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The information contained in the catalog also is available through the Institutes Internet
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RESPONSIBLE CARE
REFERENCES
hlorine Institute publications referenced in this publication are referred to by
C pamphlet number, drawing number, or by condensed name if no number exists.
At the beginning of Section 10 Selected References, complete
information about the Institute publications is provided. Other sources are referenced in
this publication in the following manner: (Reference 10.4.1). Section 10 provides
information on each of these references. In most cases, an address also is provided.
The Institute updates its publications catalog annually. This free catalog can be
obtained by downloading from the CI website or contacting the Institute Publications
Department, 2001 L Street, NW, Suite 506, Washington, DC 20036:
Ph: 202-775-2790
Fax: 202-223-7225
Web: http://www.CL2.com
1 GENERAL INFORMATION
1.1 Chlorine Manufacture metal; by electrolysis of hydrochloric acid;
and by non-electrolytic processes. Further
Most chlorine is manufactured information on electrolyzers and electrolytic
electrolytically by the diaphragm, the methods can be found in Section 7.4 of this
mercury or the membrane cell process. In pamphlet. An additional reference is the
each process a salt solution is electrolyzed Kirk-Othmer Encyclopedia of Chemical
by the action of direct electric current which Technology which contains a section on
converts chloride ions to elemental chlorine. chlorine and sodium hydroxide (Reference
Chlorine production for 1996 in short 10.18.7).
tons/year is estimated to be as follows:
world -47 million, U.S. -13 million, Canada - 1.2 Chlorine in Transportation
1.2 million, and Mexico -0.4 million.
In the diaphragm cell process, sodium 1.2.1 General
chloride brine is electrolyzed to produce
chlorine at the positive electrode (anode) Chlorine is normally shipped as a
while sodium hydroxide (caustic soda) and liquefied compressed gas. The
hydrogen are produced at the negative transportation of chlorine in all modes of
electrode (cathode). In order to prevent the transportation is controlled by regulations. It
reaction of sodium hydroxide and hydrogen is the responsibility of each person shipping
with the chlorine, the anode and cathode or transporting chlorine to know and to
chambers are separated by a porous comply with all applicable regulations.
diaphragm.
In the mercury cell process recirculating 1.2.2 United States
mercury serves as the cathode. Chlorine is
removed from the gas space above the ln the U. S., chlorine in commerce is
anodes and elemental sodium is formed at regulated by the Department of
the cathode. The sodium amalgamates with Transportation (DOT). Chlorine is a Class 2,
the mercury. The sodium-mercury amalgam Division 2.3 poison gas and is assigned a
then flows to a decomposer where it is poison Zone B inhalation hazard material.
reacted with purified water to produce For land transportation and for carriage of
sodium hydroxide and hydrogen with the containers by water, DOT regulations
mercury being recirculated. appear in Title 49 Code of Federal
The membrane cell process Regulations (CFR). DOT regulations
electrolyzes sodium chloride brine to covering tank barges appear in Title 33 and
produce chlorine at the positive electrode 46 CFR. See Section 8. Many states have
(anode) while sodium hydroxide and adopted regulations substantially the same
hydrogen are produced at the negative as DOT regulations.
electrode (cathode). An ion selective In addition there may be local
membrane prevents the reaction of sodium requirements.
hydroxide and hydrogen with chlorine.
Chlorine is also produced in a number 1.2.3 Canada
of other ways, for example, by electrolysis
of potassium chloride brine in membrane In Canada, chlorine is classified as a
and mercury cells with co-production of Class 2, Division 2.3 poison gas with a
potassium hydroxide; by electrolysis of secondary classification of Class 5, Division
molten sodium or magnesium chloride to 5.1 oxidizer. Regulations are issued by
make elemental sodium or magnesium Transport Canada (TC) for all modes of
1
transportation under the Transportation of 1.3 Other Regulatory Aspects
Dangerous Goods Act and Regulations
TDG). Chlorine manufacturers, packagers, and
Many regulations are in accordance with most consumers are subject to workplace
those issued by the U.S. DOT, but some regulations pertaining to chlorine throughout
minor differences exist. The concerned most of the world.
reader may obtain additional information
from Canada Communications Group, 45 1.3.1 United States
Sacr-Coeur Boulevard, Hull, Quebec,
Canada, K1A 0S9 or directly from the The Department of Labors (DOL)
Canadian government. Occupational Safety and Health
Administration (OSHA) issues regulations
1.2.4 Mexico involved with worker protection.
Environmental regulations are issued by the
In Mexico, chlorine is classified as a Environmental Protection Agency (EPA).
Class 2, Division 2.3 poison gas with a When used as a disinfectant (water or
secondary classification of Class 5.1 waste treatment), chlorine is considered to
Oxidizer. be a fungicide and is subject to EPA
Regulations for the transportation of regulations issued under the Federal
hazardous materials are issued as part of Insecticide, Fungicide and Rodenticide Act
Regulations for Surface Transportation of (FIFRA). In addition, many state or local
Hazardous Materials and Wastes, April 7, agencies now require that chlorine used in
1993 as published in the Diario Official de Ia the drinking water treatment industry be
Federacion. Most of the regulations are in certified to meet ANSI/NSF Standard 60
accordance with those issued by the U.S. (Reference 10.14.1).
DOT.
1.3.2 Canada
1.2.5 Other Countries
Workplace regulations are issued
International shipments of chlorine must through the Workplace Hazardous Materials
meet the requirements of the country of Information System (WHMIS) and by
origin and the country of destination. individual provinces. Environmental
Generally, hazardous material regulations regulations are primarily addressed through
throughout the world are similar as a result provincial governments in conjunction with
of standardized regulations provided Environment Canada.
through the United Nations and
implemented by intermodal U.N. agencies. 1.3.3 Other Countries
For instance, the International Maritime
Organizations (IMO) publishes the Similar regulations apply in many other
International Maritime Dangerous Goods countries. Various numbering systems of
(IMDG) Code. Shipments of chlorine chemicals apply in certain regulatory
containers by vessels meeting the programs.
standards of the IMDG Code are accepted For chlorine, the following are
in most countries. There are similar U.N. pertinent:
agencies and recommendations for road, The Chemical Abstracts Service (CAS)
rail and air transportation systems. The number is CAS 7782-50-5.
United Nations designation for chlorine is The Registry of Toxic Effects of Chemical
U.N. 1017. Substances (RTECS) number assigned
in the U.S. by the National Institute for
Occupational Safety and Health is
F02100000.
2
1.4 Chemical and Physical Properties 1.5.3 Chlorine Gas
3
pressure will cause some portion of the is frequently referred to as caustic potash.
chlorine to vaporize to a gas. [This term
should not be confused with wet or moist 1.6 Health Hazards
chlorine.]
Chlorine gas is primarily a respiratory
1.5.9 Chlorine Solution (Chlorine Water) irritant. In sufficient concentration, the gas
irritates the mucous membranes, the
A solution of chlorine in water (for respiratory tract and the eyes. In extreme
solubility of chlorine in water see Fig. 9.3). cases difficulty in breathing may increase to
[The term chlorine solution sometimes is the point where death can occur from
used incorrectly to describe hypochlorite respiratory collapse or lung failure. The
solutions. This is a misuse of the term and characteristic, penetrating odor of chlorine
the Institute discourages its use.] gas usually gives warning of its presence in
the air.
1.5.10 Liquid Bleach Also, at high concentrations, it is visible
as a greenish yellow gas. Liquid chlorine in
A solution of hypochlorite, usually sodium contact with skin or eyes will cause
hypochlorite. This term rather than liquid chemical burns and/or frostbite. See Section
chlorine should be used to describe a liquid 6.
hypochlorite product. See Section 1.5.2. The American Conference of
Governmental Industrial Hygienists (ACGIH)
1.5.11 Container (Reference 10.4.1) has established a
threshold limit value time-weighted average
In this publication, a container is a (TWA) of exposure to chlorine at 0.5 ppm.
pressure vessel authorized by an applicable The TWA is based on a normal work
regulatory body for the transport of chlorine. schedule of 8 hours/day and 40 hours/week.
It does not include pipelines or stationary ACGIH has established a threshold limit
storage tanks specifically designed and value short-term exposure limit (STEL) of 1
installed for transfer or storage. ppm for exposure to chlorine. The STEL is
defined as a 15-minute TWA exposure.
1.5.12 Filling Density In 1994, the National Institute for
Occupational Safety and Health reduced its
By DOT regulation, the weight of Immediately Dangerous to Life or Health
chlorine that is loaded into a container may (IDLH) concentration for chlorine to 10 ppm
not exceed 125% of the weight of water at (Reference 10.12.1).
60o F (15.6oC) that the container will hold.
1.7 Other Hazards
1.5.13 Sodium Hydroxide
1.7.1 Fire
Normally the co-product produced as a
solution when chlorine is generated through Chlorine is neither explosive nor flammable;
the electrolytic decomposition of sodium however, chlorine will support combustion.
chloride solution. Sodium hydroxide is
frequently referred to as caustic soda. 1.7.2 Chemical Action
4
9.3.3.2. 1.7.5.3 Oils and Grease
5
Tank Multi-Unit (TMU) Cars
Tank Cars
Tank Barges
6
2 CYLINDERS AND TON CONTAINERS
serial number, identifying symbol,
2.1 Container original tare weight, inspectors
Descriptions official mark and date of hydrostatic
test must be stamped on the metal
2.1.1 General near the cylinder neck. Usually the
owners name or symbol is
Cylinders and ton containers stamped or embossed on the
have many similarities in the cylinder in this same area. It is
way in which they are illegal to mar or deface these
handled and many users of markings. Tare weight means the
cylinders also use ton weight of the empty cylinder and
containers. Therefore, they valve, but does not include the
are considered together in valve protective housing.
this section. The terms
cylinder, ton cylinder, or 2.1.3 Ton Containers
drum should not be used to
describe the ton container. Ton containers are welded tanks
Emergency equipment for having a capacity of one short ton,
handling ton containers is 2000 lb (907 kg) and a loaded
different from that used for weight of as much as 3650 lb (1655
cylinders and confusion can kg) (Fig. 2.2). Approximate
be avoided if the proper dimensions and weight are shown
terms are used. in Table 2.1. The heads are
concave and forge welded to the
2.1.2 Cylinders shell. The sides are crimped inward
at each end to form chimes which
Chlorine cylinders are of seamless provide a substantial grip for lifting beams.
construc tion with a capacity of 1 to 150 lb The container valves are protected by a
(0.45 to 68kg); those of 100 lb
and 150 lb (45.4 and 68 kg)
capacity predominate.
