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Sixth Edition

THE CHLORINE MANUAL

THE CHLORINE INSTITUTE, INC.


2001 L Street, N.W., Suite 506
Washington, D.C. 20036
202-775-2790
Fax: 202-223-7225
http:// www.CL2.com
THE CHLORINE INSTITUTE, INC.
MISSION STATEMENT
The Chlorine Institute, Inc. exists to support the chlor-alkali industry
and serve the public by fostering the continuous evaluation of and
improvements to safety and the protection of human health and the
environment connected with the production, distribution and use of
chlorine, sodium and potassium hydroxides, and sodium hypochlorite; and
the distribution and use of hydrogen chloride. The Institute meets this
obligation by maintaining a scientific and technical organization that fully
meets its members and publics needs and expectations. The Institute
works with governmental agencies to encourage the use of credible science
and technology in developing regulations impacting the industry.

American National Standard - February 29, 2000

This Publication has been approved as an American National


Standard (ANS). Approval of an ANS requires review by The American
National Standards Institute (ANSI) that the requirement for due process,
consensus, and other criteria for approval have been met by the standards
developer. Consensus is established when, in the judgement of the ANSI
Board of Standards Review, substantial agreement has been reached by
directly and materially affected in4erests. Substantial agreement means
much more than a simple majority, but not necessarily unanimity. Consensus
requires that all views and objections be considered, and that a concerted
effort be made toward their resolution.
The use of ANSs is completely voluntary; their existence does not in any
respect preclude anyone, whether he or she has approved the standards or
not, from manufacturing, marketing, purchasing, or using products,
processes, or procedures not conforming to the standards. The ANSI does
not develop standards and will in no circumstances give an interpretation of
any ANS. Moreover, no person shall have the right or authority to issue an
interpretation of an ANS in the name of the ANSI. Requests for
interpretations should be addressed to the secretariat or sponsor whose name
appears on the title page of this standard.
Caution Notice: This ANS may be revised or withdrawn at any time.
The procedures of the ANSI require that action bc taken periodically to
reaffirm, revise, or withdraw this standard. Purchasers of ANSs may receive
current information on all standards by calling or writing the American
National Standards Institute.
TABLE OF CONTENTS
i. INTRODUCTION 5. EMPLOYEE TRAINING AND
The Chlorine Manual SAFETY 28
Commitment to Responsible Care 5.1 Employee Training 28
Checklists 5.2 Personal Protective Equipment 28
References 5.3 Confined Space Entry 29
5.4 Personal Exposure Monitoring 29
1. GENERAL INFORMATION 1
1.1 Chlorine Manufacture 1 6. MEDICAL ASPECTS AND FIRST
1.2 Chlorine in Transportation 1 AID 30
1.3 Other Regulatory Aspects 2 6.1 Hazards to Health 30
1.4 Chemical and Physical Properties 3 6.2 Preventive Health Measures 30
1.5 Terminology 3 6.3 First Aid 31
1.6 Health Hazards 4 6.4 Medical Management of
1.7 Other Hazards 4 Chlorine Exposures 31
1.8 Containers 5
7. ENGINEERING DESIGN AND
2. CYLINDERS AND TON MAINTENANCE 34
CONTIANERS 7 7.1 Structures 34
2.1 Container Descriptions 7 7.2 Ventilation 34
2.2 Container Valves 8 7.3 Material for Processing
2.3 Pressure Relief Devices 8 Equipment 35
2.4 Container Shipping 9 7.4 Electrolyzers (Cells) 35
2.5 Container Labeling and Placarding 9 7.5 Chlorinators 36
2.6 Container Handling 9 7.6 Vaporizers 36
2.7 Container Storage 10 7.7 Support Equipment 36
2.8 Container Use 10 7.8 Piping Systems for Dry Chlorine37
7.9 Piping Systems for Wet Chlorine39
3. BULK SHIPPING CONTAINERS 14 7.10 Stationary Storage 39
3.1 General 14 7.11 Equipment Maintenance 39
3.2 Tank Cars 14 7.12 Chlorine Neutralization 40
3.3 Tank Motor Vehicles 18
3.4 Portable Tanks 20 8. KEY REGULATIONS AND
3.5 Tank Barges 20 CODES 41
8.1 Occupational Safety and Health
4. EMERGENCY MEASURES 22 Regulations 29 CFR 41
4.1 General 22 8.2 Navigation and Navigable Water
4.2 Response to a Chlorine Release 22 Regulations 33 CFR 42
4.3 Response to a Fire 22 8.3 Environmental Regulations
4.4 Releases 23 40 CFR 42
4.5 Transportation Emergencies 24 8.4 Shipping Regulations 46 CFR (Water
4.6 Disposal of Chlorine 26 Transportation) 43
4.7 Absorption Systems 26 8.5 Transportation Regulations
4.8 Emergency Kits and Recovery 49 CFR 44
Vessels 26 8.6 Fire Codes 45
4.9 Reporting 27
9. TECHNICAL DATA 46 ILLUSTRATIONS
9.1 General 46
9.2 Atomic and Molecular Properties 46 Fig. 2.1 Chlorine Cylinders 7
9.3 Chemical Properties 46 Fig. 2.2 Chlorine Ton Container 7
9.4 Physical Properties 47 Fig. 2.3 Standard Cylinder Valve 8
Fig. 2.4 Standard Ton Container Valve 8
10. SELECTED REFERENCES 56 Fig. 2.5 Standard Fusible Plug
10.1 U.S. Government Regulations for Ton Containers 8
and Specifications 56 Fig. 2.6 Lifting Beam for Handling
10.2 Canadian Regulations 56 Chlorine Ton Containers 9
10.3 Chlorine Institute References 56 Fig. 2.7 Yoke & Adapter
10.4 American Conference of Type Connection 12
Governmental Industrial Fig. 3.1 Chlorine Tank Car 14
Hygienists 58 Fig. 3.2 Valve Arrangement & Manway 15
10.5 American Society of Fig. 3.3 Standard Angle Valve 15
Mechanical Engineers 58 Fig. 3.4 Excess-Flow Valve 16
10.6 American Society for Testing Fig. 3.5 Standard Pressure Relief Device 16
Materials 58 Fig. 3.6 Chlorine Tank Truck 19
10.7 American Water Works Fig. 3.7 Chlorine Barge 21
Association 59 Fig. 4.1 Chlorine Institute
10.8 Association of American Emergency Kit A
Railroads 59 for Chlorine Cylinders 27
10.9 Compressed Gas Assn. 59
10.10 National Academy of Sciences 59
10.11 National Fire Protection CHARTS
Association 59
10.12 National Institute of Fig. 9.1 Vapor Pressure
Occupational Safety and Health 59 of Liquid Chlorine 50
10.13 National Safety Council 59 Fig. 9.2 Temperature-Density Relation
10.14 NSF International 59 of Liquid Chlorine 51
10.15 Water Environment Federation 59 Fig. 9.3 Equilibrium Solubility
10.16 World Health Organization 59 of Chlorine in Water 52
10.17 Chemical Industry Inst. Of Fig. 9.4 Volume-Temperature Relation
Toxicology 59 of Liquid Chlorine in a Container
10.18 Other References 59 Loaded to its Authorized Limit 53
Fig. 9.5 Solubillity of Water
in Liquid Chlorine 54
Fig. 9.6 Solubility of Water in
Liquid Chlorine 55

