3.

Coagulación-Floculación
Dr. Miguel Ángel López Zavala
CD-403-G, Ext. 5561, Subext. 106,
miganloza@itesm.mx
 Contenido

1. Partículas coloidales y mecanismos de

coagulación
o Origen de su carga eléctrica
o Capacidad de intercambio catiónico
o Teoría de la doble capa
2. Fuerzas básicas y mecanismos de
coagulación
3. Coagulantes
4. El papel del pH y la alcalinidad
5. Floculación
6. Prueba de jarras
Role of coagulation and floccculation
processes in water treatment
Role of coagulation and floccculation
processes in water treatment
Role of coagulation and floccculation
processes in water treatment
Role of coagulation and floccculation
processes in water treatment
 Role of coagulation and floccculation
processes in water treatment

Coagulation process

Destabilization of small suspended and

colloidal particulate matter

Adsorption and/or reaction of portions

of the colloidal and dissolved NOM to
particles, and

Creation of flocculant particles that

will sweep through the water to be
treated, enmeshing small suspended,
colloidal, and dissolved material as
they settle
 Role of coagulation and floccculation
processes in water treatment

Flocculation process

To produce particles, by means of

aggregation, that can be removed by
subsequent particle separation procedures:
sedimentation and/or filtration

Microflocculation (perikinetic): particle

aggregation by the random thermal motion
of fluid molecules (Brownian motion)

Macroflocculation (orthokinetic): particle

aggregation by inducing velocity gradients
and mixing in the fluid containing the
particles
 Practical design issues

Type and concentration of coagulants

and flocculation aids

Mixing intensity and the method used

to disperse chemicals into the water
for destabilization

Mixing intensity and time for

flocculation

Selection of the liquid-solid separation

process
 Properties and stability of particles in
water: Physicochemical properties

Particle size:
Suspended particles: > 0.4 mm
Colloidal particles: 0.001 mm – 0.4 mm
Soluble constituents: < 0.001 mm
Particle number and distribution
Raw surface water: 100 - > 10,000
particles/mL
Particle number frequency distribution:
dN
F (d p ) 
d (d p )
F(dp) = function defining frequency distribution of particles d1, d2, d3
dN = particle number concentration with respect to incremental change
in particle diameter d(dp)
d(dp) = incremental change in particle diameter
 Properties and stability of particles in
water: Physicochemical properties

In natural waters:
Number of particles increases with
decreasing particle diameter
Frequency distribution typically follows a
power law distribution:
dN N
 A(d p )  b 
d (d p ) (d p )
A = power law density coefficient
dp = particle diameter, mm
b = incremental change in particle diameter

 N 
log    log A  b log(d p )
 (d p ) 
 Properties and stability of particles in
water: Physicochemical properties

If b < 1, particle size distribution

dominated by large particles

If b = 1, all particle sizes are represented

equally

If b > 1, particle size distribution

dominated by small particles
 Properties and stability of particles in
water: Physicochemical properties
Particle shape:
Varies depending on the characteristics of the
source water
Shape of particles affects the electrical properties,
the particle-particle interactions, and particle-
solvent interactions
Particle-solvent interactions
Hydrophobic (water repelling):
Well defined interface between the water and solid
phases
Low affinity for water molecules
Thermodynamically unstable and aggregate
irreversibly over time
Hydrophilic (water attracting):
Clays, metal oxides, proteins, humic acids, virus,
bacteria, protozoa, algae
Have polar or ionized surface functional groups
Micelles (organized aggregates, association of
colloids)
 Properties and stability of particles in
water: Electrical properties

Origin of particle surface charge:

Isomorphous replacement (crystal

imperfections): metal oxide minerals (silicon
replaced by aluminum), negative charge

Structural imperfections: clay, negative

charge

Preferential adsorption of specific ions: NOM

contains carboxylic groups, negative charge

Ionization of inorganic groups on particulate

surfaces: mineral surfaces contain hydroxyl
groups and their charge depends on pH
 Properties and stability of particles in
water: Electrical properties

