Chapter 2 - Particle Stability, Destabilization and

Flocculation

I. Introduction

- Water and wastewater contain particulate contaminants

Question: what are particulate contaminants in your opinion?

- Water treatment process also generates particulate matters

(e.g., chemical precipitation, biological treatment)

- Removal of particulate matters is required for public health and

aesthetic reasons
Question: can you give some examples?

- Particle treatment categories:

Gravity separation (settling or flotation): based on the
differences in the density of particles and water
Granular media filtration: particles are captured in the
media by physicochemical processes
Membrane filtration: particles are removed by sieving
(the ones larger than the pores of the membrane will be
caught and removed from water)

1
 rectangular settling tanks require additional weir length to minimize headloss and avoid
short circuiting. Headloss and short circuiting can be minimized by adding a series o
inboard launders with double weirs that are aligned either longitudinally (parallel to th
length of the settling tank) or transversely (perpendicular to the length of the settling tank
[see Fig. 5–45(c)] or both longitudinally and transversely [see Fig. 5–50(a)].

(a) (b)

(c) (d)

(e) (f)

Figure 5–50
Typical sedimentation tank appurtenances used for sedimentation tanks: (a) internal longitudinal and
transverse weirs in rectangular sedimentation tanks, (b) peripheral V-notch effluent weirs launders in
peripheral feed circular basin, (c) and (d) covered peripheral weirs to limit algal growth, and (e) and
(f) covers for primary clarifiers to eliminate the release of odors.

Wastewater Engineering - Treatment and Resource Recovery, 5th edition, 2014

met01188_ch05_382-454.indd 390 18

2
 flotation system are (1) compact size, (2) lower capital cost, and (3) capacity to remove
relatively free oil and suspended solids. The disadvantages of induced-air flotation include
higher connected power requirements than the pressurized system, performance is depen-
dent on strict hydraulic control, and less flocculation flexibility. The quantities of float

Figure 5–57 Drive

Upper portion of rotor
Dispersed-air flotation unit. Air is
draws gas down standpipe
induced and dispersed into the for dispersion in liquid
liquid by pumping action of the
Gas intake
inductors. (Courtesy of Eimco.) Disperser breaks gas
Standpipe into minute bubbles
Disperser hood

Skimmer
paddles

Launder

Disperser

Rotor

Float Float
Lower portion of rotor
draws solids upward
through rotor

Wastewater Engineering - Treatment and Resource Recovery, 5th edition, 2014

met01188_ch05_382-454.indd 405 18/07/13 5:58 PM

3
 1150 Chapter 11 Separation Processes for Removal of Residual Constituents

Figure 11–9
Views of typical filtration
installations: (a) view of empty
conventional gravity filter without
underdrain system (see
Fig. 11–20), but with washwater
troughs in place; (b) typical
traveling bridge filter (empty) with
individual cells exposed; (c) deep-
bed denitrifying filter;
(d) continuous backwash upflow
filters (courtesy Austep, Italy);
(a) (b)
(e) Fuzzy filter installation
comprised of six filters; and
(f) bank of small pressure filters
used at small wastewater
treatment plants. Additional
information on these filters is
presented in Tables 11–9
and 11–10.

(c) (d)

(e) (f)

Wastewater Engineering - Treatment and Resource Recovery, 5th edition, 2014

chemical addition is required with all of the filters to achieve an effluent turbidity of
2 NTU or less; and (3) effluent quality is directly related to influent quality if chemical
addition is not used. Typical values of effluent quality for turbidity and total suspended
solids for depth filtration using granular media are presented in Table 11–12. For com-
parison, comparable data for other advanced filtration processes (e.g. membranes) used for
the removal of particulate matter are presented in Table 11–31 in Sec 11–7.
Keeping in mind the limitations associated with turbidity measurements, the follow-
ing two relationships can be used to approximate TSS values from measured turbidity
values.
Settled secondary effluent
TSS, mg/L 5 (2.0 to 2.4) 3 (turbidity, NTU) (11–26)

met01188_ch11_1117-1240.indd 1150 25/07/13 11:46 AM

4
 11–7 Membrane Filtration Processes 1187

Figure 11–32
Views of various membrane
installations: (a) pressurized
microfiltration and (b) pressurized
ultrafiltration membranes for the
filtration of settled secondary
effluent, (c) vacuum microfiltration
membrane modules in open
vessel, (d) membrane module
used in open vessel shown in (c),
(e) typical cartridge filter used (a) (b)
before reverse osmosis, and
(f) one bank of a large reverse
osmosis installation used to treat
activated sludge effluent
following microfiltration, chemical
addition, and cartridge filtration.
Each bank of RO modules is
designed to treat 19,000 m3/d
(5 Mgal/d). The capacity of the
entire facility is 265,000 m3/d
(70 Mgal/d).
(c) (d)

(e) (f)

