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Coagulation and Flocculation: Fundamentals of

Colloidal chemistry
General size classification of solids in water
Dissolved ( <1 nm)
Colloidal (>1 nm and < 1000 nm)
Impurities in water vary in size by about
-Nano ( 1- 100 nm)
a six orders of magnitude
Suspended (> 1m and < 100 m)

Classification of particles:

Coarse gravel > 2 mm


Coarse sand - 1 to 0.5 mm
Silt 0.05 to 0 .1 mm
Clay - 0 .01 to 0.001 mm
Fine clay, algae, fungus - 0.001 to 0.0001 mm
Colloidal clay finer than 0.0001 mm
Bacteria 0.001 mm and less
Virus < 20 nm 1
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Any particle < 0.01 mm will not settle in plain sedimentation tank.
Colloidal system: A system in which particles, in a finely divided
state are dispersed in a continuous medium
Particles dispersed phase
Medium - dispersing phase
Types of colloidal systems in environmental engineering
Liquid liquid (emulsified oils)
Gas in liquid dispersion (foam)
solid in liquid dispersion (colloidal clay)
Classification based on the affinity of the dispersed phase for the
dispersing phase
Hyophobic (liquid hating)
Hydrophobic e.g. metal, clay, etc.
Hyophilic (liquid loving)
Hydrophilic e.g. proteins, soaps , etc.
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Surface charge on colloidal particles
Primary reason for colloidal stability- Electrical
charge on the surface of the particle
1. Imperfection in crystal layers

OH
OH O O O

Si Si Si Si
O OH
OH O O
Isomorphic substitution

OH
OH O O O

Si Al Si Si
O OH
OH O O
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2. Adsorption of ions onto the particle surface
-preferential adsorption of either positive or negative ion
the adsorbed ions are called peptizing ions
- e.g. oil droplets
3. Ionization of surface sites:
- Ionization of surface functional group
-e.g. Proteins ( ionization of amino or carboxyl
group)
- pH dependent

Stability of the particle


Hydrophobic Partly by electrical repulsion and may be
partly by particle solvation
Hydrophilic stabilized exclusively by electrical repulsion
force 1 4
Electrical double layer theory
First proposed by Helmholtz and later refined by
Gouy (1910), Chapman (1913), and Stern (1924)


Nernst
potential Stern layer
o
Position of Stern ions

Plane of shear

Zp

Distribution of potential in
Distribution of charges in the the electrical double layer
vicinity of a colloidal particle

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Zp = zeta potential
4q q = charge on the particle
Zp = = thickness of the zone of influence of the
charge on the particle
D D = dielectric constant of the liquid

Stability of hydrophobic colloids


Double layer repulsion
VR
Repulsive energy
Resultant curve (VR-VA)
Energy

Energy barrier

Particle separation

VA Van der Waals forces of


attraction

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Coagulation theory
Coagulation: The process of destabilizing forces and
causing the aggregation of the particles
To induce aggregation of colloidal particles
Step1: the repulsion force must be reduced (i.e., the
particle must be destabilized)
Step2: particle transport must be achieved to
provide contacts between the destabilized particles

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How to achieve particle destabilization?
mechanisms involved:
1. double layer compression
2. adsorption and charge neutralization
3. enmeshment in precipitate
4. adsorption and interparticle bridging

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1. double layer compression
Addition of ions having charge apposite to that of the
colloid
Coagulation power varies with valency of the ion Shuzlze
Hardy rule - valid only for indifferent electrolite
coagulation power of cation increased in the ration 1:10:100 as the
valence of the ions increased from 1 to 2 to 3.
A

A Counter ions
Ion conc., n

Distance from the surface


C
Co ions
C 1 9
Double layer repulsion
VR
Resultant curve (VR-VR)
Low electrolyte conc.
System is stable no
agglomeration
Energy

Energy barrier

Particle separation

VA Van der Waals forces of


attraction Double layer repulsion
VR
Energy Resultant curve (VR-VR)

Intermediate electrolyte Energy barrier


conc.
Some double layer Particle separation
compression Slow
agglomeration
VA Van der Waals forces of
attraction
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Double layer repulsion
VR
Resultant curve (VR-VR)

High electrolyte conc.


severe double layer compression
Energy

rapid agglomeration
Particle separation

VA Van der Waals forces of


attraction

Derjaguin and Landau and Verwey and Overbeek (1948) has developed a model to
calculate the conc. of an indifferent electrolyte required to cease coagulation:

According to the model, conc. of the counter ion with charge numbers 1, 2 and 3 should
be

1/16 : 1/26 : 1/36


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Important aspects of colloidal compression are:
1. Coagulation power of ions increases with increase in their
charge
2. The amount of electrolyte required to achieve coagulation
by double layer compression is practically independent of the
concentration of colloids in the dispersion
3. It is not possible to cause a charge reversal on a colloid by
double layer compression, regardless of how much electrolyte
is added.