TABLES

2.1 Container Dimensions


and Weights 9
4.1 Recommended Alkalline Solutions
for Absorption 26
i INTRODUCTION

THE CHLORINE MANUAL

T he widespread use of chlorine and the accompanying demand for reliable


information on recognized procedures for the safe handling of chlorine resulted
in the publication of the first Chlorine Manual by the Chlorine Institute in 1947.
Subsequent editions have been published in 1954, 1959, 1969, and 1986.
The Chlorine Manual is a compendium of information available to the Institute based
on experience with materials, equipment, regulations and practices contributing to the
safe handling, storage, shipment and use of chlorine. Important properties of chlorine
are included. There is a brief section on the production of chlorine, as well as methods
of dealing with potential emergencies.
The reference section will provide to readers sources for more detailed information
about matters on which the text material is based. Where questions remain -- on
protective provisions or procedures, for example -- a chlorine user should consult the
producer or supplier of the product or the chlorine handling equipment, or contact the
Chlorine Institute.
Annually, the Institute updates its publications catalog. This free catalog can be
obtained by contacting the Publications Department of the Institute.

The information contained in the catalog also is available through the Institutes Internet
website http://www.cl2.com.

RESPONSIBLE CARE

T he Institute is a Chemical Manufacturers Association (CMA) Responsible Care


Partnership Association. In this capacity, the Institute is committed to: Fostering
the adoption by its members of the Codes of Management Practices; facilitating
their implementation; and encouraging members to join the Responsible Care initiative
directly.
Chlorine Institute members who are not CMA members are encouraged to follow the
elements of similar responsible care programs through other associations such as the
National Association of Chemical Distributors (NACD) Responsible Distribution Program
or the Canadian Chemical Manufacturers Association's Responsible Care program.
CHECKLISTS
The Chlorine Institute is adding checklists to appropriate pamphlets to assist its
T members and non-members in self audits or other reviews. These checklists are
being added to new and existing pamphlets beginning in 1996.
Because the Chlorine Manual only summarizes some of the information contained in
the other pamphlets, the reader should refer to the specific pamphlets and their
checklists. These checklists are designed to emphasize major topics and highlight the
key recommendations for someone who has already read and understood the
pamphlets.
The Chlorine Institute encourages the use of the pamphlets and their checklists.

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

Chlorine is an element and a member The element, chlorine, in the gaseous


of the halogen family. Chlorine gas or liquid state.
is not explosive or flammable, but it will
support combustion. Both the liquid and gas 1.5.4 Dry Chlorine
react with many substances. Chlorine is
only slightly soluble in water. The gas has a Liquid or gaseous chlorine with its water
characteristic, penetrating odor, a greenish content dissolved in solution. The solubility
yellow color and is about two and one-half of water in chlorine varies with temperature
times as heavy as air. Thus, if chlorine and is shown in Figures 9.5 and 9.6. See
escapes from a container or system, it will Pamphlet 100. [The term dry chlorine
tend to seek the lowest level in the building sometimes is used incorrectly to describe a
or area in which the leak occurs. dry chlorinating compound (usually calcium
Liquid chlorine is amber in color and is hypochlorite or the chloroisocyanurates).
about one and one-half times as heavy as This is a misuse of the term and the Institute
water. At atmospheric pressure, it boils at discourages its use.]
about 29oF(-34oC) and freezes at about - The following are examples using
1500F (-101o C). Figures 9.5 and 9.6:
One volume of liquid chlorine, when Chlorine with a water content of 30 ppm
vaporized, yields about 460 volumes of gas. at a temperature of 50 o F (10o C) is dry. If
Although dry chlorine (gas or liquid) this same chlorine (30 ppm) were at a
normally does not react with or corrode temperature of -4o F (-20oC) the chlorine is
some metals such as copper or carbon wet.
steel, it is strongly reactive (strongly Chlorine at 41 o F (5o C) is dry if the
corrosive) when moisture is present. See water content does not exceed 100 ppm.
Section 9.3.3.2.
1.5.5 Wet Chlorine

1.5 Terminology Liquid or gaseous chlorine with its


water content exceeding the amount that is
1.5.1 Chlorine dissolved in solution. See Pamphlet 100.
Chlorine is not wet just because it is in the
The chemical element in whatever state liquid state.
or condition it may exist under the
conditions being considered. Chlorines 1.5.6 Moist Chlorine
symbol is Cl, its atomic number is 17 and its
atomic weight is 35.453. Chlorine almost Synonymous with wet chlorine.
always exists as a molecule with two
chlorine atoms bound together as Cl2. Its 1.5.7 Saturated Chlorine Gas
molecular weight is 70.906.
Chlorine gas in such condition that the
1.5.2 Liquid Chlorine removal of any heat or an increase in
pressure will cause some portion of it to
The element, chlorine, in the liquid state. condense to a liquid. [This term should not
[The term Iiquid chlorine sometimes is be confused with wet or moist chlorine.]
used incorrectly to describe a hypochlorite
solution. This is a misuse of the term and 1.5.8 Saturated Chlorine Liquid
the Institute discourages its use.]
Chlorine liquid in such condition that
the addition of any heat or a decrease in

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

1.5.14 Potassium Hydroxide Chlorine has a very strong chemical


affinity for many substances. It will react
A co-product produced as a solution with many inorganic and organic
when chlorine is generated through the compounds, usually with the evolution of
electrolytic decomposition of potassium heat. Chlorine reacts with some metals
chloride salt solution. Potassium hydroxide under a variety of conditions. See Section