Wastewater Engineering - Treatment and Resource Recovery, 5th edition, 2014

diameter, 0.9 to 5.5 m long, and a single module is placed in a pressurized vessel arranged
in racks or skids. Each module must be piped individually for feed and permeate water.
- Particle pretreatments
Typicalare oftenMF
pressurized needed
membrane modules are shown on Figs. 11–32(a) and (b). The
modules for NF and RO are 100 to 300 mm in diameter, 0.9 to 5.5 m long, and from two
Very small particles → settle
to eight modules are placedvery slow
in a single → could
pressurized vesselnot bein racks, either hori-
arranged
zontally or vertically [see Figs. 11–32 (d) and (f)]. Vertical placement helps reduce the
effectively removed
number of pipes and fittings and the total plant footprint.
In the pressurized configuration, pumps are used to pressurize the feed water and
circulate it through the membrane [see Figs. 11–33(a) and (c)]. Centrifugal pumps can
be used for MF, UF, and NF; positive displacement pumps or high-pressure turbine
Pretreatment:pumps
brings manyforsmall
are necessary particles
RO. Depending together
on the operating to and the characteristic
pressure
of the feed water, a variety of materials have been used including plastic and fiberglass
form larger flocs → plumbing
tubes and flocs will settleSteel
components. faster or tubes
pressure easier to be for some reverse
are required
osmosis applications, and stainless steel is required for seawater and brackish water hav-
removed (compared
ing high TDS.to individual particles)

Submerged (Vacuum) Type. In the submerged system, the membrane elements

are immersed in a feed water tank as shown on Fig. 11–32(c). The permeate is withdrawn
5
Flocculation: the process of bringing small particles
together to form larger particles (flocs, aggregates)

But the particles in the environments do not form flocs:

particles have surface charge → always repel each other
(stable particle)→ could not form flocs even when they
are brought close to each other through flocculation.

Destabilization (coagulation): adding chemical to

reduce particle stability → particles can to form flocs
when they are brought close to each other

Question: can you explain in your own words the role of

destabilization and flocculation?
Can you only do destabilization to remove particulate
matters?
Can you only do flocculation to remove particulate
matters?

6
 pretreatment process(es) might be needed to induce floc
formation. These pretreatment processes typically include
chemical
340 alterations
Chapter 5 Physical to
Unitthe solution and=or mixing processes
Processes

to bring about more particle–particle collisions. Thickenin

The process of bringing particles together with the inten-
Figure
tion of 5–17
creating larger particles is called flocculation Over and under baffles
and is
the
Typicalsubject
mixers usedof for Chapter 12. In this chapter, we focus on
flocculation in wastewater
characteristics
treatment facilities: (a)of
overparticles
and that affect their behavior in water
under baffled reactor, (b) paddle processes that are designed to Note: Spacing of over and under baffles
and on pretreatment alter
can be varied to alter the energy input
mixer in baffled tank, and
those characteristics
(c) turbine and thereby enhance the performance
mixer in a baffled tank.
to the water
(a)
of the subsequent particle treatment processes.
Particle removal processes are found in the process trains FIGURE 11-2. Schemati
of the vast majority of water and wastewater treatment treatment plant.
plants, as indicated in Table 11-1. Most modern drinking Paddle mixers are driven
water plants using surface water sources have flocculation, by variable speed drives. A
disadvantage of paddle flocculators
gravity separation, and granular media filtration processes; membrane
is that the supports and bearings filtration inste
for the paddles are submerged
increasingly, a membrane process is used inPaddles lieu of or in filtration. These plants al
(b)
addition to granular media filtration. A schematic diagram of cesses, including gravity t
the most common design of drinking water treatment plants ing processes. In industria
Motor Reduced speed
using surface water sources is shown in Figure 11-1.gear Flota-
drive water for specific uses an
tion is sometimes used in lieu of sedimentation as the gravity before discharge to a mu
separation process. When the raw water has a low particle one or more of these par
Turbine mixer
concentration, the gravity separation step (and sometimes plants vary widely depe
the flocculation process) can be eliminated. wastewater,
Note: Pumping action of impeller no typical sc
is important with turbine mixers
Particle removal processes are also ubiquitous in municipal The success of most pa
Baffle
wastewater treatment plants, (c) as suggested in the schematic the attachment of particl
Wastewater
diagram shown Engineering
in Figure - Treatment
11-2. Such andplants
Resourcealways Recovery,
include5th edition, particles 2014in the suspens
primary sedimentation and almost always have secondary engineered system. O’M
sedimentation
Example of particle (though some
removaluse ofhave flotation
processes
turbine or,because
flocculators increasingly, the concept that the remov
of the maintenance problems associated with pad
flocculators. be viewed as consisting
Power in a mechanical paddle system can be related steps: to the drag force on
long-range the pad
transpor
Rapid as follows.
mix Flocculation Sedimentation Filtration Disinfection other surface, and short-ra
CD Ary2p
collide with and attach to t
FD 5 dominated by forces tha (5–
2
while short-range transp
3
CD Aryp physical and chemical
P 5 FDyp 5 (5–
2 long and short range an
FIGURE 11-1. Schematicwhere of a Ftypical drinking water treatment
D 5 drag force, N
forces are often blurred, b
plant using a surface water source. CD 5 coefficient of drag of paddle moving perpendicular understanding to fluid particle pr
A 5 cross-sectional area of paddles, m2
Water Quality Engineering, Benjamin anddensity
r 5 mass Lawler of fluid, kg/m3
yp 5 relative velocity of paddles with respect to the fluid, m/s, usually assume
be 0.6 to 0.75 times the paddle-tip speed
P 5 power requirement, W (kg?m2/s3)
The application of Eq. (5–13) is illustrated in Example 5–3. 7
 Return to
headworks Water from thickening
and dewatering
(d)

