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The document is Pamphlet 1 "Chlorine Basics" published by the Chlorine Institute, an industry organization providing comprehensive guidelines for the safe handling, storage, transportation, and use of chlorine. This technical reference manual covers chlorine's physical and chemical properties, manufacturing processes, container specifications, emergency response procedures, regulatory compliance, and safety protocols for industries that produce, transport, or utilize chlorine. The document is edition 8, dated May 2014, and serves as a definitive technical resource for operations personnel, engineers, and safety professionals working with chlorine.

The pamphlet provides detailed technical specifications for chlorine containers, including cylinders and ton containers, with extensive guidance on handling, storage, transportation, and emergency response. It outlines critical safety procedures, such as proper container valve management, pressure relief mechanisms, shipping regulations, and personal protective equipment requirements. The document includes technical data on chlorine's physical properties, chemical reactions, temperature and pressure relationships, and potential hazards. It also references multiple regulatory frameworks, including OSHA, EPA, DOT, and other U.S. and international standards governing chlorine production, transportation, and usage, making it a comprehensive technical and safety reference for chlorine-related industrial operations.

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Pamphlet 1 Chlorine Basics

Edition 8

May 2014 Copyright The Chlorine Institute Provided by S&P Global under license with The Chlorine Institute

Order Number: W2416510 Sold to:BRYANT JASPER-WILLIAMS [328121100001] - BRWILLIAMS@PINELLAS.GOV, Not for Resale,2023-02-23 19:57:28 UTCNo reproduction or networking permitted without license from S&P Global i

