CV6501 Water Treatment & Process Design

Part I

Dr. Katherine Dongqing Zhang

School of Civil and Environmental Engineering

Nanyang Technological University

[email protected]
 Course Outline

week 1 – Introduction and water characteristics

week 2 – Water characteristics, standards, treatment
processes & selection
week 3 – Coagulation and flocculation
week 4 – Sedimentation
week 5 – Filtration
week 6 – Disinfection
Week 7 – Disinfection and quiz
 Disinfection

(WEEK 7)

Today’s Lecture
Flocculation and its applications in water treatment

Typical layout of a water treatment plant

6. Disinfection

 Disinfection term
 Disinfection with free & combined chlorine
 Disinfection kinetics
 Disinfection with chlorine dioxide
 Disinfection with ozonation
 Disinfection with UV light
6.1. DISINFECTION TERMS

Microbiological contaminants in drinking water is

eliminated by two strategies:
 Preventing their access to the water source;
 Employing water treatment to reduce their
concentration in water
DISINFECTION
 Disinfection: to inactivate microorganisms in
water so that the occurrence of active

CV3501 (2008-09) Lecture 9: Disinfection

disease causing microorganisms is reduced
to acceptable levels
 Sterilization: to kill all living organisms
 Methods: Autoclaving (high pressure steam
120 – 130oC for 15-20 min), poisonous gas
(ethylene oxide, chlorine dioxide etc.), UV
irradiation etc.
7
POSSIBLE DISINFECTION METHODS
 Water boiling: energy intensive;
 Iodine: difficult to deliver to water and can cause
adverse health effects;
 Silver and copper: difficult to deliver to water and are
only bacteriostatic.
 Quaternary ammonium compounds: limited in
availability, costly and not effective against viruses;
 Silver: many microbes are not inactivated at silver
concentrations;
 Silver: bacteria resistant.
METHODS OF DISINFECTION COMMONLY USED
Chemical oxidants
o Free chlorine – mostly common
o Combined chlorine (chlorine combined with
ammonia, also known as chloramines)
o Ozone – strongest oxidant
o Chlorine dioxide

Electromagnetic radiation
o UV light
HISTORY OF DISINFECTION
 1880: Kock showed chlorine could inactivate
pathogenic bacteria
 1902: First use of chlorination in Belgium
 1908: First use in USA: Jersey City
 1913: First use of Chlorine gas – Philodelphia,
USA
 1970s: Formation of THMs
 1980s: Giardia/Crypotosporidium were identified
as important waterborn pathogen
DISINFECTANT USE IN MUNICIPAL DRINKING
WATER IN US
DISINFECTION MECHANISMS
 Damage to the cell wall (ozone, chlorine)
 Alteration of the cell permeability (phenolic
compounds)
 Alteration of the colloidal nature of the
protoplasm (heat, UV radiation)
 Alteration of the organism DAN or RNA (UV
radiation)
 Oxidation of cytoplasmic enzyme (oxidizing
agents such as chlorine);
 Oxidation of nucleotide bases.
DISINFECTION TERMS
DISINFECTION TERMS
DESIRABLE CHARACTERISTICS OF A DISINFECTANT
SURFACE WATER TREATMENT RULES
GENERAL EFFECTIVENESS
6.2. DISINFECTION WITH FREE AND COMBINED
CHLORINE
CHLORINATION TERMS
CHLORINATION TERMS
MAINTAINING OF RESIDUAL
 Disinfect any recontamination;
 Prevent bacteria growth in the treated
water and distribution system;
 Control those non-pathogenic slime-
forming organisms.
 control microbiological growths when the
water is biologically unstable.
CHEMISTRY OF FREE CHLORINE
CHEMISTRY OF FREE CHLORINE
CHEMISTRY OF FREE CHLORINE
CHEMISTRY OF FREE CHLORINE
CHLORINE DEMAND VS. TOTAL ORGANIC
CARBON

2.5
Chlorine Demand (mg/L)

2
1.5
1
y = 0.51x - 0.16
0.5 R² = 0.93
0
0 1 2 3 4 5
Total Organic Carbon (mg/L)
CHLORINE DEMAND VS TURBIDITY
Chlorine Demand (mg/L)

