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Lecture
WATER TREATMENT WATER TREATMENT

Chapter 2

COAGULATION – FLOCCULATION

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Chapter2
COAGULATION - FLOCCULATION C2. COAGULATION - FLOCCULATION

Contents Why coagulation - flocculation?

• Coagulation – Theory • Removal of turbidity (clay) and colour (humic acids)

• Coagulation – Practice Æ Public health and aesthetics

• Flocculation – Theory • Public health

Removal of heavy metals and organic compounds

• Flocculation – Practice
• Aesthethics

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Attractiveness of water 4

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Surface water treatment scheme Classification

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Classification Classification

Type of Diameter, mm Settling time

particle (m-1)

Gravel 10 0.013s
Thick sand 1 1.27s
Fine sand 0.1 2.11 min
Clay 0.01 3.52 h
Bacteria 0.001 14.65 days
Colloids 0.0001 4.12 years
7 Colloids 0.00001 412.2 years 8

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Definitions
Turbidity and Color in Water

Turbidity: Color:

- Clay particle, Colloids - Humic compounds

- Size: 0.1 – 10 µm - Size: 0.01 µm

- Negative charge - Charge depending on pH

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http://www.aquasure.fr/spip.php?article74

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Principals
Objectives: Aggregating the particles causing color or turbidity into
Stable and hardly settable colloids Æ unstable and settlable
bigger particles which can be settled by gravity.

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Type of particles Zero point of charge

Stability of particles
Inorganic

• Surface charge: contributes to relative stability, causing particles to Al(OH)3 7.5 – 8.5
Al2O3 9.1
remain in suspension without aggregating for long time. Fe(OH)3 8.5

• The pH corresponding to a surface SiO2 2 – 3.5

Kaolinite 3.3 – 4.6
charge of zero: zero point of charge
Montmorillonite 2.5
(ZPC) Organic
Algae 3–5
Above ZPC: negative charge
Bacteria 2–4
Below ZPC: positive charge Humic acid 3
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Oil droplets 2-5

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Electrical properties Particle stability

• The electrical potential • The stability of particles depends

between the actual shear plane on a balance between:
and the bulk solution is zeta
(1) repulsive electrostatic force
potential ξ.
(2) attractive force known as van
• ξ < 20 mV, rapid flocculation
der Waals force.
occurs (Kruyt, 1952).

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https://vimeo.com/icheme/review/147596786/3ef4e59461

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Coagulation mechanisms Compression of the electrical double layer

• Compression of the electrical double layer • Adding counter ions into solution with high concentration

• Adsorption and charge neutralization • Increasing ionic strength

• Adsorption and interparticle bridging • Decreasing the extent of the double layer

• Reducing the zeta potential

• Enmeshment in a precipitate, or ‘‘sweep floc

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Adsorption and charge neutralization Adsorption and charge neutralization

Adsorptive coagulation occurs at a low pH, because positive

hydrolysis products are needed.

Re-stabilization: - under-dosage of coagulants

- over-dosage of coagulants 19 20

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Adsorption and interparticle bridging Adsorption and interparticle bridging

R2: Flocs formation

R1: Polymer added to particulate suspension at correct dosage

Perikinetic

Orthokinetic

Polymer Particle Destabilized particle

Destabilized Flocs

• Particle destabilization results from polymer bonding • Particles and polymer flocculate due to perikinetic and

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Adsorption and interparticle bridging Adsorption and interparticle bridging

R3: Excessive dosage of polymer added R4: Secondary adsorption

Can not contact with other

particles

Particle
Destabilized particle
Re-stabilized particle
Stabilized article (Particles
Excessive polymer enmeshed in polymer Matrix)

Insufficient mixing conditions results in particle restabilization and

23 poor floc formation 24

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Adsorption and interparticle bridging Enmeshment in a precipitate, or ‘‘sweep floc

R5: Flocs break

High or prolonged
mixing
Hard to settle
Flocs

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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Contents Coagulants

• Coagulation – Theory • Aluminum sulfate

• Aluminum chloride
• Coagulation – Practice
• Polyaluminum chloride
• Flocculation – Theory
• Ferric chloride,
• Flocculation – Practice
• Ferric sulfate

• Ferrous sulfate
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Action of alum and iron salts

Action of alum and iron salts

Al2(SO4)3 Æ 2 Al3+ + 3 SO42−

FeCl3 Æ Fe3+ + 3 Cl−

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

complexes Al(H2O)63+ and Fe(H2O)63+

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Coagulant - Reaction coefficients Solubility of metal salts

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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Source: Snoeyink & Jenkins, Water Chemistry

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

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

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

[Fe3+][OH-]3 = 2.79. 10-39 Æ [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 Æ 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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Organic Coagulants Example 1:

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

to be added.

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Jartest JarTest

Optimizing pH, Optimizing dosing

Variation in:

pH,

Dosage,

Flocculation time,

Sedimentation time,

Stirring time
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Mixer Mixer
Static

∆H

kconsultation.com 47 48

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Static mixer Mechanical mixer

G = velocity gradient, sec-1

W = energy/volume unit, N-m/s-m3
P = energy, N-m/s
V = tank volume, m3
μ = water viscosity
( μ=0.001 N-s/m2 at 20oC)

49 Propeller Turbine Turbine impeller Paddle Turbine 50

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HRT of coagulation

T (seconds) G (sec -1)

20 1000

30 900

40 790

50 or more 700

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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,

- providing an additional mechanism for promoting flocculation.

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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

- Velocity gradient flocculation 100 - 10 sec-1 63 64

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Water treatment

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