4
9.3.3.2. 1.7.5.3 Oils and Grease

1.7.3 Corrosive Action on Steel Chlorine can react, at times explosively,


with a number of organic materials such as
At ordinary temperatures, dry chlorine, oil and grease from sources such as air
either liquid or gas, does not corrode steel. compressors, valves, pumps, oil-diaphragm
Wet chlorine is highly corrosive because it instrumentation, as well as wood and rags
forms hydrochloric and hypochlorous acids. from maintenance work.
Precautions should be taken to keep
chlorine and chlorine equipment dry. Piping, 1.8 Containers
valves and containers should be closed or
capped when not in use to keep out 1.8.1 Container Specifications
atmospheric moisture. If water is used on a
chlorine leak the resulting corrosive Chlorine shipping containers other than
conditions will make the leak worse. barges must comply with the authorized,
numbered specification under which they
1.7.4 Volumetric Expansion have been fabricated. New containers must
be fabricated according to the current
The volume of liquid chlorine increases specifications and the applicable
with temperature. Precautions should be regulations. Older containers maybe
taken to avoid hydrostatic rupture of piping, continued in service in accordance with
vessels, containers or other equipment filled applicable regulations. Plans and
with liquid chlorine. See Figure 9.4. specifications for construction of barges
must be approved by the U.S. Coast Guard
1.7.5 Specific Manufacturing and Use or the Canadian Coast Guard.
Hazards
1.8.2 Container Types
1.7.5.1 Hydrogen
Cylinders (150-pound or less)
Hydrogen is a co-product of all chlorine
manufactured by the electrolysis of aqueous Fabricated to DOT (or TC) specification
brine solutions. Within a known concentra- 3A480 or 3AA480. See Section 2. Cylinders
tion range, mixtures of chlorine and conforming with some older specifications
hydrogen are flammable and potentially may still be used. Special cylinders
explosive. The reaction of chlorine and conforming to DOT (or TC) specification
hydrogen can be initiated by direct sunlight, 3BN480 or 3E1800 are applicable for
other sources of ultraviolet light, static specialized laboratory use.
electricity, or sharp impact.
Ton Containers
1.7.5.2 Nitrogen Trichloride
Fabricated to DOT (or TC) specification
Small quantities of nitrogen trichloride, 106A500X. See Section 2. Ton containers
an unstable and highly explosive conforming with older specifications may
compound, can be produced in the still be used.
manufacture of chlorine. When liquid
chlorine containing nitrogen trichloride is Portable Tanks
evaporated, the nitrogen trichloride may
reach hazardous concentrations in the Portable tanks fabricated to DOT
residue. See Pamphlets 21 and 152. Specification 51 with special requirements
for chlorine.

5
Tank Multi-Unit (TMU) Cars

Specially built railroad cars with cradles


to carry 15 one-ton containers. The TMU
car is nearly obsolete and will not be
considered further in this manual.

Tank Cars

Railroad tank cars fabricated to DOT


(or TC) specifications 105J500W or
105S500W. See Section 3.2. Cars built to
some older specifications may still be
used.

Tank Motor Vehicles

Tank trailers complying with DOT


specification MC 331. See Section 3.3.
Trailers conforming to ICC specification
MC 330 may still be used.

Tank Barges

Barges containing chlorine tanks,


usually four. See Section 3.5.

1.8.3 Container Similarities

Containers are similar in the following


aspects:

They are constructed of steel.

They are inspected and pressure


tested at regular intervals as required by
applicable regulations.

They are equipped with one or more


pressure relief devices.

They are marked, labeled and


placarded as required by applicable
regulations.

They are all built to meet federal


government specifications.

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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.

2.4.2 Ton Containers

Most ton containers are shipped by


highway. Such trucks must have suitable
holddown devices to prevent the containers
from shifting during transportation. Trucks
are sometimes equipped with a crane and
lifting beam (Figure 2.6) to facilitate loading
and unloading. See Pamphlet 76.

2.5 Container Labeling and Placarding

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.

2.8.6 Opening Valves

The container valve is


opened by turning the valve
stem in a counter-clockwise direction. One
2.8.4 Weighing full turn of the stem permits maximum
discharge. More stem turns should not be
Because chlorine is shipped as a made. Special 3/8-inch square box
compressed liquefied gas, the pressure in a wrenches are available for turning the valve
container depends on the temperature of stem. A wrench, no longer than 8 inches,
the chlorine (Fig. 9.1). The pressure is not should be used. Never use a wrench
related to the amount of chlorine in the extension (cheater bar). The valve can be
container. Container contents can be opened by striking the end of the wrench
determined accurately only by weighing. with the heel of the hand. No greater force
should be used. If this action is not
2.8.5 Connections successful, the chlorine supplier should be
contacted for assistance. Once the valve is
A flexible connection must be used opened, the wrench can be left in place so
between the container and the piping that the valve can be closed quickly.
system. Copper tubing with a diameter of
1/4-inch or 3/8-inch is recommended. Note: Loosening the packing nut may
Flexible metallic hoses or fluoroplastic increase the risk of a chlorine leak.
hoses as described in Institute Pamphlet 6 Proper precautions must be taken.
are also acceptable materials.
Once connections have been made,
If a system is to remain in operation pressurize the system with a small amount
while containers are being connected or of chlorine. Test for leaks by using vapor
disconnected, auxiliary (isolating) container from a 26o Baum aqua ammonia
valves must be used. These should be (ammonium hydroxide) solution. See
located at the container end of the flexible Section 4.4.2. If a leak is found, it must be
connector to minimize the escape of gas remedied before proceeding. After testing, if
and the entrance of atmospheric moisture no leaks exist, start continuous flow. See
Flexible connections should be inspected on Pamphlet 151.
a regular basis. They should be replaced
whenever there is any sign of deterioration. 2.8.7 Disconnecting Containers
The CGA Connection 820 yoke and
adapter is the Institute recommended As soon as a container is empty, the
connection to the container valve outlet (Fig. valve should be closed. Prior to
2.7). See Drawings 130 and 131. A flat

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 Manway Arrangement

3.2.3.1 General

Five fittings are mounted on the


manway cover within the protective housing
(Fig. 3.2). Four of these are angle valves
and the fifth, located in the center, is a
pressure relief device designed to relieve if
excessive pressure builds up in the tank
car.

3.2.3.2 Angle Valves

The manually operated angle valve con-


structed according to Drawing 104 (Institute
Standard Angle Valve) (Fig. 3.3) has a
forged steel body and a Monel stem and
seat. The outlet is a 1-inch female ANSI
standard taper pipe thread and is fitted with
a pipe plug.
The two angle valves on the longitudinal
centerline of the tank car are for liquid
discharge. The two angle valves on the
transverse centerline are connected to the
vapor space.

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

3.2.4.4 Monitoring 3.3.2.1 General

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

3.3.3 Transfer Operations See discussion for tank cars (Sections


3.2.4.2 and 3.2.4.5).
Procedures for transferring chlorine to! The driver should recheck all equipment
from tank trucks are essentially the same as by a general visual inspection before
for tank cars. There is, however, more starting the vehicle.

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.