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Adsorption and charge neutralization:

Some coagulant species are capable of adsorbing on the colloidal surface

Sorbable species are capable of destablizing colloids at much lower dosage


than non-sorbable species

e.g. dodecyle ammonium ion (C12H25NH3+) of 6x10-5 mole/l would


produce destabilization of silver iodide sol. In contrast 10 -1 moles/l of Na+
is required to achieve the same result (Tamamushi and Tamaki (1959).

Destabilization by adsorption is stocheometric: Higher dosage of coagulants


for high colloidal conc.

Higher dosage of sorbable species may cause restabilization of the colloids

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Destabilization of colloids by enmeshment in a precipitate

Certain metal salts can form precipitate in water. The colloids may serve as

condensation nuclei for these precipitate or may become enmeshed as the

precipitate settle

e.g. Al2(SO)4, FeCl3,

Removal of colloids in this manner is referred as sweep-floc coagulation

here, a inverse relationship exist between the coagulant dosage and the

colloidal conc.

Not dependent on charge neutralization, the optimum coagulation do not

correspond to a minimum zeta potential.

Solution pH is important for effective removal

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Destabilization by adsorption and inter particle
bridging
Many polymers are capable of destablizing
negatively charged particles
Neither the double layer compression model nor the
charge neutralization model can be used to explain
the phenomenon
Chemical bridging theory (LaMer and Healy (1963))
is useful in explaining the phenomenon

Natural polymers
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Initial adsorption at
Colloidal optimum polymer dose
particle

Floc formation

Secondary adsorption of
polymer

No contact with vacant


sites on another polymer

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Stable floc (no vacant
site)

Excess polymer
Rupture of floc
Floc fragments

Floc

Secondary adsorption of
polymer

Floc fragments Schematic of reaction between colloidal particles and


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Summery
Reasons for the stability of colloids in water
Major types of colloidal systems in environmental engineering ( water
and wastewater treatment)
Why most of the collides in water are negatively charged?
Coagulation?
Flocculation?
Mechanism of coagulation
Schulze- Hardy rule
Important features of double layered compression (DLC)
How adsorption and charge neutralization is different from DLC
What is Sweep floc coagulation? How it is different from other
coagulation mechanisms?
What is the effect of over dosing of absorbable coagulants on turbid?
Why sweep-floc coagulation is ineffective for less turbid water?

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Coagulation in Water Treatment

Coagulation is a two step mechanism involving particle


destabilization followed by particle transport to promote
collision between the destabilized particles.
Destabilization is induced by the addition of a suitable
coagulants
Particle contact is ensured through appropriate mixing
Coagulation occurs in the rapid mixing and
flocculation units

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Characteristics of most conventional coagulants

Al2(SO4)3.14 H2O
FeCl3
Fe2 (SO4)3
water
Al2(SO4)3.14 H2O Al3+ Al(H2O)63+
Increasing pH

Al(H2O)63 [Al(H2O)5 OH]2+ [Al(H2O)3 OH3] [Al(H2O)2 OH4]1-


+
(s)

[Al8 OH20 ]4+ [Al2O3 ]


AlOOH (s)
(s)
Polynuclear species
Crystalline phase
Hydrolysis scheme for aluminum
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Effect of pH formation of aluminium and iron hydroxide formation
Salts of Al(III) and Fe(III) as coagulants
Mechanisms:
1. Adsorption and Charge neutralization
If the concentration of the salt is less than the solubility limit of the metal
hydroxide hydrolysis product adsorb onto charge particles
2. Enmeshment in a sweep floc
If added amount is enough to exceed the solubility of the metal hydroxide,
the hydrolysis products will form as kinetic intermediates in the formation
of the metal hydroxide precipitates
Destabilization of the particle by charge neutralization ( hydrolysis
intermediates in the formation of metal hydroxide) and enmeshment in the
precipitate both contribute the coagulation
Interrelation b/w pH, colloidal conc. and coagulant dosage determents the
mechanism responsible for coagulation
Hydrolysis products posses a +ve charge at pH value below iso-electric point of
the metal hydroxide and posses ve charge at pH vale above iso-electric point.

