Coaulation Dossing

ENVE 301
Environmental Engineering Unit Operations
CHAPTER: 8
Coagulants
Assist. Prof. Bilge Alpaslan Kocamemi

Marmara University
Department of Environmental Engineering
Istanbul, Turkey
Coagulants
The most widely used coagulants in water treatment :
Aluminum sulfate (Al2(SO4)3.14H2O or Al2(SO4)3.18H2O)

Iron salts
(e.g. ferrous sulfate, ferric sulfate, ferric chloride)
Aluminum (III) and Fe (III) accomplish destabilisation of colloidal particals

by 2 mechanisims :
1. Adsorption and charge neutralization
2. Enmesment in precipitate
If an Aluminum (III) and Fe (III) salt is added to water in

concentrations less than the solubility limit of the metal hydroxide:
The hydrolysis products will form and adsorb onto the colloidal
particles, causing destabilization by charge neutralization.
If the amount of Aluminum (III) and Fe (III) salts added to water is sufficient
to exceed the solubility of metal hydroxide;
The hydrolysis products will form as intermediate in the formation of metal
hydroxide precipitate
Adsorption and charge neutralization by intermediate hydrolysis

products
Enmeshment of colloids in precipitate ( Al(OH)3 or Fe(OH)3 ) formed

4
Aluminium Sulfate (Alum)

Al2(SO4)3.14H2O
Commercial grade
(MW=594.4 Density=600-1100 kg/m3)
Al2(SO4)3.18H2O
Reagent grade
Tan to gray green in color
Available in dry or liquid form
(liquid form requires special shipping containers because of its corrosiveness)
dry form is most common

- granular (most widely used)
- powdered
- lump form
The dry chemical may be shipped in;

- bags
- barrels
6
Feeding of Alum in Water Treatment Plants:
Alum is dissolved in water at concentration of 3-7%

(5% most common)
Then fed to the raw water by chemical feeders (e.g, dosage pumps)
Reason of diluting coagulant before injection into raw water :
large volumes are easier and quicker to disperse into a large body of
raw water than smaller volumes
7
The optimum pH range = 6-8

(aluminum hydroxide is relatively insoluble within this range)
Al (OH ) 3 + OH Al (OH ) 4
If pH is high; Al (OH ) 3 + OH Al (OH ) 4

soluble
If pH is low; Al(OH) 3 + H + Al(OH)2 + H2 O

soluble
In practice, most water treatment plants utilizing alum operate;

Between a pH of 6-7.5 and
with alum dosages of 5-50 mg/L
in the range of insolubility of Al(OH)

8 3
When Al2(SO4)3.14H2O (18H2O) is added to water
It is hydrated to form Al(H2O)6+3

This complex is then pass through a series of hydrolytic reactions in which
H2O molecules in the hydration shell are placed by OH- ions.
Formation of a variety of soluble species
e.g.
AlOH
+2
Al(OH)
+
2
[Al (OH ) ]
[Al (OH ) ]
[Al O (OH) ]
+4
+5
Intermediates in the
formation of Al(OH)3
precipitate
+7
13
24
These species may adsorb very strongly onto the surface of most negative
colloids
Coagulation with adsorption and charge neutralization mechanism occurs.
(charge reversal due to overdosing is possible)
If solubility limit of Al(OH)3 is exceeded (typical in water treatment)
Adsorption and charge neutralization by intermediate soluble species

formed
Enmeshment in Al(OH)3
Both contribute to coagulation
10
Al 2 ( SO 4 ) 3 .14 H 2 O + 6 H 2 O 2 Al (OH ) 3 ( s ) + 6 H + + 3 SO 4 + 14 H 2
Liberated H+ ions
Depression of pH below the range
in which the alum is effective
Optimum pH for Al(OH)3
precipitate formation 6-8
Natural alkalinity of water (which is in the form of bicarbonate ion for

the ph range involved ) will react with liberated H+ ions and reduces
the variation in pH.
Al (SO ) 14H O + 3Ca(HCO ) 2Al(OH) +3CaSO + 14H O + 6CO