3.4 Portable Tanks 3.5.2.3 Excess-Flow Valves

Tanks suitable for multi-modal Each liquid discharge tank assembly


transportation (road, rail and water) of connection contains an excess flow valve
chlorine should be built under the provisions which incorporates a ball check that will
of DOT 51 and special provisions for close when the discharge flow rate exceeds
chlorine. See Pamphlet 49. a predetermined quantity. The gas tank
connection also contains an excess flow
3.5 Tank Barges valve. The gas flow valve may contain a
removable basket which allows inspection
3.5.1 General of the cargo tank prior to loading. Excess
flow valves are designed to close if a
The following is generalized information catastrophic leak occurs. However, they are
on chlorine tank barges. For more detailed not designed to serve as an emergency
information, see Pamphlet 79. shut-off device during transfer.
Chlorine barge design is dependent
upon its geographical operating pattern 3.5.2.4 Eduction Pipes
inland river or ocean service. The inland
river units are designed solely for chlorine Liquid chlorine is withdrawn through
transportation with either 4 or 6 eduction pipes. The eduction pipes are
independent, cylindrical uninsulated pres- attached to the excess-flow valves and
sure tanks mounted longitudinally. extend to the bottom of the tank. One or
The ocean units are multi-product de- both eduction pipes maybe used to unload
signed vessels with chlorine in cylindrical the tank.
pressure deck tanks and sodium hydroxide,
sodium chlorate, and/or sodium hypochlorite 3.5.2.5 Pressure Relief Devices
in center and wing tanks. Both barge types
are subject to U.S. Coast Guard and Depending on capacity, each barge tank
Canadian Coast Guard regulations. has two or three pressure relief devices.
These are designated 4 JQ and are
3.5.2.1 General designed to start-to-discharge pressure of
300 psig (2,070 kPa). See Pamphlet 41.
Chlorine barge tanks may have one or
more flanged openings on the top of the 3.5.3 Transfer Operations
cargo tanks. No openings are allowed below
the top surface. The arrangement of valving The following is general information. For
is not standardized. Depending on the tank more detailed information, see Pamphlet 79.
cargo capacities, each tank has either two
or three pressure relief devices and a 3.5.3.1 General
varying number of angle valves located on
the top manway openings. Loading and unloading of chlorine
barges are subject to U.S. and Canadian
3.5.2.2 Angle Valves Coast Guard regulations. Chlorine transfers
between a vessel and a marine terminal
Inland chlorine barge cargo tanks are must be supervised by individuals who have

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.

3.5.3.2 Personnel Protection

See Section 5-Employee Training and


Safety

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

4.4.2 Detection of Minor Releases and A continuous release is characterized


Leaks by the release of chlorine to the atmosphere
over a longer period of time (usually more
A plastic squeeze bottle containing than 15 minutes), resulting in a continuous
260Baum aqua ammonia can be used to plume which reaches an equilibrium size
detect a minor release or leak. If ammonia and concentration gradient. Thus, the
vapor is directed at a leak, a white cloud will concentration of chlorine monitored at any
form indicating the source of the leak. If a given point downwind from the source will
wash bottle is used, the dip tube should be be constant over time for the duration of the
cut off so that squeezing the bottle directs release. The failure of a valve or fitting on a
vapor, not liquid, out of the nozzle. Avoid large container is an example of a
contact of aqua ammonia with brass or continuous release.
copper. Portable electronic chlorine
monitors can also be used to detect leaks. If 4.4.4 Area Affected
a leak occurs in equipment or piping, the
chlorine supply should be shut off, the The area affected by a chlorine release
pressure relieved and necessary repairs and the duration of the exposure depend
made. upon the total quantity released, the rate of
Leaks around shipping container valve release, the height of the release point and
stems usually can be stopped by tightening weather conditions, as well as the physical
the packing gland. If such tightening does form of the chlorine being released. These
not stop the leak, the container valve should factors are difficult to evaluate in an
be closed. Pamphlets 66 and 151 provide emergency situation. Chlorine downwind
further details. If simple corrective measures can vary from barely detectable to high
are not sufficient, the appropriate Chlorine concentrations. Pamphlet 74 provides

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

If a leak occurs at a consuming which may be encountered in chlorine


location, it may be best to dispose of the shipping containers. The following kits and
chlorine through the regular consuming recovery vessels (Figure 4i1) are available.
process or to run a temporary line to the
consuming point. If the consuming process m Kit A - for 100 lb and 150 lb cylinders
cannot handle chlorine under emergency m Kit B - for ton containers.
conditions, a standby alkali absorption m Kit C - for tank cars and tank trucks.
system should be considered. It must be m Recovery vessels for cylinders.
recognized that systems consuming liquid
chlorine at low rates will not significantly These kits operate on the principle of
reduce pressure in the supply container. containing valve leaks by applying hoods
In order to reduce pressure in the and gaskets. For cylinders and ton
supply container, chlorine must be removed containers, patches are provided for sealing
as a gas at a rate high enough to cause off a small hole in the side wall. Capping
cooling of the remaining liquid. See Section devices are provided for fusible plugs in ton
2.8.2. containers.
The kits contain step-by-step
4.7 Absorption Systems instructions for the use of the devices. The
necessary tools are included, but personal
A simple absorption system consists of protective equipment is not included.
a suitable tank capable of holding the Pamphlets lB/A, IB/B, and lB/C provide
required alkaline solution. The alkali should
be stored in a form such that a solution can
readily be prepared when needed. After the
solution is prepared, the chlorine can be
passed from the container into the solution
through a connection weighted
to hold the outlet of the transfer hose or pipe
beneath the level of the solution. Do not
immerse the container. See Tables 4.1A
and 4.1B for recommended solution (the
recommended alkali quantities provide 20%
excess).

Note: When absorbing chlorine in


alkaline solutions, the heat of reaction is
substantial. Caustic solutions can cause
burns to personnel.

The process should be monitored to


ensure the absorption is controlled as to
heat and reaction. Do not boil the solution or
exceed the capacity of the reaction.

