PUBLISHED
BY
COMPILED
BY
SAFETY, SAFETY ENGINEERING & PUBLIC AWARENESS GROUP
HEAVY WATER BOARD (MUMBAI)
2008
CONTENT
S.N. TITLE
PAGE NO.
Introduction
History
Uses of chlorine
Occurrence
Toxic Properties
Health Hazards
10
12
chlorine tonner
10
Material of Construction
15
11
16
21
13
22
a. Engineering Controls
b. Administrative Controls
14
24
15
Case Studies
28
16
List of Suppliers
31
17
Annexure
32-37
INTRODUCTION
In 2002-2003 the total chlorine production in our Country was 1.478 million tons
(worldwide production approx. 44 million tons). Out of this approximate 0.875
million tons was liquefied and transported to various destinations in the country.
With the transportation of liquid chlorine over long distances the hazards are no
longer confined to the place of its manufacture, storage and use but are spread all
over the country.
One of the greatest hazards associated with the use of chlorine is its familiarity due
to its common use. It is often forgotten that it is potentially dangerous. The
shipment of liquid chlorine in bulk from manufacturer to consumer involves
various handling operations, in which the principal risks are common. These are
attributable due to its toxicological character, physical properties, and chemical
reactivity.
The filling, possession, transport and importation of chlorine is governed by Static
& Mobile Pressure Vessel (Unfired) Rules. In case the quantity of storage exceeds
10 MT then the statutory requirements specified under MSIHC Rules are required
to be adhered.
HISTORY:
Chlorine was discovered by Karl Wilhelm Scheele, a Swedish chemist, in 1774.
Scheele thought that chlorine was an oxide of murium, or hydrochloric acid. He
did not, however, establish chlorine as an element. In 1810, chlorine was named
and classified as an element by Humphrey Davy. It was named after the Greek
word chloros, which means pale green.
Chlorine has also been used during World War-I. It was first introduced as a
weapon on April 22, 1915 at Ypres by the Germans. The results of this weapon
were disastrous because gas masks (canister) were not invented at that time. But,
some compounds of chlorine are more dangerous and have replaced chlorine gas
on the battle field. They are phosgene, chloropicrin, Lewsite, and mustard gas.
3
USES OF CHLORINE
Although chlorine is highly toxic and hazardous in nature, at the same time it is
very useful for mankind and has become indispensable. It is used for disinfecting
drinking water, bleaching of textiles and paper, manufacture of insecticides,
pesticides and weedicides, pharmaceuticals, synthetic rubber, P.V.C./Plastics,
refrigerants, industrial solvents, rocket fuels and treatment of cooling water.
Owing to its strong oxidizing properties, chlorine is very effective in destruction of
bacteria, viruses, primitive life forms and algae. These properties are used very
widely today in the treatment of water for power stations and for drinking water
supplies. A small residue of chlorine is also left in the water to retain the necessary
antiseptic or fungicidal properties.
OCCURRENCE
The Natural Abundance of Chlorine: Chlorine's abundance is in igneous rock
which makes up 95% of the Earth's atmosphere. The most frequently seen form of
chlorine is in sodium chloride, NaCl, found in seawater.
Chlorine is never found in a free state; it combines with almost all elements.
Basic Properties of Chlorine
Atomic Mass
35.453
Atomic Number
17
Melting Point
-101 oC
Boiling Point
-34.6 oC
Isotopes of Chlorine
Nominal Mass Accurate Mass % Natural Abundance
35
Cl
34.968
75.77
37
Cl
36.965
24.23
These two isotopes have been used to define the atomic weight of chlorine to be
35.3. These isotopes have the same chemical properties, but, their masses are
different.
There is also a radioactive isotope of chlorine, including 36Cl.
This is the structure of a chlorine molecule. The shared atoms are equidistant form the
atoms. Therefore, each atom has the same relationship for the shared atoms.
Chlorine is a member of the halogen family and group 17. It has seven valence
electrons. It consists of 17 protons, 18 neutrons, and 17 electrons. Its electronic
configuration is the following:
1s2 2s2 2p6 3s2 3p5
Because the element has only seven electrons in its outer shell, the atom is
unstable and will seek to find an element to combine with. All elements want to
have 8 valence electrons to secure stability.
How is chlorine made?
Chlorine is produced by electrolysis of brine solution (common salt dissolved in
water).