2
11
If the natural alkalinity of water is insufficient, alkalinity in the form of
Ca(OH)2 hydrated lime (calcium hydroxide)
Na2CO3 sodium carbonate (soda ash)
CaO quick lime (calcium oxide)
must be added to increase buffer capacity
Al ( SO ) 14 H O + 3 Ca (OH ) 2 Al (OH ) + 3 CaSO + 14 H O

2
Al (SO ) 14H O + 3Na CO + 3H O 2Al(OH) + 3Na SO + 3CO + 14H O

2
12
Example: (Benefield, p.221)

A raw water supply is treated with an alum dosage of 25 mg/L. Calculate the
followings:
1. The amount of alum required to treat a flow of 1 MGD (million gallon /day)
2. The amount of natural alkalinity required to react with the alum added in
terms of CaCO3
3. The volume of sludge produced per MGD if it is collected at 2% solids.
Assume that the sludge has a specific gravity of 1.011 ( at 4C )
13
14
Iron Salts
Ferric sulfate (Fe2(SO4)3)
Ferric chloride (FeCl3)
Less expensive than alum but can cause color

problem if the precipitate is not removed
completely
Ferrous sulfate (FeSO4)
Ferric sulfate
Ferric chloride
Ferrous sulfate (copperas)

15
Ferric Sulfate
Fe2 (SO 4 )3.yH2O
y= 3, 7, 9
MW=399,9 g/mol
Available in dry form, as granules (most common) or as powder

Optimum pH range = 3.5 7 and above 9 (up to 12)
(ferric hydroxide is relatively insoluble within this range)
Typical dosage for Fe2(SO4)3.9H2O 10-250 mg/L
Reaction of ferric sulfate with natural bicarbonate alkalinity:
Fe 2 (SO 4 )3.yH 2O + 3Ca ( HCO 3 ) 2 2Fe(OH )3 +3CaSO 4 + 6CO 2 + yH 2O
The reaction produces a dense, rapid settling floc.
16
If the natural alkalinity is insufficient for the reaction:

Fe 2 ( SO 4 ) 3 . yH 2 O + 3Ca ( OH ) 2 2 Fe ( OH ) 3 + 3CaSO 4 + yH 2 O
Hydrated lime
Fe 2 ( SO 4 ) 3 . yH 2 O + 3 Na 2 CO 3 + 3 H 2 O 2 Fe (OH ) 3 + 3 Na 2 SO 4 + 3CO 2 + yH 2 O
The chemical is usually dry fed
17
Ferric Chloride
FeCl3 MW=162.2 g/mol
Available in dry (powder or lump,lump is most common) or liquid form
(FeCl3)
anhydrous form
(FeCl3.6H2O) heptahydrate form

Liquid form
green-black powder
yellow-brown lump
dark brown solution
Typical dosage = 5-150 mg/L as FeCl3.6H2O

Working pH range = 3.5-6.5 (or above 8.5)
18
Simplified reaction with natural alkalinity:
2 FeCl 3 + 3Ca ( HCO 3 ) 2 2 Fe ( OH ) 3 + 3CaSO 4 + 6 CO 2

If the natural alkalinity is insufficient;
2 FeCl 3 + 3Ca (OH ) 2 2 Fe ( OH ) 3 + 3CaCl 2