Variation in particle charge with pH

 Properties and stability of particles in
water: Electrical properties

Electrical double layer:

 Properties and stability of particles in
water: Electrical properties

Double layer thickness:

1/2
1  (2)(1000)e N A I 
2
κ  10  10

 εε 0 kT 
k-1 = doble -layer thickness, A
1010 = length conversion, A/m
1000 = volume conversion, L/m3
e = electron charge, 1.60219 x 10-19 C
NA = Avogadro’s number, 6.02205 x 1023/mole
1
I = ionic strength,
2
 Z 2 , mole/L
M
Z = magnitude of positive or negative charge ion
M = molar concentration of cationic or anionic species, mole/L
k = Boltzmann constant, 1.38066 x 10-23 J/K
T = absolute temperature, K (273 + oC)
 Properties and stability of particles in
water: Electrical properties

Measurement of surface charge:

highly dispersed particle systems having a

solid dispersed phase and liquid dispersion
medium

Electrophoresis: Zeta potential

Electroosmosis

Sedimentation potential

Streaming potential
 Properties and stability of particles in
water: Electrical properties

Zeta potential (electrical potential):

 Properties and stability of particles in
water: Electrical properties
Zeta potential:
Function: size and shape of the particle, number of
charges on the particles, strength of the electric
field, and nature of the ions in the diffused layer
v0 k z m
Z
ee 0
Z = zeta potential, mV
v0 = electrophoretic mobility, mm/s, V/cm
= vE/E, in natural waters (-2 to +2)
vE = electrophoretic velocity of migrating particle, mm/s,
nm/s, mm/s
E = electrical field at particle, V/cm
kz = constant that is 4p or 6p (when particle is much
smaller than thickness of double layer)
m = dynamic viscosity of water, N.s/m2
e = Permitivity relative to a vacuum (e for water is 78.54)
e0 = permitivity in a vacuum, 8.854188x10-12 C2/J.m, N/V2
When Z < 20 mV, rapid flocculation occurs
 Properties and stability of particles in
water: particle stability

Depends on:

Repulsive electrostatic force: principal mechanism

controlling the stability of hydrophobic and
hydrophilic particulates

Attractive force: Van der Waals Forces

Particle-particle interactions: aggregation by means

of Brownian motion
 Coagulation theory: mechanisms of
coagulation
Compression of the electrical double layer
Adsorption and charge neutralization
Hydrolyzed metal salts
Prehydrolyzed metal salts
Cationic organic polymers
Adsorption and interparticle bridging
Nonionic polymers and high-molecular-weigh (105 a
107)
Low-surface-charge polymers
Cationic polymers with high charge density
Enmeshment in a precipitate, or “sweep floc”
It is not influenced by type of particle present
Hydrolysis and polymerization of metal ions
Adsorption of hydrolysis products at the interface
Charge neutralization
Coagulation theory: common inorganic
coagulants
Coagulation theory: synthetic organic
polymers
Flocculation theory: mechanisms of
flocculation
 Flocculation theory: mechanisms of
flocculation
Microflocculation
Flocculation of small particles (< 0.1 mm) by
Brownian motion
Macroflocculation
Major mechanism for floculation of particles > 1
mm
Mixing causes velocity gradients and greater
number of collisions between particles
Gentle mixing
Flocculation kinetics
Tambo and Watanabe, Japan (1979)
Odegaard, Norway (1985)
 Flocculation theory: Flocculation
performance factors
Tambo and Watanabe: dimensionless flocculation
kinetics
Flocculation time required for formation of
settleable flocs is very short, compared with that
required for reaching the ultimate floc size
distribution
Decreasing rate of concentration of microflocs is
not significantly reduced if the larger flocs
disappear in the flocculator
Odegaard
Intensity of mixing
Residence time and residence time distribution
Floc volume
Flocculation theory: Aggregate shapes
formed by flocculation
 Treatability tests: Jar-tests

Objective:
To simulate, to the extent possible, the
expected or desired conditions in the
coagulation-flocculation facilities
How to conduct:
First, a rapid-mix phase (high mixing intensity)
with addition of coagulant (Coagulation)
Then, slow-mix period to simulate flocculation
(Flocculation)
Finally time for settling (Settling)
Jar-tests: Experimental device
 G values for coagulation and
flocculation

