a resin that removes charged inorganic contaminants like
arsenic, chromium, nitrate, radium, uranium, and fluoride.
• It works best with particle-free water and can be scaled to fit any size treatment
• Ion exchange is most often used to remove hardness (cation resin) or nitrate
• In both instances, it can be regenerated with salt water.
• The use of ion exchange to remove radionuclides (an atom with an
unstable nucleus) is complicated by the fact that these materials accumulate in
the resin and occur at high levels in the regenerant, greatly complicating
• Activated carbon is generally preferred for removing organic
contaminants, whereas ion exchanges often best for removing inorganic
77. Types of Ion Exchange Resin / Acid Cation
Strong Acid Cation Resins
• Behaving like strong acid
• highly ionized in both the acid (R-SO3H) and salt (R-SO3Na) form.
• Metal salt can be converted to the corresponding acid.
• They can be used for entire range of pH and are utilized for water softening
(calcium and magnesium removal).
• The regeneration takes place by contact with a strong acid solution
(hydrochloric or sulphuric)
Weak Acid Cation Resins
• Carboxylic acid (COOH) acts as the ionizable group in weak acid cation resins.
• They show more affinity for hydrogen ions. This results in the regeneration of
the hydrogen form with less acid than is required for strong acid resins.
78. Base AnionTypes of Ion Exchange Resin /
Strong Base Anion Resins
• They are suitable for entire pH range.
• They deionize water in hydroxide (OH) form.
• Acidic nature of the water can be removed and pure water can be obtained.
• The reaction can be put forward as:
• for which sodium hydroxide is used as the regenerant
Weak Base Anion Resins
• In weak base resins, intensity of ionization is affected by pH.
• They are incapable to split salts but can absorb acids
80. How ion exchange resins work
• The resins are prepared as spherical beads 0.5 to 1.0 mm in diameter.
• These appear solid even under the microscope, but on a molecular scale the
structure is quite open.
• This means that a solution passed down a resin bed can flow through the cross-
linked polymer, bringing it into intimate contact with the exchange sites.
• The affinity of sulphonic acid resins for cations varies with the ionic size and
charge of the cation.
• Generally the affinity is greatest for large ions with high valency.
• For dilute Solutions the order of affinity for some common cations is
81. The general chemical reaction of ion exchange
Cation exchange: nRA + Bn+ = RnBn+ + nA+
Anion exchange: nRA + Bn- = RnBn- + nA-
R : ionized resin molecule with an attached functional group;
A+ / A- : exchangeable ion;
Bn+ / Bn- : cation/anion dissolved in the liquid;
n+ /n- : electrical charge of the ion B.
82. The general chemical reaction of ion exchange
• Suppose a resin has greater affinity for ion B than for ion A. If the resin contains
ion A and ion B is dissolved in the water passing through it, then the following
exchange takes place, the reaction proceeding to the right:
• When the resin exchange capacity nears exhaustion, it will be in the BR form.
• A mass action relationship applies :
• Q is the equilibrium quotient, and is a constant specific for the pair of ions and
type of resin.
• This expression indicates that if a concentrated solution containing ion A is now
passed through the exhausted bed, the resin will regenerate into the AR form
ready for re-use, whilst ion B will be eluted into the water.
• All large scale applications for ion exchange resins involved such exhaustion
and regeneration cycles.
• To remove unwanted ions from a solution passed through it (heavy metals from
metal wastes - salts from fruit juices)
• To accumulate a valuable mineral from the water which can later be recovered
from the resin.
• Strong cation resins in the hydrogen form are used for the hydrolysis of starch
• Used in the laboratory to remove interfering ions during analysis or to
accumulate trace quantities of ions from dilute solutions.
• A cation resin in the hydrogen form can be used to determine the total
concentration of ions in a mixture of salts. The sample passing through a
column is converted to the equivalent quantity of acid and the amount readily
found by titration.
• Earliest applications of ion exchange was the separation of rare earth elements
(Promethium (element 61) and five new elements in the actinide series).
84. WATER TREATMENT
The two major types of treatment applied to water
• Water softening - the replacement of ‟hard‟ ions
such as Ca2+ and Mg2+ by Na+
• Demineralisation - the complete removal of
85. Water softening
• Softening is used primarily as a pretreatment method to reduce water hardness
prior to reverse osmosis (RO) processing.
• The softeners contain beads that exchange two sodium ions for every calcium
or magnesium ion removed from the "softened" water.
• In water softening a cation resin in the sodium form is used to remove hard
metal ions (calcium and magnesium) from the water along with troublesome
traces of iron and manganese
• These ions are replaced by an equivalent quantity of sodium, so that the total
dissolved solids content of the water remains unchanged as does the pH and
• At regular time intervals the resin is cleaned. This involves passing influent
water back up through the resin. In water softening the regenerant is a strong
solution of sodium chloride.
86. Example of Water softening
A) Sodium cation exchange:
• Ca+2 + 2Na.R = Ca.R + 2Na+
• Mg+2 + 2Na.R = Mg.R + 2Na+
Regeneration: using strong brine (NaCl)
• Mg. R + 2NaCl = 2Na.R + MgCl2
• Ca. R + 2NaCl = 2Na.R + CaCl2
88. Demineralisation = deionization
• Complete deionization can be achieved by using two resins.
• The water is first passed through a bed of cation exchange resin in hydrogen
• During service, cations in the water are taken up by the resin while hydrogen
ions are released.
