Chemical Unit Process

Gyeongsang National University

Enviromental Engineering Lab

Ngoc Thuan Le
** 김 투안 **

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 Overview
• The principal chemical unit processes used for wastewater treatment
a. Basic definitions
b. Chemical precipitation
c. Chemical precipitation for phosphorus removal
d. Chemical oxidation
e. Chemical neutralization

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 Application of chemical unit processes

• For the complete secondary treatment of untreated wastewater, including

the removal of either nitrogen or phosphorus or both.
• To remove phosphorus by chemical precipitation
• To be used in conjunction with biological treatment.
• For the removal of heavy metals and specific organic compounds
• For advance treatment of wastewater, the disinfection of wastewater.

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 Fundamental of chemical coagulation

Basic Definition

• Coagulant is the chemical that is added to destabilize the colloidal

particles in wastewater.
• A Flocculent is a chemical, usually positive charge typically organic,
added to enhance the flocculation process.
• Microflocculation (perikinetic flocculation), aggregation is brought about
by the random thermal motion of fluid molecules.
• Macroflocculation (orthokinetic flocculation), aggregation is brought
about by inducing velocity gradients and mixing in the fluid containing
the particles to be floccullated, (large particles overtake small particles to
form larger particles)

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Nature particles in the wastewater

• The size of colloidal particles: about 0.01-1µm, a net negative surface

charge
• The number of colloidal particles in untreated wastewater is from 106 to
1012 /ml.
• Particles solvent interactions:
 Hydrophobic or “water-hating”
 Hydrophilic or “water-loving”
 Association colloids

• Ionization

At high pH At low pH At isoelectric point

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Particle destabilization and aggregation with polyelectrolytes

• Polyelectrolytes may be devided into two categories:

 Natural: include polymers of biological origin such as cellulose derivatives
and alginates
 Synthesis: simple monomers that are polymerized into high molecular
weight substances.
• The action of polyelectrolytes:
 Charge neutralization: the cationic polyelectrolytes are used for this purpose
 Polymer bridge formation: polymers that are anionic and nonionic, a bridge
is formed when two or more particles become absorbed along the length of
polymers
 Charge neutralization and polymer bridge formation: from using cationic
polyelectrolytes of extremely high molecular weight.

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Particle destabilization and removal with hydrolyzed metal ions

• Formation of hydrolysis products: in the past, it was thought that free Al+3 and Fe+3
were responsible for particles aggregation, now their hydrolysis products are
responsible.
3+ 2+
H2O OH2 H2O OH
H2O Me OH2 H2O Me OH2 + H+
Me: Cr, Al, Fe
H2O OH2 H2O OH2

In acid: Al(OH)3(s) + 6H3O+(aq) Al3+ (aq) + 6H2O

In base: Al(OH)3(s) + OH-(aq) Al(OH)4- (aq) + 6H2O

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Chemical precipitation for improved plant performance

• In the past, chemical precipitation was used to enhance the degree of TSS and
BOD removal
• In current practice, chemical precipitation is used for:
 Primary settling facilities
 In the independent physical-chemical treatment of wastewater
 Removal of phosphorus
 Removal of heavy metals

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Inorganic chemicals used most commonly for coagulation and precipitation processes in wastewater

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Enhance removal of suspended solids in primary sedimentation

• With chemical precipitation, it is possible to remove

 80-90% TSS
 50-80% BOD
 80-90% bacteria

• Dependent factors
 Quantity of chemical used
 Mixing time
 Loading rates
 Operator

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 Chemical precipitation for phosphorus removal

• Phosphorus precipitation with calcium

 Using as form of lime, Ca(OH)2
 pH of the wastewater increases beyond about 10

10Ca2+ + 6PO43- + 2OH- Ca10 (PO4)6(OH)2

Hydroxylapatite

Dosage of lime depend on

 Amount of phosphate present
 The alkalinity of wastewater
The quantity of lime required is typically about 1.4 to 1.5 times
the total alkalinity expressed as CaCO3

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 • Phosphate precipitation with aluminum and iron
Al3+ + HnPO43-n AlPO4 + nH

Fe3+ + HnPO43-n FePO4 + nH

• There are many competing reactions because of the effects of alkalinity, pH,
trace elements, and ligands in wastewater
• Dosages are established of bench scale test and occasionally by full scale tests.

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 • Typical alum dosage requirements for various levels of phosphorus removal
Phosphorus reduction, Mole ratio, Al: P
%
Range Typical

75 1.25:1-1.5:1 1.4:1

85 1.6:1-1.9:1 1.7:1

95 2.1:1-2.6:1 2.3:1

Developed in part from US. EPA (1976)

• Theoretically, the minimum solubility of AlPO4 occurs at pH 6.3, FePO4 occurs

at pH 5.3. In practice, good phosphorus removal anywhere in the range of pH
6.5 to 7.0

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 • Factors effecting the choice of chemical for phosphorus removal
a. Influent phosphorus level
b. Wastewater suspended solids
c. Alkalinity
d. Chemical cost (including transportation)
e. Reliability of chemical supply
f. Sludge handling facilities
g. Ultimate disposal methods
h. Compatibility with other treatment processes

