Client: Bangalore Water Supply & Sewerage Board (BWSSB)

Contractor: SUEZ India Pvt Ltd (SIPL)

Site: 300 MLD WTP T K Halli

Safety Guidelines for Chlorine Applications at Chlorine

Building in Water Treatment Plants
 INDEX

1. Introduction

2. Application of Disinfectant at Water Works

3. Characteristics of Chlorine

4. Exposure Routes

5. Exposure Limits

6. Harmful Effects of Chlorine

7. Causes of Concern for Chlorine Application

8. Requirement of Safety Systems at Water Treatment Plant

9. Storage and Handling of Chlorine Cylinders

10. Chlorine Detection and Decontamination System

10.1 Detection System

10.2 Sensors & leak detection transmitters
10.3 Neutralization Pit

10.4-Scrubber System

11. Spill & Leakage Handling

12. Personal Protective Methods

13. First Aid

14. Appendices

i. Abbreviations used
1. Introduction:

Chlorine is one of the most common chemicals used in diverse industrial fields
including pharmaceuticals, pulp & paper industries, automobile components
manufacture, agrochemicals and in manufacturing products of domestic and other use
like cleaning & bleaching agent, PVC etc. Chlorine is widely used in treatment of
water as disinfectant and protection against waterborne microbes.

Chlorine is hazardous and may pose potential risk and a severe emergency may
suddenly and unexpectedly occur at chlorine storage and handling area in site. Such
eventualities should be anticipated, and proper system must be installed to tackle
them effectively.

2 Application of Disinfectants at Water Works:

A wide range of disinfectants are available such as chlorination, ozonation and UV

disinfection and all water works use them for the supply of safe potable water.
Despite being toxic, the chlorine is the most preferred disinfectant on account of
lower cost and easy availability.

2. Characteristics of Chlorine:

Chlorine gas is 2.48 times heavier than air and is greenish yellow in color with
disagreeable, sharp, pungent, and penetrating odor. It is nonflammable but strong
oxidizer and highly corrosive, very toxic to aquatic organisms and birds. It can exist as
a gas or as a liquid. The liquid chlorine is amber colored and about 1.44 times heavier
than water. It vaporizes at standard temperature and pressure with 1 litre liquid
yielding about 450 litres of gas.

 Conversion – 1 ppm = 2.89 mg/m3

 Solubility in water – 0.7%
 Freezing Point – -150 o F
 Vapor density – 2.48 g/litre
 Vapor pressure – 5.8 bar at 20 oC
 Sp. Gravity – 1.47 g/ml at 0oC
 Critical Temp. – 144 oC
 Critical pressure – 76.1 atm (7711 kPa)
 Viscosity – 0.346 centipoise at 0oC (liq)- 0.0134 centipoise at 0oC (gas)

4. Exposure Routes:
 The chlorine enters the body through Skin, Eyes, and Inhalation.

5. Exposure Limits:

 OSHA PEL (TLV) - 1 PPM (2.89 mg/m3)

 IDLH - 10 PPM
 TWA limit - 1 PPM (For skin)
(8 hours exposure)
 NIOSH-REL 0.5 PPM (1.45 mg/m3)
(15 minutes exposure)

6 Harmful Effects of Chlorine:

Chlorine in high concentration acts as an asphyxiant by causing cramps in the

muscles of the larynx (choking), swelling of the mucous membranes, nausea,
vomiting and anxiety. Acute respiratory distress including cough, hemoptysis, chest
pain, dyspnea, and later tracheobronchitis, pulmonary edema, and pneumonia may
supervene (see table below).

