PPW730

WATER TREATMENT TECHNOLOGIES

Assignment (2)
Chapter (6) Summary

Proposed to / Dr. Hisham Abd-El Halim

Prepared by/ Noor Mohammed Anter

FACULTY OF ENGINEERING, CAIRO UNIVERSITY

GIZA, EGYPT
Fall 2023
 Chapter 6 – Coagulation and Flocculation

6.1. Introduction
Coagulation is an essential process in the water clarifying cycle. Its main objective is to
improve the settleability of the soluble, colloids, and other small particles by disrupting
the suspension of the incoming influent. It can be considered the first step to create flocs
that aggregate in size and settle later on.

Coagulant type and dose are one of the important questions that shall be addressed as this
selection affects the type and amount of produced residues along the treatment cycle.
Those residues will require dewatering and handling that is costly and difficult.

6.2. Contaminants

6.2.1. Natural Organic Material

The major component of natural organic material in water is humic substances. Humic
substances are complex, naturally occurring organic compounds found in soil, and bodies
of water. They are created through the decomposition of plant and animal matter by
microorganisms over time. The concentration of NOM in water is typically expressed
using the amount of organic carbon.

Disinfection Byproducts.

The amount of produced disinfection byproducts increases with the increase of organic
carbon amount in water.

Specific Ultraviolet Light Absorbance (SUVA).

Specific Ultraviolet Absorbance (SUVA) is a measure used to assess the concentration

of dissolved organic matter in water, particularly in terms of its aromaticity or the
presence of certain carbon-based compounds. SUVA values provide insight into the
quality of organic matter present in water. Higher SUVA values often indicate a higher
concentration of aromatic or complex organic compounds.

USEPA’s Enhanced Coagulation Requirement

The USEPA's Enhanced Coagulation Requirement mandates certain water treatment

plants to implement enhanced coagulation techniques to control the levels of disinfection
byproducts (DBPs) in drinking water. This regulation aims to reduce the formation of
DBPs, such as trihalomethanes (THMs) and haloacetic acids (HAAs), which can form
when natural organic matter in water reacts with disinfectants like chlorine.

PPW730 1 Chapter (6) Summary

6.2.2. Particles
Particles in influent water come from different sources, whether air or soil or physical,
chemical, and biological processes in the water. Particle size can vary by orders of
magnitude however, coagulation for particle aggregation can be important and efficient
for most particle size in the removal of soluble, health-related pollutants.

Measuring Particle Concentration

Particle concentration can be measured by turbidity and particle counting. Turbidity

depends on the scattered light measurement. While particle counting depends on online
devices continuously measure particle concentrations in preselected size ranges.

6.3. STABILITY OF PARTICLE SUSPENSIONS

6.3.1. Introduction
Stability of particle suspension is one of the main issues facing a water treatment system
that tries to destabilize the suspension and remove the pollutants through coagulation and
flocculation processes.

6.3.2. Electrostatic Stabilization

Origins of Surface Charge

Electrically charged surfaces are present on most particles in water through different
chemical reactions between the particles surface and the water components. The charges
on those particles are usually negative. The disruption of stabilization require breaking
those electrostatic charges forces.

The Electrical Double Layer

The electrical double layer refers to a phenomenon occurring at the interface between a
solid surface (like a particle or electrode) and a surrounding fluid (such as water or an
electrolyte solution). This double layer comprises two distinct regions, the first is the
stern layer tightly adhered to the solid surface while the second is diffuse layer beyond
the stern layer.

Dynamic Aspects of the Electrical Double Layer.

The dynamic aspects of the electrical double layer involve constant ion adsorption and
desorption, influencing electrochemical reactions and electrokinetic phenomena.
External factors like pH and ionic strength can regulate surface charges, affecting the
layer's structure and properties. These dynamics play a critical role in understanding
charged interface behavior in diverse fields like colloid science and electrochemistry.

PPW730 2 Chapter (6) Summary

Secondary Minimum Aggregation

Despite repulsive forces preventing direct particle contact, particles can still form
aggregates due to weak, attractive interactions at intermediate separation distances.
These interactions are typically weaker than the repulsive forces but strong enough to
allow particles to approach each other closely, leading to temporary aggregation before
repulsion prevails again at shorter distances.