[Al(H2O)6]3+ H2O [Al(H2O)5]OH]2+ [H3O+]

[Fe(H2O)6]3+ H2O [Fe(H2O)5]OH]2+ [H3O+]


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Hydrogen ion librated by addition of alum into water will
react with natural alkalinity

[Al2(SO4)3]. 14H2O 3Ca(HCO3)2 2Al(OH)3 3CaSO4 14 H2O 6 CO2

If natural alkalinity is not sufficient to buffer the water, we


need to add the same in the form of soda or lime

[Al2(SO4)3]. 14H2O 3Ca(OH)2 2Al(OH)3 3CaSO 14 H2O


4

[Al2(SO4)3]. 14H2O 3Na2CO3 3 H2O 2Al(OH)3 3Na2SO4 3CO2

14 H2O

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Understanding the relation between colloidal conc. and coagulant
dosage

Zone 4
Coagulation
region
Coagulant dosage, C

Zone 3 Zone 2

C1
Zone 1

S1 S2 S3 S4

Colloidal conc., S

Schematic of coagulation curves at constant pH


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Understanding the relation between colloidal conc. and coagulant
dosage

Colloidal conc.
Zone 1 Zone 4 S4 (>S3)
Residual turbidity

Zone 1 Zone 2 Zone 3 Zone 4 Colloidal conc.


S3 (>S2)

2
Zone 1 Zone 2 Zone 4 Colloidal conc.
S2 (>S1)
Colloidal conc.
Zone 1 Zone 4
S1

Coagulant dosage, C

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Assignments

Draw schematic diagrams representing the effect


of coagulant dose on various modes of
destabilization [ turbidity vs dosage of
coagulants]
Show the hydrolysis scheme for ferric(III) ions
and construct a log [species] vs pH diagram for
the ion [solubility diagram]

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Questions for class-room discussion

Why coagulation using aluminum chloride is


ineffective at pH above 8.
Is presedimentation important in the treatment of
turbid surface water? Is it possible to remove the
entire turbidity through coagulation process?
Aquometal ions of Al(III) and Fe(III) salts are
acidic in nature. How do we control the pH to
establish optimum coagulation.

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Coagulant Aids
Flocs produced during
coagulation should ideally settle Zone 4
rapidly and be resistant to Coagulation
destruction by shearing forces. region

Coagulant dosage, C
Unfortunately, this is not the Zone 3 Zone 2
case with many coagulation
process, especially in the case of
waters low in turbidity or low C1
mineralized waters that are high Zone 1
in color. In such cases, certain
C3
materials referred to as
coagulant aids can be added to
the water to improve floc S1 S2 S3 S4
properties and hence
coagulation.
Colloidal conc., S

Example: Clay, activated Note: C1 > C3


silica, and polymers 1 28
Problem 1. A raw water supply is treated with an alum dosage of
25 mg/L. Calculate the following
The amount of alum required to treat a flow of 3 MLD
The amount of natural alkalinity (as CaCO3) required to react
with alum added
Total amount of sludge produced during the process.

Estimate the the variation in quantity of sludge produced if


alum is replaced by ferric chloride. Assume same dosage
Assume that the dry solids have specific gravity of 2.0. Calculate
the volume of sludge produced if it is collected at 2% solids.

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Problem 2: What concentration of alkalinity is
theoretically required to react with an alum feed of
200 kg/ML

Problem 3: What concentration of alkalinity is


theoretically required to react with an ferric chloride
feed of 200 kg/ML

Problem 4: Calculate the specific gravity of a sludge


produced from coagulation if it is collected at 2.1%
solids and the dry solids have a specific gravity of 2.4

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Problem 5: A water with alkalinity of 12 mg/L as
CaCO3 will be treated with alum-lime
coagulation. Alum dosage is 55 mg/L.
Determine the lime dosage needed to react with
alum.
Problem 6: what is the amount of natural
alkalinity required for coagulation of raw water
with dosage of 15.0 mg/L of ferric chloride.

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Determination of Coagulant Dosage
Difficult to calculate the
coagulant dosage
theoretically- normally
determined by simple
JAR TEST procedure.
The optimum dose
determined by the Jar Test
is frequently not same as
that of actual plant.

The classification of water in the next slides will serve as a guide


for selection
. of the coagulants to be studied by jar test procedure

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Derive a mathematical expression to estimate the effluent concentration (C3) for the reactor configuration given in the Figure 1. Assuming that the reaction rate is firs

Figure 1.

