Chapter 7
CHLORINE DIOXIDE
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Introduction
Chlorine dioxide (ClO2) is a disinfectant with a stronger biocidal capacity than that of
chlorine and chlorine compounds. Its selective oxidating qualities make its application an
alternative to be considered for cases where not only must the water be disinfected, but its
organoleptic qualities must also be improved. It has a major effect on controlling the taste and odor
of water, as well as destroying organic substances that color the water or are trihalomethane (THM)
precursors. For that reason, it is applied particularly when the raw water contains large
concentrations of precursors and the use of traditional chlorination would act on these precursors to
bring about the formation of disinfection by-products (DBP). Even so, its use as a disinfectant in
water treatment plants is limited by the complexity and sensitivity of its production and its
relatively high cost.
Chlorine dioxide is not sold off the shelf, but must be generated on-site. Furthermore, it is
used only as a primary disinfectant and its generating and management are complex and risky. For
those reasons, its use is not recommended for small communities with little technical expertise.
That is why it is not very popular in developing countries and is used only very occasionally for
medium-sized to large systems in developed countries. Those are quite possibly the reasons why
the use of chlorine dioxide will be given little priority in rural areas of developing countries as
compared with other, more “friendly” disinfectants like chlorine, UV radiation and SSF and its
popularity will be comparable only to the excellent, but sensitive and demanding, ozonation
process.
An explanation is due here, however. Chlorine dioxide has been the subject of a great deal of
research and in recent years new technologies and forms of production have appeared, making this
technique one of the most active and innovative, together with the synergistic methods that are
described later in this manual. It is quite possible that science will at any moment come out with a
new method that will reduce the shortcomings of today’s methods and remain the only choice that
combines all of their qualities and advantages.
Properties of chlorine dioxide as a disinfectant and description of the method
Chlorine dioxide is a yellowish-green gas that is stable and relatively soluble in water until it
reaches concentrations of up to 2%. One of the more interesting properties of chlorine dioxide is its
biocidal efficacy over a wide pH range from 3 to 10 (even better at from 4 to 9). In addition to its
disinfecting properties, chlorine dioxide also improves the quality of the drinking water –it
neutralizes odors, removes color and oxidizes iron and manganese. Chlorine dioxide is ultraviolet
light sensitive.
Although new methodologies (“SCD” or “Stabilized chlorine dioxide”) have appeared that
could change the situation, today ClO2 cannot be compressed or stored in cylinders like chlorine
gas; nor can it be transported because of its instability. As a result, it must be produced on-site by
special generators.
Two mechanisms are usually used to generate chlorine dioxide: by reacting sodium chlorite
with chlorine gas (two chemical compounds system) or by reacting sodium chlorite with sodium
hypochlorite and sulphuric acid (three chemical compounds system).
2NaClO2 + Cl2 2ClO2 + 2NaCl (two compounds)
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2NaClO2 + NaOCl + H2SO4 2ClO2 + NaCl + Na2SO4 + H2O (three compounds).
Strictly as a disinfectant, ClO2 offers the following advantages:
• Its bactericidal potential is relatively independent of the pH at between 4 and 10.
• It works better than chlorine for treating spores.
• It needs little contact time.
• It is quite soluble.
• No corrosion is produced at high concentrations, thus reducing maintenance costs.
• It does not react to ammonia or ammonium salts.
• It improves coagulation.
• It is better than chlorine for removing iron and manganese.
Chlorine dioxide has limited residual properties; for that reason, chlorine is generally used
as a secondary disinfectant to ensure additional protection of the water distribution system.
Chlorine dioxide disinfection mechanisms
Chlorine dioxide exists in the water as ClO2 (little or no dissociation) and, therefore, is able to
permeate through bacterial cell membranes and destroy those cells. Its actions on viruses include
the absorption and penetration of the protein coat of the viral capsid and reacting with the viral
RNA, thus damaging the genetic capacity of the virus.
Chlorine dioxide produces a smaller microbicidal effect than ozone, but it is a stronger
disinfectant than chlorine. Recent research in the United States and Canada demonstrates that
chlorine dioxide destroys enteroviruses, E. coli and amoebas and is effective against
Cryptosporidium cysts.
The following table compares the biocidal efficacy, stability and effect of pH efficacy of
chlorine dioxide and three common disinfectants.
Biocidal efficacy, stability and effect of the pH
Disinfectant Biocidal efficacy Stability Effect of pH efficacy
Ozone 1 4 Little influence
Chlorine dioxide 2 3 Little influence
Chlorine 3 2 Decreases considerably as pH rises
Chloramines 4 1 Little influence
1 = More ; 4 = Less
This table shows that ozone, despite having the strongest oxidation potential, is the least stable
of the four compounds. It can also be noted that chloramines may be the least effective biocide,
but exhibit a longer residual effect.
