BKC 3683

WATER AND WASTEWATER

TREATMENT

CHAPTER 3 (PART 1)
CHEMICAL METHODS FOR
WATER AND WASTEWATER
TREATMENT
TOPIC OUTCOMES
• Identify the chemical methods based on the
chemical characteristics of the pollutants
• Discuss the disadvantages and advantages of the
chemical methods
• Describe the mechanisms of each chemical
methods
Considerations & Issues of Chemical Treatment

“Chemical treatment”
Handling,
treatment and
Net increase disposal of the
in dissolved large volumes of Increase in cost
constituents sludge produced of energy &
chemical costs
Chemical methods for wastewater
treatment
• Chemical methods of wastewater treatment take
advantage of two types of properties:
1. The chemical characteristics of the pollutants
2. The chemical characteristics of the products of reaction
between pollutants and treatment chemicals
• There are 6 methods:
1. Reaction to produce an insoluble solid
2. Reduction of surface charge to produce coagulation
3. Reaction to produce an insoluble gas
4. Reaction to produce a biologically degradable substances
5. Reaction to destroy or deactivate chelating agent
6. Oxidation or reduction reaction
1. Reaction to produce an insoluble solid
• The industry standard procedure for removing
metals from wastewater is alkaline precipitation.
Alternative methods include precipitation of the
metal as the sulfide; precipitation as the
phosphate; precipitation as the carbonate; or co-
precipitation with another metal hydroxide, sulfide,
phosphate, or carbonate
 CHEMICAL PRECIPITATION:
Heavy Metal Removal
•The Heavy metals are elements with high atomic weights, eg: cadmium,
chromium, copper, lead, mercury, nickel, silver and Zinc. Heavy metals can
damage living organisms at low concentrations and tend to accumulate in
the food chain.

• Heavy metal generally precipitated as HYDROXIDE through the addition of

LIME or CAUSTIC (NaOH) to a pH of minimum solubility (several of these
compounds are AMPHOTERIC).

• The solubility for Cr3+ and Zn2+ are minimum at pH 7.5 and 10.2,
respectively and show significant increase in concentration above these pH
value.

• For many metals such as As and Cd, co-precipitation with iron or aluminum
is highly effective for removal to low residual levels
 CHEMICAL PRECIPITATION:
Heavy Metal Removal
• Objective :to convert the dissolved metal ions to an insoluble metal hydroxide
that will precipitate and be removed from the wastewater allowing the treated
wastewater to be discharged to the local sanitary sewer.

• Precipitation of heavy metals in wastewater is dependent on two factors.

1. The concentration of the metal ion
2. The pH of the wastewater.

• Heavy metals in wastewater are usually in trace amounts (1 mg/l to 100 mg/l)
and are usually present in neutral to acidic pH values. The lower the
concentration of the metal ion more difficult it is to be removed.

• When caustic or lime is added to wastewater that contains dissolved metals the
metal ion reacts with the Hydroxide Ion to form an insoluble Metal Hydroxide.

Metal + Hydroxide (caustic or Lime) = Metal Hydroxide Precipitate

HEAVY METAL REMOVAL
INDUSTRIES IMPACTED:
• Metal Finishing
• Foundry and Casting CHEMICAL PERCIPITATION: BASIC PRINCIPLES
• Mining
• Microchip / semiconductor
Production
• Automotive
• Printing
PARAMETER OF HEAVY METAL:
• Zinc
• Chromium
• Tin
• Iron 1. Add chemical precipitants to waste stream
• Silver 2. Mix thoroughly
• Cadmium
• Nickel 3. Allow solid precipitates to form floc by slow
• Copper mixing
• Mercury 4. Allow floc to settle in clarifier
• Cobalt
• Aluminum
• Arsenic
 HEAVY METAL REMOVAL
Precipitating Agents
1. Lime/Calcium Hydroxide - Ca(OH)2
2. Magnesium Hydroxide - Mg(OH)2
Precipitation Reactions: e.g.
3. Caustic/Sodium Hydroxide - Na(OH)
Zn2+ (aq) + CO3 (aq) = Zn(CO3) (ppt)
4. Soda Ash - Na2CO3 -
Sodium Sulfide - Na2S Zn2+ (aq) + 2OH (aq) = Zn(OH)2 (ppt)
5.
Lime/calcium oxide – CaO Pb2+ (aq) + 2S2- (aq) = PbS (ppt)
6.
7. Calcium carbonate – CaCO3
CHEMICAL PRECIPITATION

1. Add lime (CaO) or sodium hydroxide (NaOH) to waste

stream:
Cd2+ + Ca(OH)2 → Cd (OH)2  + Ca2+
• NaOH is easier to handle but is very corrosive.
• Will form floc and settle in clarifier.