6.3.3. Steric Stabilization

Steric stabilization occurs when polymers or molecules adsorbed onto particle surfaces
create a barrier that prevents particles from getting too close, thereby resisting
aggregation. This stabilizing layer hinders particle contact by introducing repulsive
forces, often due to the molecular size or structure of the adsorbed material, effectively
maintaining dispersion and stability in colloidal systems.

6.4. COAGULANTS

6.4.1. Introduction
Coagulants are used to destabilize suspended particles in water, causing them to clump
together, making it easier to remove impurities through processes like settling or
filtration.

6.4.2. Destabilization Mechanisms

The destabilization is the process where coagulants are used to improve the impurities
tendencies to attach and form flocs by disrupting the stabilization status.

Double-Layer Compression

Double-layer compression refers to the reduction of the electrical double layer thickness
under high surface charge densities or strong external electric fields, impacting particle
interactions and stability by allowing closer proximity between charged entities using a
simple electrolyte.

Surface Charge Neutralization

Surface charge neutralization refers to the process of balancing or eliminating the net
charge on a particle or surface by adding ions or molecules of opposite charge, reducing
its electrostatic interaction with other charged entities.

Adsorption and Interparticle

Adsorption refers to the adherence of molecules or ions onto the surface of a solid or
liquid. Interparticle refers to interactions between particles. In a colloidal system,

PPW730 3 Chapter (6) Summary

adsorption can affect interparticle forces, influencing aggregation, stability, and overall
behavior of the particles in the system.

6.4.3. Hydrolyzing Metal Salt (HMS) Coagulants

Hydrolyzing Metal Salt (HMS) coagulants are compounds like aluminum sulfate (alum)
or ferric chloride used in water treatment. They hydrolyze in water, forming charged ions
that neutralize particles, causing them to clump together, aiding in the removal of
impurities during the water treatment process.

6.4.4. Types of HMS Coagulants Used in Water Treatment

Common types of HMS (Hydrolyzing Metal Salt) coagulants used in water treatment
include:

Simple Metal Salts such as aluminum sulfate (alum), ferric sulfate, and ferric chloride.

Prehydrolyzed Metal Salts. undergo partial hydrolysis before being applied. Unlike
traditional metal salts that hydrolyze in water, these prehydrolyzed salts have undergone
some hydrolysis during their production process, resulting in more stable and effective
coagulants.

Metal Salts Plus Strong Acid such as alum which is the most commonly known
coagulant utilized in different water treatment plants. Iron salt solutions are also available
that containing sulfuric acid.

Metal Salts Plus Additives such as phosphoric acid, sodium silicate, and calcium salts.
Those additives add advantageous features to the coagulant.

Sodium Aluminate. Which is produced by dissolving aluminum oxide or hydroxide in

sodium hydroxide. Sodium aluminate is commonly used in water treatment as a
coagulant, in papermaking as a sizing agent.

PPW730 4 Chapter (6) Summary

6.4.5. Impurities in HMS Coagulant Solutions
Impurities in HMS coagulants are usually related with the way and processes of creating
them. Impurities in the aluminum source tend to appear in the alum product. The most
significant contaminant in aluminum salt coagulants is iron. Typically, the small
quantities of heavy metal impurities found in HMS coagulants generally do not exert a
substantial impact on the metal levels within treated water. These metals might already
exist in an insoluble state or are prone to precipitation.

6.4.6. Acidity of Hydrolyzing Metal Coagulants

Hydrolyzing metal coagulants, like aluminum-based (alum) or iron-based coagulants,
can contribute to the acidity of water due to their hydrolysis process. When these
coagulants dissolve in water, they form hydrolysis products that can increase the acidity
of the solution. For instance, aluminum sulfate (alum) hydrolyzes to produce aluminum
hydroxide and sulfuric acid, contributing to a decrease in pH (increase in acidity) in the
treated water. The extent of acidity depends on the specific coagulant used, its
concentration, and the conditions of the water being treated. Monitoring and adjusting
pH levels are crucial in water treatment processes to ensure regulatory compliance and
prevent adverse effects on water quality.

