Escolar Documentos
Profissional Documentos
Cultura Documentos
The above two forms of chlorine (hypochlorous acid and hypochlorite ion) are called
"free" residual chlorine, as opposed to the reaction products of chlorine with other
compounds that can also be detected using analytical techniques that are called
"combined" residual chlorine. Free residual chlorine is a more effective disinfecting
agent than combined residual chlorine, and generally hypochlorous acid is a much
more effective disinfectant than hypochlorite ion. In wastewaters, free residual chlorine
is seldom detected and chlorine is usually found in the "combined" residual form.
Chlorine is an extremely active oxidizing chemical that will react with many substances
in wastewaters. If small amounts of chlorine are added to wastewaters it will react
rapidly and is thus consumed. For example, chlorine first reacts readily with such
substances as hydrogen sulfide, ferrous iron, manganese or thiosulfates, which may
have their origin from industrial wastes. However, almost any "reducing" compound
capable
of reacting with chlorine (an oxidizing compound), will react. If all of the chlorine is
consumed in these reactions, no disinfection will result.
Chlorine generally reacts in a prescribed order, first with inorganic reducing
compounds. If enough chlorine is added to react with these substances, then the
addition of more chlorine will result in reactions of chlorine with the organic matter that
is present. This forms chloroorganic compounds, which have little or no disinfecting
action. Again, if enough chlorine is added to react with all the reducing compounds
and all the organic matter, then the addition of a little more chlorine will react with
ammonia or other nitrogeneous compounds to produce chloramines or other combined
forms of chlorine which also have disinfecting action but are not as effective as free
chlorine.
The continued addition of chlorine will result in the destruction of the chloramines and
the formation of free chlorine. While chlorine is seldom applied to this level in
wastewater treatment, the addition of chlorine in sufficient dosages to where free
chlorine is formed is called "breakpoint" chlorination.
For effective chlorine disinfection both sufficient chlorine dosages as well as contact
time are necessary. Generally both of these factors must be worked out experimentally
and other factors will affect the effectiveness of chlorination. Among the principal
factors are bacterial numbers, pH, temperature and contacting. In "pure" systems
bacterial kill at a particular chlorine dosage is directly related to the number of bacteria
present when the chlorine is first added. pH will affect the form of chlorine present and,
generally, at neutral pH's hypochlorous acid, the more effective form of chlorine, is
favored. Temperature affects the speed with which chemical reactions take place and
colder temperatures are less favorable for disinfection. Proper contacting or mixing or
agitation, is necessary to make sure that the chlorine applied contacts or reaches the
vital parts of the microbial cell.
The precise mechanism of the disinfecting action of chlorine is not fully known.
However, chlorine is capable of undergoing a wide variety of reactions and probably
reacts with the microbial cell at several levels. At high concentrations, massive
oxidation takes place and membranes and all organic components are affected. At
lower concentrations chlorine probably affects vital protein systems as well as
membranes. From the point of view of wastewater treatment, the mechanism of action
of chlorine is much less important than its effects as a disinfecting agent.
The quantity of reducing substances, both organic and inorganic, in wastewaters,
varies, so that the amount of chlorine that has to be added to wastewater for different
purposes will also vary. The chlorine used by these organic and inorganic reducing
substances is defined as the chlorine demand. Chlorine demand is equal to the
amount of chlorine added minus that remaining as combined chlorine after a period of
time, which is generally 15 minutes. This relationship can be written as:
Chlorine Demand = (Applied Chlorine Dose) - (Chlorine Residual)
It is important to note that disinfection is carried out by that amount of chlorine
remaining after the chlorine demand has been satisfied. This quantity of chlorine in
excess of the chlorine demand is defined as residual chlorine and expressed as
milligrams per liter. For example, if a chlorinator is set to feed 50 lbs. of chlorine per 24
hours and the wastewater flow is at a rate of 0.85 mgd and the chlorine as measured
after 15 minutes contact is 0.5 mg/L, the chlorine feed or dose is:
7.1
- 0.5
6.6
Purposes of Chlorination
Chlorine is added to wastewater for a number of different purposes and chlorine
dosages and management will vary with the specific purpose. In general, chlorine
applied before any treatment is given (pre-chlorination), during treatment (plant
chlorination), or after normal treatment measures have been carried out
(postchlorination). A few of the more important purposes of chlorination are listed
below.