2. Use of sulphide in the form of Na2S

• Better metal removal as sulphide salt has low solubility
limit
Cu2+ + Na2S → CuS  +2Na
• At low pH, reaction will produce H2S that has toxicity and corrosivity
hazard. Thus, require pH > 8 for safe sulphide precipitation.

Sulphide precipitation always achieved with lower residual metal concentrations than the
corresponding hydroxide precipitation. Metal sulfide sludges generally are more dense and
stable than metal hydroxide sludges
 HEAVY METAL REMOVAL
Solubility of Metals
• Major anions in controlling precipitation:
• CO32-, HCO3-, Cl-, SO42- (depends on the cation)
• H2S, HS-, S2- (reduced condition)

• Three types of important precipitates in water:

• Sulfide, carbonate and hydroxide

• “Soluble” vs. “insoluble” metals in general:

• Soluble: metal compounds with Cl-, SO42-, except AgCl,
HgCl, PbSO4
• Insoluble (< 100 mg/L H2O): CO32-, S2-, OH-
 HEAVY METAL REMOVAL
Effects of Complexation
• If a complexing agent is present during the process of chemical
precipitation, this will lower the efficiency of precipitation reactions
as metals become more solubilized in water.

• Synthetic Chelating Agents

• EDTA (sodium ethylenediaminetetraacetate): used as a cleaning
and solubilizing agent for the decontamination of metal-
contaminated equipment
• NTA (nitrilotriacetic acid): used as a detergent phosphate
substitute
• Polyphosphate (H4P2O7, H5P3O10): used for water treatment
(“sequest” Ca2+ to prevent scaling of CaCO3 in water pipers and
boilers), water softening, and as detergent builders
 HEAVY METAL REMOVAL
Factors Affecting Solubility
1. Temperature
• Solubility in solvent increases with increasing T except CaCO3,
Ca3(PO4)2, CaSO4 and FePO4. This is attributed to enthalpy
needs of crystal
dissolution.
2. Common ion effect
• When a solution contains an ion that is the same as one of the
ions which result from the dissolution of the solid, the solubility
of the solid will be less than that when the solid dissolves in pure
water. e.g. solubility of AgCl (s) in NaCl < solubility of AgCl (s) in
water
3. Complexation
• Complexation will increase solubility: e.g. Complexation of Cd
with OH- (or Cl-) will increase the solubility of Cd(OH)2 (s)
For Example: To remove copper (Cu) from wastewater
the line on the graph shows a drop in Cu
concentration as the pH is raised. A pH of about 9.0
(low point of the Cu line) as shown on the graph is
optimal for removing Cu. Higher pH values higher
than 9.0 are not advantageous.

For Zinc (Zn) note that a pH of 9.2 to 9.8 is the low

point and is therefore the desired pH value to remove
zinc.
 CHEMICAL PRECIPITATION:
Heavy Metal Removal
• When more than one metal is present the pH value is generally adjusted
to the average pH value. If three or more metals are present a step
approach may be needed. We recommend a pH value of 9.5 for multiple
metals. This should be confirmed by jar testing.

• Jar test – to determine the correct chemical dosage.

• Jar test simulate full-scale coagulation and flocculation processes to
determine optimum chemical dosages.
 CHEMICAL PRECIPITATION:
Heavy Metal Removal
• The test can be used to:
1. Select the most effective chemical
2. Select the optimum dosage
3. Determine the value of a flocculant aid and the proper dose

• Mechanism – when an insoluble precipitate is formed, individual

atoms share electrons to build a crystal lattice structure that result in
particles that grow to a size that will settle in a clarifier under the
influence of gravity
• Two distinct processes take place:
1. Formation of small crystals
2. Coagulation of the small crystalline particles.
 HEAVY METAL REMOVAL
Table 6-10 .Achievable effluent "fype of precipitation
Pr actical effluent Metal concent.olion, mg/L and technology
concentratio n levels
achievable in Arsenic 0.05 Sulfide precipitation with filtration
heavy
metals removal by 0.005 Ferric hydroxide coprecipitahon
precipitation° Barium 0.5 Sulfate precipitation
Cadmium 0.05 Hydroxide precipitation at pH 10-11
0.05 Coprecipitation with ferric hydroxide
0.008 Sulfide precipitation
Copper 0.02-0.07 Hydroxide precipitation
Sulfide precipitation
0.01-0.02
Sulfide precipitation
Mercury 0.01-0.02
Alum coprecipitation
0.001-0.0l
Ferric hydroxide coprecipitat,on
0.0005-0.005
Ion exchange
0.001-0.005
Hydroxide precipitation at pH 10
Nickel 0.12
Sulfide precipitation
Selenium 0.05
Hydroxide precipitation at pH 11
Zinc 0.1
 Typical Concentrations Obtainable
Through Chemical Precipitation
Heavy Metal Achievable Precipitating
Concentration Agent
(mg/liter)
Cadmium 0.3 Soda Ash