• Thus the effluent consists of a very weak mixture of acids.
• Then water passes through second anion exchange resin in the hydroxide form.
• Here the anions are exchanged for hydroxide ions, which react with the
hydrogen ions to form water.
• twin bed units will reduce the total solids content to approximately 1-2 mg L-1.
• it is usual to pass water leaving the cation unit through a degassing tower.
• degassing tower removes the carbonic acid produced from carbon dioxide and
bicarbonate in the feed water and reduces the load on the anion unit.
• Without degassing the carbonic acid would be taken up by the anion bed after
conversion to carbonate.
89. Mixed resin
• Mixed resin produces water with much lower levels of dissolved material than
can be achieved by distillation.
• In laboratories, mixed resin is often used in disposable cartridges. These are
only used once, but larger mixed resin units can be regenerated.
• After exhaustion the bed is subjected to an up flow of water.
• Anionic resin beads are less dense than the cationic ones and they rise to the top
so that the bed is separated into two layers of resin.
• Each is regenerated in situ with the appropriate regenerant then rinsed with
92. The ion exchange system in water treatment
a) Configuration of the ion exchanger
• Cylindrical steel tank (Diameter 1-2 m - Height 3-4 m )
• ion exchange bed occupies 1-3 meters of the tank height
• The water inters from the top (downflow) at the rate of 0.5 to 7 L/s.m2 .
• When breakthrough is reached the tank is taken off-line and backwashed by
applying water form the bottom upwards to remove any suspended solids.
• After backwashing the regeneration solution is pumped from the bottom up
wards at the rate of 0.7 to 1.5 L/s.m2.
• The same influent distributor is used to drain the upflow backwash water and
the regeneration solution ( brine, acid or base).
• At the end of the regeneration the bed is washed with clean water to remove the
residual of the regeneration solution
• An under drain piping system is installed at the bottom to collect the treated
water, and used to pump the upflow backwash water and the regeneration
93. The ion exchange system in water treatment
• The influent to the ion exchanger should be filtered to remove turbidity.
• Dissolved Organic matter should be removed by GAC before the IE because the
organic may coat the resin and reduce its exchange capacity.
• The IE is efficient for TDS less than 1000 mg/L.
c) Sizing ion exchanger : depends on the following factors:
• i) Contact time
• ii) Hydraulic loading rate
• iii) resin depth
• iv) number of columns.
d) Multiple tanks Operation:
• Ion exchange tanks can be operated in parallel or in series.
• Multiple units permit one or more units to remain in operation while one unit is
taken out of service for backwashing and generation or maintenance.
94. Exchange capacity of ion exchange resins
• The total solid phase concentration “q0” is termed ion exchange capacity.
• For cation exchange resins, “q0” is in the range of 200 to 500 meq/100 mg of
• During the exchange, the resin should be electrically neutral thus the all the
exchange sites should be occupied either by the original ion (such as Na+) or by
the replacing ions ( such as Ca+2 and Mg+2) and the ion exchange occupancy
should be equal to “q0” at any time.
95. Exchange capacity of ion exchange resins
• the Thomas kinetic equation is used for ion exchange columns.
• C = effluent concentrat ion of the ions, mg/l or meq/l
• Co = influent concentrat ion of the ions, mg/l or meq/l
• k1= rate constant, L/d . eq
• q0 maximum solid phase concentrat ion of exchange solute, eq/kg of resin
• M = mass of resin, kg
• V throughput volume, L ( )
• Q flow rate, L/d
• To apply this equation it is necessary to perform a laboratory column test or
pilot scale column to obtain the breakthrough curve.
96. Ion Exchange process analysis in the Fixed bed
a) Mass transfer inside the Ion exchange bed:
• When the polluted water is pumped on the ion exchange bed, the pollutant ions
replace the exchangeable ions in the resin.
• The area of the ion exchange bed in which the exchange occurs is called the
mass transfer zone (MTZ)
• No further adsorption occurs below the MTZ and the water leaving the MTZ
zone contains the minimum concentration value of the pollutant that the bed can
• With time a zone of saturation is created above the MTZ in which the resin has
reached its maximum exchange capacity and no further replacement occurs.
• The equilibrium concentration Ce of the pollutant in water in this zone is the
same as C0.
• The Zone below the MTZ essentially clean zone and no adsorbed material on it.
• With time the saturation zone depth increases and the MTZ is pushed down
until we reach to a point where the clean zone disappears and breakthrough
97. Breakthrough curve
• Breakthrough is said to have occurred when the effluent concentration reaches to 5% of
the influent concentration (i.e, Cb = 0.05C0).
• After additional time the MTZ start to decrease until it disappears and the bed is called
• Exhaustion of the bed is assumed to have occurred when the effluent Concentration is
equal to 95% of the influent concentration (i.e, C = 0.95C0)
• The area above the breakthrough curve is equal to the mass of the pollutant adsorbed in the
99. Detection of resin exhaustion
• A resin is considered to be exhausted when the ions in the resin have
mostly been replaced by the ions that are being removed from the solution.
• Exhaustion of demineraliser is usually detected by an electrical
conductivity cell installed at the outlet.
• When the conductivity rises to indicate ionic breakthrough, a regeneration
cycle can be initiated automatically.
• With small units it is possible to incorporate a pH indicator on the anion
resin of a mixed bed cartridge.