6.4.7. Action of Hydrolyzing Metal Coagulants

When an HMS coagulant is added to water containing particles or NOM (Natural Organic
Matter), various reaction pathways may occur. These pathways outline how the
hydrolysis products of the coagulant interact with surfaces and influence the formation
of flocs:

Pathways A and B involve the reaction of metal hydrolysis products with metal binding
sites on particle surfaces or soluble NOM. This can lead to neutralizing surface charges,
destabilizing particles, and initiating coagulation.

Pathways C and D describe the formation of metal hydroxide precipitates and how they
interact with NOM. At lower dosages, NOM adsorption prevents floc formation, but as
dosages increase, the precipitates destabilize, allowing floc formation due to a lack of
NOM on particle surfaces.

Pathway E highlights the formation of soluble metal hydrolysis species, influenced by

the final pH of the solution. Controlling the pH can minimize residual soluble metal ions
by maximizing the formation of flocculent metal hydroxide precipitates.

Factors like pH, concentration of binding sites, and NOM influence these pathways,
affecting the formation of flocs and the efficiency of the coagulation process. The
interplay of these pathways determines the effectiveness of the coagulant in water
treatment.

PPW730 5 Chapter (6) Summary

6.4.8. Interpreting Coagulation Results
HMS coagulants' effectiveness depends on dosage, water chemistry (alkalinity, pH),
initial particle and NOM levels, and metal hydroxide characteristics. Predicting their
performance in specific water is challenging due to this complexity.

Studying coagulation through jar tests helps understand mechanisms, allowing tailored
process design. Electrophoretic mobility (EM) measures particle charge, indicating
suspension stability. Changes in EM signify alterations in particle aggregation within
suspensions. Understanding these dynamics aids in optimizing coagulation for specific
water and coagulant types.

Estimating the Required Coagulant Product Acidity Using Coagulation Diagrams.

Coagulant products' effective acidity, combined with coagulation diagrams, helps select
the right coagulant and dosage. Coagulation diagrams map metal concentration and pH
to illustrate coagulant performance based on metal hydroxide stability.

For practical use, data for the diagram should match the solution's chemistry,
temperature, particle/NOM type and concentration, and coagulant type (Al or Fe).
Consistency in floc separation methods (sedimentation, filtration, etc.) is also crucial for
accurate representation.

6.4.9. Polyelectrolyte Coagulants.

Polyelectrolyte coagulants in water treatment are high-molecular-weight synthetic
polymers that readily adhere to particle surfaces, composed of variable monomer units
and exhibiting diverse chain structures like linear, branched, or cross-linked
configurations.

Types of Polyelectrolytes.

Polymers in water treatment contain monomer units that can be positively or negatively
charged, depending on ionization reactions influenced by pH and ionic strength, leading
to anionic, cationic, nonionic, or ampholyte classifications.

Impurities in Polyelectrolyte Products.

Polyelectrolyte water treatment formulations can contain manufacturing contaminants,

prompting health concerns, leading some countries to ban their use in drinking water,
while others impose strict limits, with regulatory bodies maintaining lists of accepted
products and dosages, although only a few compounds constitute these lists.

Types of Polyelectrolytes Used in Water Treatment.

Polyelectrolytes used in drinking water treatment are often classified as primary

coagulant polymers or flocculent (coagulant aid) polymers. Primary coagulant polymers,
usually cationic and low molecular weight, aid in coagulation by adsorbing and

PPW730 6 Chapter (6) Summary

neutralizing particle surface charges but excessive use can lead to restabilization,
hindering the process. While not as effective as metal salts for dilute inorganic
suspensions, primary coagulant polymers can produce high-density aggregates suitable
for direct filtration without intermediate sedimentation.

Cationic polyelectrolytes like polyDADMAC and epiDMA are commonly used and
maintain a positive charge regardless of solution chemistry, making them advantageous
for water treatment. Flocculent polymers, typically anionic or nonionic and with higher
molecular weight than primary coagulant polymers, bolster particle aggregates by
bridging or connecting particles, enhancing their size and strength after the flocculation
process.

6.4.10. Activated Silica

Activated silica, historically used with alum for improved flocculation and
sedimentation, is prepared by acidifying sodium silicate, forming charged silica sols or
gels influenced by factors like concentration, acid type, and temperature, serving as a
coagulant for several weeks despite instability, with dosage proportional to alum but
varying with water composition, offering an alternative to polyelectrolytes at a lower cost
but demanding more operator attention.