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 • Phosphorus removal using metal salts and polymers
a. Iron and aluminum salts can be added at a variety of different points in
the treatment processes
b. Polyphosphates and organic phosphorus are less easily removed than
orthophosphorus
c. Adding aluminum or iron salts after secondary treatment (where
organic phosphorus and polyphosphate are transformed into
orthophosphorus) results in the best removal.
d. Polymers may be added
(1) to the mixing zone of a highly mixed or internally recirculated
clarifier,
(2) preceding a static of dynamic mixer, or
(3) to aerated chanel

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 • Phosphorus removal using lime

5Ca2+ + 3PO43- + OH- Ca5(PO4)3(OH)

Hydroxylapatite

a. Lime treatment can be used to precipitate a portion of the phosphorus

(about 65-80%)
b. Product of precipitation: [Ca5(PO4)3(OH)].
c. pH is about 11 for high lime systems, about 8.5-9.5 for low lime
systems
d. After precipitation, the effluent must be recarbonated before biological
treatment.
e. In activated sludge systems, the pH of the primary effluent should not
exceed 9.5 or 10
MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process
 Advantages and disadvantages of chemical addition in various section of a treatment
plant for phosphorus removal
Level of treatment Advantages Aisadvantages
Primary applicable to most plant, increase Least efficient use of metal, polymer may be
BOD and TSS removal, lowest degree required for flocculation, sludge more difficult
of metal leakage, lime recovery to dewater than primary sludge
demonstrated

Secondary lower cost, lower chemical dosage overdose of metal cause low pH toxicity, with
than primary, improved stability of low alkalinity wastewaters, a pH control
activated sludge, polymer not required system may be necessary, canot use lime
because of excess pH, inert solids added to
activated sludge mixer liquor, reducing the
percentage of volatile solids

Advanced precipitation lowest phosphorus effluent, most Highest capital cost, highest metal leakage
efficient metal use, lime recovery
demonstrated
advanced single and two lower cost can be combineed wieth the Length of filter run may be reduced with
stage filtration removal of residual TSS single-stage filtration additional expense with
two stage filtration process
Adapted from US. EPA, 1976

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Chemical precipitation for removal of heavy metals and
dissolved organic substances

• Most of metal of interest in wastewater can be precipitated as hydroxides and

sulfides
• Dependent factors:
 Solubility
 pH

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Chemical oxidation

• Oxidizing agents:
 ozone (O3),

 hydrogen peroxide (H2O2),

 permanganate (MnO4),

 chloride dioxide (ClO2),

 chlorine (Cl2) or (HClO) and

 oxygen (O2)

• For reduction of:

 BOD,

 COD,

 ammonia,

 nonbiodegradable organic compounds.

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 • Oxidation-reduction reaction
 Take place between oxidizing agent and reducing agent.

Cu2+ + Zn Cu + Zn2+

Zn - 2e Zn2+ (oxidation)

Cu2+ - 2e Cu (reduction)

 Oxidation-reduction reactions often require the presence of one or more

catalysts to increase the rate of reaction.
 Requirements: transition metal cations, enzymes, pH adjustment…

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 Typical applications of chemical oxidation in wastewater collection, treatment and disposal.

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 • Chemical oxidation of BOD and COD

Organic Cl, O3, Intermediate Cl, O3, Simple end

molecule oxygenated products (e.g.,
(e.g., BOD) H2O2 molecules H2O2 CO2, H2O…)

• Chemical oxidation of nonbiodegradable organic compounds

For treatment of remaining after biological treatment: low molecular weight
polar organic compounds and complex organic compounds build around the
benzene ring structure

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 • Chemical neutralization

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 • Scaling control

 Acidifying to reduce pH and alkalinity

 Reducing calcium concentration by ion exchange or lime softening
 Adding a scale inhibitor chemical (antiscalant) to increase the apparent
solubility of CaCO3 in the concentrate stream
 Lowering the product recovering rate

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Chemical storage, feeding, piping, and control systems.

Chemical feeders

Dry feeders Liquid feeders Gas feeders

gravimetric volumetric Slurry solution Ammonia

Chlorine
Oxygen
Belt Belt Ozone
Loss in weight Revolving plate sulfur dioxide
Self-powered Rotary
Screw
Shaker
vibratory

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

Schematic of typical dry
chemical-feed system.

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 Conveyor belt Rotary

Screw Vibratory

Typical volumetric chemical feeders

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 Schematic of typical liquid chemical-feed system.

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 Typical mixing times for various chemicals used in wastewater treatment facilities
Chemical Application Recommentded
mixing times, s
Alum, Al3+ , Ferric chloride, Fe3+ Coagulation of colloidal particles <1
Alum, Al3+ , Ferric chloride, Fe3+ Sweep floc precipitation 1-10
Lime Ca(OH)2 Chemical precipitation 10-30
Chlorine, Cl2 Chemical disinfection <1
Chloramine, NH2Cl Chemical disinfection 5-10
Cationic polymers Destabilization of colloidal particles <1

Anionic polymers particle bridging 1-10

Polymers, anionic Filter aids 1-10

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process

 Thank you for your attention!

MECALF & EDDY|Wastewater Engineering-treatment and reuse Chap.6|Chemical Unit Process