• Exhaustion can be followed down the side of a transparent cartridge as the
alkaline anion resin is converted to the neutralised salt form.
100. Advantages and disadvantages in the use of
The advantages of ion exchange processes are:
• very low running costs.
• Very little energy is required,
• The regenerant chemicals are cheap and if well maintained resin
beds can last for many years before replacement is needed.
101. Disadvantages in the use of Ion-Exchange Resins
Calcium sulphate fouling
• Using Sulphuric acid as cation resin regenerant will react with calcium in water
forming calcium sulphate precipitates.
• This fouls the resin and blocks drain pipes with a build up of scale (hydrochloric
acid must be substituted).
• Aeration allows oxidation of Fe2+ to Fe3+ and consequent precipitation of ferric
hydroxide which clogs resin beads and prevents ion exchange. Iron fouling is
the commonest cause of softener failure.
Adsorption of organic matter
• the presence of dissolved organic material can become irreversibly adsorbed
within the anion beads, reducing their exchange capacity.
• Removal of organics prior to demineralisation is achieved by flocculation with
alum or ferric salts followed by filtration.
102. Disadvantages in the use of Ion-Exchange Resins
Organic contamination from the resin
• The resins themselves can be a source of non-ionized organic contamination.
New commercial grade resin often contains organics remaining after manufacture.
when removal is needed, the demineralised water can be passed through an ultra
• Resin beds do not act as filters for the removal of bacteria.
• Resin beds can generate a culture media for continued growth.
• Resins beds can be decontaminated with disinfectants such as formaldehyde
• heat or oxidising disinfectants as chlorine must not be used as these damage resins.
• chlorine damages resins. It is customary to treat such feeds by passing them
through activated carbon which removes chlorine very efficiently.
• The waste water for disposal after regeneration contains all the minerals removed
from the water plus salt from the spent regenerants.
• volume of it is equivalent to 1-5% of the treated water throughput.
103. Coagulation and Flocculation
Coagulation refers to all the reactions and mechanisms that result in particle
aggregation in the water being treated, including in situ coagulant formation
(where applicable), particle destabilization, and physical interparticle
• Coagulant formation, particle destabilization, typically occur during and
immediately after chemical dispersal in rapid mixing;
• inter particle collisions that cause aggregate (floc) formation begin during
rapid mixing but usually occur predominantly in the flocculation process.
• The physical process of producing inter-particle contacts is termed
• Flocculation defined as the uses gentle stirring to bring suspended particles
together so they will form larger more settleable clumps (groups) called floc.
104. A common classification of particles
• Molecules sizes smaller than 1 nm
• Colloids generally with
dimensions between 1 nm - 1 μm
• Suspended matter having sizes
larger than 1 μm.
• Colloids: humic
acids, proteins, colloidal
clay, silica and viruses.
• Suspended matter:
Bacteria, algae, silt, sand and
• Suspended matter-when it is larger
than 5-10 μm can be removed
quite easily by filtration or
sedimentation and filtration.
• The removal of colloids is possible
106. STABILITY OF PARTICLE SUSPENSIONS
• Coagulation process is used to increase the rate or kinetics of particle
aggregation and floc formation
• The objective is to transform a stable suspension [i.e., one that is resistant to
aggregation (or attachment to a filter grain)] into an unstable one.
• there are forces that tend to pull the interacting surfaces together
• The most important attractive force is called the London–van der Waals force.
• It arises from spontaneous electrical and magnetic polarizations that create a
fluctuating electromagnetic field within the particles and in the space between
• The most well-known repulsive force is caused by the interaction of the
electrical double layers of the surfaces (“electrostatic” stabilization).
• As particles approach one another on a collision course, the fluid between them
must move out of the way.
• The repulsive force caused by this displacement of fluid is called hydrodynamic
107. Electrostatic Stabilization
• Origins of Surface Charge. Most particles in water, mineral and organic, have
electrically charged surfaces, and the sign of the charge is usually negative.
Three important processes for producing this charge are considered in the following
• First, surface groups on the solid may react with water and accept or donate
• Second, surface groups can react in water with solutes other than protons.
• Third, a surface charge may arise because of imperfections within the
structure of the particle; this is called isomorphic replacement, or substitution
108. The Electrical Double Layer (EDL)
• In a colloidal suspension, there can be no net imbalance in the overall electrical
• the primary charge on the particle must be counterbalanced in the system.
• If the particle is negatively charged, excess ions of opposite charge (positive)
accumulate in this interfacial region
• Ions of opposite charge accumulating in the interfacial region, together with the
primary charge, form an electrical double layer.
The diffuse layer results from:
– electrostatic attraction of ions of opposite charge to the particle
– electrostatic repulsion of ions of the same charge as the particle, and
– thermal or molecular diffusion that acts against the concentration gradients
produced by the electrostatic effects
• Because of the primary charge, an electrostatic potential (voltage) exists
between the surface of the particle and the bulk of the solution
• This electric potential can be pictured as the electric pressure that must be
applied to bring a unit charge having the same sign as the primary charge from
the bulk of the solution to a given distance from the particle surface
110. The zeta potential
• It is a scientific term for electrokinetic potential in colloidal systems (ζ-potential)
• It represents the net charge between the primary charge and the counter charge
in the EDL located between the surface and the shear plane
• zeta potential is electric potential in the interfacial double layer at the location of
the slipping plane versus a point in the bulk fluid away from the interface
• zeta potential is the potential difference between the dispersion medium and the
stationary layer of fluid attached to the dispersed particle.