Toxic Effects of Chlorine

Chlorine Concentration Effects
0.03 - 0.1 ppm Range of odor threshold
1 - 3 ppm May cause mild irritation to eyes, nose, throat
3 - 5 ppm Stinging or burning in eyes, nose, throat. May cause
headache, watering eyes, sneezing, coughing, breathing
difficulty, bloody nose, and blood-tinged sputum.
5 - 15 ppm Severe irritation of eyes, nose, throat, and respiratory
tract
10 ppm Immediately Dangerous to Life & Health (IDLH)
30 - 60 ppm Immediate breathing difficulty resulting in pulmonary
edema, possibly causing suffocation and death.
430 ppm Lethal after 30 minutes.
1000 ppm or more Fatal after a few breathes

Chlorine is corrosive to the eyes, skin, and respiratory tract. Eye contact can cause
permanent damage. Inhalation of the gas can cause pulmonary edema, a medical
emergency that can be delayed for several hours. This can cause death. Rapid
evaporation of the liquid may cause frostbite. Repeated exposure may permanently
damage the lungs or cause chronic bronchitis. Chlorine may affect the teeth
resulting in erosion, and cause skin rash. A single high exposure may cause similar
health effects.
 7 Causes of concern for Chlorine Applications:

The use of chlorine for the disinfection of potable water supplies has been of great
significance from a public health perspective but its application raises serious concerns
which need prime attention from safety point of view. The causes of concern are as
follows:

1. Chlorine is a highly toxic substance that is transported by trucks/road transport

and can pose severe hazard in case of accident.

2. Chlorine is highly toxic, corrosive, and penetrating at ambient temperature

which poses potential health risk to staff at water treatment plant and public
around, if released by accident.

3. Stringent provisions for containment and neutralization needs to be maintained

at chlorine storage and handling area in site.

Chlorination Mechanism, chlorinators

8 Requirement of Safety Systems at Water Treatment Plant:

All such installations must have written safe work procedures, but not limited to, for
the following:

Cylinder change
Leak detection & control.
Use of repair kit and container repair
Checking protocol
Respiration protocol
Self-breathing apparatus protocol
Disposal of damaged containers
Routine maintenance of equipment
 At the water treatment plant, which have chlorination system and use chlorine for
disinfection should have following safety arrangements in place to meet the
emergency:

1. On-site Emergency Plan

2. Breathing apparatus
3. Emergency kit
4. Leak detectors
5. Neutralization tank
6. Scrubber system
7. Siren system.
8. Communication system.
9. Tagging system for equipments
10. First aid including tablets and cough mixtures
11. Exhaust fans
12. Facility for testing of pressure vessels, chlorine lines etc.
13. Training & mock drill
14. Safety showers & Eye fountain
15. Water curtain around storage facility
16. Protecting hoods for ton-containers.
17. Fire extinguishers.
18. Windsock
19. Placards in local language for public cautioning, first aid and list of different
authorities with phone numbers.
20. Personal protective equipments, viz. protective glass, clothes, gloves, shoes,
helmet, goggles etc.
21. Placards at strategic locations showing Material Safety Data Sheet (MSDS),
International Chemical Safety Card (ICSC) etc. of chlorine.

9 Storage & Handling of Chlorine Cylinders:

The chlorine has a great potential for creating hazard hence there is need to observe
certain precautions for the storage, use and handling of chlorine cylinders at site.
Some of the measures, that need to be observed in this regard, are given as follows:

 Do not store the cylinders in exits or egress routes.

 Cylinder storage area should be well ventilated.

 Cylinders should not be stored in damp areas, near salt or corrosive.

chemicals, fumes, heat or where exposed to the weather.

 Always use proper trunnions to place a cylinder on ground.

 Trunnions Chlorine tonners

 Chlorine tonners must be stored in proper way and that cylinders are used in the
order in which they are received.

 Avoid storing cylinder longer than one year without use.

 Cylinders shall be kept at least 20 ft. away from all flammables, combustible, or
incompatible substances.

 Cylinders should not be dragged, rolled, or physically carried. A lifter, hand truck,
monorail etc. should be used to carry or transport the cylinder in the premises.

 Magnets should not be used for lifting cylinders.

 The cylinders should not be painted by users.

 Close valves on gas tonner when the system is not in use.

 Do not open the tonner if the valve is corroded.

 Check equipment and lines frequently owing to the corrosive nature of chlorine.

 Never attempt to modify, alter, or repair containers & valves. These tasks should
be carried out by the suppliers.

 Remove regulator after use and flush with dry air or nitrogen.

 Only the wrenches and tools provided by the cylinder supplier should be used to
handle the valve. Pliers or other tools should never be used instead.