Figure 1–2
Typical flow diagrams for the treatment of wastewater and biosolids: (a) conventional biological
treatment, (b) biological nutrient removal, (c) advance treatment following conventional or nutrient
removal treatment, and (d) anaerobic treatment of sludge from primary sedimentation and excess
biological sludge.
Tertiary
Preliminary Primary Conventional treatment Disin-
treatment treatment secondary treatment (optional) fection

Screening Equal-
Raw Return and commi- Grit RemovalPrimary
ization AerobicMatterSecondary
of Residual Particulate
waste- flows nution removal (optional) settling treatment settling Filtration
water
met01188_ch01_001-032.indd 16
Tertiary
effluent
Screenings and Return activated
Metcalf_CH08.qxd 12/12/06 08:12 PM Page 390
grit to landfill Primary sludge sludge Waste Secondary
(a) and scum effluent
activated Backwash
sludge to headworks

Tertiary
Wastewater Engineering -Secondary
Treatment and
treatment withResource Recovery, 5th edition,
treatment Disin- 2014
biological nutrient removal (optional) fection
390 Chapter 8 Removal of Residual Particulate Matter

Primary Anerobic Anoxic Aerobic Secondary

Figure
effluent 8-9 treatment Chemicals
treatment treatment clarification Filtration
[see (a)] process for particle
Typical coagulation
flow diagrams used Tertiary
for the removal of effluent
Settled Depth or
Reclaimed
suspended particu- secondary surface recycle Disinfection
Internal water
late matter from effluent filtration Secondary
secondary efflu- Return activated effluent
(a) Backwash
(b) sludge
ents: (a) depth and Waste to headworks
activated
surface filtration, sludge
(b) membrane Settled
Fine
filtration, and secondary Advanced treatment Membrane Disinfection
Reclaimed
Water
screen
and purification filtration water
effluent conditioning
(c) dissolved air
filtration.
Reverse Reverse Advanced
Membrane Cartridge osmosis oxidation and Decar- Lime
Anti- osmosis/
(multi-stage) Hydrogen disinfection bonation contactor
Tertiary effluent filtration scalant filtration advanced
peroxide Lime
[see (a) and (b)] oxidation
(b)
Chemicals Purified
for particle water
Reject to coagulationConcentrate to
headworks Settled evaporation or Depth or
(c) Dissolved
dispersal Reclaimed
secondary surface Disinfection
or pond air flotation water
filtration
effluent
(c) Anaerobic
Primary digestion
Waste sludge and (biogas to engine-
activated applications,
Thickening scumused principally
DAF has been generatorfor treating pond effluents
set) containing algae
Dewatering
sludge Polymer [see (a)] Polymer
and for low-density particles that are difficult to remove by gravity sedimentation, as a
[see (a) and (b)]
Wastewater pretreatment
Reuse - Issues, stepTechnologies,
for depth or surfaceand
filtration.
Applications, 2007
Biosolids to
Process Flow ReturnTypical
flow end use
process flow diagrams that can be used for the removal of residual suspended
treatment
Diagrams particulate matter from secondary effluents are shown on Fig. 8-9 for depth and surface
(optional)
Return to filtration, membrane filtration, and dissolved air flotation. With depth and surface fil-
headworks tration, chemical addition is used commonly, often in combination with flocculation 8
Water from thickening
and sedimentation, as shown on Fig. 8-9a. For membrane filtration, a fine screen will
and dewatering
(d) often precede a membrane filter to mitigate the effects of solids that tend to clog the
membrane. Dissolved air flotation is used often with chemical coagulation to help form
520 PARTICLE TREATMENT PROCESSES: COMMON ELEMENTS

TABLE 11-1. Applications of Particle Processes

Gravity Granular Media Membrane
Application Destabilization Flocculation Separations Filtration Filtration
Drinking water (with surface Always Almost Almost Always one filtration process
water supply) always always or the other
Municipal wastewater Sometimes Rarely Always Often Occasional
Industrial wastewater Common Common Almost always Rare Rare
Industrial ultrapure process water Rare Rare Rare Common Almost always