4.8 Emergency Kits and Recovery


Vessels

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

Safety in handling chlorine depends, to 5.2.1 Availability and Use


a great extent, upon the effectiveness of
employee training, proper safety instructions Exposure to chlorine can occur
and the use of suitable equipment. It is the whenever chlorine is handled or used.
responsibility of the employer to train its Personal protective equipment (PPE) for
employees and to document such training emergency use should be available away
as appropriate and as required by from areas of likely contamination. If
regulation. It is the responsibility of chlorine is used in widely separated
employees to carry out correct operating locations, personal protective equipment
procedures safely and to properly use the should be available near each use point.
safety equipment provided. Pamphlet 65 provides recommendations for
Employee training should include: specific tasks including loading! unloading,
Instruction and periodic refresher initial line entry, material sampling, and
courses in operation of chlorine emergency response.
equipment and handling of chlorine
containers. 5.2.2 Respiratory Equipment
Instruction in the properties and physi-
ological effects of chlorine. A Material All personnel entering areas where
Safety Data Sheet (MSDS) for chlorine chlorine is stored or handled should carry or
is available from chlorine suppliers. have immediately available an escape type
Instruction to report to the proper respirator. Respiratory equipment should be
authority all equipment failures and selected based on evaluation of hazards
chlorine leaks. and degree of potential exposure. For
Instruction and periodic drills regarding: example, when tank cars, ton containers or
- Locations, purpose, and use of cylinders are connected to or disconnected
chlorine emergency equipment, fire from plant piping, small releases of chlorine
fighting equipment, fire alarms and shut- can occur. The need for respiratory
down equipment such as valves and protection during such operations should be
switches. determined. See Pamphlets 65 and 75.
- Use of emergency kits, such as the Chemical cartridge respirators or full
Chlorine Institute Emergency Kits A, B, face canister gas masks offer adequate
or C and the recovery vessel, if they are temporary protection provided the oxygen
part of emergency equipment and content in the air is greater than 19.5% and
planning at the location. Training should the chlorine concentration does not exceed
include the actual installation of kits on the rated capability of the respirator. The
containers. need to protect the eyes from chlorine
- Locations, purpose, and use of should be part of the evaluation of
personal protective equipment. appropriate respiratory equipment. Pres-
- Locations, purpose, and use of sure-demand self-contained breathing ap-
safety showers, eye baths, bubbler paratus (SCBA), with full face piece, is
fountains or the closest source of water required for performing tasks when chlorine
for use in emergencies. may be present unless air sampling verifies
- Locations, purpose, and use of the chlorine concentration is such that a
specialized first aid equipment. lower level of respiratory protection provides

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

6.3.1 Inhalation If the eyes have been exposed to any


concentration of chlorine in excess of the
6.3.1.1 Respiratory Assistance PEL, they should be flushed immediately
with copious quantities of tepid running
In all cases, first move the victim to an water or a direct stream of water for at least
area free of chlorine. If breathing has 15 minutes.
apparently ceased, the victim should be
given cardiopulmonary resuscitation (CPR) Note: Never attempt to neutralize
immediately. If breathing has not ceased, with chemicals.
the exposed individual should be placed in a
comfortable position. In severe cases, the The eyelids should be held apart during
patient should lie down with the head and this period to ensure contact of water with
trunk elevated to a 45-60 degree position. all accessible tissue of the eyes and lids.
Slow, deep breathing should be Medical assistance must be obtained as
encouraged. Trained personnel should soon as possible. If such assistance is not
administer humidified oxygen by inhalation immediately available, eye irrigation should
as soon as possible. be continued for a second 15-minute period.
Nothing but water should be applied unless
6.3.1.2 Oxygen Administration ordered by a qualified health care provider.

Oxygen should be administered by first 6.4 Medical Management of Chlorine


aid attendants trained in the use of the Exposures
specific oxygen equipment. Suitable
equipment for the administration of oxygen 6.4.1 General Principles
should be available either on site or at a

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

Note: The following notes regarding Positive pressure treatment and


therapy are intended for general nebulized detergents may be beneficial.
guidance only. Final determination of Care should be taken to maintain the
specific medical intervention(s) should patients hydration and to humidify the
only be made by skilled medical inspired air.
personnel upon full consideration of
each patients overall medical condition. 6.4.2.4 Excitement Phenomenon
Provision of any treatment without full
medical assessment by competent This occurs as a result of central
personnel is not recommended. stimulation and emotional disturbances.
Reassurance is best accomplished
6.4.2.1 Pulmonary Edema without the use of sedatives.
Use of sedatives should only be
Administer 60 to 100% humidified considered by qualified medical personnel
oxygen at 6 liters per minute. following medical assessment and only
Intermittent use of positive pressure employed under close supervision of
breathing apparatus may be valuable in respiratory function to monitor progress.
reducing edema. Caution is required if there
are coexisting medical conditions (e.g., 6.4.3 Delayed Effects
peripheral circulatory collapse) which may
be a contraindication to its use. The inhalation of any irritating gas may
Test arterial blood gases for pulmonary lead to delayed reactions such as
status. pulmonary edema. Since physical exercise
appears to have some relation with the

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.

Currently in North America, more than 7.5 Chlorinators


75% of chlorine production is from
diaphragm cell technology. The products of Chlorine gas feeding equipment must be
this type of cell are chlorine gas, hydrogen carefully selected. Vacuum operated
gas, and cell liquor composed of sodium equipment offers the safest operation for
hydroxide and sodium chloride solution. low capacities. For higher capacities a
An almost saturated brine solution enters pressure-vacuum system may be required.
the diaphragm cell anolyte compartment Pressure piping and connections should be
and flows through the diaphragm to the minimized to decrease the possibility of a
cathode section. leak. Equipment manufacturers can
Chloride ions are oxidized at the anode recommend optimum system design.
to produce chlorine gas.
Hydrogen gas and hydroxide ions are 7.6 Vaporizers
produced at the cathode. Sodium ions
migrate across the diaphragm from the High capacity chlorine gas feed
anode compartment to the cathode side to systems may need a chlorine vaporizer
produce cell liquor containing 10% to 12% (evaporator). Vaporizers are usually water-
sodium hydroxide. Chloride ions also jacketed or steam-heated. Careful attention
migrate across the diaphragm resulting in must be given to the design and operation
the cell liquor also containing about 16% of such systems. See Pamphlet 9.
sodium chloride. The cell liquor is typically
concentrated to 50% sodium hydroxide by 7.7 SupportEquipment
an evaporation process. The salt recovered
in the evaporation process is returned to the 7.7.1 General
brine systems for reuse.
Some key support equipment used in
7.4.4 Mercury Cells chlorine service are included in this section.

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

7.7.3 Heat Exchangers Piping as described in this section


pertains only to above ground fixed piping.
Metallic shell-and-tube heat exchangers For more detailed information on piping
should be designed and fabricated in accor- systems for dry chlorine, see Pamphlet 6.
dance with the TEMA Standard and proper
ASME material classifications and codes. 7.8.1 Materials
Titanium is usually the choice for wet
chlorine, and carbon steel is normally used In general, carbon steel piping is recom-
for dry chlorine. See Section 7.3.2. mended for handling dry chlorine. Stainless
steels of the 300 series have useful
7.7.4 Pumps properties for low temperature service but
can fail due to chloride stress corrosion
Pumps for aqueous solutions containing cracking, particularly in the presence of
chlorine are constructed of a wide range of moisture at ambient or elevated
materials such as certain plastic-lined or temperatures.
rubber-lined steel, reinforced polyester, and
titanium. Pumps for dry liquid chlorine are 7.8.2 Design and Installation
special items and a supplier of these pumps
should be contacted before use. 7.8.2.1 General Design

7.7.5 Compressors Piping arrangements should be routed for


the shortest distance practical with respect
Compressors used in dry chlorine to flexibility, line expansion and good engi-
service include centrifugal, non-lubricated neering practice. Piping systems should be

