CHE61203

POLLUTION CONTROL

LECTURE 4:
Water Pollution (Part 3)

Lectured by: Nurhazwani Ismail

Outline
• Chemical Unit Processes

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Chemical Unit Processes
• Those processes used for the treatment of wastewater in
which change is brought about by means of or through
chemical reactions are known as chemical unit processes.

• Usually are used in conjunction with the physical unit

operations and the biological unit processes to meet specific
treatment objectives.

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Chemical Unit Processes
The role of chemical unit processes in wastewater treatment:
• The principle chemical unit processes used for wastewater treatment
include:
– Chemical coagulation
– Chemical precipitation
– Chemical disinfection
– Chemical oxidation
– Advanced oxidation processes
– Ion exchange
– Chemical neutralization, scale control, and stabilization

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Chemical Unit Processes
Applications of chemical unit processes in wastewater treatment:
Process
Advanced oxidation processes
Chemical coagulation
Chemical disinfection
Chemical neutralization
Chemical oxidation
Application
• Removal of refractory organic compounds
• The chemical destabilization of particle in
wastewater
• Disinfection with chlorine, chlorine
compounds, bromine, and ozone
• Control of slime growths in sewers
• Control of odors
• Control of pH
• Removal of BOD, grease, etc.
• Removal of ammonia (NH4+)
• Destruction of microorganisms
• Control odors in sewers, pump stations, and
treatment plants
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Chemical Unit Processes
Applications of chemical unit processes in wastewater treatment (cond.):
Process
Chemical Precipitation
Chemical scale control
Chemical stabilization
Ion exchange
Application
• Enhancement removal of TSS and BOD in
primary sedimentation facility
• Removal of phosphorus
• Removal of heavy metals
• Corrosion control in sewers due to H2S
• Control of scaling due to calcium carbonate
and related compounds
• Stabilization of treatment effluents
• Removal of ammonia (NH4+), heavy metal,
TSS
• Removal of organic compounds
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Chemical Unit Processes
Considerations in the use of chemical unit processes:
• Chemical unit processes is an additive processes
– Something is added to the wastewater to achieve the removal of somethings
else
• Disadvantages compared with physical unit operations?
– A net increase in the dissolved constituents in the wastewater
• For example, chemicals are added to enhanced the removal efficiency of
particulate sedimentation, the TDS concentration of the wastewater is
always increased.
• When chlorine is added to wastewater, the TDS of the effluent is
increased.
– Handling, treatment, and disposal of the large volumes of sludge that is
produced
– Chemicals cost and energy cost

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Chemical Unit Processes
Fundamentals of Chemical Coagulation:
• Colloidal particles found in wastewater typically have a net negative surface
charge.

• Size of colloids (about 0.01 to 1 µm), if > 1 µm, so called as suspended particles,
which can be removed by gravity sedimentation.

• The attractive body forces between particles are considerably less than the
repelling forces of the electrical charge.

• Under these stable conditions, Brownian motion (i.e., random movement) keeps
the particles in suspensions.

• Coagulation is the process of destabilizing colloidal particles so that particle growth

can occur as a result of particle collisions (in the formation of larger particles).
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Chemical Unit Processes
Fundamentals of Chemical Coagulation:
• Coagulant and flocculent are the two common terms used in coagulation process.

• Coagulant – chemical that is added to destabilize the colloidal particles in

wastewater so that floc formation can result.

• Flocculent – a chemical, typically organic, added to enhance the flocculation

process, to enhance the performance of granular medium filters and in the
dewatering of digested biosolids.

• Typically coagulant and flooculant include natural and synthetic organic polymers,
metal salts such as alum or ferric sulfate, and prehydrolized metal salts such as
polyaluminum chloride (PACl) and polyiron chloride (PICl).

• “Flocculation” is used to describe the process whereby the size of particles

increases as a result of particle collisions.
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Chemical Unit Processes
Fundamentals of Chemical Coagulation:

microfloc macrofloc

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Chemical Unit Processes
Chemical Precipitation for Improved Plant Performance:
• Chemical precipitation – involves the addition of chemicals to alter the physical
state of dissolved and suspended solids and facilitate their removal by
sedimentation.

– As a means of improving the performance of primary settling facilities

– As a basic step in the independent physical-chemical treatment of wastewater
– For the removal of phosphorus
– For the removal of heavy metals

Chemical dosage?
Sludge production?
Design of the necessary sludge processing facilities?
Design of chemical storage, feeding, piping, and control system?