2
1.6
1.2
0.8
0.4
0
0 5 10 15

Turbidity (NTU)
CHLORINE DEMAND
 React with inorganic ions: S2-, Fe2-, Mn2+,
NH4+

 React with organic matter

 Chlorine demand = chlorine dosage –

chlorine residual
HYPOCHLORITE SALTS
SODIUM HYPOCHLORITE
WHICH FORM OF CHLORINE TO USE?
 All “chlorine” disinfectants produce HOCl, the
species most important in disinfection;

CV3501 (2008-09) Lecture 9: Disinfection

 Cl2 gas: sold in bulk, cheap, but dangerous to
transport and store due to its toxicity;
 Sodium hypochlorite (liquid) is easy to handle,
but not stable;
 Calsium hypochlorite (powder) is used in small
systems.

31
FREE CHLORINE:

 Advantages
 Effective against (almost) all types of microbes
 Relatively simple maintenance and operation

 Inexpensive

 Disadvantages
 Corrosive
 High toxicity

 High chemical hazard

 Highly sensitive to inorganic and organic loads

 Formation of harmful DBP

CHEMISTRY OF COMBINED CHLORINE
CHEMISTRY OF COMBINED CHLORINE
CHLORAMINES
 Less effective than HOCl by about 1000X;
 More stable than chlorine;
 Mch longer lasting in the water and provide

CV3501 (2008-09) Lecture 9: Disinfection

residual protection;
 Suitable as distribution disinfectant;
 Reaction between chloramines and organic
matter is weak, thus formation of DBP is
minimized;
 Not so effective against viruses, protozoan
cysts, and bacterial spores.
35
BREAK POINT CHLORINATION
BREAK POINT CHLORINATION
 Chlorine reacts first with the reducing
compounds such as Fe2+, Mn2+, S2-, and the
chlorine will be reduced to chloride ion Cl-
(from zero to point A on the figure).
 Chlorine will react with NH3 to form
chloramines (from point A to B).
 Some chloramines are oxidized to nitrogen
gas and the chlorine is reduced to Cl- ion
(from point B to C).
 Continued addition of chlorine will produced
free available chlorine (at point C). Point C is
called the break point.
CHLORINE DEMAND CURVE
BREAKPOINT CHLORINATION
 The residual = dosage – demand
 The residual between points A to C is called
combined residual because the chlorine is in
the form of chloramines.
 From point C and up, a free chlorine residual
start to appear in water in addition to the
combined residual.
 The free residual = hypochlorous acid (HOCl)
and hypochlorite ion (OCl-).
 The total residual after the break point = free +
combined.
BREAKPOINT CHLORINATION
 Breakpoint implies the addition of enough
chlorine to completely oxidize NH3, thus

CV3501 (2008-09) Lecture 9: Disinfection

producing free chlorine residual;
 Free chlorine is more effective than
chloramine, but can react with NOM to
produce THMs (MCL = 0.08 mg/L);
 About 8 g Cl2 required per g NH3-N to reach
breakpoint when pH between 6 – 8.

41
6.3. DISINFECTION KINETICS
CONTACT TIME
CONTACT TIME

dN/dt: reaction rate for the

decrease in organisms with time
CONTACT TIME
CONCENTRATION OF DISINFECTANT
CONCENTRATION OF DISINFECTANT
CONCENTRATION OF DISINFECTANT
CONCENTRATION OF DISINFECTANT
CONCENTRATION OF ORGANISMS
ENVIRONMENTAL VARIABLES
SIDE EFFECT OF CHLORINATION
6.4. DISINFECTION WITH CHLORINE DIOXIDE
CHLORINE DIOXIDE (CLO2)
 Strong oxidization and disinfecting capability
than free chlorine

CV3501 (2008-09) Lecture 9: Disinfection

 Reacts very weakly with ammonia or with THM
precursors
 Besides disinfection, use for removal of taste and
odor, color, iron, manganese, and organics
 Volatile and easily removed from water by
aeration
 Does not maintain a residual long enough; not
useful for distribution 66
CHLORINE DIOXIDE (CLO2)
 Generated onsite between chlorine (Cl2) and
sodium chlorite (NaClO2):
 2 NaClO2(aq) + Cl2(aq) = ClO2(g) + 2 NaCl