Approximate dimensions and
weights of 100 lb and 150 lb
cylinders are shown in Table
2.1 in this manual and in
Pamphlet 151. These cylinders
are the foot-ring type, bumped-
bottom type or double-bottom
type (Fig. 2.1) and are not
permitted to be fabricated with
more than one opening. The
valve connection is at the top of
the cylinder. The steel valve protective removable steel valve protective housing. (A
housing should be utilized to cover the valve few containers of different designs are in
during shipment and storage. service.)
The DOT or TC specification number,
7
Note: The Institute are special straight threads
recommends that all pre- (designated as 1.030 inch 14NGO-
1936 ton containers RH-EXT). See Section 2.8.5 for
manufactured by the details on recommended
American Welding Service connections.
Company not be used in Cylinder valves are equipped
chlorine service. with a fusible metal pressure relief
device or, as more commonly
The DOT or TC named, a fusible plug. See Section
specification number, the 2.3.1.
material and cladding
2.2.2 Ton Containers
material (if any), the owners
or the builders identifying
Each ton container is equipped
symbol and serial number,
with two identical valves near the
the inspectors mark, the test
center of one end. These valves are
date(s), and the water
standard ton container valves (Fig.
capacity must all be
2.4). See Drawing 110. They are
stamped into the chime at
different from the standard cylinder
the valve end. This
valve in that they have no fusible
information also may be
metal plug and usually have a larger
stamped on a brass plate
internal passage. Other valves also
secured to the tank head
may be recommended for chlorine
opposite the valve end. It is
service. See Pamphlet 17. Each
illegal to mar or deface these
valve connects to an internal
markings. In addition to the
eduction tube (Fig. 2.2).
above required markings,
the original tare weight is 2.3 Pressure Relief Devices
stamped either on the chime
or on the brass plate. Tare 2.3.1 Cylinders
weight means the weight of
the empty container with Cylinder valves are equipped
valves and fusible plugs, but with a fusible metal relief device or
does not include the fusible plug. Most valves have a
protective valve housing. threaded plug containing the fusible
Usually the owners name or metal screwed into a tapped hole in
symbol is stamped on the the valve body, below the valve
container or embossed on seat. (A few have fusible metal cast
the brass plate. directly into a threaded hole in the
valve body.) The fusible metal is
2.2 Container Valves designed to yield or melt between
1580F and 1650F (700C and 740C) to
2.2.1 Cylinders
relieve pressure and prevent
A standard cylinder valve
is shown in Fig. 2.3. Other container rupture if exposed to fire
valves also may be or other high temperature. The relief
recommended for chlorine device is activated only in the event
service. See Pamphlet 17. The valve outlet of a temperature increase.
threads are not standard pipe threads, but
8
2.3.2 Ton Containers Containers in transportation must be
All ton containers are equipped with suitably labeled and the vehicle placarded
fusible metal pressure relief devices (Fig. as required by regulations.
2.5). Most have six fusible metal plugs,
three in each end, spaced 120 apart. The 2.6 Container Handling
fusible metal is designed to yield or melt
between 1580F and 165 0F (700C and 740C) 2.6.1 General
to relieve pressure and prevent rupture of
the container in case of fire or other Chlorine containers must be handled
exposure to high temperature. The relief with care. During shipment and storage,
device is activated only in the event of a container valve protective housings should
temperature increase. be in place. Containers should not be
dropped and no object should be allowed to
2.4 Container Shipping strike them with force. It is convenient to
load and unload containers from a truck to a
2.4.1 Cylinders dock at truck bed height. If such a dock is
not provided, a hydraulic tail gate can be
Cylinders may be shipped by highway, used. Containers should be secured to
rail or water. Highway shipments may be prevent them from rolling. See Pamphlet 76.
truckload or less-than-truckload (LTL) lots.
Suitable restraints are necessary to prevent
cylinders from shifting during transportation.
See Pamphlet 76.
9
2.6.2 Cylinders should not be stored where heavy objects
could fall on them or where vehicles could
Cylinders can be moved about in a plant strike them. Because chlorine is heavier
area using a properly balanced hand truck. than air, subsurface storage areas should
The truck should have a clamp or chain two- be avoided. Access to storage by
thirds of the way up the cylinder wall to hold unauthorized persons should be controlled.
the cylinder in place. If cylinders must be Exposure of containers to flame, intense
elevated by hoist, a specially designed radiant heat or to steam lines must be
cradle or carrier should be used. Slings and avoided. If the metal in the vicinity of the
magnetic devices are unacceptable. fusible plug reaches approximately 158 0F
Cylinders must not be lifted by the valve (700C), the fusible metal plug is designed to
protective housing because the neck ring to melt and chlorine will be released.
which the housing is attached is not Full and empty containers should be
stored separately. Even though a container
designed to carry the weight of the cylinder.
is empty, the valve outlet cap(s) and the
valve protective housing should be in place.
2.6.3 Ton Containers Cylinders should be stored in an upright
position. OSHA regulations require cylinders
Ton containers are typically moved be properly secured to prevent toppling. Ton
using a monorail or crane with a lifting beam containers should be stored on their sides
(Fig. 2.6). See Drawing 122. They can be above the ground or floor on steel or
rolled on rails or roller conveyers designed concrete supports. In earthquake zones,
for this purpose. If a fork lift truck is used, special storage consideration should be
the ton container must be adequately made.
restrained to prevent it from falling off, Chlorine containers should be
particularly when the truck changes segregated from flammable and oxidizing
direction. The fork lift truck must be rated to materials and from materials such as
ammonia, hydrocarbons and other materials
handle the gross weight of the container
which are reactive with chlorine. Easy
(3300-3650 lb or 1500-1655 kg).
access to containers is important in the
event of a leak.
2.7 Container Storage
2.8 Container Use
Containers may be stored indoors or
outdoors. If stored indoors, the storage area 2.8.1 General
should comply with the provision of Sections
7.1 and 7.2. If stored outdoors, the storage Before connecting or disconnecting a
area should be clean so that accumulated container, the operator should make sure
trash or other combustible material does not that all safety and emergency equipment is
present a fire hazard. Containers should not available and operable. Containers and
be stored near elevators or ventilating valves must not be modified, altered, or
systems because dangerous concentrations repaired by anyone other than the owner.
of gas may spread rapidly if a leak occurs.
All containers should be stored to minimize 2.8.2 Gas Discharge
external corrosion. If standing water can
collect around the containers, suitable Cylinders are normally secured in the
platforms or supports should be provided. upright position and deliver chlorine as gas.
Provisions should be made to permit routine Ton containers chocked in a horizontal
inspection of all containers. Containers position and with the valves in a vertical line
(Fig. 2.2) deliver gas from the upper valve
10
and liquid from the lower valve See tinuous discharge rate of chlorine gas from
Pamphlet 17. a cylinder is about 1-1.5 lb/day/0F. This
The flow of chlorine gas from a discharge rate assumes an ambient
container depends on the internal pressure temperature of at least 600F (about 15 0C)
which, in turn, depends on the temperature and natural air circulation. The maximum
of the liquid chlorine. In order to withdraw dependable discharge rate for a ton
gas, liquid chlorine must vaporize. Unless container under similar conditions is about
enough external heat is available, the 6-8 lb/day/0F.
temperature of the chlorine will be reduced If the gas discharge rate from a single
as the liquid vaporizes and, consequently, container will not meet the flow
the pressure in the container will fall. At low requirements, two or more may be
withdrawal rates, surrounding air may manifolded together. Alternately, liquid from
provide sufficient heat so that the pressure one or more containers may be sent to a
in the container remains adequate to vaporizer for increasing the chlorine gas
maintain a uniform flow. At high withdrawal delivery rate. See Section 2.8.3.
rates, the temperature and pressure within When discharging through a gas
the container may fall because of the manifold, all containers should be at the
cooling effect of vaporization. As this same temperature to prevent transfer of gas
happens, the rate of flow will gradually from a warm container to a cool container.
diminish and may even appear to stop,
giving a false indication of an empty 2.8.3 Liquid Discharge
cylinder.
In humid conditions, condensation will For special use, cylinders can be
form on the outside of the container. At inverted to deliver liquid chlorine. In such
excessive withdrawal rates, the liquid will be cases, appropriate racks should be used.
cooled to such an extent that frost will form Liquid chlorine is delivered from the
on the outside of the container. The lower valve of a ton container. Very high
insulating effect of the frost will cause a liquid withdrawal rates can be obtained. The
further decrease in the discharge rate. rate depends on the temperature of the
Discharge rates will diminish as the chlorine in the container and on the back
container empties because there is progres- pressure. The dependable continuous
sively less area of container wall in contact discharge rate of liquid chlorine under
with the remaining liquid chlorine. Discharge normal temperature conditions and against
rates may be increased by circulating room a pressure of35 psig (241 kPag) is at least
temperature air around the container with a 400 lb/hr (181 kg/hr) for ton containers. The
fan. manifolding of ton containers discharging
liquid chlorine should not be attempted
Note: Never heat a container in a bath without taking precautions to equalize the
of water, or apply direct steam, heat pressure. Drawing 183 depicts a system for
belts, etc. equalizing pressures by manifolding the gas
valves. It is not sufficient to depend on ton
Chlorine gas discharge rate results vary containers reaching the same pressure
significantly because of local ambient merely by storing them in the same working
temperature, humidity and air circulation, as area. Piping evacuation procedures should
well as the variations in the piping system be established so liquid chlorine is not
and feeding equipment connected to the trapped in the system.
container. The maximum dependable, con-
11
gasket on the face of the valve is
part of the connection. The CGA
660 connection is not
recommended for connecting to
a cylinder or ton container valve.
A new gasket should be
used each time a connection is
made.
12
disconnecting, a means of removing the
chlorine trapped in the flexible connecting
line should be provided. This can be
accomplished by either purging the line with
dry air or nitrogen with a dew point of -400F
(-400C) or lower or by applying a vacuum.
The container should be cautiously
disconnected in case residual chlorine
remains in the lines. The outlet cap should
be applied promptly and the valve protective
housing should be replaced. The open end
of the disconnected flexible line should be
capped promptly to keep atmospheric
moisture from entering the system.
13
3 BULK SHIPPING CONTAINERS
3.1 General with chlorine in excess of these nominal
weights.