Essential by-products are caustic soda (sodium hydroxide (NaOH)) and hydrogen
(H2).
Volumetric Expansion
Relative density
Fire / explosion hazards
Incompatibility
Corrosivity
HCl + HOCl
That why moist chlorine is corrosive to most metals
1. At ambient temp. dry Cl2 reacts with Al, As, Au, Sn, Ti and
Hg
2. It reacts with steels, Fe, Cu, Pb, Pt, Ag & Ni on heating above
120oC
3. At certain temp, Cl2 reacts spontaneously with H2 to form
HCl. This occurs slowly in dark but explosively in sunlight or at
more than 2500C.
6
Reactivity
a. With metals
Dry chlorine reacts with aluminium, arsenic, gold, mercury, selenium,
tellurium, tin and titanium
At certain temperatures potassium and sodium burn in dry chlorine
Carbon steel ignites at temperatures above 250C
b. With other elements Chlorine reacts with most elements under specified
conditions. Mixtures of chlorine and hydrogen composed of more than 5 percent
of either component may react with explosion. It reacts with ammonia, alkalis and
alkaline earth metal hydroxides.
c. With inorganic compounds Chlorine has great affinity for hydrogen and as
such, removes hydrogen from some inorganic compounds to form hydrochloric
acid. It reacts with ammonia and ammonium compounds to form various mixtures
of chloramines and under proper conditions nitrogen trichloride which is
explosive. Chlorine reacts readily with lime and caustic soda to form hypochlorite
which is well-known bleaching agents.
The following chemical reactions take place between chlorine and lime or caustic
soda:
2Ca(OH)2 + 2Cl2 + 2H2O = Ca(OCl)2.4H2O + CaCl2
2CaO + 2Cl2 + 4H2O
= Ca(OCl)2.4H2O + CaCl2
2NaOH
Cl2
These reactions are important because lime and caustic soda solutions are used for
handling chlorine leaks. Chlorine reacts with moisture to liberate nascent oxygen
and form hydrochloric acid.
d. With organic compounds Chlorine reacts with organic compounds to form
chlorinated derivatives and hydrogen chloride. Some of these reactions,
particularly those with hydrocarbons, alcohols and ethers may become explosive.
Gaseous chlorine, wet or dry, may be used with hard rubber equipment at normal
temperatures and pressures. However, neither soft nor hard rubber can be used
with liquid chlorine.
7
Effect
Order of threshold
TLV - TWA(ACGIH), Nasal Irritation & Coughing
STEL
Least amount for detectable odour
Threshold of irritation
Noxiousness, impossible to breathe
Least amount causing irritation of throat
Least amount causing cough
Amount dangerous in - 1 hour
Concentration dangerous, for even short exposure
IHL-RAT LC 50 (Lethal Concentration Inhalation)
Fatal even if the exposure is brief
HEALTH HAZARDS
General Chlorine gas is primarily a respiratory irritant. The characteristic
penetrating odour of chlorine gas usually gives warning of its presence. At higher
concentration it is visible as greenish yellow gas.
Acute Local Chlorine gas exposure to the skin is not much irritating or
corrosive for short time. Splashes of liquid chlorine on the eyes, skin and clothing
may cause immediate irritation, chemical burns and severe damage to body
tissues.
Acute, Systemic Chlorine gas is extremely irritating to the mucous membranes,
the eyes and the respiratory tract. If the duration of exposure or the concentration
of chlorine is excessive, it will cause restlessness, throat irritation, sneezing and
copious salivation. In extreme cases, lung tissues may be attacked resulting in
pulmonary edema. The physiological effects of various concentrations of chlorine
gas are shown in table above.
9
in hold up of the gas in the pipe lines and allied equipment. This will cause
back pressure inside the cells and escape of chlorine into air or into the
hydrogen chamber resulting in explosion
Since liquid chlorine increases considerably in volume when evaporated,
hydrostatic rupture in containers, pipe lines and other equipments may occur
due to build up of excessive pressure. Particularly, the danger due to pressure
build up in a heated cylinder can lead to an explosion.
11
Design pressure
Design temperature
Capacity
Code of design
Corrosion Allowance
3.0 mm.
Joint Efficiency
95%
Radiography
Full
Stress Relief
Yes
Filling Ratio
1.19
10
Gross weight
11
Colour of Paint
Golden yellow
12
Supports
13
Branches
14
Approval
b) Valve protection hood: This protects the valves from any accidental damage
during loading/unloading and transportation of toners.