Trivalent Chrome 0.5 Caustic, Lime

Copper 0.5 Caustic, Lime

Iron 1.0 Caustic, Lime

Nickel 0.5 Soda Ash

Zinc 0.5 Caustic, Lime

 HEAVY METAL REMOVAL
CHROMIUM REDUCTION & PRECIPITATION PROCESS

• For CHROMIUM waste treatment, HEXAVALENT

chromium (Cr6+) must first be reduced to the
TRIVALENT state (Cr3+) and the precipitate with LIME.
• The reducing agents commonly used for chromium waste
are FERROUS SULFATE and SODIUM
METABISULFATE.
eg; FEROUS SULFATE as reducing agent:
• Ferrous ion reacts with Cr6+ in oxidation-reduction
reaction, reducing the chromium to a trivalent state and
oxidizing the ferrous ions to the ferric state (this reaction
occurs rapidly at pH level below 3).
 HEAVY METAL REMOVAL
Chromium Reduction & Precipitation Process

Cr 6+ + Fe 2+ + H + → Cr 3+ + Fe3+
Cr 3+ + 3OH − → Cr(OH) 3 

Alkali for pH
Acid for control and metal
pH control precipitation

Mixer Mixer Settler

Chromium
wastewater
Reducing Sludge
 HEAVY METAL REMOVAL
Iron Oxidation & Precipitation Process
• In aerated water, oxidation of the ferrous iron in ferric iron
occurs before Fe3+ precipitates as iron hydroxide, Fe(OH)3,
thus allowing a natural removal of dissolved iron by settling:
4 Fe + 3 O2 --> 2 Fe2O3
Fe2O3 + 3 H2O --> 2Fe(OH)3
• The form of iron in water depends on the water pH and redox
potential.
1. Oxidation Process (Aeration):
Fe2+ →Fe3+ at pH > 6.0 (fast reaction ≤ 10 min)
2. Precipitate:
Fe3+ as Fe(OH)3 at pH 7.0 – 7.5
 Chemical Precipitation
Table 6-3
Inorganic chemicals used most commonly for coagulation and precipitation processes in wastewater
treatment

Molecular Eq uiva lent Availability

Chemical Formula weight weight Form
Alum A l2(SO,i!J· l 8H200 666.5 Liquid 8.5 (A l20 3)
Lump 17 (Al20 3'
Al2(SO,ib · l 4H200 594.4 114 Liquid 8.5 (A l20 3
)
Lump 17 (Al20 3)
A luminum chloride A ICl3 13 3.3 44 Liquid
Calcium hydroxide Co(O Hb 56.1 OS CoO 40 Lump 63- 73 as CaO
(lime) Powder 85-99
Slurry 15 - 20
Ferric chloride FeCl3 16 2.2 91 Liquid 20 (Fe)
Lump 20 (Fe)
Ferric sulfate Fe2(S 0 4' 3 400 51. 5 Granular 18.5 (Fe)
Ferrous sulfate FeS0 4·7H 20 278.1 13 9 Granular 20 (Fe)
(copperos)
Sodium oluminote N o � 20 4 16 3.9 10 0 Flake 46 (Al201'
CHEMICAL PRECIPITATION FOR
PHOSPHORUS REMOVAL
 Phosphorus Removal
• Phosphorus may remain in excess after biological treatment since
only 1:100 P:BOD is needed by microorganisms.
• Phosphorus is taken out to prevent excess growth of algae.
• Most phosphate in the form of (HPO42-)
• Usually accomplished with chemical precipitation (salts)
• Ferric chloride: FeCl3
• Alum: Al2(SO4)3•14H2O
• Lime: CaO or Ca(OH)2