Table of Contents

1. INTRODUCTION

1.1 CHLORINE BASICS

1.2 CHLORINE INSTITUTE STEWARDSHIP PROGRAM

1.3 DISCLAIMER

1.4 APPROVAL

1.5 REVISIONS

1.6 SIGNIFICANT REVISIONS IN CURRENT EDITION

1.7 CHECKLISTS

1.8 ABBREVIATIONS AND ACRONYMS

2. GENERAL INFORMATION

2.1 WHAT IS CHLORINE?

2.2 CHLORINE MANUFACTURE

2.3 CHLORINE TRANSPORTATION

2.4 OTHER REGULATORY ASPECTS

2.5 TERMINOLOGY

2.6 SPECIFIC MANUFACTURING AND USE HAZARDS

3. CYLINDERS AND TON CONTAINERS

3.1 CONTAINER DESCRIPTIONS

3.2 CONTAINER VALVES

3.3 PRESSURE RELIEF DEVICES

3.4 CONTAINER SHIPPING

3.5 CONTAINER MARKING/LABELING AND VEHICLE PLACARDING

3.6 CONTAINER HANDLING

3.7 CONTAINER STORAGE

3.8 CONTAINER USE

4. BULK SHIPPING CONTAINER

4.1 GENERAL

4.2 TANK CARS

4.3 CARGO TANK MOTOR VEHICLES

4.4 PORTABLE TANKS

4.5 TANK BARGES

5. EMERGENCY MEASURES

5.1 GENERAL

5.2 RESPONSE TO A CHLORINE RELEASE

5.3 RESPONSE TO A FIRE

5.4 RELEASES

5.5 TRANSPORTATION EMERGENCIES

5.6 CHLORINE LEAK AT A CONSUMING LOCATION

5.7 ABSORPTION SYSTEMS

5.8 EMERGENCY KITS AND RECOVERY VESSELS

5.9 REPORTING

6. EMPLOYEE TRAINING AND SAFETY

6.1 EMPLOYEE TRAINING

6.2 PERSONAL PROTECTIVE EQUIPMENT

6.3 CONFINED SPACE ENTRY

6.4 PERSONAL EXPOSURE MONITORING

7. MEDICAL ASPECTS AND FIRST AID

7.1 HAZARDS TO HEALTH

7.2 FIRST AID

7.3 MEDICAL SURVEILLANCE

8. ENGINEERING DESIGN AND MAINTENANCE

8.1 STRUCTURES

8.2 VENTILATION

8.3 MATERIAL FOR PROCESSING EQUIPMENT

8.4 VAPORIZERS

8.5 SUPPORT EQUIPMENT

8.6 PIPING SYSTEMS FOR DRY CHLORINE

8.7 PIPING SYSTEMS FOR WET CHLORINE

8.8 STATIONARY STORAGE

8.9 EQUIPMENT MAINTENANCE

8.10 CHLORINE NEUTRALIZATION

9. U.S. REGULATIONS AND CODES

9.1 OCCUPATIONAL SAFETY AND HEALTH REGULATIONS -29 CFR

9.2 NAVIGATION AND NAVIGABLE WATER REGULATIONS -33 CFR

9.3 ENVIRONMENTAL REGULATIONS - 40 CFR

9.4 SHIPPING REGULATIONS - 46 CFR

9.5 TRANSPORTATION REGULATIONS - 49 CFR

9.6 DEPARTMENT OF HOMELAND SECURITY – 6 CFR

9.7 FIRE CODES

10. TECHNICAL DATA

10.1 GENERAL

10.2 ATOMIC AND MOLECULAR PROPERTIES

10.3 CHEMICAL PROPERTIES

10.4 PHYSICAL PROPERTIES

11. REFERENCES

11.1 CHLORINE INSTITUTE REFERENCES

11.2 U.S. GOVERNMENT REGULATIONS AND SPECIFICATIONS

11.3 CANADIAN REGULATIONS

11.4 AMERICAN CONFERENCE OF GOVERNMENTAL INDUSTRIAL HYGIENISTS (ACGIH)

11.5 AMERICAN SOCIETY OF MECHANICAL ENGINEERS (ASME)

11.6 ASTM INTERNATIONAL (ASTM)

11.7 COMPRESSED GAS ASSOCIATION (CGA)

11.8 NATIONAL ACADEMY OF SCIENCES (NAS)

11.9 NATIONAL FIRE PROTECTION ASSOCIATION (NFPA)

11.10 NATIONAL INSTITUTE OF OCCUPATIONAL SAFETY AND HEALTH (NIOSH)

11.11 NSF INTERNATIONAL

11.12 U.S. PHARMACOPEIAL CONVENTION

CHLORINE: THE ESSENTIAL ELEMENT

PRODUCTS OF CHLORINE CHEMISTRY

DRAWINGS

DRAWING 122-2: TON CONTAINER LIFTING BEAM

DRAWING 183-3: MANIFOLDING TON CONTAINERS FOR LIQUID CHLORINE WITHDRAWAL

DRAWING 189-2: CLOSED YOKE CHLORINE CONTAINER VALVE

CHLORINE BASICS 1

1. INTRODUCTION

1.1 CHLORINE BASICS

The first Chlorine Manual was published by The Chlorine Institute in 1947. It was a comprehensive compilation of information to assist chlorine producers, packagers, and end users in the safe handling, storage, shipment, and use of chlorine. In the years since the original Chlorine Manual was published, the Institute has developed numerous documents that provide more detailed information on safe chlorine management.

With Edition 7 of Pamphlet 1 (2008), the Chlorine Manual was renamed Chlorine Basics.

This change reflected the fact that a single document could no longer adequately communicate the detailed information required to safely handle, store, transport, and use chlorine. This pamphlet remains a valued resource, providing basic information for general users and providing an overview and references to more detailed information in other publications available from The Chlorine Institute.

The principal target audiences for this pamphlet are:

Operations personnel – this is a primary resource document for this group, especially in small companies

Engineering personnel – this is a roadmap to more detailed information in other pamphlets

New employees – this is a good “primer” for new employee training and orientation, where the needs are the same as for operations personnel

Users of Chlorine Institute Emergency Kits A, B, and C (since this document is included in each Kit) – the needs are the same as for operations personnel

For more detailed information, an online catalog is available on the Chlorine Institute’s website – www.chlorineinstitute.org.

1.2 CHLORINE INSTITUTE STEWARDSHIP PROGRAM

The Chlorine Institute (CI) exists to support the chlor-alkali industry and serve the public by fostering continuous 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. This support extends to giving continued attention to the security of chlorine handling operations.