Bulk chlorine is shipped in tank cars, Chlorine tank cars must comply with 49
tank motor vehicles, portable tanks and CFR 179.102-2. Similar text appears in TC
barge tanks. Most common chlorine Regulations at 79.102-2. An exception for
shipments are made in single-unit tank cars older cars appears in 49 CFR 173.314(c)
of 55 or 90 ton capacity. Chlorine may also note 12 and TC regulation 73.314(c) note
be transferred in bulk by pipeline which is 12.
discussed in Pamphlet 60. The regulations require tank cars to be
equipped with a pressure relief device
3.2 Tank Cars whose setting is stenciled on the side of the
car. Tank cars equipped with manual angle
3.2.1 General valves must have interior eduction pipes
used for liquid discharge equipped with
The following is generalized information excess flow valves of approved design.
on chlorine tank cars. For more detailed Tank cars equipped with pneumatically
information, see Pamphlet 66. operated valves (POVs) should be equipped
with a ball-check valve on all four valve
3.2.2 Specifications openings.
Tank cars must be insulated with four
The most commonly used tank cars inches of insulating material. The insulation
(Fig. 3.1) have a chlorine capacity of 55 or reduces the increase in vapor pressure
90 tons. However, 16, 30, and 85 ton cars during hot weather and helps maintain
are authorized and are in use. By pressure needed to unload the car during
regulation, tank cars may not be loaded cold weather. The current standard is two
14
inches of glass fiber placed over two inches
of ceramic fiber. Older cars are equipped
with four inches of cork or urethane foam.
3.2.3.1 General
15
Equivalent manual angle valves from against the flow of liquid chlorine if the angle
various valve producers and approved by valve is broken off in transit. It may close if a
the Association of American Railroads Tank catastrophic leak involving a broken
Car Committee may also be used. The connection occurs but it is not designed to
exterior appearance of these valves is act as an emergency shut-off device during
similar to the Institute standard angle valve, transfer. The excess-flow valves have a
but may have different design features, e.g., maximum operating flow rate of 7,000 lb/hr
replacement outlet port, bellows-seals, stem (3,200 kg/hr), 11,000 lb/hr (5,000 kg/hr) or
packing arrangements. 15,000 lb/hr (6,800 kg/hr). Tank cars equip-
Chlorine tank cars may also be ped with POVs are equipped with a ball
equipped with pneumatically operated check valve under both the liquid and vapor
valves (POVs). The manway cover for tank outlets.
cars equipped with POVs is different. The
POV is a dual valve system consisting of an 3.2.3.4 Eduction Pipes
external bellows seal, angle globe valve,
and a spring loaded ball check valve with a Liquid chlorine is withdrawn through 1 -
top-mounted pneumatic actuator, including inch eduction pipes (Fig. 3.2). (Bottom
provisions for a manual override. Actuating outlets are not permitted in chlorine cars.)
the valve simultaneously operates the The eduction pipes are attached to the
spring loaded check valve mounted beneath excess-flow valves, or directly to the bottom
the angle globe valve. The valves are of the tank car dome if equipped with POVs,
designed to be opened or closed and extend to the bottom of the car. One or
pneumatically and are of a fail-safe/fail- both eduction pipes may be used to unload
closed design with a loss of pneumatic the car.
pressure. The valve also may be opened
manually with a specially designed device 3.2.3.5 Pressure Relief Device
that mounts on top of the angle globe valve.
The device may be attached to a cord In the center of the manway cover is a
allowing the spring loaded pressure relief device (Fig.
valve to be 3.5). The device is set to start-to-discharge
tripped
safe/closed.
See Pamphlet
93.
3.2.3.3 Excess
Flow Valves
Except for
tank cars
equipped with
pneumatically
operated
valves, under
each liquid
valve there is
an excess-
flow valve (Fig. 3.4). The excess-flow valve
consists of a rising ball which closes when
the rate of flow exceeds a predetermined
value. It does not respond to pressure in the
car. It is designed to close automatically
16
at a gage pressure of 225 psig (1551 kPag) approxlmately one car length from the car(s)
on cars stenciled 105J300W or 105S300W being transferred, unless the tank car(s) is
or at a gage pressure of 375 psig (2586 protected by a closed and locked switch.
kPag) on cars stenciled 105J500W or Before the transfer valves are opened,
105S500W. the loading/unloading connections must be
attached securely to the tank car
3.2.4 Transfer Operations connections. All connections should be
leak-checked. See Section 4.4.2.
The following is general information. For The transfer area should be checked to
more detailed information, refer to Pamphlet make sure all safety equipment (e.g., self-
66. contained breathing apparatus, emergency
kits, eye wash fountains) is in its proper
3.2.4.1 Precautions place and operable.
A suitable operating platform should be
Every site handling chlorine should provided at the transfer station for easy
have an on-going safety program. Special access to the protective housing, for
attention should be directed to the connection of lines, for the operation of
appropriateness of emergency procedures valves and for rapid escape, if required. See
and to equipment to be used in an Pamphlet 66.
emergency.
All personnel responsible for transfer 3.2.4.2 Connections
operations should be knowledgeable about
the facilitys emergency response plan for Transfer operations should be done
handling spills and leaks of products. through a suitable flexible connector to
DOT, OSHA and IC have specific permit the movement of the tank car on its
training requirements applicable to handling springs. Recommended specifications for
of hazardous materials. Chlorine transfer chlorine transfer hose as well as more
operations must be performed only by detailed information pertaining to piping and
personnel who are trained as required by other components are contained in
applicable hazardous material regulations. Pamphlet 6.
Chlorine tank cars must be loaded or Nipples for insertion into the tank car
unloaded on a private track or siding. angle valve should have clean, sharp
Chlorine transfer operations should threads. A non-reactive lubricating pipe
incorporate an emergency shut-off system dope or PTFE tape should be used to
to reduce the possibility of a major release. prevent galling of the threads. It should be
See Pamphlet 57. applied in such a manner as to prevent its
It is recommended that chlorine tank entry into the piping. After the connections
cars be loaded on a track scale. are tight, add a small amount of chlorine to
The transfer operation area should be the system by slightly opening the liquid
adequately illuminated during transfer angle valve for a second or two to
operations. pressurize the piping with chlorine gas and
During all times when the tank car(s) is test for leaks. See Section 4.4.2.
connected for transfer of product: During unloading, if the liquid angle
- Tank car brakes must be set and valve is opened too rapidly or an unusually
wheels chocked. high flow rate is established, the excess-
- Caution signs (blue flags or lights) must flow valve will close. If this situation occurs,
be so placed on the track to give necessary the angle valve should be closed until the
warning to persons approaching the tank metal ball in the excess-flow valve drops
cars from the open end(s) of the siding. back into place. A click will be heard when
- Derail devices should be placed at the the ball drops.
open end(s) of the siding not less than
17
If this action is unsuccessful, the car is connected, the car must be attended
manway cover next to the valve may be by the operator. There may be exceptions to
tapped sharply with a hammer. this general rule. It is the responsibility of
each transfer site to ensure all applicable
Note: The valve must never be regulations are followed. See Pamphlet 66.
directly struck.
3.2.4.5 Disconnecting
If the ball in the excess flow valve is still
not dislodged, nitrogen from a cylinder, or A noticeable drop in tank car pressure
some other non-reactive gas, may be usually indicates that the tank car is empty.
applied to the down-stream side of the It is desirable to discharge as much of the
excess flow valve. Do not exceed the residual chlorine as possible to the process.
design pressure of the piping system. Liquid Chlorine lines should be purged with dry air
angle valve(s) must never be used to or nonreactive gas to an absorption system
regulate the flow rate of chlorine. These or vented to a vacuum system before
valves, if opened, should be kept completely disconnecting.
open. After the transfer lines have been
disconnected, the valve outlet plugs should
3.2.4.3 Pressure Padding be installed immediately. This is essential to
prevent corrosion of the threads by
Liquid chlorine usually is unloaded by atmospheric moisture. After checking for
tank car pressure. See Pamphlet 66. The leaks the protective housing cover must be
vapor pressure of the chlorine is frequently closed. After unloading, the DOT placards
augmented by a pad of dry air or non- must indicate the car last contained
reactive gas. It is essential that the air used chlorine. The open end of the chlorine
for padding be free from oil and foreign transfer lines should also be protected from
matter and be dried to a dew point -400F (- atmospheric moisture with suitable closures.
400C) or below.
Air for padding should be supplied by a 3.3 Tank Motor Vehicles
separate air compressor which is not used
for any other purpose. To minimize the 3.3.1 General
potential of a chlorine-hydrocarbon oil
reaction, either a non-lubricated compressor The following is generalized information
or a compressor lubricated with a non- on chlorine tank motor vehicles. For more
reactive synthetic oil, should be utilized. detailed information, see Pamphlet 49. In
Filters ahead of the dryers are required to North America they usually have a capacity
ensure oil free dry air if a lubricated ranging from 15 to 22 tons (13,600 kg to
compressor is used. 20,000 kg) with certain exceptions (Fig.
The air pad system should be designed 3.6). DOT specifications apply only to the
to prevent the backflow of chlorine vapors tank; such cargo tanks comply with
from the car. Lack of a positive backflow specification MC331 including the special
protection with a hydrocarbon lubricated requirements for chlorine, but tanks built to
compressor may result in a violent reaction specification MC330 maybe continued in
of chlorine and oil. A check valve alone service.
should not be considered adequate to
prevent back flow. See Pamphlet #6. 3.3.2 Manway Arrangement
Current DOT and TC regulations require The manway arrangement is the same
that throughout the entire period the tank as that on chlorine tank cars (see Section
18
3.2.3.1) except that special excess-flow variation in facilities and conditions at
valves are required under the gas valves. customers plants, and these may require
modifications of methods and equipment.
3.3.2.2 Angle Valves
3.3.3.1 Precautions
The angle valves are the same as those
on tank cars (see Section 3.2.3.2). Angle The engine should be shut off, hand
valves must be tested before installation brakes must be set and wheel chocks must
and every two years. be in place during transfer. The tank motor
vehicle must not be left unattended. The
3.3.2.3 Excess-Flow Valves tank motor vehicle must not be moved when
loading or unloading connections are
Under each liquid angle valve there is attached to the vehicle (see discussion of
an excess-flow valve with a maximum tank car transfer, Section 3.2.4.1, for
operating flow rate of 7,000 lb/hr (3,200 additional, applicable precautions.)
kg/hr). There are eduction pipes connected
to the two liquid excess-flow valves as in a 3.3.3.2 Emergency Equipment
tank car.