 Never attempt to apply PTFE tape or other sealing material to tight the seal. The
tightening should be achieved metal to metal else the valve or regulator should
be replaced.
 Never use oil or grease on the regulator of a cylinder valve.
 An operator must be given proper training to handle the cylinder.

 Always follow the chlorine suppliers' recommendations to dispose off leaking or

damaged cylinders.

The maintenance of the Chlorination Plant is very essential for smooth operation.
Following steps must be followed for satisfactory running of chlorination system.

o Check all the joints once in a week by Ammonia for any leakage
o While replacing the chlorine tonner always use new lead gasket
o Check all the probes on the system once in three months’ time for
functioning.
o Cleaning of the chlorinator shall be watched for proper operation
o All the valves on gas line must be operated irrespective of the usage in a
week, otherwise the valve will become jammed and non-operative in
emergency

Equipment Failure

See relevant manufacturer's manual.

Shutdown

Less than one week:

Simple shutdown of each unit

 Normal restarting
 Rinsing of suction and delivery systems
 In the case of reagents in the form of slurry NEVER STOP THE STIRRERS.

A polymer solution can last one week. If the solution is not used after this period, it
must be drained.

From one week to one month:

 Empty, clean, rinse and fill polymer preparation unit with water.

More than one month:

 Same procedure for all the reagents but drain the polymer preparation unit.
10 Chlorine Detection and Decontamination System:

10.1 Detection System

Chlorine detection and neutralization facility is essentially required at water treatment

plants where chlorine tonners are used for disinfection purpose. This system activates
the emergency services and decontaminates the spilled material to tackle the
chemical emergency.

The chlorine detection equipment should be installed at strategic locations in the

plant area, including at chlorinators area, cylinders storage area, cylinder off-load site
etc, so that it can sense the odor even at 0.1 ppm (0.289 mg/m3) and activate the
siren to alert the people in and around. The chlorine detection systems should
function in on-line as well as off-line mode, i.e., in the event of leakage when the
chlorination is in progress, i.e., tonners in use, and when the chlorination process is
off, or tonners are kept offline.

In addition to gas detection equipment, ammonia torch test should be performed

periodically at strategic locations in the plant area to check the chlorine leakage.
Silver nitrate test can also be tried to check the presence of chlorine, but the former
should be preferred. Handy electronic detectors can also be used to check the leakage
of chlorine.

Ammonia torch test electronic detectors

 Ammonia torch Test: A glass rod having cotton wrapper on one end, dipped in liquor
ammonia, gives white smoke of ammonium chloride when meets chlorine.

Silver nitrate Test: When a glass rod, dipped in silver nitrate solution, meets chlorine,
a white precipitate is formed at its tip.

10.2 Sensors & leak detection transmitters:

In the chlorination system, the sequence that is taken into SCADA is the chlorine leak
detection. It consists of the sensors, gas detectors and the caustic system. The gas sensors
generate a current proportional to the gas concentration in the room air. The gas detector-
warning unit amplifies the current from the sensors and triggers a preliminary warning
when the first limit is violated. The sensor activates appropriate warning and protection
units when the second limit is violated. Then the sensor outputs the measured
concentration of the two sensors in 4-20mA via current outputs and is further displayed.

Detection: 4 sensors are provided in the chlorine facility. The sensors at 0.5 ppm detect the
leak. At 1.5 PPM, the first limit is set and at 3.0 PPM, the second limit is set in the leak

Chlorine Leak Detectors Sensors

detector. The preliminary warning is given when the first limit is reached, and the chlorine
neutralization system is started when the leak reaches the second limit.
Audio Visual Alarm: one audio-visual alarm is fixed and connected with sensors by
controllers. As soon the concentration of chlorine reaches to 3.O PPM level, an alarm will be
raised automatically. The start and the stop sequence are as below.

