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Lecture
WATER TREATMENT WATER TREATMENT

Chapter 2

COAGULATION – FLOCCULATION

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HCM UTE - Department of Environmental Technology

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Definitions Contents

• Coagulation – Theory

• Coagulation – Practice

• Flocculation – Theory

• Flocculation – Practice

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Why coagulation - flocculation?

• Removal of turbidity (clay) and colour (humic acids)

 Public health and aesthetics

• Public health

Removal of heavy metals and organic compounds

• Aesthethics

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Surface water treatment scheme Classification

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Classification Turbidity and Color in Water

Type of particle Diameter, Settling time (m-1),

mm Sp gravity 2.65 Turbidity: Color:
Gravel 10 0.013s
- Clay particle, Colloids - Humic compounds
Thick sand 1 1.27s
Fine sand 0.1 2.11 min - Size: 0.1 – 10 µm - Size: 0.01 µm

Clay 0.01 3.52 h - Negative charge - Charge depending on pH

Bacteria 0.001 14.65 days
Colloids 0.0001 4.12 years
Colloids 0.00001 412.2 years 9 10

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Definitions
Objectives: Aggregating the particles causing color or turbidity into

bigger particles which can be settled by gravity.

Coagulant Flocculation tank Clarifier II

Water
Mixing tanks

Colloids Destabilization Flocculation Sedimentation

(Growth of aggregates)
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http://www.aquasure.fr/spip.php?article74

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Principals Stability of particles

Stable and hardly settable colloids  unstable and settlable

• Surface charge: contributes to relative stability, causing particles to

remain in suspension without aggregating for long time.

• The pH corresponding to a surface

charge of zero: zero point of charge

(ZPC)

Above ZPC: negative charge

Below ZPC: positive charge

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Type of particles Zero point of charge

Stability of particles –
Inorganic
Al(OH)3 7.5 – 8.5
Electrical properties
Fe(OH)3 8.5
• The electrical potential
SiO2 2 – 3.5
Kaolinite 3.3 – 4.6 between the actual shear plane
Montmorillonite 2.5
and the bulk solution is zeta
Organic
Algae 3–5 potential ξ.
Bacteria 2–4 • ξ = 0 mV, a system is unstable
Humic acid 3
Oil droplets 2-5 and easily to aggregation.
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Source: From Parks (1967) and Stumm and Morgan (1981) https://vimeo.com/icheme/review/147596786/3ef4e59461

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Particle stability Coagulation mechanisms

• Compression of the electrical double layer

• The stability of particles depends

on a balance between: • Adsorption and charge neutralization

(1) repulsive electrostatic force • Adsorption and interparticle bridging

(2) attractive force known as van • Enmeshment in a precipitate, or ‘‘sweep floc”

der Waals force.

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Compression of the electrical double layer Adsorption and charge neutralization

• Adding counter ions into solution with high concentration

• Increasing ionic strength

• Decreasing the extent of the double layer

Adsorptive coagulation occurs at a low pH, because positive
• Reducing the zeta potential
hydrolysis products are needed.

Re-stabilization: - under-dosage of coagulants

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Adsorption and charge neutralization Adsorption and interparticle bridging

R1: Polymer added to particulate suspension at correct dosage

Polymer Particle Destabilized particle

• Particle destabilization results from polymer bonding

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Adsorption and interparticle bridging Adsorption and interparticle bridging

R2: Flocs formation R3: Excessive dosage of polymer added

Perikinetic

Orthokinetic
Particle

Stabilized article (Particles

Destabilized Flocs Excessive polymer enmeshed in polymer Matrix)

• Particles and polymer flocculate due to perikinetic and

orthokinetic forces. 23 24

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Adsorption and interparticle bridging Adsorption and interparticle bridging

R4: Secondary adsorption R5: Flocs break

Can not contact with other

particles

High or prolonged
Destabilized particle mixing
Re-stabilized particle
Hard to settle
Flocs
Insufficient mixing conditions results in particle restabilization and
Floc break due to high or prolonged mixing conditions
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Enmeshment in a precipitate, or ‘‘sweep floc Coagulation mechanisms

• Electrostatic coagulation: Not important in water treatment.