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

7.8.2.2 Liquid Expansion All portions of new piping systems must


be cleaned before use because chlorine can
Liquid chlorine has a high coefficient of react violently with cutting oil, grease, and
thermal expansion. See Figure 9.2. If liquid other foreign materials. Cleaning must not
chlorine is trapped between two valves, an be done with hydrocarbons or alcohols,
increase in temperature of the trapped liquid since chlorine may react violently with many
will result in high pressures potentially solvents. New valves or other equipment
leading to a rupture of the line. The causes received in an oily condition should be
of possible rupture must be considered in dismantled and cleaned before use. See
the design of any piping systems. Protection Pamphlet 6.
may be either a suitably designed, operated
and maintained expansion chamber, a 7.8.3.2 Pressure Testing
pressure relief valve, or a rupture disc.
New chlorine piping systems should be
7.8.2.3 Condensation tested according to one of the methods
recommended in Pamphlet 6. Components
Condensation or reliquefaction of which may be damaged during testing
chlorine may occur in chlorine gas lines should be removed or blocked off After
which pass through areas where the testing, all moisture-absorbing gaskets and
temperature is below the temperature- valve packings should be replaced; it is
pressure equilibrium indicated in the vapor essential that chlorine systems be dried as
pressure curve (Fig. 9.1). described below prior to being placed into
Condensation can usually be prevented service.
by the use of a pressure reducing valve or
heat tracing and insulating the line. Any 7.8.3.3 Drying
heat tracing installation should be designed
such that the surface temperature of the Chlorine piping systems must always
pipe shall not exceed 300 0F (l490C) to limit be dried prior to use. Even if water has not
the possibility of a chlorine - carbon steel been purposely introduced into the system
reaction. from hydrostatic testing or cleaning, drying
is still required due to the introduction of
7.8.2.4 Installation moisture from the atmosphere or other
sources during maintenance and new
Joints in chlorine piping may be construction.

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.

7.11.3 Entering Tanks

Chlorine tank inspection, cleaning and


repair, are discussed in Pamphlet 5. All
piping to the tank should be disconnected
and blanked before entering. See Section
5.3.

7.12 Chlorine Neutralization

If a chlorine consuming process in-


volves the discharge of a waste containing
chlorine, special processes may be re-
quired. All governmental regulations

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

8.1 Occupational Safety and Health Requirements for personal


Regulations -29 CFR protective equipment for personnel
potentially exposed to chemical or
8.1.1 Part 1904 - Recordkeeping other hazards.

Requirements for recordkeeping. 8.1.8 Section 1910.134 - Respiratory


Equipment
8.1.2 Section 1910.20 - Access to
Exposure and Medical Records Requirements for respiratory use for
personnel potentially exposed to
Requirements for employee access chemical hazards.
to exposure and medical records.
8.1.9 Section 1910.146 - Confined Space
8.1.3 Section 1910.38 Employee Entry
Emergency Plans and Fire
Protection Plans Requirements for entry into permit
required confined spaces.
Requirements for emergency action
plans when such plans are required 8.1.10 Section 1910.147 - Control of
by a specific OSHA regulation. Hazardous Energy (Lockout/Tagout)

8.1.4 Section 1910.95 - Occupational Requirements for locking out


Noise Exposure electrical equipment.

Requirements for protection against 8.1.11 Section 1910.151-First Aid/Medical


high noise levels. Service

8.1.5 Section 1910.119 - Process Safety Requirements for first aid/medical


Management of Highly Hazardous service providers.
Chemicals
8.1.12 Sections 1910.331 to 335Electrical
Required management practices for Safety
preventing or minimizing the
consequences of catastrophic Requirements for cell house
release of toxic, reactive, flammable, electrical safety.

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

8.1.14 Section 1910.1200 - Hazard Requirements intended to prevent


Communications and mitigate pollution and assure
safe operations at facilities during
Requirements for transmitting marine transfers.
information about hazardous
chemicals to employees. 8.2.7 Part 155 -Oil or Hazardous Material
Pollution Prevention Regulations for
8.2 Navigation and Navigable Water Vessels
Regulations -33 CFR
Requirements to prevent and
8.2.1 Parts I to 26, Subchapter A - mitigate pollution from vessels while
General delegation of authority, in navigable waters.
rulemaking procedures and
enforcement regulations. 8.2.8 Part 156-Oil and Hazardous Material
Transfer Operations
8.2.2 Part 126 - Handling Explosives or
Other Dangerous Cargoes Within or Requirements for the operational
Contiguous to Waterfront Facilities control of the transfer of oil or
hazardous materials between
Requirements for waterfront facilities vessels and marine terminals.
that handle hazardous materials.
8.2.9 Parts 160 to 167, Subchapter P -
8.2.3 Part 127 - Waterfront Facilities Ports and Waterways Safety
Handling Liquefied Hazardous Gas
Requirements for traffic
Requirements in addition to those in management, port arrival
Part 126 for waterfront facilities that notification, vessel navigational
handle liquefied hazardous gases equipment
including chlorine.
8.3 Environmental Regulations - 40
8.2.4 Part 130- Financial Responsibility for CFR
Water Pollution
8.3.1 Part 61 - National Emissions
Requirements for vessel operators Standards for Hazardous Air
to demonstrate the ability to meet Pollutants
financial liability resulting from the
discharge of oil or hazardous Emission standards for chlorine
substance(s). manufacturing faciliites.

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.

Requirements for the use of ozone 8.4 Shipping Regulations - 46 CFR


depleting substances and labeling of (Water Transportation)
products using such substances.
8.4.1 Part 2-Vessel Inspections
8.3.4 Part 141 - Safe Drinking Water
Requirements and procedures for
Requirements for Limiting obtaining vessel certification and ap-
contaminants in drinking water. provals.