Start Sequence
Range of leakage Intensity of leakage Equipment triggering in this range
 (in PPM)
0-1.5 O.K. Alarm
1.5-3.0 Low leakage Exhaust fan ‘ON’
Above 3.0 High leakage After 90 seconds of high leakage:
1) Exhaust fan ‘OFF’
2) Emergency siren ‘ON’

Stop Sequence
Range of leakage (in Intensity of Equipment triggering in this range
PPM) leakage
Above 3.0 High leakage After 90 seconds of high leakage:
1) Exhaust fan ‘OFF’
2) Emergency siren ‘ON’
3.0-1.5 Low leakage 1) Exhaust fan ‘ON’
2) Emergency siren ‘OFF'
Below 1.5 O.K. 1) Exhaust fan ‘OFF’
2) Emergency siren ‘OFF'

10.3 Neutralization Pit

The chlorine storage and handling area in a water treatment/purification plant must
have chlorine neutralization facility, viz. neutralization pit as well as scrubber system.
The neutralization pit should be constructed close to chlorination site and chlorine
storage area. There should be sufficient slope between platform and neutralization pit
so that the leaked or defected chlorine cylinder/tonner can be rolled down easily and
swiftly into the neutralization pit. The surface area and the volume of pit should be
planned in such a manner that chlorine container is immersed completely in the alkali
solution.
The caustic solution, sodium hydroxide, is preferred for the neutralization purpose
owing to its faster and better absorption efficiency as against lime which cause
problem of sludge formation and choking of treatment system pipelines. A ready
prepared caustic solution should be used in the pit instead of pouring sodium
hydroxide pallets in the pit water as the absorption efficiency in the later case would
be less. Ideally the quantity of NaOH needed for the neutralizing one tonner, i.e., 900
kg, would be 1066 kg. The reaction between NaOH and Cl2 goes as follows:

Cl2 + 2NaOH NaOCl + NaCl + H2O

Considering the stoichiometry and mass balance equation, 1 kg of Cl2 and 1.3 kg of
NaOH will produce 1.05 kg sodium hypochlorite, as evident from the above equation.
The other chemicals that can also be used for chlorine neutralization are as follows:

* Potassium hydroxide (KOH)

* Sodium carbonate (NA2CO3)
* Calcium hydroxide (Ca(OH)2
* Sodium sulphite (Na2SO3
* Sodium thiosulphate (Na2S2O3)

The quantity of other chemicals required for neutralization of chlorine is given on the
following page:

Neutralization Pit

10.4 Scrubber Unit

In addition to a chlorine neutralization pit, all the water treatment plants should have
an effective automated chlorine scrubber system that can activate automatically
immediately on sensing the chlorine presence in the ambient environment to absorb
the leaked gas and neutralize it in the scrubber.

The Chlorine Gas Leakage Detection, Absorption, and Neutralization System reduces
the risk of chlorine gas spreading into the atmosphere. It automatically controls and
absorbs heavy leaks from 100 kg or from 900 kg ton containers to absorb in a caustic
solution, thus forming hypochlorite that can be reused as a cleaning agent.
 Th
e scrubber system consists of a blower, absorption tower packed with ranching rings,
an alkali (NaOH) tank, alkali circulation pump, piping valves and light weight FRP duct.
The chlorine gas is sucked by blower and is delivered to the absorption tower where it
is absorbed by absorbent and the air is vented at the top of the tower. As the
extracted air, contaminated with chlorine gas, is blown up through the column the
caustic soda reacts with it to form sodium chloride and sodium hypochlorite. As this
absorption is accompanied by a chemical reaction, there is negligible chlorine in the
air vent.
Cl2 + 2NAOH NaOCl + NaCl + H2O

It should be ensured that enough absorbent is continuously circulated in the

absorption tower from the absorbent tank till the tonner gets emptied. The spent
absorbent, after completion of neutralization of all chlorine, will contain only sodium
chloride or sodium hypochlorite which are innocuous.

11. Spill / leakage handling

In the event of spillage or leakage of chlorine following measures may be observed for
speedy control and minimizing the extent of damage:

 Contact Emergency Response Centre on phone no. -------------------------- and

other concerned expert agencies for emergency support.

 Evacuate the danger area around the incident site. Evacuate and restrict persons
not wearing protective equipment from areas of spill or leak until cleanup is
complete.

 Stop or reduce leaks if it is safe to do so and prevent chlorine from entering

sewers, waterways, or confined spaces.
  Supply sufficient replacement air to make up for air removed by exhaust
systems.

 The person should wear protective gloves, protective clothing, safety goggles,
breathing apparatus as specified above.