Chlorine Institute members are committed to adopting CI safety and stewardship initiatives including pamphlets, checklists, and incident sharing that will assist members in achieving measurable improvement. For more information on CI’s stewardship program visit the CI website at www.chlorineinstitute.org.

2 PAMPHLET 1

1.3 DISCLAIMER

The information in this pamphlet is drawn from sources believed to be reliable. CI and its members, jointly and severally, make no guarantee, and assume no liability, in connection with any of this information. Moreover, it should not be assumed that every acceptable procedure is included, or that special circumstances may not warrant modified or additional procedures. The user should be aware that changing technology or regulations may require changes in the recommendations contained herein.

Appropriate steps should be taken to ensure that the information is current, when used.

These recommendations should not be confused with federal, state, provincial or municipal regulations, insurance requirements, or with national safety codes.

1.4 APPROVAL

CI’s Customer Stewardship Issue Team approved Edition 8 of this pamphlet on May 19, 2014.

1.5 REVISIONS

Suggestions for revisions should be directed to the Secretary of the Institute.

1.6 SIGNIFICANT REVISIONS IN CURRENT EDITION

This edition includes numerous enhancements, e.g. more illustrations, updated content and expanded text, especially in the following Sections:

Section 2 – Specific manufacturing and use hazards Section 4 – Tank car and cargo tank manway arrangements Section 7 – Hazards to health and first aid Section 8 – Engineering and maintenance Section 10 – Reactivity and flammability

These changes were implemented to make the document more useful to the diverse audience that values it as a source of basic information on chlorine.

1.7 CHECKLISTS

Several pamphlets contain checklists to assist members and non-members in self-audits or other reviews.

Because this pamphlet only summarizes some of the information contained in other pamphlets, the reader should refer to specific referenced 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 checklists.

1.8 ABBREVIATIONS AND ACRONYMS

ANSI American National Standards Institute

CHLORINE BASICS 3

API American Petroleum Institute

ASME American Society of Mechanical Engineers

ASTM American Society for Testing and Materials, now referred to as ASTM International

CAS Chemical Abstracts Service

CFR Code of Federal Regulations

CI The Chlorine Institute

DHS U.S. Department of Homeland Security

DOT U.S. Department of Transportation

EPA U.S. Environmental Protection Agency

IMDG International Maritime Dangerous Goods kPa Kilopascal

NFPA National Fire Protection Association

NIOSH National Institute for Occupational Safety and Health

OSHA Occupational Safety and Health Administration ppm Parts per million psia Pounds per square inch, absolute pressure psig Pounds per square inch, gauge pressure

PSM Process Safety Management

RMP Risk Management Plan

4 PAMPHLET 1

SDS Safety Data Sheet (Material Safety Data Sheet)

TC Transport Canada

TEMA Tubular Exchanger Manufacturers Association, Inc.

TLV Threshold Limit Value

2. GENERAL INFORMATION

2.1 WHAT IS CHLORINE?

Chlorine is one of 90 natural elements, the basic building blocks of our world. Since it is highly reactive, it is usually found chemically bonded to other elements. Sodium chloride, or common table salt, is one example.

Chlorine plays a vital role in many key uses and applications:

Chlorine is used to control bacteria and viruses in drinking water that can cause devastating illnesses such as cholera and typhoid. Approximately 98% of modern drinking water systems in the U.S. use chlorine chemistry to ensure the drinking water remains safe from bacterial contamination.

93% of all pharmaceuticals rely on chlorine chemistry, including medicines that treat heart disease, cancer, AIDS, and many other life-threatening diseases.

Chlorine chemistry is involved in the production of over 86% of crop protection chemicals.

Chlorine is used to produce polyvinyl chloride (PVC) and other plastics.

These plastics are used in many diverse products that you use every day.

The chlorine industry contributes more than $46 billion to the North American economy annually and helps provide thousands of essential products.