Coagulation: Rapid mixing

Contact time: 20 s G = 1000 s-1
Contact time: 30 s G = 900 s-1
Contact time: 40 s G = 790 s-1
Contact time: > 40 s G = 700 s-1

Flocculation: Slow mixing

G = 20 – 50 s-1 paddles, 10 – 80 s-1 turbines
Contact time: 20 - 30 min
 Treatability tests: Jar-tests

Parameters to measure:
Turbidity, suspended solids removal
Dissolved solids, DQO
DOC or UV absorbance at 254 (260) nm
Metals concentration
Residual dissolved coagulant
concentration
Sludge volume that is produced
Treatability tests: Jar-tests
Treatability tests: Jar-tests
Treatability tests: Jar-tests
Treatability tests: Jar-tests
Treatability tests: Jar-tests
Treatability tests: Jar-tests
Treatability tests: Jar-tests
 Coagulation-flocculation-Mixing

Mixing is a central part of coagulation-flocculation process

Chemical reactors in water treatment and biological
aeration basins in wastewater processing are designed as
either completely mixed or plug-flow basins
Applications of complete mixing in water treatment are:
Rapid (flash or quick) mix tanks used to blend
chemicals into raw water for coagulation
Mixing and reaction zone in flocculator-clarifiers
High–rate activated sludge and extended aeration
basins
Flocculation basins in chemical water processing are
designed as plug-flow units
Coagulation mixing
Coagulation mixing
 Flocculation-Mixing

Common types flocculation

mixing systems:
1.Vertical-shaft turbine system

2.Horizontal paddle wheel system

3.Hydraulic mixing systems

 Flocculation-Mixing

For complete mixing and steady-state conditions,

the first-order reaction kinetics is given by Eq. 1

V 1  Co 
t    1 (1)
Q k  Ct 

where t = detention time

V = volume of basin
Q = flow rate
k = rate constant for first order kinetics
Co = influent reactant concentration
Ct = effluent reactant concentration
 Flocculation-Mixing
For an ideal plug-flow system and steady-state
conditions, the relationship between detention
time and concentration, applying first-order
reaction kinetics, is given in Eq. 2

V L 1  Co  (2)
t    ln 
Q v k  Ct 

where t, V, Q, Co, Ct are same as Eq. 1

L = length of rectangular basin
n = horizontal flow velocity
Q = flow rate
k = rate constant for first-order kinetics
 Mixing theory and practice

Camp and Stein equation (1943)

P Nd 2 P  KrN 3 d 5
G NR   1x105 (3)
mV n
G = Velocity gradient, s-1
P = Power of mixing input to vessel, W, J/s
V = Volume of mixing vessel, m3
K = Constant, propeller 2 or 3 wings: 1
r = Water density, kg/m3
d = Propeller diameter, m
N = Propeller velocity, rps
Coagulation: Rapid mixing
Contact time: 20 s G = 1000 s-1
Contact time: 30 s G = 900 s-1
Contact time: 40 s G = 790 s-1
Contact time: > 40 s G = 700 s-1
Flocculation: Slow mixing
G = 20 – 50 s-1 paddles, 10 – 80 s-1 turbines
Design of mixing systems: vertical
turbine mixers
 Design of flocculation mixing systems:
vertical turbine mixers
Design considerations:
Displacement capacity: rate at which impeller pumps water
Power consumption
Pumping head

Camp and Stein equation (1943)

P Nd 2
G , Re   1x105 Turbulent regimen
mV 
P  KrN 3d 5 (4)