Water Quality Engineering, Benjamin and Lawler

sedimentation tank. Bringing many small particles together Preliminary Primary Biological Secondary
to form a larger, more rapidly settling floc allows them to be treatment sedimentation treatment sedimentation
removed more easily. However, the fact that the particles To
are not present as flocs in the influent suggests that some tertiary

II. Particle Stability (used together with EN2005

treatment
pretreatment process(es) might be needed to induce floc
formation. These pretreatment processes typically include
material)
chemical alterations to the solution and=or mixing processes
to bring about more particle–particle collisions.
Thickening Digestion Dewatering
The process of bringing particles together with the inten-
tion of creating larger particles is called flocculation and is
- Stable particles: do not attach to each other (particle size
the subject of Chapter 12. In this chapter, we focus on
characteristics of particles that affect their behavior in water

distribution does not change for a long time)

and on pretreatment processes that are designed to alter
those characteristics and thereby enhance the performance
Water recycle
to head of plant
of the subsequent particle treatment processes.
Question: what happens if the particles
FIGURE 11-2.are notofstable?
Particle removal processes are found in the process trains
Schematic a typical municipal wastewater
of the vast majority of water and wastewater treatment treatment plant.
plants, as indicated in Table 11-1. Most modern drinking
water plants using surface water sources have flocculation,

- Reasons for particles being stable

gravity separation, and granular media filtration processes; membrane filtration instead); some also have granular media
in water:
filtration. These plantssurface
increasingly, a membrane process is used in lieu of or in charge
also have sludge concentrating pro-
addition to granular media filtration. A schematic diagram of cesses, including gravity thickening and mechanical dewater-
Particles with the same sign of surface charge
the most common design of drinking water treatment plants
using surface water sources is shown in Figure 11-1. Flota-
ing processes. In industrial settings, the production of process
water for specific uses and the pretreatment of wastewaters

experience repulsive interaction → no particle collision

tion is sometimes used in lieu of sedimentation as the gravity before discharge to a municipal sewer system often require
separation process. When the raw water has a low particle one or more of these particle removal processes since such
concentration, the gravity separation step (and sometimes plants vary widely depending on the contaminants in the
no particle attachment
the flocculation process) can be eliminated. wastewater, no typical schematic can be shown.
Particle removal processes are also ubiquitous in municipal The success of most particle removal processes depends on
wastewater treatment plants, as suggested in the schematic the attachment of particles to other surfaces—either other
diagram shown in Figure 11-2. Such plants always include particles in the suspension or a surface provided in the
engineered system. O’Melia and Stumm (1967) introduced
- Origins of particle surface charge
primary sedimentation and almost always have secondary
sedimentation (though some have flotation or, increasingly, the concept that the removal of a particle in such processes can
be viewed as consisting of two (more or less) independent
Rapid
mix
Dissociation
Flocculation
Sedimentation
of surface charge functional groups
Filtration Disinfection
steps: long-range transport of the particle to the vicinity of that
other surface, and short-range transport to allow the particle to
collide with and attach to that surface. Long-range transport is
Isomorphic substitution dominated by forces that are primarily physical in nature,
while short-range transport and attachment rely on both
Adsorption on the particle surface (the attachment of physical and chemical forces. The distinctions between
long and short range and between physical and chemical

ions or natural organic molecules, NOMs, on the surface

FIGURE 11-1. Schematic of a typical drinking water treatment
plant using a surface water source.
forces are often blurred, but the concept is still a useful one in
understanding particle processes. Details of the long-range

of particles)

9
 Question: in your opinion, what can affect the surface
charge of particulate matters?

- Electrical double layer

Fixed layer (Stern/rigid layer) + Diffuse layer

Described in term of charge density (σ) and potential (ψ)

๏ For particles in symmetrical electrolytes (cation and
anion have the same absolute charge) and have small
zeψ
potentials ( <1, kB: Boltzmann’s constant =
kBT

1.3807 × 10−23 J/K, T: absolute temperature (K), e:

elementary charge = 1.6022 × 10−19 C)

σ0 = ϵκ ψ0 (2.17 - Elimelech)

σ0: charge density of the particle surface

ϵ: permittivity in water at 25 oC
ϵ = 78.5 × 8.854 × 10−12C 2 /(Jm)
ψ0: potential of the particle surface
κ: Debye-Hückel parameter (unit m-1), at 25 oC
κ = 2.32 × 109( ci zi2)1/2 (2.14 - Elimelech)
∑
ci: molar ion concentration of species i (mol/L)

10
 zi: charge number for ion species i

๏ When the particle surface potential is smaller than

25.7 mV
ψ (x) = ψ0exp(−κx) (11.3 - Lawler)

ψ (x): potential at the distance x from the surface

1
At x = κ , ψ (x) = ψ0 → κ −1 can be understood
−1
e
as the distance required to reduce the potential to
1/e of its value at the surface = Debye length or
"double layer thickness"
Question: in your opinion, what is the importance of
equation 11.3?