• A value of 25 mV (positive or negative) can be taken as the arbitrary value that
separates low-charged surfaces from highly-charged surfaces.
• The zeta potential indicates the degree of repulsion between
adjacent, similarly charged particles in a dispersion.
111. The zeta potential
Zeta potential [mV] Stability behavior of the colloid
from 0 to ±5, Rapid coagulation or flocculation
from ±10 to ±30 Incipient instability
from ±30 to ±40 Moderate stability
from ±40 to ±60 Good stability
more than ±61 Excellent stability
• For molecules and particles that are small enough, a high zeta potential will
confer stability, i.e., the solution or dispersion will resist aggregation.
• When the potential is low, attraction exceeds repulsion and the dispersion will
break and flocculate.
• Colloids with high zeta potential (negative or positive) are electrically stabilized
while colloids with low zeta potentials tend to coagulate or flocculate
112. a net electrostatic repulsion/attraction developed
between colloids as a result of EDL
The net resultant force is a result of:
• Attractive potential energy (mostly
van der Waals forces).
• Repulsion potential energy
113. Relative strength of forces
Dipole-dipole interactions: electrostatic interactions of permanent dipoles in
These interactions tend to align the molecules to increase the attraction
(reducing potential energy).
An example of dipole-dipole interactions can be seen in hydrogen chloride (HCl)
Hydrogen bond : is the attractive interaction between a hydrogen atom and
an electronegative atom, such as nitrogen, oxygen, or fluorine.
The hydrogen bond is a strong electrostatic dipole-dipole interaction.
It is stronger than a van der Waals interaction, produces interatomic distances shorter
than sum of van der Waals radii
Relative strength of forces
Bond type Dissociation energy (kcal)
Hydrogen bonds 12-16
Dipole-dipole 0.5 - 2
London (van der Waals) Forces <1
114. Calculation of the zeta potential***
The magnitude of these forces is measured by the zeta potential, which is:
• Z is the zeta potential,
• q is the charge per unit area,
• d is the thickness of the effective charge layer, and
• D is the dielectric constant of the liquid.
The greater the zeta potential, the greater are the repulsion forces between the
colloids and, therefore, the more stable is the colloidal suspension
There are two major forces acting on colloids:
1) electrostatic repulsion
(simply, negative colloids repel other negatively charged colloids)
2) intermolecular, or van der Waals, attraction
• Coagulants can be used to reduce the electrostatic repulsive forces. The
electrostatic repulsion reduced by the addition of countercharged ions such as
116. Process Description
Purpose to aid in the removal of nonsettleable solids from water.
Coagulation is defined as:
• the destabilization of colloidal solids;
• the water treatment process which causes very small suspended solids to attract
one another and form larger particles.
Suspended particles in water resist settling for two primary reasons:
1. Particle size; and,
2. Natural forces between particles.
• Suspended particles in water normally have a negative (-) charge.
• Since these particles all have the same charge, they repel each other, keeping
each other from settling.
• This natural repelling force is called the zeta potential.
• Coagulation neutralizes the forces (zeta potential), which cause suspended solids
in water to repel each other and resist settling.
• Once the repulsive forces have been neutralized these particles can stick together
(agglomerate) when they collide.
• The force which holds the floc together is called the van der Waals force.
• After coagulation the destabilized particles can collide, aggregate so flocs can
be formed. This step is called flocculation.
• Flocculation: The process of agglomeration of the destabilized particles to
such a size that separation by sedimentation and filtration is possible.
• In flocculation one can make a distinction between peri-kinetic and ortho-
• Brownian motion is the driving force in the agglomeration of destabilized
particles up to 1μm-level peri-kinetic flocculation).
• Above ~ 1 μm the influence of Brownian motion on the collision rate of the
particles can be neglected, then artificial mixing is necessary to get an efficient
flocculation. That part of the flocculation process is called ortho-kinetic
• Flocculation uses gentle stirring to cause the particles to collide so that they
can stick together, for a particle (floc) large enough and heavy enough to settle
118. Flocculation Practice in Water Treatment***
• Coagulation and Flocculation Process Design
• G = velocity gradient, s-1
• P = power input, W
• V = volume of water in mixing tank, m3
• μ = dynamic viscosity, Pa.s
• Viscosity is a measure of the resistance of a fluid which is being deformed. The
SI physical unit of dynamic viscosity is the pascal-second (Pa·s), which is
identical to N·m−2·s
• Velocity gradient velocity gradient is the change in relative velocity between
parallel planes with respect to the change in perpendicular distance throughout
the depth of the material. Velocity gradient has the dimensions as rate of
shear, which is reciprocal seconds.
119. Types of Flocculation Tanks
Paddle wheel Type (vertical and Horizontal Types)
Foil Type Mixing Blade
120. Types of Flocculation Tanks
• Hydraulic Flocculators
• The axial flow flocculators are typically used because they impart a nearly
constant gradient in each compartment.
• Flocculators are designed to have a minimum of three compartments to provide
for tapered (to make smaller gradually) mixing.
• The velocity gradient, G is tapered so that it is larger in the first compartment
and less is the other compartments as the floc grows.
121. Chemicals are used to neutralize the zeta potential
• These chemicals are coagulants, sometimes called primary coagulants, and
• Since most suspended particles in water carry a negative (-) charge, coagulants
consist of chemicals that provide positively (+) charged ions.