G = Velocity gradient, s-1

P = Power of mixing input to vessel, W, J/s
V = Volume of mixing vessel, m3
K = Constant, impeller 2 or 3 wings: 1
r = Water density, kg/m3
d = Propeller diameter, m
N = Propeller velocity, rps
 Design of mixing systems: vertical
turbine mixers
Three parameters important for design of mixing
devices:
Power number
P
Np 
rN 3d 5 (5)
Pumping number
Q
NQ 
Nd 3 (6)
Head number
Hg
NH 
(Nd ) 2 (7)
where Np = power number, dimensionless
NQ = pumping number, dimensionless
NH = head number, dimensionless
Q = flow rate imparted by impeller, m3/s
H = head impeller imparts to impeller flow, m
G = acceleration due to gravity, 9.81 m/s2
Design of mixing systems: vertical
turbine mixers
Design of mixing systems: vertical
turbine mixers
 Design of mixing systems: vertical
turbine mixers

Example
Design of mixing systems: vertical
turbine mixers
Design of mixing systems: horizontal
paddle wheel
 Design of mixing systems: horizontal
paddle wheel
Application:
High degree of solids removal by sedimentation is required
Disadvantage: requires more maintenance and expense, mainly
because bearings and packing are submerged

The power input to the water by horizontal paddles may

be estimated by the expression:

C D AP rvr3 (8)
P
2
where CD = drag coefficient on paddle (for turbulent flow), unitless
AP = projected area of paddle, m2
r = density, kg/m3
vr = velocity of paddle relative to fluid, m/s. 70 to 80 percent of the
paddle speed without tank baffles. With tank baffles 100 percent of
the paddle speed is approached
2
Nd pw (9)
Re 

where dpw = diameter of paddle wheel
 Design of mixing systems: horizontal
paddle wheel

Example
 Design of mixing systems: horizontal
paddle wheel

Example
 Design of mixing systems: hydraulic
mixer
Three groups of hydraulic
flocculators:

Baffled channels: most

common of hydraulic
flocculators

Hydraulic –jet
flocculators

Coarse-media
flocculators
Design of mixing systems: hydraulic
mixer
 Design of mixing systems: Hydraulic
flocculators

Baffled channels:
Velocity gradient can be determined from the
following expression
rgH (10)
G
mt
where r = density of water, kg/m3
g = acceleration due to gravity, 9.81 m/s2
H = head losses through basin, m
 m = dynamic viscosity, N*s/m2 (kg/(m*s)
t = detention time, s
Lv 2
H  2 (11)
C Rh
where L = length of the channel, m
v = velocity of flow in channel, m/s
C = Chezy coefficient, unitless
Rh = hydraulic radius of channel, m
 Design of mixing systems: Hydraulic
flocculators
Head loss resulting from each 180o turn can be estimated
as follows:
v2 (12)
H  k
2g
where k = empirical constant (typically 2.5 to 4), unitless

Coarse-media flocculators:
Head loss through the porus media can be estimated by
the following equation:
H  m   (1  e 2  1   1  1  e  1  2
2

 a        3  v

v  b (13)
L  rg   e  d   g  e  d 
3

where a, b = empirical coeffcients

d = size of media particles (determined by sieve
analysis), m
e = bulk porosity through media bed, m3/m3
v = superficial velocity through media bed (flow
rate divided by media bed cross-sectional area), m/s

Design of mixing systems: hydraulic
mixer
Design of mixing systems: hydraulic
mixer
 Project: Coagulation-flocculation of
surface water and graywater

Three working teams

Six students each
Jar-tests:
Water Center Lab. or Chemical Engineering Lab.
Water source: surface water and graywater from
different detergents (powder and liquid)
Objective: Determine optimum coagulation-
flocculation conditions for removal of turbidity,
suspended solids, dissolved solids, TDOC, cations (Na,
NH, Ca, Mg, k) and anions (Cl, F, sulfates, phosphates,
nitrates and nitrites: pH, coagulant dosage, mixing
intensity, mixing duration, settling time
 Project: Coagulation-flocculation of
surface water and graywater

Design of mixing systems:

Objective: Based on jar tests conduct the
design of the following systems: vertical
turbine mixer, horizontal paddle wheel y
hydraulic mixer
Report: introduction, objectives, methodology,
results analysis, conclusions and
recommendations, references
Extension of report: 16 pages in English (scientific
paper style: water research)
Submission: Presentation day