6.4.11. Combinations of Coagulants

In 1982, treatment plants commonly used cationic polymers with alum, providing
benefits like reduced sludge and improved filtration, while studies highlighted a trade-
off in alum and polymer amounts for turbidity removal.

Certain coagulant solutions combined aluminum salts with cationic polymers. Research
found that low-molecular-weight cationic polymers alone were less effective and might
exceed safety limits at high dosages. High-charge-density cationic polymers with alum
proved effective for NOM removal and reduced solids.

6.4.12. Ozone and Coagulation

Ozone, gaining popularity in North American water treatment, not only disinfects but
also destabilizes particles, enhancing filtration efficiency. While its exact mechanisms
aren't fully understood, it's believed to oxidize metal ions, modify humic materials, and
potentially remove natural organic substances from mineral surfaces.

PPW730 7 Chapter (6) Summary

6.5. THE FLOCCULATION PROCESS

6.5.1. Purpose of Flocculation

Flocculation helps particles bond for easier removal, typically by adding a coagulant to
destabilize the suspension.

6.5.2. Transport Mechanisms

Flocculation relies on particle collisions caused by Brownian motion, flow gradients,
differing settling speeds, and diffusion. Equations describing flocculation rates consider
collision rates between particles, accounting for factors like double-layer repulsion and
hydrodynamic effects. These equations correct for short-range forces affecting particle
motion, including attraction and repulsion, determining collision efficiency

Brownian Diffusion.

Particles suspended in fluid move erratically due to thermal energy (Brownian diffusion),
impacting flocculation rates. This flocculation, affected by temperature, hydrodynamic
forces, and repulsion, occurs more notably near larger floc particles despite being less
influential in well-mixed systems.

Transport in Laminar Shear

Particles in a fluid with varying speeds due to different fluid velocities can collide in a
laminar flow, known as orthokinetic flocculation. The rate constant, ko, relies on the
fluid's velocity gradient, while the correction factor, αo, considers hydrodynamic
retardation’s impact on collision rates, especially when double-layer repulsion is
minimal, more affecting larger particles and higher shear rates.

Differential Settling.

Differential settling flocculation arises when particles of varying settling rates align
vertically due to gravity. The rate constant, kd, considers particle sizes, gravity, and
viscosity, most effective with notably different sizes in larger, denser particles.

Turbulent Transport.

In turbulent flows, varying eddy sizes cause particle motion, impacting flocculation.
Particle collision rates in turbulence relate to energy dissipation and sizes, dictating their
interaction based on models associated with the Kolmogoroff microscale.

G Value Concept.

Camp and Stein developed an equation in the 1940s, adapting Smoluchowski's equation
for turbulent flow using a root-mean-square velocity gradient. This equation, based on
the power input and fluid volume, approximates flocculation rates in turbulent

PPW730 8 Chapter (6) Summary

conditions. However, its accuracy and universal application have been questioned due to
variations in energy distribution, local dissipation rates, and the impact of particle size
on flocculation kinetics in turbulent settings, presenting challenges in its practical
application.

6.5.3. Flocculation Kinetics in Batch and Plug Flow Reactors

The equation below outlines how particle concentration changes during flocculation in
batch reactors. It overlooks aggregate breakup and needs complex values for accurate
use. Simplified models are preferred for continuous-flow flocculators to predict
performance based on particle transport and size distributions.

6.5.4. Ideal Continuous-Flow Flocculation Reactors

Argaman and Kaufman (1970) proposed a model for continuous-flow flocculation
reactors, assuming each compartment holds a mix of primary particles and larger flocs.
They derived equations based on this idea and assumed a steady state. The model
examines how mixing intensity, residence time, and influent particle concentration affect
performance. In practice, systems treating water with higher particle concentrations tend
to perform better due to increased floc volume concentration. The model's simplifications
impact accuracy, but it helps understand factors influencing continuous-flow flocculation
reactors.