The ton container is equipped with two identical valves near the centre of one
end. Each valve connects with an ejection pipe fitted inside the container. Ton
container in a horizontal position and with valves in a vertical line delivers gas
from the upper and liquid from the lower valve.
A cylinder has one valve at the top for drawing chlorine as liquid or gas.
Cylinders deliver chlorine gas when in an upright position, and liquid in an
inverted position. A steel removable cap is provided for the protection of the
valve.
13
c)
24 hours storage after filling for observation: During this period liquid
chlorine attains ambient temperature and the pressure in the container is
10Kg/cm2 (during summer months) or 6 kg/cm2 (during winter months). This
should be checked before the containers leave the factory.
d)
Limitation of filling: 900 Kgs. liquid chlorine filling in the tonner: The
quantity of liquid chlorine to be filled in a tonner is dependent on its water
capacity.
Quantity of liquid chlorine (Kgs.) = Water capacity (1) X Filling density
(kg/l) = Water capacity x 1.19
14
Filling density means the ratio of weight of liquefiable gas allowed in pressure
vessel to the weight of water that the vessel will hold at 150 C.
Generally the water capacity of tonners in our country is 760 liters.
MATERIAL OF CONSTRUCTION
1. Mild steel is suitable for dry chlorine handling.
2. Fiber reinforced plastic is commonly used for wet chlorine. However,
ebonite lined mild steel& rubber lined vessels and pipes are also suitable for
wet chlorine. Titanium is also suitable for wet chlorine.
15
SAFETY IN STORAGE
STORAGE OF TON CONTAINERS
Toner shall be kept in cool, dry & relatively isolated area protected from
weather and extreme temperature changes
Tonner shall be kept under cover, should not be exposed to the Sun
Ventilation should be sufficient to prevent accumulation of Cl2 vapors
No welding/gas cutting work should be done near the place of storage
Due to high expansion ratio, danger of pressure build-up is there. Hence, they
should be kept away from direct source of heat
Floor should be maintained dry where container / cylinders are stored. Failing
which the container will be externally corroded and its life will be reduced
Toner shall be kept on their sides on rollers, a few inches above floor. They
should not be stacked or racked more than one high
Keep enough room between the containers so that they are accessible in case of
an emergency
Store Cl2 in areas where there is no contact with such a material with which it
reacts.
Storage area shall be constructed of non-combustible materials
Keep inventory as low as possible
Filled & empty containers should be stored separately. Even if the container is
empty, valve outlet caps and valve protection hoods should be in place.
Provision must be made to permit inspection and facilitate prompt removal if
any leak occurs.
Chlorine should be used on FIFO (first in -first out) basis because valve
packing can harden during prolonged storage and may cause leakage when
containers are finally used
The storage area should be separate from the area where other compressed gas
cylinders / containers are stored.
16
Storage of cylinders
Cylinders should be stored in an upright position.
They should be secured to prevent from falling over.
Full and empty cylinders should not be stored together.
The storage area should be dry, well-ventilated, clean of trash, and protected
from external heat sources (steam pipes, etc). Sub-surface areas should be
avoided for storing chlorine cylinders.
The valves on cylinders and ton containers should be protected by a stout metal
cap securely attached to the cylinder body. This cap should always be kept in
place on all containers in storage and at all times except during use of chlorine
17
occur and the container valve remains closed, hydrostatic pressure may
cause bursting. For this reason, extra precautions shall be observed when
closing valves of containers connected to a manifold. Connection of
cylinders or ton containers discharging liquid chlorine to a manifold is not
recommended.
5 A flexible connection between the container and the piping should be used;
annealed copper tubing (9.5 mm outside diameter 0.889 mm wall), suitable
for 35.2 kg/cm2 service is recommended. A clamp and adapter connector is
preferred; if a union connector is used, the threads on the connector shall match
the valve outlet thread. (Valve outlet threads are straight threads, not standard
taper pipe threads.) A new gasket (lead) should be used when making a
connection.
6 Valves should be opened counter-clockwise with square box wrench not over
152 mm long. If the valve is difficult to open, the packing nut may be struck
with the heel of the hand, no other implements should be used.
7 Tonner/cylinder valves should not be used as controlling valve for flow of
liquid/gas. Separate valve should be provided at the source of consumption for
regulating the flow.