Chlorine dioxide reacts with phenolic compounds, humic substances, organic substances and
metal ions in the water. This oxidation potential frequently improves the taste, odor and color of the
water and also eliminates the possibility of THM production when the constituent elements of
chlorine dioxide are appropriately dosed in the water at the site.
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By-products of disinfection with chlorine dioxide
Where chlorine disinfectants react with different substances through oxidation and
electrophilic substitution, chlorine dioxide reacts only via oxidation. That is why the use of
chlorine dioxide can result in reduced THM formation in treated water. Production of high levels of
THM in chlorine dioxide treated water can usually be attributed to poor chlorine dioxide generator
performance, generally because of excess chlorine, a substance that participates per se in THM
formation.
Often the products of chlorine dioxide oxidation do not contain halogen atoms and more
specifically, in the presence of humic substances, chlorine dioxide does not generate high levels of
THM. No formation of trihalomethane containing bromine has been noted when treating humic
materials with chlorine dioxide. Nor does it react with ammonia to form chloramines.
Even so, the existence of DBP cannot be denied and the products formed by the reaction of
chlorine dioxide with organic material in the water include chlorophenols and maleic, fumaric and
oxalic acids. A study of the by-products of chlorine dioxide in a pilot treatment project revealed the
presence of more than 40 DBP, most of them of unknown toxicity.
During the oxidation of organic material, the chlorine dioxide breaks down to a chlorite ion.
Chlorite and the chlorates are precisely the most important DBPs produced by the use of this
disinfectant.
The WHO has not yet established a guideline value for chlorine dioxide because of its rapid
breakdown into chlorite, chlorate and chloride and because the provisional WHO guideline value
for chlorite of 200 mg/liter offers adequate protection against the potential toxicity of chlorine
dioxide.
Equipment
There is no industrial standard for the performance of chlorine dioxide generators. Generator
efficiency is defined not only in terms of the conversion of sodium chlorite into chlorine dioxide,
but also of the generating of by-products such as chlorate ion, free chlorine and surplus chlorite. If
the generator fails to operate properly, it can produce these by-products in excessive amounts and
reduce the expected results. Poor generator performance will also result in higher operating costs
than desired.
Modern chlorine dioxide generators are capable of consistently performing at the desired
levels, when properly operated.
It should be borne in mind that disinfection with chlorine dioxide is recommended only for
cities that have human and material resources necessary for good operation and maintenance, as
well as for the follow-up of appropriate safety measures.
• Chlorine dioxide generator with automatic proportional feeding
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Although each component of a ClO2 generating plant is relatively simple (pumps,
flowmeters, mixers, injectors, etc.), together they make up a complex system requiring trained
personnel for its understanding, operation, maintenance and repair.
The figure illustrates a typical chlorine dioxide installation that uses an air pressure signal to
provide a proportional control over the supply of chemical substances. The same results can be
obtained if some internal components of the pneumatic or electrical system are changed.
The chlorination station may consist of a diaphragm pump that feeds a sodium chlorite
solution to the reaction tower, installed in the chlorine dioxide discharge line. The diaphragm pump
is controlled pneumatically in such a way that it is compatible with the feeder’s automatic
proportional control.
The water flow treated by the chlorine dioxide station is governed by the degree of
concentration of the chlorine solution. The maximum concentration possible under ideal hydraulic
conditions is 5,000 ppm, while the lowest limit for producing the necessary reaction is 500 ppm.
Flowmeter
G
G Calibrator ClO2
R Regulator and filter
Chlorine dioxide
generator tower
G
Rings Pneumatic
pump
controller
Chlorinator
Mixer Sodium chlorite Diaphragm
solution pump R
Cl2 Injector
Application
point
Valve
Chlorinator G Water supply
pneumatic Air
R
controller plant
Chlorine dioxide generator (two-component system)
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Plant for producing
100 Kg of ClO2/hour
Concepción, Chile
(600,000 inhabitants)
ClO2
Chlorine dioxide
generating tower Application
point
Diaphragm Double-head
pump diaphragm
pump
Mixer
Sulfuric acid
Sodium chlorite Hypochlorite
ClO2 Generator (three-component system)
• Equipment adapted to generate chlorine dioxide from hypochlorite
The figure illustrates the equipment for water works that use hypochlorite. These
installations usually treat only a flow of from 30 to 45 l/s, which is equivalent to a maximum
population of between 30,000 and 40,000 people. They can also be used in small well water supply
systems with only one automatic start-up and stopping operation.
• Modern chlorine dioxide generating equipment
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As already stated, a ClO2 system can be relatively complex, using modern technology to permit
a dosage proportional to the water flow through digital flow controllers. The efficiency of the
operation makes it possible, on the one hand, to optimize operating costs; it is more economic,
because no surplus sodium chlorite or chlorhydric acid is produced. On the other hand, such careful
operation makes THM formation impossible, inasmuch as trihalomethanes appear when the dosages
of chlorine dioxide components are not properly proportioned. This equipment can generate 30 to
4,000 g/h of chlorine dioxide, making it possible to treat flows of from 20 l/s to as much as 2.5 m3/s
for a 0.5 mg/l dose in the water. The flexibility of this equipment allows for the supply of any size
population from a small town of 20,000 to a city of two million.