In addition under each gas angle valve Approved respiratory equipment is
there is an excess-flow valve of different required on the transport vehicle. In the
design; these valves have a removable U.S., all personnel authorized to use the
basket so that the ball can be removed and equipment must meet the medical and
the interior of the tank inspected. training requirements of OSHA 29 CFR
1910.134. An Emergency Kit C must be on
3.3.2.4 Pressure Relief Device the transport vehicle.
It also is recommended that the
The pressure relief device is the same transport vehicle have 2-way
type as that used on tank cars (see Section communication equipment of radio
3.2.3.5). On all cargo tanks the start-to- transmitter type or cellular phone.
discharge pressure is 225 psig (1,551
kPag). 3.3.3.3 Connections/Disconnecting
19
normally equipped with 4 one-inch Chlorine
3.3.3.4 Pressure Padding Institute Standard Valves utilized for the pad
gas and liquid discharge control. The ocean
See discussion for tank cars (Section service barge cargo tanks are equipped with
3.2.4.3). a similar number of two-inch valves.
20
been designated as the Person in Charge.
Procedures for withdrawing chlorine from
barges are essentially the same as for tank
cars except that diagonal barge cargo tanks
must be discharged together to prevent the
barge from becoming unstable. Variation in
facilities and conditions at customers plants
may require modifications of methods and
equipment and should be considered before
discharge is initiated.
21
4 EMERGENCY MEASURES
4.1 General chlorine release should be evacuated or
sheltered in place as circumstances
A chlorine emergency may occur during warrant.
manufacture, use or transportation. Trained Area chlorine monitors and wind
employees, along with a comprehensive, direction indicators can supply timely
written emergency response plan (Pamphlet information (e.g., escape routes) to help
64), are necessary to mitigate the determine whether personnel are to be
consequences of the emergency. Federal, evacuated or sheltered in place.
state and provincial regulations, as well as When evacuation is utilized, potentially
various local fire and building codes, exposed persons should move to a point
regulate chemical emergency preparedness upwind of the leak. Because chlorine is
and response. All persons handling, or heavier than air, higher elevations are
responsible for the handling of chlorine, preferable. To escape in the shortest time,
must be familiar with the contents of those persons already in a contaminated area
varied requirements. should move crosswind.
Regulatory requirements deal generally When inside a building and sheltering in
with preparation and response to chemical place is selected, shelter by closing all
and other emergencies. This section is windows, doors and other openings, and
designed to provide additional information turning off air conditioners and air intake
for use in chlorine emergencies. Help is also systems. Personnel should move to the side
available from CHLOREP (see Sections of the building furthest from the release.
4.5.1 to 4.5.3) through CHEMTREC in the Care must be taken not to position
U.S. and through CANUTEC in Canada. personnel without an escape route. A safe
position may be made hazardous by a
4.2 Response to a Chlorine Release change in wind direction. New leaks may
occur or the existing leak may get larger.
As soon as there is any indication of a If notification of local authorities is
chlorine release, immediate steps must be required, the following information should be
taken to correct the condition. provided:
Chlorine leaks always get worse if they Company name, address, telephone
are not promptly corrected. When a chlorine number and the name of the person(s)
leak occurs, authorized, trained personnel to contact for further information
equipped with respiratory and appropriate Description of the emergency
other personal protective equipment (PPE) Travel directions to the site
should investigate and take proper action. Type and size of container involved
Personnel should not enter into Corrective measure being applied
atmospheres containing concentrations of Other pertinent information, i.e., weather
chlorine in excess of the Immediately conditions, injuries, etc.
Dangerous to Life and Health Concentration
(10 ppm) without appropriate personal 4.3 Response to a Fire
protective equipment and back-up
personnel. If fire is present or imminent, chlorine
Pamphlet 65 provides PPE containers and equipment should be moved
recommendations for responders to a away from the fire, if possible. If a non-
chlorine release. Keep unnecessary leaking container or equipment cannot be
personnel away and isolate the hazard moved, it should be kept cool by applying
area. Persons potentially affected by a water on it.
22
Water should not be used directly on a Institute Emergency Kit should be applied or
chlorine leak. Chlorine and water react the cylinder should be placed in a recovery
forming acids and the leak quickly will get vessel designed to contain the leak, and the
worse. However, where several containers chlorine supplier notified. See Section 4.8.
are involved and some are leaking, it may
be prudent to use a water spray to help 4.4.3 Types of Releases
prevent over-pressurization of the non-
leaking containers. Whenever containers Chlorine releases can be classified as
have been exposed to flames, cooling water either instantaneous (puffs) or continuous.
should be applied until well after the fire is See Pamphlet 74.
out and the containers are cooled.
Containers exposed to fire should be 4.4.3.1 Instantaneous Release
isolated and the supplier should be
contacted as soon as possible. An instantaneous release is
characterized by the release of chlorine to
4.4 Releases the atmosphere in a relatively short period
of time (a few minutes), resulting in a cloud
4.4.1 General which moves across the downwind range
while growing in size and decreasing in
Chlorine facilities should be designed concentration. Thus, the concentration of
and operated so that the risk ofa chlorine chlorine monitored at any given point
release into the environment is minimized. downwind will vary overtime depending on
However, accidental releases and leaks of the position of the chlorine cloud.
chlorine may occur. The overall effects of
such releases must be considered. 4.4.3 2 Continuous Release
23
information on the area affected by specific
chlorine release scenarios. 4.4.6.2 Animals
4.4.5 Physical Form of the Chlorine The U.S. National Institute for Occupa-
Released tional Safety and Health 1980 Registry of
Toxic Effects of Chemical Substances lists
Chlorine occurs as a gas or a liquid the following inhalation LC 50s (concentration
depending on the pressure and of chlorine in air lethal to 50% of the test
temperature. Typically, chlorine is stored population of the defined animal, exposed
and transported as a liquid under pressure. over the specified time period):
Whether the release source is a liquid or Human 840ppm/30 minutes
gas significantly affects the downwind Rat 293ppm/60 minutes
dispersion since liquid chlorine expands in Mouse 137ppm/60 minutes
volume by nearly 460 times when it The lowest concentration of chlorine in
vaporizes. air (other than LC 50) which has been
During a release, chlorine can escape reported to cause death in humans or
as a gas, a liquid, or both. When animals is listed as 500ppm/5 minutes.
pressurized liquid or gas is released from a
container, the temperature and pressure 4.4.6.3 Aquatic Life
inside the container will decrease thus
reducing the release rate. Chlorine is only slightly soluble in water
Escaping liquid may collect in a pool and there would be little absorption from a
and may actually form a running stream. cloud of chlorine gas. Many forms of aquatic
Chlorine will immediately cool to its boiling life are adversely affected by chlorine in
point (-290F, -340C) as it enters the concentrations well below 0.1 ppm. Chlorine
atmosphere. Upon contact with any heat is listed as a marine pollutant by DOT.
source the air, the ground, or water the
heat will cause the chlorine to boil readily. 4.5 Transportation Emergencies
Typically, the boiling-off rate will be
relatively high initially and then decline as DOT and TC require that any person
the heat source surrounding the chlorine is who offers chlorine for transportation must
cooled. provide a staffed 24-hour emergency
Since water in bulk provides a vast heat response telephone number that can be
source for evaporating liquid chlorine, any called in the event of an emergency
liquid falling into water should be assumed involving chlorine. For emergencies
to vaporize. For this reason, water should involving the transportation of chlorine, the
be prevented from coming in contact with a Chlorine Institutes CHLOREP, the Chlorine
liquid chlorine pool, and chlorine should be Emergency Plan, can provide assistance.
prevented from flowing into water drains.
4.5.1 CHLOREP
4.4.6 Effect of Chlorine on the
Environment The Chlorine Emergency Plan
(CHLOREP) was established in January
4.4.6.1 Vegetation 1973 by the Institute as an industry-wide
program to improve the speed and
Chlorine causes bleached spots on effectiveness of response to chlorine
leafy plants due to attack on chlorophyll in emergencies in the United States and
leaves. Mature leaves are most susceptible Canada.
to chlorine injury. Usually the plant itself is The primary purpose of the formalized
not destroyed although yield or growth rate plan is to minimize the risk of injury arising
may be retarded. from the actual or potential release of
24
chlorine during emergencies occurring in 70-226. For calls originating in Mexico City
the course of transportation, at distribution and the metropolitan area, the telephone
points, or at chlorine user locations. Under number is 7-04-11-69 or 7-05-31-48.
this plan, the United States and Canada If a chlorine leak develops in transit
have been divided into regional sectors through a populated area, appropriate
where trained emergency teams from emergency measures should be taken as
producing, packaging, distribution and quickly as possible. If a vehicle transporting
consum ing plants are on constant alert on a chlorine cylinders or ton containers is
24-hour basis to handle possible or actual disabled and there is any possibility of fire,
chlorine releases. the containers should be removed from the
During a chlorine emergency, any vehicle.
carrier, customer, or civil authority can If a tank car or cargo tank trailer is
obtain basic emergency information and be disabled and chlorine is leaking, appropriate
put in contact with the closest chlorine emergency procedures should be instituted
emergency group through either in consultation with local authorities.
CHEMTREC (U.S.) or CANUTEC (Canada). Clearing of track or highway should not be
CHEMTREC and CANUTEC can be started until safe working conditions are
contacted as indicated in the next section. established. See Section 4.3 for action to
take if a fire occurs.
4.52 CHEMTREC, CANUTEC, & CECOM These additional specific actions may
be taken to contain or reduce leaks:
In the United States, the Chemical If a container is leaking chlorine, turn it,
Transportation Emergency Center if possible, so that gas instead of liquid
(CHEMTREC), in Arlington, VA is the escapes. The quantity of chlorine that
dispatch agency which is utilized. escapes from a gas leak is much less than
CHEMTREC operates around the clock, 24 the amount that escapes from a liquid leak
hours a day, 7 days per week, to receive through the same size hole.
direct dial toll free calls from any point in the If practical, reduce pressure in the
continental United States at 1-800-424- container by removing the chlorine as gas
9300. The number for Alaska and Hawaii (not as liquid) to process or a disposal
and for calls from marine radio telephones system as described below.
is 703-527-3887. It may be desirable to move the
CHEMTREC provides immediate advice container to an isolated spot where the
for those at the scene of emergencies, then consequences will be mitigated.
promptly contacts the appropriate responder Apply the appropriate Chlorine Institute
group as required. ln many cases, this will Emergency Kit or place the cylinder in a
be the shipper. However, in some cases the recovery vessel designed to contain the
designated response group is called and leak (see Section 4.8).
then the shipper is notified. A leaking chlorine container must not
In Canada, the Canadian Transport be immersed or thrown into a body of water;
Emergency Center (CANUTEC) in Ottawa, the leak will be aggravated and the
is the dispatch agency. Its telephone container may float when still partially full of
number is 613-996-6666. It may be called liquid chlorine allowing gas evolution at the
collect. CANUTEC, administered by surface.