Common coagulants are:
• 1. Metal Salts
• a. Aluminum Salts (Alum (aluminum sulfate) - PACs (polyaluminum
chlorohydrate, and other variations)
• b. Iron Salts (Ferric Chloride - Ferric Sulfate - Ferrous Sulfate)
• 2. Polymers (polyelectrolytes)
122. Common coagulants / Polymers
• Polymers (polyelectrolytes) are extremely large molecules which produce
thousands of charged ions when dissolved in water.
1. Cationic Polyelectrolytes - Have a positive (+) charge. Used as either a primary
coagulant or as a coagulant aid. Cationic polymers:
• allow reduced coagulant dose;
• improve floc settling;
• are less sensitive to pH;
• improve flocculation of organisms such as bacteria and algae.
2. Anionic Polyelectrolytes- Have a negative (-) charge. Used primarily as a
coagulant aid. Anionic polymers are used to:
• increase floc size;
• improve settling;
• produce a stronger floc;
• They are not materially affected by pH, alkalinity, hardness or turbidity.
3. Nonionic Polyelectrolytes- Balanced or neutral charge.
• Used as a primary coagulant or coagulant aid.
123. Coagulant aids
Coagulant aids are chemicals which are added to water during coagulation to
improve coagulation by:
• building a stronger, more settleable floc;
• overcoming slow floc formation in cold water;
• reducing the amount of coagulant required;
• reducing the amount of sludge produced.
• The key reason coagulant aids are used is to reduce the amount of alum
used, which, in turn, decreases the amount of alum sludge produced.
• Alum sludge is difficult to dewater and to dispose of.
124. Types of Coagulant Aids
• increases the coagulation rate;
• reduces the amount of coagulant needed;
• widens the pH range for effective coagulation;
• strengthens floc
Weighting agents (Bentonite Clay, Powdered Limestone; Powdered Silica)
provide additional particles that can enhance floc formation.
They are used to treat water that is:
• high in color; or,
• low in turbidity; or,
• low in mineral content.
125. Factors Which Affect How Well a Coagulant Work
Factors Which Affect How Well a Coagulant Work
(1) Mixing Conditions
(4) Water Temperature
• If the alkalinity concentration in the water is not high enough, and effective floc
will not form when either alum or ferric sulfate is used. Metal salts (alum, ferric
sulfate, ferric chloride) consume natural alkalinity.
• Each mg/L of alum will consume 0.5 mg/l total alkalinity (as CaCO3).
• Each mg/L ferric sulfate will consume 0.75 mg/L total alkalinity (as as CaCO3).
• Each mg/L ferric chloride will consume 0.92 mg/L total alkalinity (as CaCO3).
• It may be necessary to add alkalinity to the water (lime, soda ash, caustic soda)
to the water in order for the metal salts to work properly. The doses should be
confirmed with jar testing.
126. Coagulation/Flocculation Facilities
• Flash Mix - purpose is to distribute the coagulant rapidly and evenly throughout
• Water should be stirred violently for a brief time to encourage the greatest
number of collisions between particles as possible.
• Types of Mixers: Mechanical - Pumps and Conduits
• Detention time should be 30 seconds or less (Design Criteria).
• Flocculation - provides for gentle mixing to encourage floc formation.
• Detention time of at least 30 minutes, with a detention time of 45 minutes
128. Process Control / Chemical Selection
• A. Chemical Selection - These raw water characteristics should be monitored in
order to do a thorough job of chemical selection.
• Low water temperatures slow chemical reactions, causing decreased efficiency
and slow floc formation.
• Higher coagulant doses may be required to maintain acceptable results.
• Extremes can interfere with the coagulation/flocculation process.
• The optimum pH depends on the specific coagulant.
• Low alkalinity causes poor coagulation.
• May be necessary to add alkalinity (lime, caustic soda, soda ash).
• Difficult to form floc with low turbidity water, may need to add weighting agents.
5. Color - Indicates presence of organic chemicals which can react with the
coagulant, and with chlorine to form disinfection byproducts.
129. Process Control / Chemical Application
B. Chemical Application:
• For Example when preparing potassium permanganate solutions, a three
percent solution is best. Potassium permanganate has a limited solubility of
about five percent at normal temperatures.
In order to prepare the solution needed the following information is required:
• Chemical required
• Volume of water required
• Specific gravity
• Weight of solution
130. Process Control / Monitoring Process
C- Monitoring Process Effectiveness
• (1) Jar Test
• (2) pH
• (3) Turbidity
• (4) Temperature
• (5) Alkalinity
131. Process Evaluation and Troubleshooting
• Problems with coagulation and flocculation normally show up in subsequent
processes (sedimentation and filtration). Actual plant performance should be
Poor or inadequate flash mixing
• Gentle flocculation
• Adequate flocculation time
• Settled- and filtered water quality.
Indication of poor or inadequate flash mixing:
1. Very small floc (pin floc)
2. High turbidity in settled water should be less than 1.0 NTU when the raw water
turbidity is less than 1 NTU 95 percent of the time; less than 2.0 NTU when the
raw water turbidity is more than 1 NTU 95 percent of the time.