8.3.5 Part 152-Pesticide Registration 8.4.2 Parts 10 to 12-Licensing and


Certification of Maritime Personnel
Requirements for the registration of
materials used as pesticides. Requirements for licensing and
certification of maritime personnel
8.3.6 Parts 260 to 269 - Hazardous Waste including eligibility, fees, procedures
Management System for renewals, and the certification of
tankermen. Provides authorization
Requirements for the classification, for an individual to act as the person
handling, treatment, and disposal of in charge on the vessel of a marine
hazardous wastes. transfer of an oil or hazardous
material.
8.3.7 Parts 302 and 355 - Release of
Hazardous Substances, Emergency 8.4.3 Part 15-Manning Requirements
Planning and Notification
Requirements for the minimum man-
Requirements for the planning, ning of vessels.
reporting, and notification of
hazardous and highly hazardous 8.4.4 Parts 30 to 40, Subchapter D
substances. - Tank Vessels

8.3.8 Parts 370 and 372-Hazardous Requirements for vessels carrying


Chemicals Reporting: Community flammable or combustible liquid car-
Right to Know goes. Subchapter regulates vessel
design, operation, fire fighting and
Requirements for providing the life saving equipment and
public with information on hazardous equipment testing. Generally,
chemicals. vessels carrying nonflammable
hazardous materials are also
8.3.9 Part 415, Subpart F - Effluent regulated under this subchapter.
Guidelines/Chlor-Alkali Production
8.4.5 Part 151 - Barges Carrying Bulk
Effluent guidelines for chlorine pro- Liquid Hazardous Materials Cargoes
duction facilities.
Requirements for vessels carrying
8.3.10 Subchapter R, Parts 700 to 799 - hazardous materials in barges.
Toxic Substances Control Act Regulations include barge design,
saving equipment, equipment test-
Requirements for recordkeeping and ing and special requirements for

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:

Requirements for pipeline facilities 1. NFPA Standards or Codes


and the transportation of gases.
National Fire Protection Association
8.5.15 Part 195 - Transportation of 1 Batterymarch Park
Hazardous Liquids by Pipeline PO Box 9101
Quincy, MA 02269-9101
Safety standards and reporting Phone (800) 344-3555
requirements for pipeline facilities
used in the transportation of 2. The BOCA National Fire Prevention
hazardous liquids or carbon dioxide. Code or the BOCA
While the regulations do not National Building Code
currently include chlorine, the
Institute recommends adhering to Building Officials & Code
these requirements. Administrators International, Inc.
4051 W. Flossmoor Road
8.6 Fire Codes Country Club Hills, IL 60478-5 795
Phone (708) 799-2300
Numerous fire and building codes exist
that affect chlorine production, storage, 3. Standard Fire Prevention Code or
packaging, distribution and use. Code Standard Building Code
requirements may include, but are not
limited to minimum separation distance Southern Building Code Congress
between classes of chemicals, design of International, Inc.
piping systems, secondary containment, 900 Montclair Road
need for treatment systems or gas Birmingham, AL 35213-1206
detectors, emergency response Phone (205) 591-1853
requirements and the need for sprinklers.
To properly address these codes, the 4. Uniform Building Code
local government (e.g., city or county)
should be contacted. Determine what International Conference of Building
specific fire and building codes, including Officials
the code year, were passed by the 5360 Workman Mill Road
governing jurisdiction. Whittier, CA 90601-2298
Some local or state authorities develop Phone (310) 699-0541
their own codes. However, many
jurisdictions adopt a model code or 5. Uniform Fire Code
reference National Fire Protection International Fire Code Institute
Association (NFPA) Standards. Either of 9300 Jollyville Road, Suite 105
these may serve as the local code(s). Austin, TX 78759-7455

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.

9.3.3.4 Reactions With Inorganic 9.4.2.2 Critical Pressure


Compounds 9.4.2.3 Critical Temperature
1157.0 psia (7977 kPa) -The vapor pres-
The preparation of soda and lime sure of liquid chloride at the critical
bleaches (sodium and calcium hypochlorite) temperature.
are typical reactions of chlorine with the
alkali and alkaline earth metal hydroxides; 9.4.2.3 Critical Temperature
the hypochlorites formed are powerful
oxidizing agents. Because of its great 290.750F (143.750C) -The temperature
affinity for hydrogen, chlorine removes above which chlorine exists only as a gas
hydrogen from some compounds such as no matter how great the pressure.
the reaction with hydrogen sulfide to form
hydrochloric acid and sulfur. Chlorine, as 9.4.2.4 Critical Volume
the hypochlorous ion, reacts with
ammonium ions to form various mixtures of 0.02795 ft3/lb (0.00 1745 m3/kg) -The
chloramines. At low pH the predominant volume of a unit mass of chlorine at the
chloramine formed is explosive nitrogen critical pressure and temperature.
trichloride (NCl3).
9.43 Density
9.3.3.5 Reactions With Organic Compounds
The mass of a unit volume of chlorine at
Chlorine reacts with many organic com- specified conditions of temperature and
pounds to form chlorinated derivatives. pressure. See Figure 9.2.
Hydrogen chloride is often formed as a by-
product of the reaction. Some reactions can 9.4.3.1 Gas at Standard Conditions
be extremely violent, especially those with
hydrocarbons, alcohols and ethers. Proper 0.2006 lb/ft3 (3.213 kg/m 3)
methods must be followed, whether in
laboratory or plant, when organic materials 9.4.3.2 Saturated Gas
are reacted with chlorine.
At 320F (O0C) 0.7632 lb/ft3 (12.23
9.4 Physical Properties Kg/m 3). (Absolute pressure at 320F (00C) is
53.51 psi (368.9 kPa)).
The following properties are for pure
chlorine. Standard conditions, where 9.4.3.3 Saturated Liquid
referenced, are 320F (O0C) and an absolute
pressure of 14.696 psi (101.325 kPa). 91.56 lb/ft3 (1467 kg/m 3) at 320F (00C);
88.76 lb/ft 3 (11.87 lb/gal; 1422 kg/m 3) at
9.4.1 Roiling Point (Liquefying Point) 600F (15.60C) - (Absolute pressure of liquid
chlorine at 600F is 86.58 psi (597.0 kPa)).
-29.l50F (-33.97 0C) -The temperature at
which liquid chlorine vaporizes under one 9.4.4 Freezing Point
atmosphere pressure (101.325 kPa).
See Melting Point, 9.4.7.
9.4.2 Critical Properties

9.4.2.1 Critical Density

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

kg 0K) at 770F (250C).


9.4.6 Liquid-Gas Volume Relationship
9.4.10.2 Saturated Gas
At standard conditions the weight of one At Constant Volume (Cv)
volume of liquid chlorine equals the weight
of 456.5 volumes of chlorine gas. 0.088 87 Btu/lb 0F (0.372 1 kJ/kg 0K) at
32 F (00C); 0.093 03 Btu/lb 0F (0.3895
0

9.4.7 Melting Point - Freezing Point kJ/kg 0K) at 77 0F (250C).

-149.760F (-100.980C) -The temperature 9.4.10.3 Saturated Liquid


at which solid chlorine melts or liquid
chlorine solidifies at one atmosphere. 0.2264 Btu/lb 0F (0.948 kJ/kg 0K) at 32 0F
(0 C); 0.2329 Btu/lb 0F (0.975 kJ/kg 0K) at
0

9.4.8 Solubility in Water 770F (250C).

The weight of chlorine which can be 9.4.10.4 Ratio


dissolved in a given amount of water at a
given temperature when the total vapor Ratio of gas specific heat at constant
pressure of chlorine and the water equals a pressure to gas specific heat at constant
designated value. See Fig. 9.3. At 600F volume, Cp/Cv. 1.400 for saturated gas at
(15.60C) and one atmosphere (101.325 320F (00C); 1.448 for saturated gas at 770F
kPa) it is 6.93 lbs/100 gals (8.30 kg/m 3). (250C).