Transport Canada, operates similarly to Regulations prohibit the normal
CHEMTREC. shipment of a leaking chlorine container or a
In Mexico, Centro de Comunicaciones container which has been exposed to fire,
de la Direccion General de Protecion Civil whether full or partially full. It may he
(CECOM) is the dispatch agency and necessary in some instances to ship a
operates similarly to CHEMTREC and defective chlorine container. In such cases
CANUTEC. Its telephone number is 91-800- special arrangements are required and the
25
chlorine supplier should be consulted first. Chlorine Institute Emergency Kits and
cylinder recovery vessels are designed to
4.6 Disposal of Chlorine contain most leaks
26
information on these kits and their use. 4.9 Reporting
Many chlorine consumers incorporate plans
for the use of these kits in their emergency Most governmental agencies have
programs. Further information on the utility, reporting requirements for chlorine releases.
availability and purchase of kits, kit Producers, transporters and users of
components and audio visual training aids is chlorine should be aware of the reportable
available from the Institute. quantity and of all relevant requirements. In
Chlorine recovery vessels are commer- the U.S., any chlorine release of 10 pounds
cially available equipment designed to hold or more within a twenty-four hour period not
an entire cylinder. Pamphlet IB/RV provides specifically allowed by an operating permit
detailed information on recovery vessels for must be reported immediately to the
100- and 150- lb. cylinders. A leaking National Response Center at 1-800-424-
cylinder can be placed in a recovery vessel 8802 or 202-426-2675.
which is then closed, thus containing the A written follow-up report is required
leak. The chlorine can then be recaptured within 30 days. See 49 CFR 171.16.
from the recovery vessel.
It is the responsibility of the user to
provide instruction in the use of kits and
recovery vessels and to properly maintain
them. The chlorine supplier can provide
assistance in these matters.
Chlorine use or storage locations
should either have the appropriate Institute
emergency kit(s) or containment vessel(s)
readily available with emergency
responders trained in their use or have a
formal arrangement with an outside
emergency response group that can
respond to emergencies using such equip-
ment.
27
5 EMPLOYEE TRAINING AND SAFETY
5.1 Employee Training 5.2 Personal Protective Equipment
28
CONFINED SPACE ENTRY TIPS
Suitable respiratory and other protective equipment for anyone entering
confined space;
Safety harness and life line for all workers in a confined space;
Supervision of the operation from outside the confined space at all
times;
No entry for rescues without appropriate respiratory protection, safety
harness, life line, and back-up personnel;
See OSHA standard 29 CFR 1910.164.
protection. must be equipped with suitable
Self-contained breathing apparatuses respiratory and other protective
should be located on site near the chlorine equipment;
storage and use areas readily accessible to Workers must be equipped with a safety
the trained responders. Documented, harness and life line;
regularly scheduled training is required to A person must oversee the operation
assure competency with self-contained from outside thc confined space at all
breathing apparatuses. If arrangements times;
have been made to use an approved Neither the overseer nor any other
outside emergency response group, then person should enter the confined space
emergency responders and the self- to rescue a victim without appropriate
contained breathing apparatuses may be respiratory protection, safety harness,
located off-site. life line, and backup personnel.
Fit testing and regular maintenance
programs for respirator equipment are 5.4 Personal Exposure Monitoring
necessary.
The characteristic odor of chlorine
5.2.3 Other Personal Protective Equipment makes its presence known at
concentrations well below the permissible
Specialized personal protective exposure level (PEL). Because the odor of
equipment is not required for performing chlorine in itself is an inadequate indicator
many routine plant operations. However, of concentration, it is essential that some
plant practice may dictate the need for eye quantitative measure of exposure be
and head protection as well as long pants, determined. This is necessary to insure that
shirts, and safety shoes. the health of workers is not impaired and to
determine compliance with any applicable
5.3 Confined Space Entry regulations.
The OSHA PEL is 1 ppm, expressed as
Confined space entry procedures must a ceiling exposure level. The American
comply with all applicable local codes and Conference of Governmental Industrial
regulations. The OSHA standard 29 CFR Hygienists (ACGIH) has set the following
1910.146 must be adhered to by most threshold limit values (TLVs): TLV-TWA (8
facilities in the United States. hours) at 0.5 ppm and the TLV-STEL (15
Some key points to be considered: minutes) at 1.0 ppm.
Workers entering the confined space
29
6 MEDICAL ASPECTS AND FIRST AID
6.1 Hazards to Health progress to the point of death through
suffocation. An exposed person with pre-
6.1.1 General existing medical/cardiovascular condition
can have an exaggerated response.
Chlorine gas is primarily a respiratory Liquid chlorine in contact with the eyes
irritant. It is so intensely irritating that low or skin will cause local irritation and/or
concentrations in air (well below l ppm) are bums. All symptoms and signs result
readily detectable by most people. At low directly or indirectly from its direct irritating
concentrations chlorine gas has an odor action. There are no known systemic
similar to household bleach. As the effects.
concentrations increase from the level of
detection by smell so does symptomatology 6.1.3 Chronic Toxicity
in the exposed individual. At chlorine
concentrations above 5 ppm the gas is very Most studies indicate no significant
irritating and it is unlikely that any person connection between adverse health effects
would remain in such an exposure for more and chronic exposure to low concentrations
than a very brief time unless the person is of chlorine. A 1983 Finish study (Reference
trapped or unconscious. The effects of 10.18.14) did show an increase in chronic
exposure to chlorine may become more coughs and a tendency for hypersecretion
severe for up to 36 hours after the incident. of mucous among workers. However, these
Close observation of exposed individuals workers showed no abnormal pulmonary
should be a part of the medical response function in tests or chest x-rays.
program. See Pamphlets 63 and 90 and the In December 1993, the Chemical Indus-
video Health Effects from Short-Term try Institute of Toxicology issued its report
Chlorine Exposure. on a study on the chronic inhalation of
chlorine in rats and mice (Reference
6.1.2 Acute Toxicity 10.17.1). Rats and mice were exposed to
chlorine gas at 0.4, 1.0 or 2.5 ppm for up to
In concentrations near the threshold of 6 hours a day and 3-5 days/week for up to 2
smell, chlorine gas will, after several hours years. There was no evidence of cancer.
of exposure, cause mild irritation of the eyes Exposure to chlorine at all levels produced
and of the mucous membrane of the nasal lesions. Because rodents are
respiratory tract. As concentrations increase obligatory nasal breathers, how these
there is an increase in the irritating effect on results should be interpreted for humans is
the eyes, coughing mechanism and on the not clear.
upper and lower respiratory tract with
eventual difficulty in breathing. As the 6.2 Preventive Health Measures
duration of exposure and/or the
concentration increase, the affected 6.2.1 Physical Examinations
individual may become apprehensive and
restless with coughing accompanied by The Institute recommends that chlor-
throat irritation, sneezing, and excess alkali producers provide baseline and
salivation. At higher levels there is vomiting periodic medical examinations for
associated with labored breathing. In employees potentially exposed to chlorine.
extreme cases difficulty in breathing can The examination should consist of a
complete medical history and physical
30
examination, including chest x-ray (14 inch nearby facility. Such equipment should be
x 17 inch) and baseline respiratory function periodically tested. More sophisticated
studies (FVC, FEVI). Specific reference to inhalation equipment is available in most
respiratory allergies, congenital or acquired emergency facilities. Humidified oxygen
pulmonary and/or cardiac disease is should be used whenever possible.
necessary. Chronic eye conditions (i.e.
chronic conjunctivitis) should be 6.3.2 Contact With Skin
ascertained. It should be determined that
the employee is physically capable of If liquid chlorine has contaminated the
wearing respiratory protection equipment. skin or clothing, an emergency shower
See Pamphlet 126. should be used immediately and contami-
Chlorine users should adopt a medical nated clothing should be removed under the
surveillance program suitable to their needs. shower. Flush contaminated skin with
copious amounts of running water for 15
6.3 First Aid minutes or longer. Thermal burns, due to
the cold temperature of liquid chlorine, may
First aid is the immediate temporary be more damaging than any chemical
treatment given to an exposed individual reaction of chlorine and the skin. Exposure
before the services or recommendations of to gaseous chlorine can irritate the skin. Do
a physician are obtained. Prompt action is not attempt chemical neutralization or apply
essential. Firmness and assurance will help any salves or ointments to damaged skin.
to alleviate anxiety. Medical assistance Refer to a physician if irritation persists after
must be obtained as soon as possible. irrigation or if skin is broken or blistered.
Never give anything by mouth to an
unconscious or convulsing person. 6.3.3 Contact With The Eyes
31
All individuals who have developed Chest X-rays: Baseline and follow-up
symptoms as a result of an acute are indicated (pulmonary edema may not be
overexposure to chlorine gas by inhalation evidentfor up to 36 hours after exposure).
should be placed under the supervision of Cardiac monitoring should be employed.
medical personnel trained in the treatment A diuretic furosemide (lasix) may be
of chlorine exposure. used.
There is no known specific antidote for There is inconclusive evidence regarding
acute chlorine exposure. However, prompt the use of corticosteroids to prevent or
medical assessment and supportive alleviate pulmonary edema. The dosage
measures are necessary to obtain good and frequency of administration of any
therapeutic results. steroid therapy should only be determined
If individual is unconscious and by a qualified physician in keeping with
vomiting, take steps necessary to protect clinical findings of a medical assessment.
the airway from obstruction. The use of antibiotics may be
Alleviate anxiety by communicating with considered to protect against secondary
the patient the various procedures pulmonary infection.
undertaken and elicit his/her cooperation,
especially in breathing exercises. 6.4.2.2 Bronchospasm
Position patient in chair; in severe cases
have the patient lie down with the head and Systemic bronchodilators administered
trunk elevated to a 45-60 degree position. either by subcutaneous injection,
Encourage slow, regular respiration. intravenously or nebulized into the
Humidify air. inspiratory air may be beneficial if patient is
conscious and when spasm is present.