1
2
13 24
10
11 12
16
9
8
17 20
3
14
23
15 7
5
6 6
22 21
4
18 19
Installation layout of a modern chlorine dioxide generating system
Where: 13. Air valve
1. Water intake 14. Suction device
2. Main pipe 15. Equipment frame
3. Shunt for the disinfection system 16. Check valve
4. Booster pump 17. Production level control device
5. Branch pipe for monitoring. 18. Safety container for acid
6. Metering pumps 19. Safety container for chlorite
7. Flow Sensor 20. Supplied chlorine dioxide meter
8. Reactor 21. Chlorine dioxide test probe
9. Reactor support 22. Water level controller
10. Proportioning valve (pressure sensitive) 23. Connector
11. Mixer 24. Contact chamber (10 – 15 minutes)
12. Check valve
Installation
Small system for a low water flow
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Installation and requirements
Chlorine dioxide in aqueous solution is highly corrosive –even more so than chlorine in some
aspects. By way of example, there are rubber hoses for chlorine concentrations of from 1,500 to
2,000 ppm that are known to have been in service for 20 years. Those same hoses could not be used
in a generating tower chlorine dioxide feeder for more than 4 or 5 years. The recommended
materials for chlorine dioxide feeding lines are, in order of preference: type I PVC and
polyethylene. The use of rubber hoses should be avoided.
Special care should be taken in storing sodium chlorite and safety experts should be
consulted about the subject. The compound should be stored in an outside structure, preferably
away from the main buildings, and built, insofar as possible, of non-burning material, such as
corrugated steel, prefabricated concrete or brick. In hot climates, sufficient water should be
available to keep the sodium chlorite area fresh and prevent its deterioration from the heat.
Electric power and trained personnel are needed to install this equipment. The installation
must be carried out appropriately to ensure safe management of the supplies used to generate
chlorine dioxide. The necessary chemical substances must also be available, such as chlorhydric or
sulphuric acid, sodium chlorite, sodium hypochlorite or chlorine gas, according to the chosen type
of equipment.
Operation and maintenance
Sodium chlorite must be handled with great care to avoid its spillage during the operation. If
spilled, an absorbent cloth must never be used; the surface must always be flushed with plenty of
water; too little is worse than none.
Monitoring
Because chlorine dioxide reactions include the formation of chlorite ion as a by-product, a
simple test kit cannot provide the analytical data required for its control. The analysis of the
chlorine dioxide generator stream and treated water is required to accurately quantify the dosage
and by-products. It is necessary to differentiate specifically between the chlorine dioxide, chlorite
ion and free chlorine in the generator stream in order to determine both yield and efficiency. Four-
step amperometric titration is the recommended method for determining the generator’s yield and
efficiency. Test equipment is available for concentrations of less than 5 mg/l in the treated water,
but it has its limitations and interferences.
The truth is that ClO2 monitoring is a further disadvantage, because trained personnel are
needed for routine analyses and it should be kept in mind that an average of 45 minutes are needed
to determine each chemical.
Advantages and disadvantages of the method
Advantages Disadvantages
• Effective against many microorganisms and • Complex.
more potent than chlorine over a short contact • Costs more than chlorine.
period. • Chlorite and chlorate by-products
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• Stronger oxidant and contributes to the are formed.
removal of odor, color and bad taste. • Must be generated on-site.
• No trihalomethane formation. • Trained workers are required for
• Apparently not affected by variations in pH. its operation and maintenance.
• Improves iron and manganese removal. • Difficult to analyze in the
laboratory.
Costs
The capital costs of chlorine dioxide production equipment vary according to a number of
elements. The costs cannot be evaluated generically with any precision. In each case, budgets must
be requested from the suppliers, which will analyze the type of process, quality of raw water
involved, treatment plant characteristics, country, site, installation conditions, and so forth.
From the operational viewpoint, the United States Environmental Protection Agency study is
generally the standard. In 1998, the EPA analyzed the cost of supplementing the Safe Drinking
Water Act (the country’s federal standard) through disinfection with ClO2 .
Operational costs of chlorine dioxide in dollars (1998)
For a population of Cost of
(inhabitants) Disinfection
($/m3)
10,000 0.02
60,000 0.01
Information sources
ALLDOS International; Photos; www.alldos.de
Cowley, G. Disinfection with Chlorine Dioxide. Published by Sterling Pulp Chemicals, Toronto
(2002).
Deininger, R.; Ancheta, A.; Ziegler, A. Chlorine dioxide. Paper presented at the PAHO
Symposium: Water Quality: Effective Disinfection (1998). Also published in CD-Rom. Available
from PAHO/CEPIS.
White, C. Handbook of chlorination. Van Nostrand Reinhold (1972).
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