Co C1 C2 C3

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Comparison of Various coagulants
Types of water Alum Ferric salt Polymer Magnesium

Hihg turbidity, Effective for pH 5-7 . Effective for pH 6-7 Cationic polymer very Effective due to
high alkalinity ( Coagulant aid no Coagulant aid no effective high precipitation of
Type 1) Alkalinity - no Alkalinity - no molecular wt best Mg(OH)2

Hihg turbidity, low Effective for pH 5-7. If Effective for pH 6-7. Cationic polymer very Effective and results
alkalinity (Type 2) pH drops-need to add If pH drops-need to effective high increased alkalinity-
alkalinity add alkalinity molecular wt best makes water easier to
stabilize

Low turbidity, high Effective in large dosage- Effective in large Coagulant aids such Effective due to
alkalinity (Type 3) dosage- as clay should be precipitation of
Coagulant aid : yes to added ahead of Mg(OH)2
weight floc and improve Coagulant aid : yes polymer
settling to weight floc and
improve settling

Low turbidity, low Effective in large dosage: Effective in large Coagulant aids such Results in increased
alkalinity (Type 4) sweep flocculation dosage: sweep as clay should be alkalinity, which
flocculation added ahead of makes water easier to
Must add alkalinity to polymer stablize
produce type 3 or clay to Must add alkalinity to
produce type 2 water produce type 3 or clay
to produce type 2
water 1 34
Mechanism of coagulation Field condition
High turbidity and High alkalinity (type 1)
Sweep floc coagulation
Less lowering of pH
Adsorption and charge neutralization less effective
High turbidity and Low alkalinity (Type 11)
Adsorption and charge neutralization
Care should be taken to prevent excessive lowering of pH
Low turbidity and high alkalinity (Type III)
Sweep floc coagulation
Addition of coagulant aid is preferred
Low turbidity and Low alkalinity (Type IV)
Very difficult to treat
Addition of coagulant aid or alkalinity or both required

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Rapid Mixing and Flocculation
Rapid mixing and flocculation units to achieve chemical
mixing and particle transport
Coagulation and Particle transport is interdependent
process
Rapid Mixing
To provide complete mixing of the raw water and coagulants
Proper design of rapid mixing units can reduce coagulant demands
and improved aggregation in flocculation unit (Letterman et al.,
1973)
Devices for rapid mixing baffle chambers; hydraulic jumps and
mechanically mixed tanks.
Most common device is completely mixed tanks detention time
of 2 min and G value of 700/s to 1000/s
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Non uniform mixing: Problems

Because of short circuiting of flow and mass rotation of water some


portion will have high conc. of chemical and other portion will have low
conc.
Nonuniform mixing is not acceptable if stabilization by adsorption and
charge neutralization is desired Coagulation using Alum
In the case of hydrolyzing metal ions - variation in pH and metal ion conc.
may cause great variation in type and hydrolysis product formed and will
cause the rate of hydrolysis, adsorption and precipitation.
Destabilization will be poor in areas of low chemical conc.
Destabilization may also be poor in areas of high conc.
Continuous mixers not recommended in this mechanism in line
blenders are more suitable option
Non- uniform mixing is not a big a concern in the case of double layer
compression please remember that coagulation by double layer compression is
independent of colloidal conc.....no change in the surface charge

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Types of Rapid Mixers

impeller

Coagulant feed
Square tank with Back mix impellers ( most common configuration

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In-line mixers
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Important design parameter for rapid mixers
Velocity gradient, G (1/sec)
optimum design values G = 700 to 1000/sec
Mixing time, Sec
Typical mixing time 0.5 to 2 min

Calculate the G value of two particles moving at a


relative velocity of 2 m/sec. The particles are separated
each other at a distance of 0. 15 m.

Ans: G =[( 2 m/sec)/0.15]= 13. 3/ sec

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velocity gradient varies through the mixing basin Camp and
Stein (1943) proposed a mean velocity gradient G to describe the
average condition

P Qh
G= G=
V = V
G = mean velocity gradient, 1/sec
P = power input, W (N.m/s)
V = volume of mixing basin
= dynamic viscosity, N.s/m2
Q = flow rate of water ( m3/sec)
= weight of water ( kg/m3)
H = head loss ( m) ( head loss due to friction + head loss due to
baffles) 1 41
Flocculation
Particle contact : Mechanisms
Thermal motion (Brownian motion)
Bulk liquid motion (stirring)
Differential settling
Perikintic flocculation or microflocculation
Aggregation of the particle are brought about by random thermal
motion of the fluid molecules (Brownian motion)

Orthokintic flocculation or Macroflocculation


When particle contacts are produced by mixing or settling
Aggregation due to induced velocity gradient of the particle