6.4.2 Therapy for Specific Physiological
Disturbances 6.4.2.3 Increased Mucus Secretion
32
incidence of delayed reaction, it is
recommended that any patient who has had
severe inhalation exposure should be kept
at rest for a period of observation. The
length of observation will depend on the
clinical assessment of the exposed
individual. Observation may be required up
to several days after exposure. Excitement,
apprehension and/or emotional distress
may persist after a period of observation
following a severe exposure.
33
7 ENGINEERING DESIGN AND MAINTENANCE
7.1 Structures
be provided.
Buildings and structures to house Previously, the Institute has
chlorine equipment or containers should recommended that the building ventilation
conform with local building and fire codes, allow for a complete change of air with fresh
and with this document. Any building used air in less than four minutes. The Institute
to house chlorine equipment or containers now believes such a recommendation may
should be designed and constructed to not be compatible with current design
protect all elements of the chlorine system philosophies as follows:
from fire hazards. If flammable materials are
stored or used in the same building, then a Section 8003.1.8.2 of the 1994
fire wall should be erected to separate the Uniform Fire Code (see Section 8.6)
two areas. Non-combustible construction is requires mechanical ventilation at
recommended. the rate of not less than one (1)
Chlorine monitoring equipment which ft3/minute per square foot for floor
continuously samples the air and detects area for storage buildings.
the presence of chlorine is available and
should be considered in any storage or Industrial Ventilation (10.4.2)
operating area where chlorine can be cautions in Section 7.7 that Air
released. See Pamphlet 73. changes per hour is a poor basis for
At least two exits should be provided ventilation criteria where envi-
from each separate room or building in ronmental control of hazards, heat,
which chlorine is stored, handled or used. and/or odors is required ... there is
Exit doors should not be locked and should little relationship between air
open outward. Platforms should be changes and the required con-
designed to facilitate egress and two or taminant control.
more access stairways or ladders should be
considered. Steel structures should be The Institute now recommends that
protected to prevent corrosion. ventilation requirements be determined on a
site-specific basis. Safeguards should be in
7.2 Ventilation place to insure that persons do not remain
in nor enter buildings where chlorine is
7.2.1 General present due to a leak or equipment failure
without the appropriate personal protective
All ventilation systems for buildings that equipment.
house equipment or containers should
conform with applicable building code 7.2.2 Air Openings
requirements, American Conference of Gov-
ernmental Industrial Hygienists (ACGIH) Chlorine gas is heavier than air and
recommendations (Reference 10.4.2) and has a tendency to collect at floor level. The
with this manual. The building ventilation exhaust air intake should be located at or
system should provide fresh air for normal near floor level. An elevated fresh air inlet
operation and should take into consideration must be provided and should be located for
the possibility of a leak. In some cases adequate cross ventilation. Multiple fresh air
natural ventilation may be adequate; other- inlets and fans may be necessary to
wise, mechanical ventilation systems should facilitate adequate ventilation. Fans, if used,
34
should be made to start and stop from a 3920F (2000C) chlorine rapidly attacks steel.
safe, remote location. Above 4830F (2510C) the reaction is
Alternatively, it maybe desirable to immediate as carbon steel flames in the
pressurize an installation with fresh air and presence of chlorine. Impurities in the
to exhaust the contaminated air through chlorine and/or a high surface area of the
outlets at floor level. steel may significantly lower the auto-
ignition temperature of chlorine and steel.
7.2.3 Heating There is also a possibility of brittle
fracturing in certain chlorine processing
Rooms containing chlorinator feed equipment and storage tanks. Where this is
equipment should he maintained at a the case, a type of steel should be used that
normal indoor temperature of about 60 - can withstand the lowest temperatures
700F (about 15 - 200C) to facilitate gas possible in the process.
discharge rates from the container.
7.3.4 Chemicals
7.3 Material for Processing Equipment
Several chemicals are normally
7.3.1 General involved in the manufacture of chlorine,
including sulfuric acid, mercury, certain
Commercial liquid chlorine contains only salts, oxygen and various products of their
minor amounts of impurities and is dry reaction with chlorine. Materials of
enough to be handled in carbon steel construction should be selected to guard
equipment. In the manufacturing process, against these corrosive or hazardous
certain properties unique to chlorine should materials that are present in the
be considered when considering the manufacturing process.
materials of construction.
7.3.5 Alternative Materials
7.3.2 Water
Other than steel, a wide variety of
Wet chlorine may be safely handled materials may be used in chlorine handling.
with a variety of materials which can be A number of them, particularly plastics, are
chosen to suit the process conditions. Some suitable but have pressure and temperature
materials, such as titanium, are suitable for limitations that must be considered. Care
wet chlorine but not for dry chlorine. must be taken to prevent external
Titanium reacts violently with dry chlorine. mechanical damage.
Reference 10.18.13 indicates that titanium
is a safe material in wet gaseous chlorine 7.4 Electrolyzers (Cells)
provided the partial pressure of water
component is greater than 14 mbar (0.20 7.4.1 General
psi) and the temperature is between 15 0C
(590F) and 700C (158 0F). Chlorine can be produced
electrolytically by either membrane
7.3.3 Temperature electrolyzers, diaphragm cells, or mercury
cells. Reference 10.18.7 provides a detailed
Carbon steel used in the handling of discussion of the electrolytic methods of
dry chlorine must be kept within definite chlorine manufacture.
temperature limits. Where process
temperatures are expected to exceed 3000F 7.4.2 Membrane Electrolyzers
(1490C), the material used should be more
resistant than carbon steel to high The membrane electrolyzer is the
temperature corrosion by chlorine. Above newest technology for producing chlorine
35
electrolytically. Sheets of perfluorinated In a mercury cell, the cathode is a
polymer ion exchange membrane separate stream of mercury flowing along the bottom
the anodes and cathodes within the of the electrolyzer The anodes are
electrolyzer. Ultra-pure sodium chloride suspended parallel to the base of the cell, a
solution (brine) is fed to the anode few millimeters above the flowing mercury.
compartments, where chloride ions are Brine is fed into one end of the cell box and
oxidize to form chlorine gas. The flows by gravity between the anodes and
membranes are cation selective resulting in the cathode. Chlorine gas is evolved and
predominantly sodium ions and water released at the anode.
migrating across the membranes to the The sodium ions are deposited along the
cathode compartments. Water is reduced to surface of the flowing mercury cathode. The
form hydrogen gas and hydroxide ions at alkali metal dissolves in the mercury,
the cathodes. In the cathode compartment, forming a liquid amalgam. The amalgam
hydroxide ions and sodium ions combine to flows, by gravity, from the electrolyzer to the
form sodium hydroxide. carbon-filled decomposer, where deionized
Membrane electrolyzers typically water is added. The water chemically strips
produce 30% to 35% sodium hydroxide, the alkali metal from the mercury, producing
containing less than 50 ppm of sodium hydrogen and 50% sodium hydroxide. (In
chloride. The sodium hydroxide can be the decomposer, the amalgam is the anode
concentrated further, typically to 50%, in an and the graphite packing is the cathode.)
evaporation system. The stripped mercury is then pumped back
to the cell box, where the electrolysis
7.4.3 DiaphragmCells process is repeated.
36
Equipment used in chlorine must be reciprocating, and liquid-ring sealed (sulfuric
designed either for dry chlorine or for wet acid). Compressors should be built in
chlorine so that proper materials of accordance with the applicable ASME Code
construction are selected. Most equipment and supplier specifications proper for the
used in chlorine service is built to a specific application. Aluminum, copper, and copper
design code or regulation. Such codes or alloys must be avoided.
regulations include ANSI, API, ASME and Fans are sometimes used to boost
TEMA standards and OSHA regulations. pressure or move chlorine gas in vent or
scrubber systems. In wet chlorine service,
7.7.2 Vessels rubber-lined, fiberglass reinforced polyester
or titanium are normally used. In dry
Materials of construction for vessels chlorine service, carbon steel is normally
used in wet chlorine applications include used.
certain plastic-lined or rubber-lined steel,
reinforced polyesters, and titanium. Vessels 7.7.6 Scrubbers
used in dry chlorine service are usually
carbon steel. While scrubbers are an effective means
The minimum fabrication standard for of absorbing chlorine, the need for a
metal vessels operating at greater than 15 scrubber should be based on a site specific
psig is that given in the ASME Code hazard assessment that considers factors
(Reference 10.5.1) for pressure vessels. such as the quantity of chlorine on site, the
Vessels operating at less than 15 psig have likelihood of a release, and the
no ASME code requirements, but should be consequences of a release. See Pamphlet
designed according to a manufacturers 89.
specification. Vessels in vacuum service
require special designs to prevent collapse. 7.8 Piping Systems for Dry Chlorine
37
properly supported, adequately sloped to flanged, screwed or welded depending on
allow drainage, and low spots should be pipe size. Flanged and screwed joints
minimized. should be kept to a minimum. If screwed
Avoid installing lines next to steam joints are used, extreme care should be
lines, acid lines, etc. that could cause taken to obtain clean, sharp threads. A
corrosion of the chlorine line. Protect thread sealant compatible with chlorine
chlorine piping from all risks of excessive should be used.
heat or fire. Before cutting or welding on a chlorine
Sprinklers are not needed for chlorine line, a determination must be made that the
storage or use areas that have been system is chlorine free. Dry chlorine can
constructed and maintained per Institute support combustion of carbon steel, nickel
recommendations. In such situations, no and other materials.
combustible or flammable materials should
be present. If sprinklers are installed, they 7.8.3 Preparation of Systems for Use
should be used only to suppress fires and/or
cool containers threatened by fire. 7.8.3.1 Cleaning
38
Drying can be facilitated as the system must be selected with care. For higher
is cleaned by passing steam through the pressures, lined metallic or compatible
lines from the high end until the lines are metallic systems should be used.
heated. While steaming, the condensate In the metallic systems, Hastelloy C,
and foreign matter is drained out. The titanium and tantalum have been used.
steam supply then should be disconnected Within limits, titanium may be used with wet
and all the pockets and low spots in the line chlorine but must not be used with dry
drained. While the line is still warm, dry air chlorine under any circumstances, as it
or inert gas (e.g., nitrogen) having a dew burns spontaneously on contact. Tantalum
point of -40 0F (-400C) or below should be is inert to wet and dry chlorine at
blown through the line until the discharge temperatures up to 3000F (149 0C).
gas is also at a dew point of -40 0F (-400C)
or below. 7.10 Stationary Storage
If steam or dry utility system air are not
available, particular care must be taken in Consumers receiving chlorine in
cleaning sections of pipe and other barges, tank cars or trucks may require
equipment before assembly, and careful stationary storage facilities. The facilities
inspection is necessary as construction should be properly designed and should be
proceeds. The final assembled system operated and periodically inspected in
should be purged with dry cylinder air or accordance with Institute recommendations.
nitrogen until the discharge gas is at a dew See Pamphlets 5 and 78.
point of -40 0F (-400C) or below. A tank should not be filled beyond its
rated chlorine capacity because liquid
7.8.3.4 Leak Testing chlorine will expand as it warms. At normal
storage temperatures, the thermal-
After drying, the system should be leak- expansion rate of liquid chlorine is high and,
tested with dry air or nitrogen. A soap if room for expansion is not provided, could
solution should be utilized to test for leaks at increase the hydrostatic pressure enough to
piping joints. Chlorine gas may then be rupture the tank. The maximum chlorine
introduced gradually and the system further level should be determined by the filling
tested for leaks with 200 Baume aqua density as discussed in Section 1.5.12.
ammonia vapor. Care must be taken that
chlorine has diffused throughout the piping 7.11 Equipment Maintenance
systems before testing for leaks. Never
attempt to repair leaks by welding until all 7.11.1 General
chlorine has been purged from the system.