• Adsorptive coagulation: optimum remove colour (organics) at

low pH, low dosing, high dosing results in re-stabilisation.

• Precipitation coagulation: no re-stabilisation, high dosing, for

turbidity removal, evident optimum pH 8 with iron, pH 6 with

aluminum.
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Solubility of metal salts Contents

• Coagulation – Theory

• Coagulation – Practice

• Flocculation – Theory

• Flocculation – Practice

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Coagulants Action of alum and iron salts

• Aluminum sulfate Al2(SO4)3  2 Al3+ + 3 SO42−

• Aluminum chloride
FeCl3  Fe3+ + 3 Cl−

• Polyaluminum chloride Trivalent ions of Al3+ and Fe3+ then hydrate to form the aquometal

• Ferric chloride, complexes Al(H2O)63+ and Fe(H2O)63+

• Ferric sulfate

• Ferrous sulfate
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Action of alum and iron salts Coagulant - Reaction coefficients

Fe3+ + 2H2O → Fe(OH)2+ + H3O+

Fe(OH)2+ + 2H2O → Fe(OH)2+ + H3O+

Fe(OH)2+ + 2H2O → Fe(OH)3 ↓ + H3O+

Fe(OH)3 + 2H2O → Fe(OH)4- + H3O+

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Coagulant Coagulant
Calculation of Fe3+ concentration A concentration of Fe3+ ions of 0.05 mg/l is desired

Fe(OH)3  Fe3+ + 3 OH- Ksp = 2.79.10-39 [Fe3+] = 0.05 mg/l = 9.10-4 mmol/L = 9.10-7 mol/L

H2O  H+ + OH- Kw = 10-14 Log [Fe3+] = log [9.10-7] = 3.5 – 3 pH  pH = 3.2

Kw = [H+][OH-]  [OH-] = 10-14/[H+] pH < 3.2 then more Fe3+

[Fe3+][OH-]3 = 2.79. 10-39  [Fe3+] = 2.79.10-39 / [OH-]3 pH > 3.2 then less Fe3+

[Fe3+] = 2.79. 10-38/(10-14)3 * [H+]3 = 2.79. 103 [H+]3 pH of surface water = 7  max.10-17.5 mol/L Fe3+ can be dissolved.

Log [Fe3+] = log (2.79.103) + 3 log [H+] = 3.5 – 3 pH 35 36

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Coagulant Stoichiometry of metal ion – Aluminum sulfate

Dosing in practice:
• To have Al(OH)3 in water, need enough natural alkalinity
10-4 mol/l Fe = 5.6 mg/l Fe = 27 mg/l FeCl3·6H2O

Dosing of iron is done with FeCl3

• If alkalinity is not enough, add NaOH or Ca(OH)2
FeCl3.6H2O → Fe3+ + 3 Cl-+ 6 H2O
(pH = 4.5 – 8)
Fe3+ + 3 OH- → Fe(OH)3 ↓

Result of dosing coagulants = pH decrease, thus conditioning.

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Ferrous Sulfate Ferric Sulfate

• Need to add [Ca(OH)2] to get enough alkalinity • React with alkalinity in water

• pH ≥ 9.5 and need to use extra Ca(OH)2 amount • Fe(OH)3 condense and settle well

• More expensive than Alum salt • If the alkalinity is not enough, add lime

• pH = 4 – 12

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Organic Coagulants
Ferric Chloride