CV3501 (2008-09) Lecture 9: Disinfection

pH~2
 Forms by-products unreacted chlorite and
chlorate ClO3-
 ClO2 does not dissociate to HOCl, thus
disinfecting power relatively independent of pH
 Cost 5 – 10X more than chlorination
 Health effects not well established
67
DISINFECTION BY-PRODUCTS (DBP)
 Chlorination of water containing humic organic
substances produces toxic chlorinated by-
products

CV3501 (2008-09) Lecture 9: Disinfection

 Volatile hydrophobic compounds
 Trihalomethanes (THMs)
 Haloacetic acids (HAA5)
 Non-volatile hydrophilic compounds
 Chlorinated and non-chlorinated aromatic and
aliphatic compounds
 R-C(O)-CH3 + HOCl produce R-C(O)-OH +
68
CHCl3
 DISINFECTION BY-PRODUCTS (DBP)
 Examples of DBP:
 Trichloromethane (Chloroform) CHCl3
 Bromodichloromethane CHBrCl2

CV3501 (2008-09) Lecture 9: Disinfection

 Tribromomethane (Bromoform) CHBr3

 Dibromochloromethane CHBr2Cl

 Ways of reducing level of by-products in treated

water
 Application of chlorine after chemical coagulation and
sedimentation
 Improvement of clarification process

 Use of alternate disinfectants

69
 Application of powdered activated carbon
ADVANTAGES AND DISADVANTAGES
 Advantages
 Very effective against all type of microbes
 Disadvantages
 Unstable (must be produced on-site)
 High toxicity
 2ClO2 + 2OH- = H2O + ClO3- (Chlorate) + ClO2-(Chlorite): in
alkaline pH
 High chemical hazards
 Highly sensitive to inorganic and organic loads
 Formation of harmful disinfection by-products
(DBP’s)
 Expensive
6.5. DISINFECTION WITH OZONATION

 Ozone: colorless gas; relatively unstable;

highly reactive;
 Alternative primary disinfectant to free
chorine; the strongest oxidant;
 When dissolved in water, ozone begins a
decay process and form the hydroxyl
radical (HO·);
 Reacts with contaminants and microbes
by either direct oxidation or through the
action of HO·.
OZONATION
OZONE GENERATION
OZONE GENERATION
APPLICATION OF OZONE: FLOW DIAGRAM
APPLICATION OF OZONE: FLOW DIAGRAM
OZONE DISINFECTION RESULTS FOR
CRYPTOSPORIDIUM
ADVANTAGES AND DISADVANTAGES
 Advantages
 Highly effective against all type of microbes
 Disadvantages
 Unstable (must be produced on-site)
 High toxicity
 High chemical hazards
 Highly sensitive to inorganic and organic loads
 Formation of harmful disinfection by-products
(DBP’s)
 Highly complicated maintenance and operation
 Very expensive
COMPARISON OF DISINFECTION ALTERNATIVES
6.6. DISINFECTION WITH UV LIGHT
ELECTROMAGNETIC SPECTRUM
UV DISINFECTION
 UV radiation causes damage to nucleic acid of
organism preventing it from reproducing
 Photons in UV react directly with the nucleic acids
inorganis, damaging them
 200-300 nm wavelength is absorbed by DNA –
disinfecting rage for UV
UV DISINFECTION
 Eliminate the use of chlorine as disinfectant since
concern over disinfection-byproduct formation
associated with chlorine
 Effective against protozoan pathogens Giardia
and Cryprosporidum
 Water quality can significantly influence
effectiveness of UV disinfection
 For small scale water treatment
 Simplicity of operation
UV DISINFECTION
 Reduction in effectiveness results from direct
absorbance of UV radiation by water as well as
the various constituents in the water
 Shielding of organisms by particles that caused
high turbidities and by scales (fouling) on lamp
sleeves
 UV contactors have very short residence time –
seconds to minutes
 Short-circuiting is a potential problem
ADVANTAGES OF UV DISINFECTION
 No hazardous chemicals storage
 No known byproducts
 No residuals to remove
 Note affected by pH or temperature
 Requires short contact time = smaller contact
chamber
 No danger of overdosing