When leaks have been repaired, the line Maintenance of chlorine equipment
should be retested. and tanks should be under the direction of
trained personnel. All precautions pertaining
7.9 Piping Systems for Wet Chlorine to safety education, protective equipment,
health and fire hazards should be reviewed
Wet chlorine is very corrosive to all of the and understood. Workers should not
more common construction metals. At low attempt to repair chlorine piping or other
pressures wet chlorine can be handled in equipment while it is in service. When a
chemical stoneware, glass or porcelain chlorine system is to be cleaned or repaired,
equipment and in certain alloys. Hard tanks, piping and other equipment should
rubber, unplasticized polyvinyl chloride, always be purged with dry air or non-
fiberglass reinforced polyester, reactive gas.
polyvinylidene chloride or fluoride and fully Decontamination is especially impor-
halogenated fluorcarbon resins have been tant where cutting or welding operations are
used successfully. All of these materials undertaken because iron and steel will
39
ignite in chlorine near 4830F (2510C). regarding health and safety or the pollution
Immediate drying of a chlorine pipe or of natural resources must be followed.
container into which water has been A system should be provided to
introduced or which has been opened for neutralize any chlorine vented for
repairs or cleaning is essential to prevent maintenance preparation or process upset,
corrosion. such as a sudden failure of the chlorine
compressor, trouble during the start-up of a
7.11.2 Cleaning of Piping circuit, or a breakdown of the tail gas
and Other Equipment handling system.
The neutralization is usually accom-
If moisture enters a chlorine system plished by causing the chlorine to react with
containing metallic components, such as sodium hydroxide solution or, in certain
when connections are being made or situations, with another alkaline compound.
broken at a chlorine container or while Neutralization can take place in an
maintenance is being performed, ferric appropriately designed tank or in a
chloride, already present in small amounts, scrubber. The sodium hydroxide concen-
will absorb moisture and change to a tration should be less than 20% to prevent
corrosive, brown, viscous liquid. If not precipitation of sodium chloride crystals
removed, this viscous liquid will continue to (salting-out) and excessive heat of reaction.
corrode the metal and can rapidly plug See Pamphlet 89.
chlorine lines and equipment such as
vaporizers. This hydrated ferric chloride is
corrosive to many metals including
Hastelloy C.
Steam or hot water rapidly dissolves
ferric chloride. However, lines or equipment
cleaned in this manner must be dried
carefully before they are put back in service.
Steam should not be used on plastic
equipment unless it is known that the
specific plastic material can stand the
temperature. Any in-line instrumentation
should be protected during the cleaning
process. Cleaning of piping and various
other equipment is addressed in Pamphlet
6.
40
8 KEY REGULATIONS AND CODES
Note: The purpose of this section is or explosive chemicals.
to provide a list of some of the key
OSHA, EPA, and DOT regulations that 8.1.6 Section 1910.120 - Hazardous
significantly affect the production, Waste Operations and Emergency
storage, packaging, distribution, or use Response
of chlorine in the United States.
Additionally, information is provided Requirements for responding to a
on some of the Fire Codes that similarly chemical emergency.
affect chlorine. This section is not meant
to cover all such regulations affecting 8.1.7 Sections 1910.132 to.139-Personal
chlorine. Protective Equipment
41
substances.
8.1.13 Section 1910.1000-AirContaminants
8.2.6 Part 154 - Facilities Transferring Oil
Exposure limits to chemicals. or Hazardous Materials in Bulk
8.2.5 Part 153 -Control of Pollution by Oil 8.3.2 Part 68 - Clean Air Act/Accidental
and Hazardous Substances; Releases
Discharge Removal
Requirements to prevent or mitigate
Requirements concerning the consequences of hazardous
notification of the Coast Guard of materials with off-site effects.
the discharge of oil or hazardous
42
8.3.3 Part 82 - Protection of Stratospheric reporting for various chemical
Ozone substances.
43
specific hazardous cargoes retesting.
including chlorine.
8.5.6 Part 174 - Carriage by Rail
8.5 Transportation Regulations - 49
CFR Requirements for handling, loading,
unloading and storage of tank cars.
8.5.1 Part 106 - Rulemaking Procedures
8.5.7 Part 176 - Carriage by Vessel
General rulemaking procedures for
issuing, amending, and repealing Requirements for packaged
regulations. hazardous materials transported by
vessel.
8.5.2 Part 107 - Hazardous Materials
Program Procedures 8.5.8 Part 177 - Carriage by Public
Highway
Requirements for exemptions,
preemptions, enforcement, Requirements on the handling,
compliance orders, civil and criminal transportation, loading and
penalties, registration of cargo tank unloading and segregation of
manufacturers and repairers, hazardous materials.
registration and fees.
8.5.9 Part 178 - Specifications for
8.5.3 Part 171 - General Information, Packagings
Regulations, Definitions
Specifications for cylinders, portable
Use and applicability of tanks and cargo tanks.
transportation regulations within and
outside the U.S. and reporting 8.5.10 Part 179 Specifications for Tank
requirements for hazardous material Cars
incidents.
Design requirements and
8.5.4 Part 172 - Hazardous Materials specifications for bulk rail tank cars.
Table, Special Provisions,
Hazardous Materials 8.5.11 Part 180 Continuing Qualifications
Communications, Emergency and Maintenance of Packagings
Response Information, and Training
Requirements Requirements for qualifying existing
cargo tanks for hazardous
Requirements for shipping papers, materials.
marking, labeling and placarding and
the training of hazmat employees. 8.5.12 Part 190 - Pipeline Safety Program
Procedures
8.5.5 Part 173 - Shippers - General
Requirements for Shipments and Enforcement regulations pursuant to
Packagings the Natural Gas Pipeline Safety Act,
the Hazardous Liquid Pipeline
Definitions of hazardous materials Safety Act and the Hazardous
for transportation purposes. Materials Transportation Act as
Requirements for preparing amended.
hazardous materials shipments, for
container inspections, testing and 8.5.13 Part 191 - Transportation of Natural
44
and Other Gas by Pipeline; Annual The model codes are modified annually
Reports, Incident Reports and and yearly supplements are issued.
Safety Related Condition Reports Completely new editions of the codes are
published every third year. Therefore, the
Requirements for reporting code year is important in determining which
incidents, safety related conditions, code is applicable. The specific
and pipeline data. requirements are contained in the
applicable code.
8.5.14 Part 192 - Transportation of Natural The NFPA Standards and the major
and other Gas by Pipeline: Minimum model building and fire codes can be
Federal Safety Standards obtained from these organizations:
45
9 TECHNICAL DATA
9.1 General Chlorine is only slightly soluble in water.
When it reacts with pure water, a weak
Chlorine has a characteristic penetrating solution of hydrochloric and hypochlorous
and irritating odor. The gas is greenish acids is formed. Chlorine hydrate (Cl2
yellow in color and the liquid is clear amber. 8H20) may crystallize below 49.3 0F (9.60C)
The data on physical properties of chlorine at atmospheric pressure and higher
as determined by different investigators temperatures at increased pressures.
show some variations. Values for physical
properties below are taken from Pamphlet 9.3.3.2 Reactions With Metals
72.
The reaction rate of dry chlorine with
9.2 Atomic and Molecular Properties most metals increases rapidly above a
temperature which is characteristic for the
Atomic Symbol - Cl metal. Below 2500F (1210C) iron, copper,
Atomic Weight - 35.453 steel, lead, nickel, platinum, silver and
Atomic Number - 17 tantalum are resistant to dry chlorine, gas or
Molecular Weight - 70.906 liquid. At ordinary temperatures dry chlorine,
gas or liquid, reacts with aluminum, arsenic,
Elemental chlorine exists in the form of two gold, mercury, selenium, tellurium, and tin.
naturally occurring isotopes with mass Dry chlorine reacts violently with titanium. At
numbers of 35 and 37. Ordinary molecular certain temperatures, sodium and
chlorine consists of a mixture of about 76% potassium burn in chlorine gas. Carbon
chlorine 35 and 24% chlorine 37. There are steel ignites near 483 0F (251 0C) depending
also at least 13 artificially produced isotopes on its physical form. For piping
of chlorine. recommendations, see Pamphlet 6. Moist
chlorine, primarily because of the
9.3 Chemical Properties hydrochloric and hypochlorous acids formed
through hydrolysis, is very corrosive to most
9.3.1 Flammability common metals. Platinum, silver, tantalum
and titanium are resistant.
Chlorine, gas or liquid, is non-explosive and
non-flammable; however, like oxygen, it is 9.3.3.3 Reactions With Other Elements
an oxidizer and is capable of supporting
combustion of certain substances. Many Chlorine unites under specific conditions
organic chemicals react readily with with most of the elements; these reactions
chlorine, sometimes violently. may be extremely rapid. At its boiling point
chlorine reacts with sulfur. It does not react
9.3.2 Valence directly with oxygen or nitrogen; the oxides
and nitrogen compounds are well known but
Chlorine usually forms compounds with a can only be prepared by indirect methods.
valence of -1 but it can combine with a Mixtures of hydrogen and chlorine can react
valence of +l, +2, +3, +4, +5 or +7. violently. Ignition limits depend on
temperature, pressure and concentration.