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Chemical Unit Processes
Inorganic chemicals used most commonly for coagulation and precipitation processes in
wastewater treatment:

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Chemical Unit Processes
•1. Alum
Chemical Precipitation for Improved Plant Performance:
  – When alum is added to wastewater containing calcium and magnesium
bicarbonate alkalinity, a precipitate of aluminum hydroxide will form.

3 × 100 (as CaCO3) 666.5 3 × 78 3 × 136 6 × 44 18 × 18

Calcium bicarbonate Aluminum sulfate Aluminum Hydroxide Calcium Carbon

(soluble) (soluble) (insoluble) sulfate dioxide
(soluble) (soluble)

• The precipitation reaction also occurs with the addition of aluminum chloride (AlCl 3)
• The insoluble aluminum hydroxide is a gelatinous floc that settle slowly through the
wastewater.
• The reaction is exactly analogous when magnesium bicarbonate is substituted for
the calcium salt.

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Chemical Unit Processes
•1.  Alum
Chemical Precipitation for Improved Plant Performance:

3 × 100 (as CaCO3) 666.5 3 × 78 3 × 136 6 × 44 18 × 18

Calcium bicarbonate Aluminum sulfate Aluminum Hydroxide Calcium Carbon

(soluble) (soluble) (insoluble) sulfate dioxide
(soluble) (soluble)

Because alkalinity is reported in term of calcium carbonate (CaCO3), the molecular weight of
which is 100, the quantity of alkalinity required to react with 10 mg/L of alum is:

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Chemical Unit Processes
•2. Lime
Chemical Precipitation for Improved Plant Performance:
  – When lime alone is added as precipitant, the principles of clarification are
explained below for carbonic acid the alkalinity:

44 (as CO2) 56 (as CaO) 100 2 × 18

Carbonic Calcium Calcium

acid hydroxide carbonate
(soluble) (slightly (somewhat
soluble) soluble)

100 (as CaCO3) 56 (as CaO) 2 × 100 2 × 18

Carbonic Calcium Calcium

bicarbonate hydroxide carbonate
(soluble) (slightly (somewhat
soluble) soluble)

• A sufficient quantity of lime must therefore be added to combine with all the free carbonic
acid and with the carbonic acid of the bicarbonates to produce calcium carbonate.
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Chemical Unit Processes
•3.  Ferrous Sulfate and Lime – In most cases, ferrous sulfate cannot be used alone as
Chemical Precipitation for Improved Plant Performance:

a precipitant because lime must be added at the same time to form a precipitate.
When ferrous sulfate alone is added to wastewater, following reaction occur:

278 100 (as CaCO3) 178 136 7 × 18

Ferrous sulfate Calcium Ferrous Calcium

(soluble) carbonate bicarbonate sulfate
(soluble) (soluble) (soluble)

if sufficient alkalinity is not available, lime is added in excess in conjunction with

ferrous sulfate. The resulting reaction is
178 2 × 56 (as CaO) 89.9 2 × 100 2 × 18

Ferrous Calcium Ferrous Calcium

bicarbonate hydroxide hydroxide carbonate
(soluble) (slightly soluble) (very slightly (somewhat
soluble) soluble)
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Chemical Unit Processes
•3.  Ferrous Sulfate and Lime
Chemical Precipitation for Improved Plant Performance:

The ferrous hydroxide can be oxidized to ferric hydroxide, the final form desired, by
oxygen dissolved in the wastewater. The reaction is:

89.9 ¼ × 32 1/2 × 18 106.9

Ferrous hydroxide Oxygen Ferric

(very slightly soluble) (soluble) hydroxide
(insoluble)

The insoluble ferric hydroxide is formed as a bulky, gelatinous floc similar to the
alum floc. The alkalinity required for a 10 mg/L dosage of ferrous sulfate is:

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Chemical Unit Processes
•3.  Ferrous Sulfate and Lime
Chemical Precipitation for Improved Plant Performance:

The lime required is:

The oxygen required is:

Because the formation of ferric hydroxide is dependent on the presence of dissolved

oxygen, the reaction given cannot be completed in most wastewater, and , as a
result, ferrous sulfate is not used commonly in wastewater.

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Chemical Unit Processes
•4.  Ferric Chloride – Because of the many problems associated with the use of
Chemical Precipitation for Improved Plant Performance:

ferrous sulfate, ferric chloride is the iron salt used most commonly in
precipitation applications. When ferric chloride is added to wastewater, the
following reaction take place.