8 When chlorine is being absorbed in liquid, a barometric leg should be provided
to prevent suck-back of the liquid into the container when it becomes empty.
BAROMETRIC LEG
A suck back of process liquid can occur whenever Chlorine gas is injected into
the process liquid if there is a loss of pressure on the supply side. This
condition occurs if the supply container is emptied or if the chlorine supply is
interrupted. This suck back of liquid results in internal corrosion in the
Chlorine containers thereby decreasing their life. This can be prevented by
installing a suitably designed BAROMETRIC LEG in the system. In systems
working at atmospheric pressure, the height of the Barometric Leg should be
h = 34/d ft
19
where d is the density of the liquid (water or liquid used) in gm/cc (in case
there is a change in the density of the process liquid during Chlorination
reaction then the lowest value of density should be taken into consideration).
9. Always empty ton containers on scale, in order to know at all times the amount
of Chlorine in the container. The pressure in container is not a measure of the
amount of Chlorine in the container. The pressure varies with the temperature
of Chlorine gas. At any given Chlorine temperature, the pressure on the
container holding one Kg and 900 Kgs Chlorine will be the same.
As soon as the container is empty, the valve should be closed and the lines
disconnected. The outlet cap should be applied promptly and valve protection
hood attached. The open end of the disconnected line should be plugged to
keep atmospheric moisture out of the system.
10 OTHER FACTORS
a. TEMPERATURE
Liquid chlorine expands about 0.15 % in volume for every F increase in
temperature this factor is very significant in handling chlorine in pipelines,
since liquid chlorine trapped in length of pipe subjected to a rise in
temperature can easily build up enough hydrostatic pressure to rupture the
pipe.
b. OVERFILLING
Over filled containers can also fail for the same reason.
20
ENGINEERING CONTROLS
a. Local exhaust ventilation system should be provided.
b. Proper access for maintenance and inspection
c. The storage shall be preferably located in open air.
d. Online monitoring devise (chlorine monitors) shall be installed in storage area
to get early warning alarm.
e. The low lying areas, trenches and drains near storage / handling areas shall be
avoided.
f.
g. The tonner / cylinder storage area shall be located such that there is no air
intake for the ventilation system of buildings like control rooms etc & fumes
can spread to other areas.
h. Care to be taken against possible damage from flooding
i.
j.
k. Adequate storage space for emergency equipment (gas canisters, breathing air
sets, & other PPEs) should be provided in a safe location to be readily
available.
22
ADMINISTRATIVE CONTROLS
a. Operator selection: Trained operator should be deployed.
b. Operating instructions: Detailed operating instructions and procedure for
unloading the tonner and use of Cl2 shall be displayed in operating area.
c. Training: Periodic training should be conducted for both new and old
employees to keep them conscious and informed of the hazards. Periodic
emergency exercises and instruction regarding location, purpose and use of
personal protective equipment, safety showers, eye fountains, chlorine
emergency kit, first aid box, etc. be a part of periodic training. They should
be told to report to proper authorities immediately in case of any leakage for
abnormal condition.
d. Monitoring & Surveillance: Containers, piping and equipment should be
checked for leaks daily. If a leak is detected it should be reported and
immediate steps taken to correct the conditions.
e. Availability of emergency equipments: Eye wash fountain cum safety
shower, BA set & Cl2 emergency kit shall be available promptly
f. Pre-placement medical examination: It is recommended for all new entrants
and follow-up medical examinations at suitable intervals for all workers
handling chlorine
23
EMERGENCY MEASURES
General wherever chlorine is handled a potential risk is involved and a serious
emergency might suddenly and unexpectedly occur. Emergency situations should
be anticipated, emergency action plans should be established and persons trained
to counteract emergencies, if any.
Handling Leaks Chlorine leaks always get worse unless they are corrected
promptly. Chlorine leaks should be investigated by authorized, trained personnel
equipped with suitable gas masks. If the leak is extensive an effort should be made
to warn all persons in the path of the gas. Chlorine is heavier than air; therefore
persons should be instructed to keep above and upwind or perpendicular to wind
direction prevailing.
a. Water shall never be used on a chlorine leak as it always makes the leak worse
due to the corrosive effect. In addition, heat supplied by even the coldest water
to a leaking container causes liquid chlorine to evaporate faster. A leaking
container shall not be immersed or thrown into a body of water as the leak will
be aggravated due to the corrosive effect and the container may float when
partially full, allowing gas evolution and dispersion at the surface.
b. Equipment and Piping Leaks If a leak occurs in equipment in which chlorine
is being used, the supply of chlorine shall be shut off and chlorine which is
under pressure at the leak shall be disposed off safely.
c. Leaks around valve stems usually may be stopped by tightening the packing nut
or gland. If this does not stop the leak, the container valve shall be closed and
the chlorine, which is under pressure in the outlet piping, shall be disposed off.