• React with natural alkalinity in water

• If alkalinity is not enough, add lime

• pH = 4 - 12

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Example 1: Example 1:
Mole of alkalinity = 12 / 100 = 0.12
Coagulation by Al2(SO4)3 with dose of 55 mg/L for water with the

alkalinity of 12 mg CaCO3/L. Calculate the dose of lime which need Mole of coagulants which reacted: = 0.12 / 3 = 0.04 mmol/L

to be added. = 0.04 x 666 = 26.64 mg/l

Remaining amount of coagulant = 55 – 26.64 = 28.36 mg/l

Needed Ca(OH)2 = 3 x (28.36 / 666) x 74 = 9.45 mg/L

43 = 7.15 mg CaO/L 44

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Jartest JarTest

Optimizing pH, Optimizing dosing

Variation in:

pH,

Dosage,

Flocculation time,

Sedimentation time,

Stirring energy
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Mixer Mixer
Static

ΔH

kconsultation.com 47 48

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Inline static mixer Inline mixer

Provide continuous, instantaneous

blending of coagulant in raw water.

The homogeneous, millisecond blending of

Model 2800 coagulant results in optimum floc formation

and maximizes chemical economy.

InstoMix Inline flash mixer

www.walker-process.com

http://www.fluidpartners.co.uk/static-mixers/
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Mechanical mixer Mechanical mixer P = energy, N-m/s (W)

ρ: density , kg/m3
D: impeller diameter, m
G = velocity gradient, sec-1 n: rotational speed, rps
W = energy/volume unit, N-m/s-m3 K: impeller constant
P = energy, N-m/s (W)
V = tank volume, m3
 = water viscosity
( =0.001 N-s/m2 at 20oC)

Propeller Turbine Turbine impeller Paddle Turbine 51 52

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Type of mixer - Application

Mixing device Typical mixing Applications

time (s)
Static inline mixer <1 For Al3+, Fe3+, cationic
polymer, Chlorine
Inline mixer <1 For Al3+, Fe3+, cationic
polymer, Chlorine
Turbine and Propeller 2 – 20 s Actual time depends on the
mixer configuration of the tank.
Mixing chemical in feed
tank.
Source: Wastewater engineering – Mecaft Eddy
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Flocculation theory Flocculation mechanism

Flocculation theories have evolved from the following observations: - Perikinetic flocculation

(1) small particles undergo random Brownian motion due to - Orthokinetic flocculation

collisions with fluid molecules resulting in particle–particle - Differential settling

collisions.

(2) stirring water containing particles creates velocity gradients that

bring about particle collisions.

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Flocculation mechanism Flocculation mechanism

Perikinetic flocculation Orthokinetic flocculation

- Driving force : Brownian movement

- Driving force : turbulence = mixing
- The rate of flocculation of small particles ~ the rate at which
- The mixing causes velocity gradients that causes collisions
particles diffuse toward one another.
between suspended particle
- As aggregation of small particles proceeds, larger particles (1-

100 μm) are formed after short time (seconds)

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Flocculation mechanism Flocculation: Practice

Differential settling
• Hydraulic mixing:
- Aggregation and growth of flocs can result from particles settling
• Simple
at different velocities.
• Mechnical mixing:
- The velocity of particles of similar densities settling is
• Paddle wheels (most common)
proportional to the square of their size.
• Turbines
- Differential particle settling occurs during sedimentation,

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Flocculation: Practice Flocculation: Practice

Hydraulic mixing: Mechanical mixing (Paddle wheels):

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Flocculation: Practice
Flocculation: Practice
Mechanical mixing (Turbine): Table 2.1 : Gt values for flocculation

Type G (s-1) Gt (unitless)

Low-turbidity, color 20 – 70 60,000 to 200,000

removal
High-turbidity, solids 30 - 80 36,000 to 96,000
removal

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Optimum parameters for coagulation – flocculation (ref) Flocculation

Coagulation

- Mixing time 1-10 sec

- Velocity gradient mixing > 1,500 sec-1

Flocculation

- Flocculation time = 30 minutes

- 3 - 4 compartments, length/width ratio = 3 to 6

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- Velocity gradient flocculation 100 - 10 sec-1

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Water treatment

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