2 x 162.3 3 x 100 (as CaCO3) 2 × 106.9

Ferric chloride Calcium Ferric Calcium Carbon

(soluble) bicarbonate hydroxide chloride dioxide
(soluble) (insoluble) (soluble) (soluble)

5. Ferric Chloride and Lime – If lime is added to supplement the natural alkalinity of
the wastewater, the following reaction can be assumed to occur:
2 x 162.3 3 x 56 (as CaO) 2 × 106.9 3 × 111

Ferric chloride Calcium Ferric Calcium

(soluble) hydroxide hydroxide chloride
(slightly soluble) (insoluble) (soluble)
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Chemical Unit Processes
•6.  Ferric Sulfate and Lime – The overall reaction that occurs when ferric sulfate and
Chemical Precipitation for Improved Plant Performance:

lime are added to wastewater maybe presented as follows:

399.9 3 x 56 (as CaO) 2 × 106.9 3 × 136

Ferric sulfate Calcium Ferric Calcium

(soluble) hydroxide hydroxide sulfate
(slightly soluble) (insoluble) (soluble)

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Chemical Unit Processes
Enhanced removal of suspended solids in primary sedimentation:
With chemical precipitation, it is possible to remove:
 80-90% of TSS including some colloidal particles
 50-80 of BOD
 80-90 of bacteria

Comparable removal value for well-designed and well-operated primary

sedimentation tanks without the addition of chemicals are:
 50-70% of TSS
 25-40% of BOD
 25-75% of bacteria

Because of the variable characteristics, the required chemical dosage should be

determine from bench- or pilot-scale tests.

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Chemical Unit Processes
Enhanced removal of suspended solids in primary sedimentation:
Recommended surface loading rates for various chemical suspensions to be used in
the design of sedimentation facilities:

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Chemical Unit Processes
Estimation of Sludge Quantities from Chemical Precipitation
• The handling and disposal of the sludge resulting from chemical precipitation is
one of the greatest difficulties associated with chemical treatment.

• Sludge is produced in great volume from most chemical precipitation operations,

often reaching 0.5% of the volume of wastewater treated when lime is used.

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Chemical Unit Processes
Estimation of Sludge Quantities from Chemical Precipitation

Example:
Estimate the mass and volume of sludge produced from untreated wastewater without and with the use of
ferric chloride for the enhanced removal of TSS. Also estimate the amount of lime required for the specified
ferric chloride dose. Assume that 60% of TSS is removed in primary settling tank without the addition of
chemicals, and that the addition of ferric chloride results in an increased removal of TSS 85%. Also, assume
that following data apply to this situation:

 Wastewater flowrate = 1000 m3/day

 Wastewater TSS = 220 mg/L
 Wastewater alkalinity as CaCO3 = 136 mg/L
 Ferric chloride (FeCl3) added = 40 kg/1000 m3
 Raw sludge properties:
 Specific gravity = 1.03
 Moisture content = 94%
 Chemical sludge properties
 Specific gravity = 1.05
 Moisture content = 92.5%
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Chemical Unit Processes
•  
Chemical Precipitation for Phosphorus Removal
Phosphate Precipitation with Calcium:
• Calcium is usually added in the form of lime Ca(OH)2.
• When lime added to water it reacts with natural bicarbonate alkalinity to
precipitate CaCO3.
• When there is excess calcium ions (pH value increase beyond 10), the excess
calcium will reacts with phosphate to precipitate hydroxylapatite Ca10(PO4)6(OH)2.

Hydroxylapatite

• The quantity of lime required will be independent of the amount of phosphate

present but will depend primarily on the alkalinity of the wastewater.

• The quantity of lime required to precipitate the phosphorus in wastewater is

typically about 1.4 to 1.5 times the total alkalinity expressed as CaCO3.
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Chemical Unit Processes
•  
Chemical Precipitation for Phosphorus Removal
Phosphate Precipitation with Aluminum and Iron:
• The basic reactions involved in the precipitation of phosphorus with aluminum and
iron are as follows:

• Phosphate precipitation with aluminum:

• Phosphate precipitation with aluminum:

In the case of alum and iron, 1 mole will precipitate 1 mole of phosphate.
The above equations cannot be used to estimate the required chemical dosages
directly. Therefore, dosages are generally established on the basis of bench-scale tests.
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Thank you for your attention