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Flocculation contd.
Perikinetic Orthokinetic

t =0

t =t
Bulk Differential
liquid settling
Effective for particle size -0.001 to 1 m
motion
Effective for particle size 1 to 2 m

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dN 2 G d T
0 3
J ok = = 0 2
(N ) 1

dt 3
dN 4kT
0
J pk = = 0 2
(N ) 2

dt 3
Where N0= total conc. of particles in suspension at time t
= collision efficiency factor
K = Boltzmanns constant (1.38 x 10-16 erg/degree)
T = absolute temperature in K
= fluid viscosity (g/cm-s)
G = velocity gradient
d = particle diameter (cm)
Jpk = rate of change of particle conc. by perikinetic flocculation
Jok = rate of change of particle conc. by orthokintic flocculation
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Design parameter Flocculation unit

Gt = 104 to 105
t ranging from 10 to 30 min
Larger G value with short time produce small, dense floc
Low G value with long time produce, lighter and larger
flocs
Reduction in G value from the influent end to the effluent
end results better settling floc.

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A rapid mixing tank is 1 m x 1 m x 1.2 m. The
power input is 746 W. Find the G value.
= 0.00102 Ns/m2 (at 20 0C).

Determine the theoretical power requirement


(water temp = 20 0C) to achieve a G value of
100/s in a tank with a volume of 3000 m3. What
would be the power requirement when the water
temperature is 30 0C.

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Design of Paddle Mixers

Power requirement in a mechanical paddle


system Drag force on the paddle, FD
C D Av 2 C D Av 3

vp =
p
Power, P = FD x vp =
p

2 2
1/ 2
C D Av 3
2rn
G=
p
vp =
2V 60
FD = drag force, N
CD = Coefficient of drag of paddle moving perpendicular to fluid, 1.8 for flat blades
Ap = cross-sectional area of paddles, m2
vp = relative velocity of paddles w.r.t . the fluid, m/s (0.75 times paddle tip speed, v)
n= no. of revolution per min, rpm
r = distance from shaft to centre line of the paddle,
1 m 47
Design tips

The paddle velocity should be less than 1 m/s


A distance of 0.3 m ( minimum) should be given
between the paddle tips and all other structures in the
flocculator.
Coefficient of drag for a rectangular paddle = 1.8
The velocity of the paddle tip is the velocity relative
to the water = 75% of actual paddle speed.
Extreme care should be taken while transferring
liquid from flocculator basin to settling basin this is
to avoid turbulence and thus break up of floc

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Problems for practice

Problem: A baffled basin with detention time of 30 min. Estimate the


head loss if G = 30/sec. = 0.00102 Ns/m2 (at 20 0C)

A baffled flocculation basin is divided into 16 channels by 15 around


the end baffles. The velocities at the channels and the slots are 0.18 and
0.6 m/s, respectively. The flow rate is 0.34 m3/s. Find (a) total head loss
neglecting channel friction; (b) the power dissipated; the mean
velocity gradient at 20 0C and Gt value. The basin size is 5 x 4.5 x 24.5
m3.

Calculate the theoretical power requirement for a basin of size 5 x 4.5 x


24.5 m3. Also calculate the paddle area required to achieve a Gt value of
a 104 ( assume detention time of 30 min). Assume that the water
temperature is 20 0C and the paddle tip velocity is 0.6 m/s. ( =999.1
kg/m3)
Example 4-6( Peavy and Rowe, page 147 )
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A water treatment plant is being designed to process 50,000 m3/d of
water. Jar test and pilot-plant analysis indicate that an alum dosage of
40 mg/L with flocculation at a Gt value of 40000 produces optimal
results at the expected water temperature of 15 oC. Determine the
following.

The monthly alum requirement


the flocculation basin dimensions if three cross-flow horizontal
paddles are to be used. The flocculator should be a maximum of 12
m wide and 5 m deep in order to connect appropriately with the
settling basin.
The power requirement
The paddle configuration

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A flocculator is 4.88 m deep, 12.2 m wide, and 24.4 m long. The
flow of the water to the plant is 0.566 m3/s. Rotating paddles are
supported parallel to four horizontal shafts. The rotating speed is 2.0
rpm. The center line of the paddles 1.68 m from the shaft ( mid depth
of the basin). Each shaft is equipped with 6 paddles . Each blade is
25 cm wide and 11.6 m long. Assume the mean velocity of the water
is 28% of the velocity of the paddles and their drag coefficient is 1.9
m. Estimate

1. the difference in velocity between the paddles and water


The useful power input
The energy consumption / million liters
The value of G and Gt at 20 oC
The loading rate of the flocculator

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