If a container valve does not shut off tight, the outlet cap or plug should be
applied. In case of a valve leak on a ton-container, the container shall be rolled
so that the valves are in a vertical plane with the leaking valve on top; so that
gaseous chlorine leaks & not the liquid.
d. If practical, the pressure in the container should be reduced by removing the
chlorine as gas (not as liquid) to process or a disposal system. In some cases it
24
may be desirable to move the container to an isolated spot where it will do the
least harm.
e. In case of chlorine leaks all exhaust mechanisms should be turned on
immediately. BA sets & other PPEs should be located outside the probable area
of contamination so that it will be possible to reach them in emergency.
f. As a regular part of chlorine storage and use, provisions shall be made for
emergency disposal of chlorine from leaking cylinders or ton-containers. One
vessel should always be kept empty as to allow transfer the content in case of
emergency.
i) Chlorine may be absorbed in solutions of caustic soda or soda ash, or in
agitated hydrated-lime slurries. Caustic soda is recommended as it absorbs
chlorine more readily.
ii) A suitable tank to hold the solution should be provided in a convenient
location. Chlorine gas should be passed into the solution through an iron
pipe or rubber hose properly weighted to hold it under the surface; the
container should not be immersed.
g. Display of MSDS will help as ready reckoner during emergency.
h. Chlorine Emergency Kits It is advisable for the consumers to purchase
chlorine leak arrest kit and to train employees in their use. These kits may be
used to stop most of the leaks in a chlorine cylinder, ton container etc. (Ref.
annexure)
i). In Case of Fire In the event of fire, chlorine containers should be moved
from the fire zone immediately. If chlorine containers cannot be moved, water
should be applied to cool them provided no chlorine is escaping.
25
FIRST-AID
General All minor accidents and also report any sickness should be reported.
Any one overcome by or seriously exposed to chlorine gas should be removed at
once to uncontaminated area.
Inhalation If breathing has not ceased, the patient should be placed on his
back, with head and back elevated, and kept warm, using blankets, if necessary.
Rest is essential.
i. If breathing apparently has ceased, artificial respiration shall be started
immediately. A physician shall be called immediately. If oxygen-inhalation
apparatus is available, oxygen should be administered immediately.
ii. Adequate oxygenation should be maintained, and any drugs for shock treatment
should be given only by a physician. Milk may be given in mild cases as a
relief from throat irritation. Nothing should ever be given by mouth to an
unconscious patient.
iii. Skin and Clothing If liquid chlorine or chlorinated water has contaminated
skin or clothing, the emergency shower shall be used immediately. Skin areas
should be washed with large quantities of soap and water. No attempt shall be
made to neutralize chlorine with chemicals. No ointment shall be applied for 24
hours. Contaminated clothing should be removed immediately.
iv. Eyes If eyes have been affected with liquid chlorine or high concentrations
of chlorine gas, they shall be flushed immediately with running water for at
least 15 minutes. (No attempt shall be made to neutralize with chemicals). No
oils or oily ointment should be used unless prescribed by an eye specialist.
v. Ingestion The swallowing of liquid chlorine is extremely unlikely. However,
if a person has swallowed chlorine and is conscious, he should immediately be
made to drink copious amounts of lime water, milk of magnesia, or fresh water
if the others are not readily available. Sodium bicarbonate shall not be given.
The victim may be expected to vomit spontaneously, but no attempt should be
made to induce vomiting. A physician shall be called immediately.
26
27
28
29
30
LIST OF SUPPLIERS
S.
Name of supplier,
Address of supplier
Phone Number
No.
M/s
Chlorination
022 - 25967882
Systems
S M Polymers
022 - 25368908
Banaco
022 - 39516813
Ltd.
Mumbai - 400095
Pennwalt Limited
31
022 - 27632503
Annexure-I
32
Annexure-II
33
Annexure-III
34
Annexure-V
35
Annexure-VI
BAROMETRIC LEG
36
Annexure-VII
37