Floc Disaggregation

In continuous-flow flocculators, high mixing intensity (G > 100 s−1) and prolonged
mixing can lead to significant floc disaggregation. This phenomenon, observed in batch
reactors, can stabilize floc sizes over time. Disaggregation mechanisms, such as surface
erosion and floc fracture, were investigated by Argaman and Kaufman (1970), who
proposed an equation that considers both particle aggregation and floc erosion. This

PPW730 9 Chapter (6) Summary

model demonstrates the impact of floc disaggregation on flocculator performance,
suggesting an optimal mixing intensity, contrary to models ignoring disaggregation.
However, this equation is suitable only for completely mixed reactors with a constant
floc size distribution, not for plug flow reactors where floc size distribution varies.

Floc Size and Density

In turbulent conditions, floc size distribution hinges on turbulence intensity (G) and floc
structure. Studies propose that as G increases, characteristic floc size (df) decreases
following a relationship where df = P * G^(-b). This suggests an inverse relation between
floc size and turbulence strength, observed experimentally with b around 1.0, indicating
smaller floc sizes as turbulence intensifies. Additionally, floc density tends to decrease
as floc size increases, captured by Vold's equation: ρf - ρw = B * df^(-0.7).

This inverse correlation aligns with experimental findings, implying that higher
turbulence intensity leads to smaller floc sizes and higher buoyant densities. Increased
buoyant densities due to smaller floc sizes may adversely affect flocculator performance,
leaving more primary particles in the effluent, counteracting the positive impact of higher
turbulence.

Fractal geometry, used to describe aggregate structures, links density and size via the
fractal dimension (F), suggesting irregularities in aggregate structures. Fractal
dimensions typically range from 1.6 to 2, indicating varying levels of irregularity in
aggregates.

Floc Density—Significance of Enmeshment by Hydroxide Precipitates

Metal hydroxide precipitates, like alum, significantly alter floc characteristics and
flocculator performance. Their presence affects floc volume concentration (Φ),
influenced by an empirical relationship involving alum dosage (Q) and primary particle
mass concentration. Reducing coagulant amounts boosts floc density but lowers floc
volume concentration, impacting flocculator performance.

Yet, when coagulant levels drop below a certain threshold, particle aggregation
diminishes. This impact is noticeable at lower influent particle concentrations (Co = S =
5 mg/L), where flocs formed with or without aluminum hydroxide precipitate greatly
differ in their efficiency in trapping particles. At higher influent particle concentrations
(e.g., Co = 100 mg/L), the precipitate's influence on floc volume concentration becomes
less critical, resulting in similar particle removal efficiency regardless of its presence.

6.5.5. Rapid Mixing

Rapid mixing jump-starts flocculation by dispersing coagulants and initiating particle
aggregation. It ensures even coagulant distribution among particles, vital for forming
larger flocs. For polyelectrolyte coagulants, it prevents uneven adsorption that could slow
aggregation.

PPW730 10 Chapter (6) Summary

This step destabilizes particles, prompts quick aggregation, and leads to a steady state of
smaller aggregates after mixing. Yet, extended high-intensity mixing might hinder
subsequent processes by altering particle surfaces, making reforming aggregates more
challenging.

6.5.6. Effect of Temperature on Coagulation and Flocculation

Temperature's a big deal in coagulation and flocculation. When it drops, floc formation
and particle removal slow down, especially in diluted suspensions. It messes with how
metal hydroxide precipitates form and dissolve, affecting the process efficiency. Some
studies argue over whether it's mostly chemistry or physics driving these effects at
different temperatures.

6.5.7. Electrokinetic Measurements

Electrokinetic measurements track how coagulants and solution changes impact particle
surfaces in water treatment, guiding coagulant dosing for optimal performance.

Electrophoretic Mobility Measurements.

EM and zeta-potential measurements are tools to control coagulation in engineering.

They use an electric field to understand particle surface charges or potentials.
Microelectrophoresis is a key method where particles in a tube move under an electric
field to measure EM, although corrections for other influences might be needed. Despite
their potential, inconsistent results and complexities limit their widespread use in
treatment plant operations.

Streaming Current Measurements.

Streaming current detectors (SCDs), pioneered by Gerdes in 1965, gauge the net charge
on treated particle surfaces in water treatment. A typical SCD contains a chamber where
a piston-driven flow detects charged particles adhering to its walls. This movement of
fluid past stationary particles generates a current, amplified for analysis, reflecting
particle charge.

PPW730 11 Chapter (6) Summary