2.2 CHLORINE MANUFACTURE

Most chlorine is manufactured electrolytically by the diaphragm, membrane, or mercury cell process. The use of mercury cell technology is declining. Any new or updated production facility will most likely use the membrane process. In each process, a salt solution (sodium or potassium chloride) is electrolyzed by the action of direct electric current which converts chloride ions to elemental chlorine. Chlorine is also produced in a number of other ways, for example, by electrolysis of molten sodium or magnesium chloride to make elemental sodium or magnesium metal; by electrolysis of hydrochloric acid; and by non-electrolytic processes. Euro Chlor (www.eurochlor.org) has a very detailed animated production process description that can be found at http://eurochlor.org/the-chlorine-universe/how-is-chlorine-produced.aspx.

CHLORINE BASICS 5

Figure 2.2 – Diaphragm Cell Technology

Figure 2.1. Basic Chlor-Alkali Chemical Reaction Equation

Chlorine production for 2012 is estimated to be as follows:

Table 2.1 Chlorine Production

Area Million Short Tons Globally 69 United States 11.4 Canada 0.6 Mexico 0.3

2.2.1 Diaphragm Cell Technology

Currently in North America, a large percentage of chlorine production is from diaphragm cell technology (Fig. 2.2). The products of this type of cell are chlorine gas, hydrogen gas, and cell liquor composed of sodium hydroxide and sodium chloride solution.

A nearly saturated sodium chloride solution (brine) enters the diaphragm cell anode compartment and flows through the diaphragm to the cathode section. Chloride ions are oxidized at the anode to produce chlorine gas. Hydrogen gas and hydroxide ions are produced at the cathode. Sodium ions migrate across the diaphragm from the anode compartment to the cathode side to produce cell liquor containing 10% to 12% sodium hydroxide. Some chloride ions also migrate across the diaphragm resulting in the cell liquor containing 12 - 16% sodium chloride. The cell liquor is typically concentrated to 50% sodium hydroxide by an evaporation process. The salt recovered in the evaporation process is returned to the brine system for reuse.

HydrogenCausticChlorineyElectricitWaterSalt

2 HNaOHCleOHNaCl

6 PAMPHLET 1

2.2.2 Membrane Cell Technology

Membrane cell technology (Fig. 2.3) uses sheets of perfluorinated polymer ion exchange membranes to separate the anodes and cathodes within the electrolyzer. Ultra-pure brine is fed to the anode compartments, where chloride ions are oxidized to form chlorine gas. The membranes are cation selective resulting in predominantly sodium ions and water migrating across the membranes to the cathode compartments. Water is reduced to form hydrogen gas and hydroxide ions at the cathodes. In the cathode compartment, hydroxide ions and sodium ions combine to form sodium hydroxide.

Membrane electrolyzers typically produce 30% to 35% sodium hydroxide, containing less than 100 ppm of sodium chloride. The sodium hydroxide can be concentrated further, typically to 50%, using evaporators.

Figure 2.3 Membrane Cell Technology

2.2.3 Mercury Cell Technology

Mercury cell technology (Fig. 2.4) uses a stream of mercury flowing along the bottom of the electrolyzer as the cathode. The anodes are suspended parallel to the base of the cell, a few millimeters above the flowing mercury. Brine is fed into one end of the cell box and flows by gravity between the anodes and the cathode. Chlorine gas is evolved and released at the anode.

The sodium ions are deposited along the surface of the flowing mercury cathode. The alkali metal dissolves in the mercury, forming a liquid amalgam. The amalgam flows by gravity from the electrolyzer to the carbon-filled decomposer, where deionized water is added. The water chemically strips the alkali metal from the mercury, producing hydrogen and 50% sodium hydroxide. The mercury is then pumped back to the cell inlet, where the electrolysis process is repeated.

CHLORINE BASICS 7

Figure 2.4 – Mercury Cell Technology

2.3 CHLORINE TRANSPORTATION

2.3.1 General

Chlorine is normally shipped as a liquefied compressed gas. The transportation of chlorine by all modes is controlled by various regulations. It is the responsibility of each person shipping or transporting chlorine to know and to comply with all applicable regulations.

2.4 OTHER REGULATORY ASPECTS

Chlorine manufacturers, packagers, and most consumers are subject to workplace regulations pertaining to chlorine.