An Introduction to Interfaces and Colloids, Berg

11
- Interaction of charged particles
Question: what are the roles of interaction of charged particles
in natural environment and in engineered systems?

Electrostatic repulsion: particles with the same sign of

surface charge come closer one another →
electrostatic repulsion increases

VR = potential energy associated with the interaction of

electrical double layers of two particles

For 2 identical spheres in symmetric electrolytes (NaCl

for example)
2
nbkBT ap zeψ0
VR,ss = 64π 2 [tanh( )]exp(−κs)
κ s + 2ap 4kBT

(11.8 - Lawler)
nb: number concentration of counter ions in the bulk
solution (no./m3)
kB: Boltzmann’s constant = 1.3807 × 10−23 J/K
T: absolute temperature (K)
ap: particle radius

12
 ψ0: potential of the particle surface ~ measured zeta
potential
s: separation distance between particle surfaces
e: elementary charge = 1.6022 × 10−19 C

VR depends on both surface potential (ψ0) and solution

condition (κ)

Question: can you list the parameters you would need to

calculate the VR interaction energy between identical
spherical particles?

Question: can you imagine what information you would get

from a VR value?

13
large enough that either c1 or c2 is negligible at each point with increasing z value. He
between them, so in this case, VR would be 0. ionic strength, but one mad
the other with polyvalent
tion of particles is smaller
solution. These effects are
s+2ap ering the energy associated
interactions.

Van der Waals Attractio

ap
The electron cloud arou
motion, deviating slightly
first in one direction, then
disturbances and attemptin
s
lowest energy state alway
of the electrons causes the
Ψ distribution, so the molecu
slightly unstable state to an
symmetric, “nonpolar” mo
Ψ1 Ψ2
always slightly asymmetr
actually slightly polar at a
0 on a time-averaged basis.
When two such mole
closely, the electrons in
FIGURE 11-6. Schematic of the interaction of charged particles affect the motion of the
surrounded by diffuse layers. (Particles, including adsorbed layers
within the d plane, have a radius ap and are shown as solid circles;
the surrounding diffuse layers have the characteristic thickness k#1, 4
Recall that nb ¼ cb N A ð1000L=
indicated by the dotted circles; and the separation distance between that kB ¼ R=N A , where R i
particle surfaces is s.) nb kB ¼ cb Rð1000L=m3 Þ.

Water Quality Engineering, Benjamin and Lawler

Van der Waals attraction: when the particles are at very

short distance, they experience Van der Waals attraction
interaction (VA). For two identical spheres
AH 2 2 s̄2 − 4
VA,ss = − ( + 2 + ln 2 ) (11.9 - Lawler)
6 s̄ − 4 s̄ s̄

14
 s + 2ap
s̄ = = dimensionless separation distance
ap

between particle center

AH: Hamaker constant (J)

Question: Can you tell the main differences between VR

and VA?

Total interaction energy: = sum of electrostatic

repulsive and Van der Waals attractive interactions
(DLVO theory)

528
VTot,ss = VR,ss + VA,ss
PARTICLE TREATMENT PROCESSES: COMMON ELEMENTS
(11.11 - Lawler)
1×10–19
Repulsion

–4

–19
5×10–20
Energy of interaction (J)

Energy
barrier
0
Attraction

–5×10–20

–1×10–19
0 20 40 60 80 100 120 140
Separation distance (nm)

FIGURE 11-7. Energy of interaction as one particle approaches another. (Born repulsion, acting at
extremely close distances, is not shown.)

Water Quality Engineering, Benjamin and Lawler

particles are drawn together. Hence, getting over the energy location. Therefore, it is unlikely that two particles15
would be
barrier is the criterion for the particles to come together. In held together at this separation distance. Other conditions
the example shown in the figure, the maximum negative can lead to a much deeper secondary minimum, which
slope occurs at a separation distance of !24 nm, and calcu- would hold particles together more strongly.
 In order for 2 particles come into attachment, their
kinetic energy must he higher than energy barrier

Question: what is your opinion about the presence of energy

barrier? Is it good or bad for treating particles?

Question: Can you list some methods to reduce the energy

barrier?