1. Disinfection
Chlorine is a very effective disinfecting agent and has been the agent of choice in
reducing bacterial numbers in wastewater effluents. As noted, neither primary
nor secondary methods of wastewater treatment can completely eliminate
pathogenic bacteria which are always potentially present. When wastewaters or
treated effluents are discharged to bodies of water which are, or may be used as
a source of public water supply, or for recreational purposes, treatment or
disinfection for the destruction of pathogenic organisms is required to minimize
the health hazards of pollution to these receiving waters.
Chlorination for disinfection requires that essentially all of the pathogens in the
wastewater plant effluent be destroyed. At the same time it should be noted that
many but not all of the nonpathogenic microorganisms are also destroyed. As
noted, no attempt is made to sterilize wastewater and this is not only
unnecessary but impractical. In some instances sterilization might be detrimental
where other treatment dependent upon microbial activity may follow chlorination.
Fortunately
is obtained. Since the chlorine demand of wastewater varies during the day,
the chlorine feed required to maintain a 0.5 mg/L residual will vary. In a small
wastewater plant (less than 1 mgd), the operator may not have time to check
the residual chlorine repeatedly and adjust the rate of chlorine application. In
this case, the chlorine feed is adjusted once daily to give the required residual
at the time of maximum wastewater flow, which generally coincides with the
time of maximum chlorine demand and in most plants occurs about 10:00 a.m.
Then at all other times during the day the chlorine residual should be greater
than 0.5 mg/L. This means that chlorine is being wasted, but the operator is
sure that disinfection is being accomplished.
The amount of chlorine required to produce 0.5 mg/L residual in most secondary
effluents will be between 40 and 50 lbs. per million gallons. By frequent
adjustment of the chlorine feed it might be possible to save about five to ten lbs.
of chlorine per million gallons. This can represent an economic factor in
wastewater treatment plant operation and will vary with plant size. In a larger
plant (10 mgd) the waste of chlorine might be significant and is worth trying to
save. Therefore, residual chlorine values are measured possibly three or four
times a day and the chlorinator adjusted each time. In still larger plants, it pays
to make measurements frequently and it is often the practice to adjust the
chlorine feed rate hourly.
Where the outlet sewer does not provide 15 minutes holding time at peak hourly
flow, or 30 minutes holding at average rate of flow, a chlorine contact tank is built
and so designed as to give the required 15 or 30 minutes contact time at
maximum or average flows, respectively. In this case, chlorine is applied to the
influent of the contact tank and the residual measured in the effluent.
The object of disinfection is the destruction of pathogenic bacteria and the
The
ultimate measure of effectiveness is in the bacteriological result.
measurement of residual chlorine does supply a tool for practical control. The
0.5 mg/L residual chlorine, while generally effective, is not a rigid standard but a
guide that may be changed to meet local requirements. One special case would
be the use of chlorine in the effluent from a plant serving a tuberculosis hospital.
Studies have indicated that a residual of at least 2.0 mg/L should be maintained
in the effluent from this type institution and that the detention period should be at
least two hours at the average rate of flow instead of the 30 minutes which is
normally used for basis of design.
Fish Toxicity
Chlorine as well as chloramines are generally toxic to fish as well as harmful to aquatic
biota even at low concentrations. The toxicity to aquatic life in a receiving water will
depend upon the concentration of the residual chlorine, the relative amounts of
chloramines if they are present, the amount of free chlorine, as well as the dilutions that
take place in the receiving waters. Fifty percent of all rainbow trout and minnows, for
example, have been reported killed by levels of about 0.2 mg/L of residual chlorine in
96 hours. Trout have been shown to "avoid" free chlorine levels of 0.001 mg/L.
However, it should also be noted that this would represent chlorine levels measured
after mixing and dilution in the receiving waters rather than in the effluent. It should
also be noted that residual chlorine concentrations diminish with time and mixing as
well as by temperature elevations.