2.4.1 United States

There are many regulations at the federal, state, and local levels that apply to chlorine manufacture, transport, and use. Agencies such as OSHA, EPA, DOT, and DHS regulate various aspects of the chlorine industry and should be consulted. Refer to Section 9 of this pamphlet for more information.

8 PAMPHLET 1

Table 2.2 Chlorine Classification

Country Hazard Class Division Key Regulation Other

United States

Primary: 2

Secondary:

5, 8

Primary: 2.3 Poison Gas

Secondary: 5.1 Oxidizer

Secondary: 8 Corrosive

Land: 49 CFR Barge: 33 CFR and 46 CFR

Poison Zone B inhalation hazard material rating.

Various state and/or local regulations.

Canada Primary: 2

Secondary: 5

Primary: 2.3 Poison Gas

Secondary: 5.1 Oxidizer

Transportation of Dangerous Goods Act and Regulations

(TDG)

Various provincial and/or local regulations

Mexico Primary: 2

Secondary: 5

Primary: 2.3 Poison Gas

Secondary: 5.1 Oxidizer

Regulation for Surface Transportation of Hazardous Materials and Waste

Various state and/or local regulations.

International International Maritime Dangerous Goods Code

(IMDG)

Designation for chlorine:

UN1017

2.4.2 Canada

There are many regulations at the federal, provincial, and local levels that apply to chlorine manufacture, transport, and use. Agencies such as Health Canada, Environment Canada, and Transport Canada regulate various aspects of the chlorine industry and should be consulted.

2.5 TERMINOLOGY

2.5.1 Elemental Chlorine

Chlorine’s symbol is Cl, its atomic number is 17, and its atomic weight is 35.453.

Elemental chlorine almost always exists as a molecule with two chlorine atoms bound together as Cl2. Its molecular weight is 70.906. The CAS registry number is 7782-50-5.

CHLORINE BASICS 9

2.5.2 Liquid Chlorine

Liquid chlorine is chlorine (Cl2) which has been cooled and compressed to a liquid form.

Under atmospheric temperature and pressure, liquid chlorine evaporates quickly, with one pound of liquid forming about 5.4 cubic feet of chlorine gas.

Liquid chlorine is NOT the same as a hypochlorite or chlorine bleach solutions and this terminology should not be used to describe such solutions.

2.5.3 Chlorine Gas

At atmospheric conditions, chlorine is a gas.

2.5.4 Dry Chlorine/Wet Chlorine

Dry chlorine is defined as chlorine with its water content dissolved in solution. If a condition is reached anywhere in the system that will allow the water to exceed its solubility and form a second aqueous liquid phase, the chlorine is defined as wet chlorine. Wet chlorine will form corrosive compounds affecting the safety and integrity of the system. See CI Pamphlet 100 (11.1).

Dry Chlorine is NOT a dry chlorinating compound such as calcium hypochlorite or chloroisocyanurates and this terminology should not be used to describe such a substance.

2.5.5 Moist Chlorine

Synonymous with wet chlorine.

2.5.6 Saturated Chlorine Gas

Chlorine gas in such condition that the removal of any heat or an increase in pressure will cause some portion of it to condense to a liquid. This term does not describe or refer to the relative moisture content of the chlorine.

2.5.7 Saturated Chlorine Liquid

Chlorine liquid in such condition that the addition of any heat or a decrease in pressure will cause some portion of the chlorine to vaporize to a gas. This term does not describe or refer to the relative moisture content of the chlorine.

2.5.8 Chlorine Solution (Chlorine Water)

A solution of chlorine in water (see Figure 10.3).

A chlorine solution is NOT the same as hypochlorite or chlorine bleach solutions and this terminology should not be used to describe such solutions.

2.5.9 Liquid Bleach

An aqueous solution of hypochlorite, usually sodium hypochlorite (NaOCl).

10 PAMPHLET 1

2.5.10 Container

In this publication, a container is a pressure vessel authorized by an applicable regulatory body for the transport of chlorine. It does not include pipelines or stationary storage tanks.

2.5.11 Filling Density

By DOT and TC regulation, the weight of chlorine that is loaded into a container may not exceed 125% of the weight of water at 60°F (15.6°C) that the container will hold.