9.4.9 Specific Gravity 9.4.11 Specific Volume

9.4.9.1 Gas The volume of a unit mass of chlorine at


specified conditions of temperature and
2.485 The ratio of the density of pressure.
chlorine gas at standard conditions to the
density of air under the same conditions. 9.4.11.1 Gas at Standard Conditions
(Density of air, free of moisture, at standard
conditions is 1.2929 kg/m 3.) 4.986 ft3/lb (0.3113 m 3/kg).

9.4.9.2 Liquid 9.4.11.2 Saturated Gas at 320F (00C)

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

The measure of internal molecular


friction when chlorine molecules are in
motion.

9.4.13.1 Saturated Gas

0.0 125 centipoise (0.0 125 mPa s) at


320F (00C); 0.0132 centipoise (0.0132
mPa s) at 600F (15.60C)

9.4.13.2 Liquid

0.3863 centipoise (0.3863 mPa s) at


320F (00C); 0.3538 centipoise (0.3538
mPa.s) at 600F (15.60C).

9.4.14 Volume- Temperature Relation of


Liquid Chlorine in a Container
Loaded to its Authorized Limit

See Figure 9.4

9.4.15 Solubility of Water in Liquid


Chlorine

See Figures 9.5 and 9.6

49
50
51
52
53
54
55
10 SELECTED REFERENCES

10.1 U.S. Government Regulations and 39 Maintenance Instructions for Chlorine


Specifications Institute Standard Safety Valves, Type
1-1/2JQ
All U.S. regulations and specifications
are available from the Superintendent of 40 Maintenance lnstructions for Chlorine
Documents, U.S. Government Printing Institute Standard Angle Valve
Office, Washington, D.C. 20402.
41 Maintenance Instructions for Chlorine
10.1.1 Code of Federal Regulations (CFR), Institute Standard Safety Valves, Type
Various Sections 4 JQ

10.1.2 Chlorine Technical, Liquid; Federal 42 Maintenance lnstructions for Chlorine


Specification BB-C 120 C. Institute Standard Excess Flow Valves

10.2 Canadian Regulations 49 Handling Chlorine Tank Motor


Vehicles
Most Canadian regulations can be
obtained from the Canadian Government 57 Emergency Shut-Off Facilities for Tank
Publishing Center, Supply and Services Car/Tank Truck Transfer of Chlorine
Canada, Ottawa, Canada K1A 059.
60 Chlorine Pipelines
10.3 Chlorine Institute References
63 First Aid and Medical Management of
10.3.1 Pamphlets and Instructional Chlorine Exposures
Booklets
64 Emergency Response Plans for
5 Non-Refrigerated Liquid Chlorine Facilities
Chlorine Storage
65 Personal Protective Equipment for
5 Piping Systems for Dry Chlorine Chlorine and Sodium Hydroxide

9 Chlorine Vaporizing Systems 66 Recommended Practices for Handling


Chlorine Tank Cars
17 Cylinder and Ton Container Proce-
dures for Chlorine Packaging 72 Properties of Chlorine in SI Units

21 Nitrogen Trichloride - A Collection of 73 Atmospheric Monitoring Equipment for


Reports and Papers Chlorine

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)

10.3.3 Audio/Visual Materials 10.6.5 ASTM-D2022-89, Standard Methods


of Sampling and Chemical Analysis
H-VIDEO Health Effects from Short-Term of Chlorine-Containing Bleaches

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.

10.9 Compressed Gas Association 10.14 NSF lnternational


1725 JeffersonDavis Highway, Suite 3475 Plymouth Road
1004 Arlington, VA 22202. Ann Arbor, MI 48113

10.9.1 Handbook of Compressed Gases 10.14.1ANSI/NSF Standard 60


Van Nostrand Reinhold, New York, -Drinking Water Additives-Health
NY Effects; updated annually.

10.9.2 Pamphlet C-i, Methodsfor Hydrostatic 10.15 Water Environment Foundation


Testing of Compressed Gas 601 Wythe Street
Cylinders Alexandria, VA 22314

10.9.3 Pamphlet C-6, Standardsfor Visual 10.16 World Health Organization


Inspection ofCompressed Gas Distribution and Sales Service
Cylinders 1211 Geneva 27, Switzerland

10.9.4 Pamphlet P-i, Safe Handling of Com- 10.16.1Environmental Health Criteria 21


pressed Gases in Containers Chlorine and Hydrogen Chloride,
1982.
10.9.5 Pamphlet V-i, Compressed Gas
Cylinder Valve Outlet and Inlet Con- 10.17 Chemical Industry Inst. of
nections (This pamphlet is also Toxicology
designated as ANSI B57.1 and CSA 6 Davis Drive
b96.) Research Triangle Park, NC 27709
10.9.6
10.10 National Academy of Sciences 10.17.1A Chronic Inhalation Study of
Printing and Publishing Office Chlorine in Female and Male B6C3]
National Academy of Sciences Mice and Fischer344Rats; Chemical
2101 Constitution Avenue, NW Industry Institute of
Washington, DC 20418. toxicology: 1993.

10.10.1Water Chemicals Codex, 1982. 10.18 Other References

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.

10.18.5 Heinemann, G.; Garrison, F.G.; 10.18.14 Grenquist-Norden, B.; Institute of


Haber, P.A.; I & EC. 1946, 38, 497. Occupational Health, 1983, pp 1-83.

10.18.6Interpretive Review of the Potential


Adverse Effects of Chlorinated
Organic
Chemicals on Human Health and the
Environment, Report of an Expert
Panel;
Coulston, F. and Kolbye, A.C., Eds.;
Regulatory Toxicology and Pharma
cology Journal; Academic Press:
New York, NY, 1994.

10.18.7 Alkali and Chlorine Products and


Chlorine and Sodium Hydroxide;
Kirk-Othrner Encyclopedia of
Chemical Technology; ed. 4; Editor:
John Wiley & Sons, New York, NY,
1991.

10.18.8 Kowitz, T. A.; Reba, R. C.; Parker,


R. T.; Spicer, W. S.; Arch. of
Environmental Health, 1967, 14,
545.

10.18.9 Modern Chlor-Alkali Technology;


Jackson, C., Ed.; Society of
Chemical Industry; John Wiley &
Sons: New York, NY, 1983; Vol. 2.

10.18.10 Patty, F. A.; Industrial Hygiene and


Toxicology; Interscience: New York,
NY.

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

Topics in this manual include: Chlorine and . . .

Bulk Shipments First Aid


Containers Maintenance
Emergencies References
Employee Safety Regulations
Engineering Technical Data
Environment Training