III. Particle Destabilization (used together with EN2005

material)

- Stable particles are undesired for particle removal processes

→ we need to destabilize particles

- Chemicals changing the characteristics of solutions, surface

charge, or the interaction between particles can be used for
particle destabilization (destabilizing chemicals, coagulants)
In organic species: Al2(SO4)3.xH2O (x = 14 - 18),
Fe2(SO4)3, FeCl3
Organic polymer (can also improve floc strength):
positively charged low-molecular weight molecules

16
 Question: can you give an example of coagulant agents
used at your home to make river water clean?

- Four mechanisms of particle destabilization

Compression of diffuse layer
๏ Critical coagulation concentration = minimum salt
concentration leading to a net interaction energy of
dVTot
zero (VTot= 0) at the energy barrier ( = 0)
ds
๏ Shulze-Hardy rule: CCC depend on 1/z 6

17
536 PARTICLE TREATMENT PROCESSES: COMMON ELEMENTS

(a) Adsorption and Charge N

Repulsion
1.5×10–19

Particle radius 0.1 µm A second mechanism of des

Energy of interaction (J)

1×10–19 of the charge on the particle

opposite charge. If just the r
c
5×10–20
charge on the particles be
surrounding diffuse layer,
existent, and the problems
0 eliminated.
Attraction

Adsorption of a charg
–5×10–20
because of specific chem
destabilizing chemical and
(b) 1.5×10–19
Repulsion

because the molecule is hy

c to a particle surface rather
Energy of interaction (J)

1×10–19 such adsorption occurs a

charge opposite to that of
the particle surface is reduc
5×10–20
is being titrated by the
chemical. In the top porti
0 is illustrated. The charge
Attraction

(positive in the illustration,

charge) changes the net sur
–5×10–20
chemical, the surface cha
magnitude is reduced; at s
charge has been neutralized
FIGURE 11-15. Effects of electrolyte concentration (a) and The driving force for thi
valence (b) on energy of interaction as particles approach one
electrostatic, so further add
another.
ical beyond the dose nee
Water Quality Engineering, Benjamin and Lawler results in charge reversal,

have a high ionic strength (i.e., high salt content). However,

it can beAttachment on particle
used in a situation in whichsurface (adsorption)
the blending of two and charge
Positive

waste streams, one with high ionic strength and another with
neutralization
high particle content but low ionic strength, could lead to the
Surface charge
density(C/m2)

effective flocculation of the particles without need for

additional chemicals. Compression of the double layer
0

has also Enmeshment in a precipitate-weep

frequently been employed flocculation
in research on physical
aspects of particle processes since this mechanism is the best
Negative

understood mathematically. In that case, the chemicals that Lo

are added are inorganic electrolytes that do not change the 18
pH, such as sodium chloride, sodium nitrate, or calcium co
chloride.
)
mber concentration of larger
decrease of small particles,
one-micrometer particles to
as one 5-mm particle. The
centration of 1-mm particles
scale of the ordinate, but one
r gain of the 5-mm particles.
was diminished (or even
emoved some of the largest Attachment on particle surface (adsorption) and
is small batch experiment.
e size distribution shown in interparticle bridging
ent to facilitate the desired
still small enough that they
y in a subsequent sedimen-
IV. Flocculation (used together with EN2005 material)
this chapter, flocculation is
oncentration, and the con-
he experiment reported in
A suspension with a low
- Flocculation: bringing destabilized particles together to induce
mall particles is better desta-
ism; the new solids created
and easier to remove. particle
An collision and attachment (to form larger flocs/
batch experiments is shown
aggregates)
ts shown as both the volume
FIGURE 12-2. Changes in the particle size distribution brought
he particle size distribution
about by sweep flocculation. (a) Volume distribution, and (b)
lume distribution changes
particle size distribution function. Source: Results from Li (1996).
water, in which most of the
-
particles less than 3 mm A two
culated water (after 14 min),
in stage process
external forces on the fluid, which generate fluid motion;
gravity, which causes vertical motion of the particles relative
volume is in particles larger
at the area under the volume
Particles
to the fluid; andmust
thermal be moved
activity in such
of molecules a way that collisions
in solution,
leading to Brownian motion of the particles. A simplified
es of the abscissa represents
mv) of particles in that size
occurs.
view of theseThis
collisionlong range
mechanisms transport
is shown of particles can be
in Figure 12-3.
When particles get quite close to one another, other forces
on function (Part B) shows
n allows one to see more
achieved
become significant;by Brownian
these short-rangediffusion,
forces include,fluid
at the motion, or
e distribution—the greatest least, the van der Waals attraction and electric double layer
er of magnitude) occurred sedimentation. Distance
repulsion (or, perhaps, attraction) of the
explained in the motion
previous ≥ 100X diameter
ed, while all particles with chapter, as well as viscous forces relevant as the water
eased in number. The dra- of particle
separating the two particles moves out of the way.
cles in this experiment in
ncrease in the previous one
H)3 (s) precipitate.

DELING

e collision of particles and

o form a floc. Forces that Brownian motion Fluid shear Differential
particles (i.e., motion over sedimentation
more orders of magnitude
icles under consideration) FIGURE 12-3. Particle paths leading to collisions by various
another, making collisions mechanisms. (For fluid shear and differential sedimentation, the
ong-range motion include length of the arrows reflects the particle velocities.)