FeCl3 + HPO42- = FePO4 (s) + HCl

Al2(SO4)3·14H2O + 2 HPO42- = 2AlPO4 (s) + 2H+ + 3SO42-
• Effective range for alum or ferric chloride is pH 5.5 to 7.0
• If insufficient alkalinity - must add lime to neutralize H+
 Phosphorus Removal

Phosphate precipitation with Aluminum and Iron

- Because many competing reactions and effects of pH,

alkalinity, trace elements, etc.., chemical dosages are
obtained by bench-scale tests not stoichiometry.
 Phosphorus Removal

Phosphate precipitation with Aluminum

Weight Ratio: Al+3 : P = 0.87 : 1
Al2(SO4)3•14H2O: P = 9.6 : 1

Starting Dosage 40-50 mg/L

Phosphate precipitation with Iron (Fe)

Weight Ratio: Fe+3 : P = 1.8 : 1
FeCl3 : P = 5.2 : 1

Starting Dosage 20-25 mg/L

 Phosphorus Removal
1. Calcium is added in the form of lime Ca(OH)2.
2. Quantity of lime required to precipitate P is
dependent of wastewater alkalinity.
3. As the pH value of the wastewater increases > 10,
excess calcium ions will then react with the
phosphate, to precipitate in hydroxylapatite form:
10 Ca2+ + 6 PO43- + 2 OH- ↔ Ca10(PO4).6(OH)2 (s)
4. Amount of lime required depends on pH of water
rather than amount of phosphate present
5. Neutralization may be required to lower the pH
before further treatment or disposal.
 Phosphorus Removal

Alum or FeCl3

Secondary Rapid Reaction Settling

Effluent
Mix Basin Basin

Activated Sludge
Primary
Effluent Alum
or Secondary
FeCl3 Clarifier
 Disadvantages of treatment by production of
insoluble compounds

• Occasionally inability of the precipitated solid to build into particles that

are sufficiently large to settle

• Often voluminous sludge, which is difficult to dewater.

• Sludge produced by precipitation of heavy metals must be handled and

disposed as “hazardous waste”
Schematic of suggested model for design of facility for removal by forming an insoluble substance
2. CHEMICAL COAGULATION
 2. Reduction of surface charge to produce
coagulation of a colloidal suspension

• A colloidal suspension consists of one substance in a fine state of

aggregation evenly dispersed throughout a second.
• The first phase, which may consist of single polymers or aggregates of
smaller molecules, is called the dispersed or discontinuous phase
• The second phase is called the dispersing medium or continuous phase.
• The size of the dispersed particles ranges between 1 and 100 microns,
placing them between molecules and true particles.
• Colloidal systems can be further classified into emulsions, gels, or sols.
• The most common colloidal system encountered in industrial wastes consists
of organic particles or polymers, and/or inorganic particles, dispersed in a
liquid to yield a fluid system known as a sol.
• The particles or polymers belong to one of two classes :
1. lyophobic (solvent-hating) for those substances that do not have an
attraction
2. lyophilic (solvent-loving), for those substances that do. In the case of
industrial wastes, where the dispersion medium is water

• In the case of industrial wastes for which the dispersion medium is water,
the classes are called hydrophobic and hydrophilic.
 Coagulation of colloidal waste systems

• Coagulation or agglomeration of the particles in a lyophobic colloidal system

can be brought about by neutralization of the surface charge on each particle.
• Zeta potential directly indicates the strength of the net charge on each particle
• Zeta potential must be reduced only to within a certain minimum range,
referred to as the “critical zeta potential zone”

• The zeta potential can be reduced by one or a combination of several methods:

1. Increasing the electrolyte concentration of the sol
2. Reducing the potential on the surface of the dispersed solid by external
manipulation of the pH
3. Adding multivalent counterions
 Chemical Coagulation
• Colloidal particles found in wastewater :
1. net negative surface charge and 0.01 to 1 µm in size
2. attractive body forces between particles < repelling
forces
3. this stable conditions plus Brownian random motion
keeps the particles in suspension.

• Coagulation is the process of destabilizing colloidal

particles so that particle growth can occur as a result of
particle collisions.
 Chemical Coagulation
• This includes all reactions and mechanisms involved in the
chemical destabilization of particles and in the formation of larger
particles through flocculation.