9.3.3 Chemical Reactions Between 70 and 80 0F (210 and 270C) the
ignition limits range from 3% to 93% by
9.3.3.1 Reactions With Water volume of hydrogen. Ignition can be initiated
46
by direct sunlight, other source(s) of 35.77 lb/ft 3 (573.0 kg/m 3) - The mass of a
ultraviolet light, static electricity, or sharp unit volume of chlorine at the critical
impact. pressure and temperature.
47
9.4.5 Latent Heat of Vaporization 9.4.10.1 Saturated Gas
At Constant Pressure (Cp)
123.9 Btu/lb (288.1 kJ/kg) at the normal
boiling point - The heat required to 0.1244 Btu/lb 0F (0.521 kJ/kg 0K) at
evaporate a unit weight of chlorine. 32 F (00C); 0.1347 Btu/lb 0F (0.564 kJ/
0
1.467 0/40C The ratio of the density 1.3 10 ft3/lb (0.08179 m 3/kg).
of saturated liquid chlorine at 320F (00C) to
the density of water at its maximum density 9.4.11.3 Saturated Liquid at 320F (00C)
(approximately 390F (40C)).
0.0 1092 ft 3/lb (0.000 681 8 m 3/kg.).
9.4.10 Specific Heat
9.4.12 Vapor Pressure
The heat required to raise the
temperature of a unit weight of chlorine one The absolute pressure of chlorine gas
degree. above liquid chlorine when they are in
equilibrium. 53.51 psi (368.9 kPa) at 32 0F
48
(00C); 112.95 psi (778.8 kPa) at 770F
(250C). See Fig. 9.1.
9.4.13 Viscosity
9.4.13.2 Liquid
49
50
51
52
53
54
55
10 SELECTED REFERENCES
56
100 Dry Chlorine: Definitions and
74 Estimating the Area Affected by a Analytical Issues
Chlorine Release
121 Explosive Properties of Gaseous Mix-
75 Respiratory Protection Guidelines for tures Containing Hydrogen and
Chlor-Alkali Manufacturing Facilities Chlorine
76 Guidelines for the Safe Motor 126 Guidelines: Medical Surveillance and
Vehicular Transportation of Chlorine Hygiene Monitoring Practices for Con-
Containers trol of Worker Exposure to Chlorine in
the Chlor-Alkali Industry
77 Sampling Liquid Chlorine
134 The Drying and Liquefaction of Chlo-
78 Refrigerated Liquid Chlorine Storage rine and the Phase Diaphragm Cl2
H2O
79 Recommended Practices for Handling
Chlorine Barges 139 Electrical Safety in Chlor-Alkali Cell
Facilities
82 Chlorine Safety at Non-Residential
Swimming Pools 151 Training Guide for Distributors and
End-Users of Packaged Chlorine
84 Environmental Fate of Chlorine in the
Atmosphere 152 Safe Handling of Chlorine Containing
Nitrogen Trichloride
85 Recommendations for Prevention of
Personnel Injuries for Chlorine IB/A Instruction Booklet: Chlorine Institute
Producer and User Facilities Emergency Kit A for 100- and 150-
lb. Chlorine Cylinders
86 Recommendations to Chlor-Alkali
Manufacturing Facilities for the lB/B Instruction Booklet: Chlorine Institute
Prevention of Chlorine Releases Emergency Kit B for Chlorine Ton
Containers
89 Chlorine Scrubbing Systems
IB/C Instruction Booklet: Chlorine Institute
90 Toxicity Summary for Chlorine and Emergency Kit C for Chlorine Tank
Hypochlorite and Chlorine in Drinking Cars and Tank Trucks
Water
IB/RV Instruction Booklet: Cl Recovery Ves-
91 Checklist for Chlorine Packaging sel for 100-and 150-lb. Chlorine
Plants, Chlorine Distributors and Tank Cylinders
Car Users of Chlorine
VPC The Vapor Pressure of Chlorine
93 Pneumatically Operated Valves for
Use on Chlorine Tank Cars 10.3.2 Drawings
95 Gaskets for Chlorine Service The reader should refer to the current
Institute catalog for a complete list of
97 Safety Guidelines for Swimming Pool drawings.
Applicators
DWG 104 Standard Chlorine Angle Valve
Assembly
57
DWG 110 Valve for Chlorine Cylinders and Chlorine Exposure
Ton Containers - Assembly
10.4 American Conference of Govern-
DWG 111 Fusible Plugs for Chlorine Cylin- mental Industrial Hygienists
ders and Ton Containers 1330 Kemper Meadow Drive
Cincinnati, OH 45240
DWG 112 Valves and Fusible Plugs for
Chlorine Ton Containers 10.4.1 Threshold Limit Values and
Biological Exposure Indices ,
DWG 113 Valves for Chlorine Cylinders Published Annually
and Ton Containers
10.4.2 Industrial Ventilation Manual: A
DWG 114 Excess Flow Valve with Manual of Recommended Practices,
Removable Seat - 15,000 lb/hr 22nd Edition, 1995.
DWG 118 Chlorine Tank Car Unloading 10.5 American Society of Mechanical
Connections Engineers, United Engineering
Center, 345 East 47th Street
DWG 121 Limiting Dimensions for Chlorine New York, NY 10017.
Cylinders
10.5.1 Rules for Construction of Pressure
DWG 122 Ton Container Lifting Beam Vessels, Sections VIII, Division
ASME
DWG 130 Standard Chlorine Cylinder and Boiler and Pressure Vessel Code
Ton Container Valve Adapter ANSI/ASME BPV-VIII- 1.
DWG 131 Chlorine Cylinder Valve Yoke 10.6 American Society for Testing
Materials
DWG 136 Chlorine Expansion Chambers 1916 Race Street
Philadelphia, PA 19103.
DWG 162 Excess Flow Valve with
Removable Seat - 30,000 lb/hr 10.6.1 ASTM-E4 10-92, Standard Method
of Testing for Moisture and Residue
DWG 163 Excess Flow Valve with in Liquid Chlorine
Removable Seat - 11,000 lb/hr
10.6.2 ASTM-E4 12-86, Standard Method of
DWG 167 Chlorine Tank Car Marking Assaying Liquid Chlorine
(Zinc Amalgam Method)
DWG 168 Chlorine Cargo Tank Marking
10.6.3 ASTM-E649-94, Standard Test
DWG 181 DOT 106A500X - Ton Container Method for Bromine in Chlorine
DWG 183 Manifolding Ton Containers for 10.6.4 ASTM-E806-93, Standard Test Met
Liquid Chlorine Withdrawal hod for the Determination of Carbon
Tetrachloride and Chloroform in
DWG 188 Chlorine Cylinder Recovery Liquid Chlorine by Direct Irqection
Vessel (Gas Chromatographic Procedure)
58
10.12 National Institute of Occupational
10.7 American Water Works Safety and Health
Association
6666 West Quincy Avenue 10.12.1Pocket Guide to Chemical Hazards
Denver, CO 80235. U.S. Department of Health
and Hmnan Services: 1994.
10.8 Association of American
Railroads 10.13 National Safety Council
50 F St., NW 444 North Michigan Avenue
Washington, DC 20001 Chicago, IL 60610.
10.10.2 Food Chemicals Codex II, 10.18.1 Adams, F. W.; Edmonds, R. G.; I&
Fourth Edition, 1996 EC,
1937, 29, 447.
10.11 National Fire Protection
Association Batterymarch Park,
Quincy, MA 02269.
59
10.18.2 Ambrose, D.; Hall, D. J.; Lee, D. A.; 10.18.11 Rotman, Harold H., etal.;Journal of
Lewis, G. B.; Mash, C. J. J.; the American Physiological
Chemical Thermodynamics, 1979, Society, 1983, 1120, 983.
11, 1089.
10.18.12 Weill, H.; George, R.; Schwartz,
10.18.3Chlorine Bicentennial Symposium; M.; Ziskind, M. ; Am. Review of
Jeffery, T.; Danna, P. A.; Holden, H. Respiratory Diseases, 1969, 29,
S., Eds.; Electrochemical Sociely: 373.
Princeton, NJ, 1974.
10.18.13 Weston, P.C. Modern Chlor-Alkali
10.18.4 Chlorine, Its Manufacture, Technology; Coulter, M.O., et al,
Properties and Uses; Sconce, J. S. Eds.; Society of Chemical Industry;
ed.; ACS Monograph 154; Robert E. Royal Society of Chemistry:
Krieger: Huntington, NY, 1972. Cambridge, 1994; Vol.6, pp 62-69.
60
CHLORINE
The Essential Element
Over 200 years ago, a young Swedish researcher, Carl Wilhelm Scheele,
discovered chlorine. Because of its reactivity and bonding characteristics, chlorine
has become a popular building block in chemistry and it is essential in everyones
life. Drinking water, agricultural abundance, disinfected waste water, essential
industrial chemicals, bleaches and fuels all depend on chlorine. Pharmaceutical,
plastics, dyes, cosmetics, coatings, electronics, adhesives, clothing and automobile
parts are examples of product groups that depend on chlorine chemistry.
APPLICATIONS OF CHLORINE
Automotive Electronics Metal Production
Foam Seating Semiconductors Magnesium
Paints Computer Disks Nickel
Plastic Bumpers Molding Wire Insulation Bismuth
Instruments Titanium
Floor Mats Food Production Zirconium
Fabric & Handling Zinc
Seat Belts Herbicides
Tire Cords Vitamins B1 & B6 Outdoor Recreation
Dashboards Cleaners Neoprene Wet Suits
Hoses Disinfectants Inflatable Rafts
Thermal Insulation Golf Grip
Construction Sterile Packaging Surf Boards
Carpeting Nylon Ropes
Upholstery Health Care Tents
Wire Insulation Electronic Instruments Sleeping Bags
Pipes Sterile Packaging Coats
Siding Surgical Equipment Backpacks
Flooring Cleaning Compounds Waterproof Clothing
Paints Prescription Eye Wear
Coatings Laboratory Reagents Water Treatment
Safe Drinking Water
Defense Medicines Wastewater Treatment
Bullet-Proof Vests Antibiotics
Helmets Cancer Treatment
Parachutes Pain Relievers
Water Repellant Fibers Local Anesthetics
Shatter-Resistant Glass Antihistamines
Titanium Aircraft Decongestants
Jet Engines
Missiles
Chlorine Institute Pamphlet 1, Edition 6 January 1997 Second Printing March 2000