2 FeCl 3 + 3 Na 2 CO 3 + 3 H 2 O 2 Fe ( OH ) 3 + 6 NaCl + 3CO 2
19
Ferrous Sulfate (Copperas)

FeSO4.7H2O = 287 g/mol
FeSO4.5H2O = 242 g/mol
Effective pH range = 8.5 or above
Slaked (or hydrated) lime is usually added to raise the pH to a level where the
ferrous ions are precipitated as ferric hydroxide.
FeSO 4 .7 H 2 O + 2 Ca ( OH ) 2 Fe ( OH ) 2 + CaSO 4 + 7 H 2 O
4 Fe ( OH ) 2 + O 2 + 2 H 2 O 4 Fe ( OH ) 3
is available in dry (granule or lump) or liquid form. Dry form is most

common
20
Chlorinated Copperas
3 FeSO 4 .7 H 2 O + 1 .5Cl 2 Fe 2 ( SO 4 ) 3 + FeCl 3 + 21 H 2 O
Effective coagulants
This reaction occurs at a pH as low as about 4
effective pH range = 3.5-6.5 or above 8.5
21
Polyelectrolytes (Polymeric Coagulants)

Polymer
Long chain, high molecular weight molecules

Comprises of many subunits (MONOMERS)
may be classified according to their ionic characteristics as:

Anionic (negatively charged)
Cationic (positively charged)
Ampholytic (contains both positive and negative groups)
may be of natural origin (e.g. starch, polysaccharide gums) OR synthetic in

origin
22
23
May be used as coagulant not cost effective

Commonly used as coagulant aid in conjuction with coagulants
When they are added to water,

Chemical bridging between reactive groups on the polyelectrolyte and floc occurs
Polyelectrolyte binds small flocs together by bridging to make larger masses for
settling
Usual dosage as coagulant aid = 0.5-1.5 mg/L

Overdosing will result in restabilization of colloids
are not acidic and do not lower the pH of water as alum does
24
Determination of Coagulant Dosage

JAR TEST
is used to determine the most effective and economical dose of

coagulant for a particular mixing intensity and duration
25
Samples of the
water are poured
into a series of
glass beakers
Various dosages of the

coagulant and
coagulant aid are
added to beakers
Then the coagulants are

gently stirred to simulate
FLOCCULATION
Contents are rapidly

stirred to simulate
RAPID MIXING
(coagulation)
After a given time, the

stirring is ceased and the
floc formed is allowed to
settle
26
Determination of Optimum Coagulant Dose

Raw sample pH and turbidity measurement
Flash mix (at 80 rpm) 1-3 min
Slow mix (at 10-20 rpm) 30 min
Settle for 20 min
Turbidity of supernatant
10 mg/L alum
20 mg/L alum
50 mg/L alum
No coagulant
(blank)
27
28
Determination of Optimum pH for Optimum Coagulant Dose

Rapid mix 1-3 min (at 80 rpm)
Slow mix 30 min (at 10-20 rpm)
Settle for 20 min
Turbidity of supernatant
Optimum coagulant dosage determined in part A
as-is pH
adjust
pH 6
adjust
pH 5
adjust
pH 8
NaOH
W/
H2 SO 4
29
30
The most important aspects to note during the JAR TEST:
Time for floc formation

The floc size
Flocs settling characteristics
Turbidity removed
pH
31
32
33
34
35
36
37
Classification of Surface Water with Regard to Coagulation

Low turbidity < 10 JTU
Low alkalinity < 50 mg/L as CaCO3
High turbidity > 100 JTU
High alkalinity >250 mg/L as CaCO3
Group 1 (High turbidity Low alkalinity)
With relatively small dosages of coagulant water of this type should be

easily coagulated by adsorption and charge neutralization
May need to add alkalinity if ph drops during treatment

Group 2 (High turbidity High alkalinity)
Because of the high alkalinity, adsorption and charge neutralization will be

less effective mechanism than in waters of low alkalinity
Higher coagulant dosage should be used to ensure sweep coagulation