• Coagulant – chemical, inorganic; usually trivalent metal, that is

added to destabilize the colloidal particles in wastewater so that
floc formation can occur.
• metal salts, and prehydrolized metal salts (alum, ferric
sulfate, polyaluminum chloride, ferric chloride, etc )

• Flocculant – chemical, typically organic polymer, added to

enhance the flocculation process.
• natural and synthetic organic polymers.
• Coagulation and flocculation neutralize or reduce the natural repellent negative
electrical charge that particles in water carry.
• The electrical charge keeps particles separate and in suspension.
• By chemically removing the charge, then ensuring the particles contact,
coagulation and flocculation alter the colloids so that they adhere to form
floc particles.
 Factors influence the chemical coagulation

• Various other factors influence the chemical coagulation process including:

1. Temperature
2. Influent quality
3. Alkalinity
4. Type and amount of coagulant used
5. Type and length of flocculation
6. Type and length of mixing
 Chemical Coagulation: Mechanism
Development of Surface Charges in Wastewater

a) Preferential Adsorption
- when oil droplets, gas bubbles, or other inert
substances are dispersed in water, they will acquire –ve
charge through adsorption of ions (hydroxyl ions)

b) Ionization
- ionization of carboxyl and amino groups (at
different level of pH)
 Chemical
Coagulation:
Mechanism
a) Coagulant addition
and charge neutralization

When coagulants such as Al2(SO4)3 are added to the water supply, they
• Hydrolyze to cations thus neutralize -ve charged particles
• Form solid precipitates of hydroxide [Al(OH)3] that sweep down particles into settling
mass.

Al2(SO4)3.18H20+ 3Ca(HCO3) 2AI(OH)3+ 3CaSO4+ 6C02 + 18H20

AI(OH)3 or Al2O3 ( form as floc) is the key element causing destabilisation of charge. Alum
is the most commonly used coagulant in the water treatment and is most effective between
pH ranges 5.0 – 7.5
Chemical Coagulation: Mechanism
Common Coagulants
 Coagulants & Coagulant Aids

Alum
Magnesium chloride

Polyacrylamide

Chitosan (natural) Ferric Chloride

 Chemical Coagulation
COAGULANT AIDS

The addition of some chemicals will enhance coagulation

by promoting the growth of large settling sludge.

Activated silica
• A short chain polymer that serves to bind together
particles of fine aluminum hydrate. At high dosage,
silica will inhibit floc formation because of its
electronegative properties.
• The usual dosage is 5-10mg/L.

Acid or base
• For pH adjustment at optimum value for coagulation.
 Chemical Coagulation
Polyelectrolyte
• High molecular weight polymers which contain adsorbable groups and
form ridges between particles or charged flocs.
• Large flocs (0.3-1.0mm) are created when small dosages of
polyelectrolyte (1-5 mg/L) are added in conjunction with alum or FeCl3

There are 3 types of polyelectrolyte;

CATIONIC
• Which adsorbed on a negative colloid or floc particles
ANIONIC
• Which replaces the anionic group on a colloidal particle and permit
hydrogen bonding between the colloid and polymer
NON-IONIC
• Which adsorbs and flocculates
Chemical Coagulation: Process Schematic
 Chemical Coagulation: EQUIPMENT
Basic water treatment unit processes:
The conventional system of mixing and coagulation /flocculation

• By rapidly mixing coagulant chemicals in water, then slowly and gently stirring the mixture
before sedimentation, the particles form floc.
• The larger and heavier the floc particles settle, then can be removed by subsequent
settling and filtration.
3. Reaction to produce an insoluble gas

𝐴+𝐵 ↔𝐶+𝐷 Equilibrium state

• If product C or D is a gas that is very poorly soluble in the wastewater being

treated, it will remove itself from solution
• Thus forcing the equilibrium to the right until the target substance (A or B) has
essentially disappeared.
• An example of this treatment technology is the removal of nitrite ion by
chlorination, as shown by following equation:
• The basic process of breakpoint chlorination is that chlorine reacts with
ammonia in four different stages to ultimately produce nitrogen gas,
hydrogen ions, chloride ions, and possibly some nitrous oxide, and some
nitrate
 Alkaline chlorination of cyanide

• Cyanide is used in metal plating baths

• Metal cyanides are soluble in water to relatively high degrees. (TOXIC!!)
• Chlorine will react instantaneously with cyanide, at all pH levels, to produce
cyanogen
chloride, as follows:

• The cyanogen chloride will persist as a volatile, toxic, odorous gas

• In the presence of hydroxide alkalinity, however, cyanogen chloride is converted
to cyanate, which is a thousand times less toxic than cyanide:
• If chlorine is present in excess, it will oxidize the cyanate to carbon dioxide and nitrogen
gases, both only sparingly soluble in water
THANK YOU