19
 Question: how do you think about long-range transport?

Interactions between colliding particles must result in

permanent attachment

๏ When particles get close to one another, short range

forces determine if attachment occurs (e.g., electrical
double layer repulsion and Van der Waals attraction)

ate Equation for๏Floc Formation

→ Only a fraction of collisions will result in
Interpretatio
n light of the earlier attachment,
discussion, unless the particles
flocculation can be areviewed
completely In Equation 1
s a two-step, sequential process,
destabilized analogous
(i.e., to a will
every collision two-step
result in parts, a and b
ementary chemical attachment)
reaction. In the first step, the particles approach) freq
e transported from locations where they have no influence tual meaning
n one another to locations where they do affect each other’s
Question: what is the main difference between "long range"a #
ovement, and in the second, they overcome the short-range ij
g f ;ij
and "short range"?
arriers to collision and form a floc. Based on this analogy
etween flocculation and chemical reactions, and assuming
- Assuming thefloc
formation of the flocthe
is irreversible, the
aij ¼
at the formation of the is irreversible, flocculation Rat
rocess mightflocculation
be represented
processas: can be presented as
bij g f ;ij
Pi þ P j "! Pi # Pj !!!! Pk (12-2) Thus, aij can b
g b;ij
(12.3 - Lawler) of Pi and Pj p
here Pi and P Pji are
and two particles
Pj: two in in
particles thethe
system
system(types “i ” and The analog
”); Pi Pj is a pair of particles that have approached each other entirely consis
osely enoughPthat
i Pj: athey
pairaffect
of particles at very subsequent
each other’s short separation distance tion provided
motion;
k isaflocthatisformedbythecollisionofPi andPj;andbij,g f,ij, (as envisioned
nd g b,ij are rate constants for the respective reactions the20same thing
As noted, the rate constant bij, commonly called the Pi # Pj envisio
Pk: a floc formed by the collision of Pi and Pj
β, γ: rate constants

βij: collision frequency function. It characterizes the transport

of Pi and Pj to a short separation distances where short-range

forces are significant

Three mechanisms for transporting the particles close to

one another: (i) differential sedimentation, (ii) Brownian
motion, and (iii) fluid shear - Figure 12.3

Define αij as collision efficiency function

rate of formation of Pk focs

αij =
rate of close approaches of Pi and Pk particles

close approaches of Pi and Pj particles resulted in flocs

αij =
close approaches of Pi and Pj particles

21
- Smoluchowski equation
Key concepts
๏ Each floc can be formed by the flocculation of smaller
flocs and lost by the flocculation to become larger
flocs
๏ Only two flocs collisions need to be considered
๏ In formation of floc, floc volume is conserved (Vi + Vj =
Vk)
Equation for Pk flocs

Rate of increase in the number

Rate of change of
number
concentration of Pk
= concentration of Pk by
flocculation of two smaller flocs
-
Rate of decrease in the number
concentration of Pk by
flocculation of t Pk with other
flocs

Smoluchowski equation
1
∑ ∑
rk = αij βij ninj − nk αik βik ni
2 all i and j with Vi+Vj=Vk all i

rk: rate of change of number concentration of Pk

ni: number concentration of Pi floc [L-3]
Vi: volume of Pi floc [L3]

22
 Question: can you describe how we can determine the rate
of floc formation based on Smoluchowski equation?

Question: can you tell the importance of particle

concentration on the floc formation?

Question: can you tell the difference between ɑ and β?

- Estimation of βij - collision frequency function

Collision by fluid shear

sh 4
βij = G(ai + aj)
3
G: velocity gradient (s-1) (depends in the mixing
intensity)

Collision by differential settling

πg
DS
βij = (ρp − ρL)(di + dj)3 | di − dj |3
72μ

μ: viscosity of the liquid (M/L/T)

ρp and ρL: densities of particles and liquid, respectively
(M/L3)

23
d: diameter (L)

Collision by Brownian motion

Br
2kBT
βij = (1/di + 1/dj)(di + dj)
3μ

kB: Boltzman constant (1.38 × 10−16gcm 2 /(s 2K )

T: absolute temperature (K)