The pH will be relatively unaffected by coagulant addition
38
Group 3 (Low turbidity High alkalinity)
The small number of colloids make coagulation difficult. Addition of some

turbidity may decrease the amount of coagulant needed.
The principal coagulation mechanism is sweep flocculation with moderate

coagulant dosage
Group 4 (Low turbidity Low alkalinity)
The small number of colloids make coagulation difficult and low alkalinity prevents
effective Al(OH)3 formation
Additional turbidity can be added to convert this water to that of group 1 or

additional alkalinity can be added to convert it to group 3
It may be adventegous to add both turbidity and alkalinity

39

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ENVE 301

Environmental Engineering Unit Operations

Assist. Prof. Bilge Alpaslan Kocamemi

The most widely used coagulants in water treatment :

Aluminum sulfate (Al2(SO4)3.14H2O or Al2(SO4)3.18H2O)

Aluminum (III) and Fe (III) accomplish destabilisation of colloidal particals

If an Aluminum (III) and Fe (III) salt is added to water in

Adsorption and charge neutralization by intermediate hydrolysis

Enmeshment of colloids in precipitate ( Al(OH)3 or Fe(OH)3 ) formed

Aluminium Sulfate (Alum)

(MW=594.4 Density=600-1100 kg/m3)

Tan to gray green in color

Available in dry or liquid form

(liquid form requires special shipping containers because of its corrosiveness)

dry form is most common

The dry chemical may be shipped in;

Feeding of Alum in Water Treatment Plants:

Alum is dissolved in water at concentration of 3-7%

The optimum pH range = 6-8

If pH is high; Al (OH ) 3 + OH Al (OH ) 4

If pH is low; Al(OH) 3 + H + Al(OH)2 + H2 O

In practice, most water treatment plants utilizing alum operate;

in the range of insolubility of Al(OH)

When Al2(SO4)3.14H2O (18H2O) is added to water

It is hydrated to form Al(H2O)6+3

If solubility limit of Al(OH)3 is exceeded (typical in water treatment)

Adsorption and charge neutralization by intermediate soluble species

Both contribute to coagulation

Natural alkalinity of water (which is in the form of bicarbonate ion for

Al (SO ) 14H O + 3Ca(HCO ) 2Al(OH) +3CaSO + 14H O + 6CO

If the natural alkalinity of water is insufficient, alkalinity in the form of

Ca(OH)2 hydrated lime (calcium hydroxide)

Na2CO3 sodium carbonate (soda ash)

CaO quick lime (calcium oxide)

must be added to increase buffer capacity

Al ( SO ) 14 H O + 3 Ca (OH ) 2 Al (OH ) + 3 CaSO + 14 H O

Al (SO ) 14H O + 3Na CO + 3H O 2Al(OH) + 3Na SO + 3CO + 14H O

Example: (Benefield, p.221)

Less expensive than alum but can cause color

Ferrous sulfate (FeSO4)

Ferrous sulfate (copperas)

Available in dry form, as granules (most common) or as powder

Reaction of ferric sulfate with natural bicarbonate alkalinity:

Fe 2 (SO 4 )3.yH 2O + 3Ca ( HCO 3 ) 2 2Fe(OH )3 +3CaSO 4 + 6CO 2 + yH 2O

The reaction produces a dense, rapid settling floc.

If the natural alkalinity is insufficient for the reaction:

The chemical is usually dry fed

(FeCl3.6H2O) heptahydrate form

Typical dosage = 5-150 mg/L as FeCl3.6H2O

Simplified reaction with natural alkalinity:

2 FeCl 3 + 3Ca ( HCO 3 ) 2 2 Fe ( OH ) 3 + 3CaSO 4 + 6 CO 2

2 FeCl 3 + 3Ca (OH ) 2 2 Fe ( OH ) 3 + 3CaCl 2

Ferrous Sulfate (Copperas)

is available in dry (granule or lump) or liquid form. Dry form is most

Polyelectrolytes (Polymeric Coagulants)

Long chain, high molecular weight molecules

may be classified according to their ionic characteristics as:

may be of natural origin (e.g. starch, polysaccharide gums) OR synthetic in

May be used as coagulant not cost effective