Dechlorination
At times it is necessary to dechlorinate, or remove chlorine from a wastewater by the
addition of dechlorinating agents. Generally this must be done to counteract the
reactive effects of chlorine in effluent samples, for example, in determining coliforms or
BOD's. At present only a small number of treatment plants in New York State
dechlorinate, however, in the future it may become a more common practice to
dechlorinate treated wastewater.
Generally, the most common chemicals used for dechlorination are sulfur dioxide,
sodium bisulfate, sodium sulfite, sodium thiosulfate and activated carbon. The
chemical equivalents required for dechlorination can be calculated, however, laboratory
experiments should be used to help to define the required dose. For laboratory
samples Standard Methods give the recommended dosages for dechlorinating
chemicals.
Chlorine Hazards
Chlorine is a yellow green gas that is extremely toxic as well as corrosive in moist
atmospheres. Chlorine is about two-and-a-half times as heavy as air. Chlorine is not
flammable or explosive and will not freeze, even at the lowest temperatures. Chlorine
will react readily with water, moisture or moist tissues. While dry chlorine gas will not
attack iron, copper, lead and some other metals and alloys, moist chlorine readily
attacks most metals. Thus, with moisture, chlorine must be handled in corrosion
resisting materials such as silver, glass, rubber and certain plastics. Chlorine can be
detected at very low levels and has a characteristic sharp odor. At moderately low
levels chlorine can be penetrating and very irritating to mucous membranes. A very
small percentage in air causes severe coughing. Heavy exposure can be fatal.
Effect of Exposure
By Volume (ppm)
10 - 15
30
40 - 60
1000 ppm
5. Eyes. If even small quantities of chlorine have entered the eyes, hold the
eyelids apart and flush copiously with lukewarm running water. Continue
flushing for about fifteen minutes. Do not attempt any medication except under
specific instructions from a physician.
Chlorine Leaks
In general, daily inspection of all chlorine cylinders will avoid major problems. Small
leaks, detected in early stages can usually be corrected. Before any new system is
put into service it should be cleaned, dried and tested for leaks by pressurizing with
150 psi dry air and testing with soapy water applications. Prompt measures are
necessary since chlorine leaks become progressively greater. Small leaks around
valve stems can usually be corrected by tightening the packing nut or closing the
valve. A leak can also be reduced by removing the chlorine as rapidly as possible. If
it cannot be added to the process there are several chemicals which can be used to
absorb the chlorine gas. For example, chlorine can be absorbed by using 1 1/4
pounds of caustic soda or hydrated line, or 3 pounds of soda ash per pound of
chlorine. Therefore, to absorb 100 pounds of chlorine use 125 pounds of solid or flake
caustic soda dissolved in 40 gallons of water. A 55 gallon drum may be used. The
chlorine line should be well below the surface and mixing improves removal of
chlorine.
If the leaking container can be moved, it should be transported to an outdoors area
where minimal harm will occur. Keep the leaking part the most elevated so that
gaseous chlorine will leak rather than liquid chlorine.
If the leak is large, all persons in the adjacent area must be warned and evacuated.
Only authorized persons equipped with the proper breathing apparatus, and protective
measures to the eyes and body should investigate. As noted, help should be standing
by and all other persons should be cleared from the affected area. The following
generalizations can serve as guidelines.
1. The leak may be located by using a rag or brush on a stick soaked in a strong
ammonia solution (about 5% ammonia). When the rag is held close to the leak
a white gas will be formed.
2. Never apply water to a leak, nor consider submerging a chlorine cylinder (for
example, in a pond or tank), since it will probably float and water is not an
efficient absorbent for chlorine.
3. Remember to keep windward of the leak.
4. Remember that chlorine gas is heavier than air and will accumulate in the lower
parts of a room or building.
7. Leaks around valve stems and discharge outlets can usually be stopped.
8. Leaks at fusible plugs and cylinder valves requires special handling and
emergency equipment. The chlorine supplier must be notified immediately.
9. Pin hole leaks in cylinder walls or ton tanks can usually be stopped by
mechanical pressure applications (clamps, turnbuckles, etc.).
This only
temporary and may require your ingenuity.
10. Leaking containers cannot be shipped.