 If the gas is leaked, stop the flow of gas if it can be done safely. If the source of
the leak is a cylinder and the leak cannot be stopped in place, remove the leaking
cylinder to a safe place in the open air, and repair the leak, if possible, using a
standard kit.

 If the leak can be stopped in place, bubble chlorine left in the service line
through a sodium sulfide and excess sodium bicarbonate solution with the help
of a trap in the line.

 Follow the neutralization process as stated in above.

 For liquid spills, ventilate area and wash down spill with water.

12. Personal Protective Measures:

There is always chance of leakage or spillage of chlorine gas at chlorine building in
water treatment facility and there is likelihood of excessive gas levels in case the
leaked gas is not controlled, and this can adversely affect the plant staff and people
in the vicinity area. It is, therefore, strongly recommended to have respiratory
protection in the form of full-face gas masks with proper canisters or supplied air
respirators (SAR) at site which can be used by the staff in times of emergency.

The skin effects of chlorine can generally be controlled by good personal hygiene
practices. If very high gas concentrations or liquid chlorine is present, full protective
clothing, gloves, and eye protection should be used. The following are
recommended in this regard:

 Butyl rubber, Neoprene, Teflon™, Saranex ™, Barricade ™, CPF3 ™, Responder ™,

Viton ™, Trellchem HPS ™, Tychem 10000 ™ (Resistance to breakthrough longer than
8 hour) are among the recommended protective materials.

 Nitrile rubber, 4H ™ (Resistance to breakthrough longer than 4 hours) is also

recommended.

 It is not recommended to use very thin natural rubber, neoprene, nitrile, and PVC
gloves of 0.3 mm or less.

 Polyethylene and polyvinyl chloride are also not recommended.

  Use supplied air respirator (SAR) or chemical cartridge respirator with cartridge to
protect against Cl2 up to 5 ppm.

SCBA Boiler suit Goggles Rubber gloves

Gumboots Helmet with face guard SCBA

Personal Protective gadgets

 Use SAR operated in a continuous flow mode with cartridge / full face piece
chemical cartridge respirator with cartridge / gas mask with canister / full face piece
self-contained breathing apparatus (SCBA) or full-face piece SAR to protect against
chlorine up to 10 ppm.

13. First Aid:

 In the event of an exposure to chlorine, the following first aid measures can be
adopted to minimize the damage to body systems:
  The aids that should be made available at chlorine storage and handling site for
immediate assistance include Compressed oxygen, forced-oxygen mask, soap, water,
normal saline, D5W, Ringer's lactate, isoproterenol inhaler, sodium bicarbonate etc.

D5W is 5% dextrose in water which consists of 278 mmol/L dextrose. Ringer's lactate
is basically crystalloids which include saline and dextrose.

 In case of skin exposure, remove the contaminated clothes immediately, rinse skin
with plenty of water for at least 15 minutes and wash the skin with soap and water.

 In case of exposure to eyes, rinse the eyes with plenty of lukewarm water for at
least 15 minutes. Contact doctors for medical aid.

 Do not allow the victim to drink alcohol or smoke.

 Give plenty of milk to the victim if he can drink.

 In case of inhalation try to get fresh air or artificial respiration. Check respiratory rate
and note any trauma. In case if no pulse is detected, provide cardiopulmonary
resuscitation (CPR). If not breathing, provide artificial respiration. If breathing is
labored, administer oxygen or respiratory support.

Abbreviations Used

CPR - Cardiopulmonary Resuscitation

ERC - Emergency Response Centre

FRP - Fiber Reinforced Plastic

ICSC - International Chemical Safety Card

IDLH - Immediately Dangerous to Life & Health

MSDS - Material Safety Data Sheet

mg/m3 - Milligram per cubic meter

Mmol/L - Millimole per liter

NIOSH - National Institute of Occupational Safety & Health

PPM - Parts Per Million

PEL - Permissible Exposure Limit

PTFE - Polytetrafluoroethylene

REL - Recommended Exposure Limit

SAR - Supplied Air Respirator

SCBA - Self Contained Breathing Apparatus

TLV - Threshold Limit Value

TWA - Time Weightage Average

PVC - Polyvinyl Chloride