Total collision frequency function

tot
βij =Sh βij +DS βij +Br βij

24
and dominated by differential sedimentation when the sec- Design Implications of the Long-Range Force Model
ond particle is quite large. For all sizes in between,
In the light of this analysis, it is not surprising that design and
approaches by fluid shear are the most likely. The ranges
operation of flocculators has been based almost exclusively
where each mechanism dominates are a function of the COLLISION FREQUENCY: LONG-RANGE FORCE MODEL 579
on fluid shear as the cause of collisions. Because the
choice of the nonvarying particle size (di) and all the
collision frequency is linearly dependent on G according
parameters describing the particles, suspension, and opera-
to Equation 12-18, the highest mixing intensity that does not
tion. Generally, however, one can say that formation of
result in floc breakup has been thought best by many. Camp
proto-flocs between two small particles is dominated by
(1955) suggested that the dimensionless product Gt (where
Brownian motion, while collisions involving a very large
t is the detention time) be used as the primary design factor
particle and a much smaller particle are dominated by
for flocculation basins; the mathematical basis for the
differential sedimentation, and all others by fluid shear.
importance of this product relies on the assumption that
Considering all possible combinations of particle sizes
all of the particles in the suspension are the same size. This
leads to a more general understanding of the relative
assumption leads to simplified equations for the collision
importance of the three mechanisms in this model. In
frequency (b) and the rate of flocculation that are suggested
Figure 12-12, regions of dominance for each of the three
as an exercise at the end of this chapter. In a review of several
mechanisms are shown for collisions between any two
existing facilities, Camp found that the product Gt ranged
particle sizes. Only half of the region is used because the
from !23,000 to 210,000 and suggested that designers
graph would be symmetric around the center line represent-
should use this range as a guideline. Even today, most
ing equi-sized particles; that is, the choice of i and j is
flocculators are designed to meet this guideline.
arbitrary for collisions of any two sizes. The results in Figure
According to the assumption made by Smoluchowski and
12-12 indicate that, when only long-range forces are con-
accepted by most subsequent researchers, the total particle
sidered, most collisions are predicted to occur by fluid shear.
volume does not change during flocculation. This concen-
The regions are dependent on the specific conditions chosen,
tration can be represented as the dimensionless volume
but the general conclusion that most collisions are predicted
fraction, f (i.e., f ¼ particle volume=suspensionvolume);
to occur by shear is general for any reasonable conditions.
Ives (1968) suggested that the effect of concentration on
Increasing the velocity gradient or shear rate, G, increases the
flocculation rate could be accounted for by including the floc
region of dominance by shear. Decreasing the temperature
volume fraction in the design parameter; that is, he sug-
increases the fluid FIGURE
viscosity 12-11.
and decreases the regions domi-
Total collision frequency function usingthat
the long-range force model.
gested the key parameter is the dimensionless product
nated by Brownian motion and differential sedimentation.

walter, 1977) have questioned the correctness of this
mption on the basis that the mechanisms are not com-
ly independent, but to the accuracy of these collision
ency functions, it can be considered correct.
EXAMPLE 12-6. Find the total collision frequency
ion according to the long-range force model for collisions
mm diameter particles with 0.4-, 2-, and 30-mm particles.
density of all particles is 1.2 g=cm3, and the water
erature is 20! C (i.e., 293 K) where the density is
8 g=cm3 and the viscosity is 1.002 " 10# 2 g=cm s. For
pair of collisions, find the collision mechanism that
ibutes the most to the total collision frequency function
. ent particles. A graph illustrating the relative importance of
olution. The collision frequency function values for
collision mechanism for these particles have been
lated in the previous examples. They are collected in
ollowing table, and then summed for each collision pair.
According to the long-range force model, fluid shear
contributes most to the overall collision frequency function
for all three collision pairs under consideration. For the
collisions between two 2-mm particles, shear is responsible
for 96% of the total. Brownian motion is a significant
contributor to the collisions between 0.4- and 2-mm parti-
cles, and differential sedimentation is substantial in the
collisions of 2- and 30-mm particles. &
A comparison of the magnitudes of the three terms in
Equation 12-24 can indicate which transport process or
processes are most significant in terms of providing possi-
bilities for collisions (i.e., near approaches) between differ-
the three mechanisms under conditions representative of
water treatment plants is shown in Figure 12-11. Under
conditions shown on the figure, it is clear that close
approaches to 2-mm diameter particles are dominated by
Brownian motion when the second particle (j) is quite small,

FIGURE 12-12. Dominant regions for each collision mechanism in the long-range force model.
eters of (Borders between regions vary Fluid
Brownian Shearwith conditions.)Differential
somewhat Total Dominant
sion Pairs Motion Br bij Sh
bij Sedimentation DS bij Tot
bij Collision
(cm3=s) (cm3=s) (cm3=s) (cm3=s) Mechanism
Water Quality Engineering, Benjamin and Lawler
# 11
1.94 " 10 # 11
5.76 " 10 # 12
1.91 " 10 7.89 " 10# 11 Sh 25
1.08 " 10# 11 2.67 " 10# 10 0 2.78 " 10# 10 Sh
4.59 " 10# 11 1.37 " 10# 7 7.92 " 10# 8 2.16 " 10# 7 Sh
 From Figure 12-12: Most collisions are predicted to
occur by fluid shear → Designing and operating of
flocculators are mostly based on the assumption that
fluid shear causes collision
๏ A dimensionless product G𝛕 (Camp, 1955) is used as

the design factor for flocculation basins

G: the velocity gradient or shear rate = degree of
agitation in a mixing unit provided by the mixers (unit
1/s). Typical value of G in flocculators is 10 - 50 s-1
𝛕: detention time of particles in the mixing unit

๏ Mixing consideration
Mixing intensity is enough to keep the particles come
closer to each other
Mixing is not too strong to avoid floc breakup
Typical G𝛕 in flocculation basin is ~ 23,000 - 210,000

Question: what is your opinion about Camp number?

26