3. Too frequent filter backwashing
If any of these symptoms occur, check:
(1) detention time and mixing energy in the flash mix (detention time should be less
than 30 seconds);
(2) stirring speed in the flocculator – should have a peripheral speed of between 0.5
and 2.0 feet per second;
(3) flocculation detention time – should be at least 30 minutes, with 45 minutes
132. Jar Test
• Coagulation/flocculation is the process of binding small particles in the water
together into larger, heavier clumps which settle out relatively quickly.
• The larger particles are known as floc.
• changing water characteristics require the operator to adjust coagulant dosages
at intervals to achieve optimal coagulation.
• Different dosages of coagulants are tested using a jar test, which mimics the
conditions found in the treatment plant.
• The first step of the jar test involves adding coagulant to the source water and
mixing the water rapidly (as it would be mixed in the flash mix chamber) to
completely dissolve the coagulant in the water.
• Then the water is mixed more slowly for a longer time period (as flocculation
basin conditions and allowing the forming floc particles to cluster together).
• Finally, the mixer is stopped and the floc is allowed to settle out, as it would in
the sedimentation basin.
133. Jar Test
• A major goal of water treatment is turbidity removal.
• The jar test is a simulation of the treatment processes that have been developed
to accomplish turbidity removal
• Alum, ferrous sulfate, and ferric chloride are three common coagulants
• The best dose will also be a function of pH. The optimum pH for alum
coagulation is usually between 5.5 and 6.5.
• There is no way to “calculate” the best dose. It must be determined by trial and
error; hence, the jar test.
• The reaction chemistry varies according to the pH and alkalinity of the test
Alum coagulation proceeds according to the following equation
• if there is enough alkalinity in the water to react with the amount of alum
Al2(SO4)3 • 14H2O + 6HCO3
- ↔ 2Al(OH)3(s) + 6CO2 + 14H2O + 3SO4
• If there is insufficient alkalinity, the reaction will proceed according to the
• Al2(SO4)3 • 14H2O ↔ 2Al(OH)3 + 3H2SO4 + 8H2O
• An alkalinity test is usually performed before initiating a jar test to determine
whether alkalinity supplements might be required.
134. JAR TEST PROCEDURE
1. measure the initial pH, alkalinity, and turbidity of the sample to be tested.
Make any pH adjustment necessary.
calculate for the maximum alum dose you plan to use, what alkalinity
concentration is required to prevent significant pH reduction.
Compare this required amount to the amount measured in step 1, and
supplement the sample with alkalinity if necessary.
Al2(SO4)3 • 14H2O + 6HCO3
- ↔ 2Al(OH)3(s) + 6CO2 + 14H2O + 3SO4
Decide on six dosages of the chemical(s) include coagulants, coagulant
aids, and lime
2. Prepare a stock solution of the chemical(s).
3. Collect a two gallon sample of the water to be tested. This should be the raw
4. Measure 1,000 mL of raw water and place in a beaker. Repeat for the remaining
5. Place beakers in the stirring machine.
6. With a measuring pipet, add the correct dosage of lime and then of coagulant
solution to each beaker as rapidly as possible.
135. JAR TEST PROCEDURE
7. With the stirring paddles lowered into the beakers, start the stirring machine and
operate it for one minute at a speed of 80 RPM.
8. Reduce the stirring speed to 20 RPM and continue stirring for 30 minutes
9. Stop the stirring apparatus and allow the samples in the beakers to settle for 30
10. Determine which coagulant dosage has the best flocculation time and the most
floc settled out.
11. Test the turbidity of the water in each beaker using a turbidometer
12. If lime or a coagulant aid is fed at your plant in addition to the primary
coagulant, you should repeat the jar test to determine the optimum dosage of
lime or coagulant aid. Use the concentration of coagulant chosen in steps 10 and
11 and alter the dosage of lime or coagulant aid.
13. Using the procedure outlined in step 11, measure the turbidity of water at three
locations in the treatment plant - influent, top of filter, and filter effluent.
14. Prepare a graph of alum dose vs. remaining turbidity in order to identify the
dosage that produced optimum turbidity removal
138. Explanation of Jar Test Example
• Water A had low alkalinity and required less coagulant to achieve good
coagulation and flocculation than the higher alkalinity of Water B
• Plots of turbidity versus coagulant dose showed a continual decrease in turbidity
with an increase in coagulant dose.
• Water A, with FeCl3, showed a decrease followed by an increase (at 40 mg/L) in
• This dictates that adsorption and charge neutralization is taking place due to the
colloids restabilizing and not coagulating.
• Addition of coagulant to the low alkalinity waters lead to a drop in the pH of
Water A, which enhanced adsorption and charge neutralization.
• higher coagulant doses are needed with high alkalinity waters where pH remains
• Although slightly less alum than FeCl3 was needed to reach an optimum
level, the residual turbidity when using the alum coagulant did not fall below 1
• This means that even though alum may require a slightly smaller dose, it still
may not be able to meet the desired effluent regulations without the additional
help of a filter or polymer
• After separating most floc, the water is filtered as the final step to remove
remaining suspended particles and unsettled floc
1. Rapid sand filters
• use relatively coarse sand and other granular media to remove particles and
impurities that have been trapped in a floc through the use
of flocculation chemicals-typically salts of aluminium or iron.
• Water and flocs flows through the filter medium under gravity or under pumped
• Water moves vertically through sand which often has a layer of activated
carbon or anthracite coal (a hard, compact variety of mineral coal).
• The top layer removes organic compounds
• Most particles pass through surface layers but are trapped in pore spaces or
adhere to sand particles
• To clean the filter, water is passed quickly upward through the filter, opposite
the normal direction (called backflushing or backwashing)
• compressed air may be blown up through the bottom of the filter to break up the
compacted filter media to aid the backwashing process
141. Rapid sand filters / Advantages and disadvantages
• Much higher flow rate than a slow sand filter;
• Requires relatively small land area
• Less sensitive to changes in raw water quality, e.g. turbidity
• requires less quantity of sand
• Requires greater maintenance than a slow sand filter. For this reason, it is not
usually classed as an "appropriate technology,".
• Generally ineffective against taste and odour problems.
• Produces large volumes of sludge for disposal.
• Requires on-going investment in costly flocculation reagents.
• treatment of raw water with chemicals is essential
• skilled supervision is essential
• cost of maintenance is more
• it cannot remove bacteria
142. Slow sand filters
• Slow "artificial" filtration (a variation of bank filtration) to the ground, Water
• The filters are carefully constructed using graded layers of sand with the coarsest
sand, along with some gravel, at the bottom and finest sand at the top.
• Drains at the base convey treated water away for disinfection
• effective slow sand filter may remain in service for many weeks or even months
• produces water with a very low available nutrient level and low disinfectant
• Slow sand filters are not backwashed; they are maintained by having the top
layer of sand scraped off
• A 'large-scale' form of slow sand filter is the process of bank filtration in a
144. Slow sand filters / Advantages and disadvantages
• require little or no mechanical power, chemicals or replaceable parts,
• require minimal operator training and only periodic maintenance,
• often an appropriate technology for poor and isolated areas.
• simple design
• Due to the low filtration rate, slow sand filters require extensive land area
for a large municipal system.
• Many municipal systems in grown cities installed rapid sand filters, due to
increased demand for drinking water.
145. Membrane filtration
• is a treatment process based on the physical separation of compounds from the
water phase with the use of a semi-permeable membrane.
• Most of the membranes used are synthetic membranes made of organic
Can be divided into two catego-ries based on the pore sizes of the membrane:
• micro- and ultrafiltration (MF and UF) remove colloidal substances and
• nanofiltration and reverse osmosis (NF and RO) remove colloidal substances
and microor-ganisms but also dissolved substances like micropollutants and ions
• Micro- and ultrafiltration remove substances from the water phase by a sieve
• Microfiltration removes bacteria and the larger viruses (to a size of 0.05 μm).
• Ultrafiltration also removes bacteria, but because of the smaller pore size all the
larger viruses are removed
• The removal of suspended solids of MF and UF is at least 99%.
146. Membrane filtration
• The removal of microorganisms is referred to in log units.
• A removal of one log unit corresponds to a 90% removal. The removal of 4 log
units cor-responds to a 99.99% removal.
• molecular weight cut-off (MWCO) can also be used as an indication of the
ability of membranes to reject compounds
• MWCO is the molecular weight of spherical molecules which are 90% rejected
by the membrane‟s pores.
• The unit of MWCO is Dalton (1 Dalton is the mass of one hydrogen atom =
• The MWCO for MF/UF is in the range of 10,000 to 500,000 Dalton (10 to 500
150. MF/UF for drinking water
• In drinking water treatment, UF can be used in different stages of the process:
– as a pre-treatment of surface water to remove suspended solids, heavy
metals, bacteria and viruses in order to prevent pollution of the dunes, or to
prevent clogging of the NF/RO membranes
– as treatment of backwash water from rapid sand filtration
– treatment of surface water as the first step in drinking water production.
In some cases, the MF/UF installation is preceded by a conventional
coagulation/flocculation/floc removal treatment process in order to reduce
the risk of membrane fouling
• The membrane is the barrier responsible for the separation of compounds out of
the water phase. The membrane is semi-permeable.
• The pore size determines the removal of different compounds.
• The removed compounds remain at the raw waterside of the membrane and
accumulate on the membrane.
• Three water streams can be distinguished:
– the dirty water or raw water is called feed water
– the water passing the membrane is called the permeate or product water.
– the water with the rejected particles is called concentrate or retentate.
155. Dead-end filtration mode
• In dead-end filtration, all the feed water is through the membrane.
• The suspended solids remain on the feed side of the membrane.
• As a consequence, the resistance of permeation will increase in time.
• The water flux decreases if the pressure is constant, or the pressure increases if
the flux is constant.
• Periodically the membrane has to be cleaned in order to reduce the resistance of
• The period of permeation is called filtration time. A filtration run is the filtration
time together with the cleaning time (also called filtration cycle).
156. Inside-out filtration
• In a configuration with inside-out filtration, feed water enters the inside of the
capillaries or tubular membranes.
• The water is pushed from the inside to the outside of the membrane.
• Permeate is collected outside the membrane and transported to the permeate
157. Membrane fouling
• During filtration the resistance increases as a result of fouling of the membrane
• The resistance increases because the pores in the membrane are blocked and
because caked suspended matter is built up on the membrane surface.
• This resistance increase is referred to as fouling.
• The definition of fouling is: the deposition of suspended or dissolved substances
on the membrane surface or in front of the pores or in the membrane pores.
• fouling can be subdivided into different mechanisms:
- membrane resistance
- pore blocking
- adsorption in the pores
- cake resistance
- high concentration of dissolved substances near the surface.
158. Membrane fouling
• Due to the accumulation of solids on and in the membrane during dead-end
filtration, the total resistance increases with time.
• The mass of a cake layer is difficult to measure. The thickness of the cake layer
depends on The trans membrane pressure TMP.
• The thickness of the cake layer is in the range of several micrometers, depending
on the rejected compounds.
• As a result of the dead-end mode, the membrane has to be cleaned often in order
to remove the rejected compounds.
• The cleaning intervals can be constant in time or can be determined by a
• If possible, cleaning of membranes should be avoided because during the
cleaning no permeate is produced.
• Also, permeate and energy are used for the cleaning. With specific cleanings
chemicals are also used.
• Different methods or a combination of methods can be used to clean a
- forward flush (FF)
- back flush (BF)
- air flush (AF)
- chemical enhanced flush (CEF) or enhanced back flush (EBF)
- cleaning in place (CIP) or chemical soaking
160. Forward flush (FF) and back flush (BF)
The forward flush is a turbulent cross-flow
along the feed side of the membrane surface
This is the opposite of the filtration mode
where the flow is through the membrane
(flow direction perpendicular to the
In the back flush, filtration direction is reversed
After removing the particles from the pores and
the membrane surface, the particles and the cake
have to be transported out of the module.
A combined back flush and forward flush can be
used. First, a back flush is used to clean the pores
and to lift the cake. Then, a forward flush is used
to transport the dirt out of the module
161. Air/water flush
• An air/water flush can be used to clean the membrane wall from adhering
• The air/water flush is actually a forward flush with a combination of air and
• The air is used to create a turbulent flow in the membrane under process
conditions where no turbulence is attained with the water flow.
• The cleaning efficiency depends on the kind of two-phase flow obtained in the
• If the water/air ratio is high, only small air bubbles are present in the water and
the turbulence is only slightly enhanced.
• When the water/air ratio is too small, the air flows through the middle of the
membrane and the cleaning effect is low.
• The best cleaning is obtained with bullet-like air bubbles.
163. Chemical cleaning
• If forward flush, back flush and air flush are not enough to clean the
membrane, a chemical cleaning (often called enhanced back flush or chemical
back flush) can also decrease the clean water resistance.
• This kind of cleaning means that the module is soaked with a solution of
hypochloric acid, hydrogen chloride, hydrogen peroxide.
• After the soaking, a backwash or a forward flush removes the dissolved dirt.
• The main drawback of chemical cleaning is that the membranes age because of
the chemicals, and the lifetime of the membranes, therefore will be shortened.
• Also, the chemicals are a cost factor and with a chemical cleaning a chemical
waste stream should be discharged.
• Besides the periodical chemical cleaning which is part of the automated process
control of the installation, a more intensive chemical cleaning might also be
• The so-called “cleaning in place” (CIP) can last from a few hours to several days
and is typically not automated.
• If the CIP is not able to clean the membranes, they are replaced by new ones.
166. Membrane Processes / Electro-dialysis
• What is a Membrane?
• The membrane can be defined essentially as a barrier, which separates two
phases and restricts transport of various chemicals in a selective manner.
• Membrane Separation Technology
• A membrane separation system separates an influent stream into two effluent
streams known as the permeate and the concentrate.
• The permeate is the portion of the fluid that has passed through the semi-
• The concentrate stream contains the constituents that have been rejected by the
167. Membrane Processes
The main membrane processes are
• Reverse osmosis
Driving forces that cause mass transfer of solutes are:
• Difference in concentration (dialysis)
• Difference in electric potential (electro-dialysis)
• Difference in pressure (reverse osmosis)
168. Dialysis Theory
• Dialysis depends on separating solutes of different ionic or molecular size in a
solution by means of a selectively permeable membrane.
• The driving force for dialysis is the difference in the solute concentration across
The mass transfer of solute through the membrane is given by:
• M = mass transferred per unit time (gram/hour)
• K = mass transfer coefficient [gram/(hr-cm2)(gram/cm3)]
• A = membrane area (cm2)
• ΔC = difference in concentration of solute passing through
the membrane (gram/cm3)
• In environmental engineering, Dialysis is not used to an appreciable extent.
• In industrial applications, Dialysis can be used to recover Sodium Hydroxide
from textile wastewater.
• Dialysis is limited to small flows due to small mass transfer coefficient (K)
169. Electrodialysis (ED)
• ED is used to transport salt ions from one solution through ion exchange
membranes to another solution under the influence of an applied electric
• The cell consists of a feed (diluate) compartment and a concentrate (brine)
compartment formed by an anion exchange membrane and a cation exchange
membrane placed between two electrodes
• multiple electrodialysis cells are arranged into a configuration called an
electrodialysis stack, with alternating anion and cation exchange membranes
forming the multiple electrodialysis cells
• dissolved species are moved away from the feed stream rather than the reverse
In an electrodialysis stack, the diluate (D) feed stream, brine or concentrate (C)
stream, and electrode (E) stream are allowed to flow through the appropriate cell
compartments formed by the ion exchange membranes
171. Anode and Cathode Reactions
At the cathode 2e- + 2 H2O → H2 (g) + 2 OH-
At the anode H2O → 2 H+ + ½ O2 (g) + 2e- or 2 Cl- → Cl2 (g) + 2e-
• Small amounts of hydrogen gas are generated at the cathode and small amounts
of either oxygen or chlorine gas (depending on composition of the E stream and
end ion exchange membrane arrangement) at the anode.
• These gases are combined