2.5.12 Sodium Hydroxide

Normally sodium hydroxide (NaOH) is the co-product produced as a solution when chlorine is generated through the electrolytic decomposition of sodium chloride solution.

Sodium hydroxide is frequently referred to as caustic soda or lye.

2.5.13 Potassium Hydroxide

A co-product produced as a solution when chlorine is generated through the electrolytic decomposition of potassium chloride salt solution. Potassium hydroxide (KOH) is frequently referred to as caustic potash.

2.6 SPECIFIC MANUFACTURING AND USE HAZARDS

Refer to your supplier’s Safety Data Sheet (SDS) and referenced CI pamphlets for additional safety and handling precautions.

2.6.1 Hydrogen

Hydrogen (H2) is a co-product of all chlorine manufactured by the electrolysis of aqueous brine solutions. Within a known concentration range, mixtures of chlorine and hydrogen are flammable and potentially explosive. The reaction of chlorine and hydrogen can be initiated by direct sunlight, other sources of ultraviolet light, static electricity, or sharp impact. See CI Pamphlet 121 (11.1).

2.6.2 Nitrogen Trichloride

Small quantities of nitrogen trichloride (NCl3), an unstable and highly explosive compound, can be produced in the manufacture of chlorine. When liquid chlorine containing nitrogen trichloride is evaporated, the nitrogen trichloride may concentrate to hazardous concentrations in the residue (see CI Pamphlets 21 and 152 (11.1)).

2.6.3 Oils and Grease

Chlorine can react, at times explosively, with a number of organic materials such as oil and grease from sources such as air compressors, valves, pumps, oil-diaphragm instrumentation, pipe thread lubricants. Equipment and piping must be cleaned prior to use to remove any oils. See CI Pamphlet 6 (11.1). Ensure that non-reactive lubricants are used in chlorine service (e.g. Fluorolube® and Krytox®).

CHLORINE BASICS 11

2.6.4 Fire

Chlorine is neither explosive nor flammable. Chlorine will support combustion under certain conditions. Many materials that burn in oxygen (air) atmospheres will also burn in chlorine atmospheres.

2.6.5 Chemical Action/Reactions

Chlorine has a very strong chemical affinity for many substances. It will react with many inorganic and organic compounds, usually with the evolution of heat. Chlorine reacts with some metals under a variety of conditions (see Section 10.3.3). It is especially important to not use any titanium in dry chlorine service. Chlorine will react with steel and other metals at temperatures above 149°C (300°F). Do not weld piping and other equipment without properly evacuating and purging chlorine from the equipment.

2.6.6 Corrosive Action on Steel and Other Metals

At ambient temperatures, dry chlorine, either liquid or gas, does not corrode steel. Wet chlorine is highly corrosive because it forms hydrochloric and hypochlorous acids.

Precautions should be taken to keep chlorine and chlorine equipment dry. Piping, valves, and containers should be closed or capped when not in use to keep out atmospheric moisture such as precipitation or humidity. Materials of construction must be chosen carefully, depending on the conditions that are expected. If water is used on a chlorine leak, the resulting corrosive conditions will make the leak worse.

2.6.7 Volumetric Expansion

The volume of liquid chlorine increases with temperature. Precautions should be taken to avoid hydrostatic rupture of piping, vessels, containers, or other equipment filled with liquid chlorine (see Figure 10.4). Any time liquid chlorine can be trapped between two valves, an expansion device should be present.

2.6.8 Personal Protection

The most significant health hazard associated with chlorine is being exposed to chlorine vapors. Respiratory protection must be assured by process design, operating procedures and personal protective equipment. Skin contact with liquid chlorine can result in frostbite. See CI Pamphlet 65 (11.1).

3. CYLINDERS AND TON CONTAINERS

3.1 CONTAINER DESCRIPTIONS

3.1.1 General

Cylinders and ton containers have many similarities in the way in which they are handled. The terms “cylinder,’’ ‘‘ton cylinder,’’ or “drum” should not be used to describe the ton container. Emergency and other equipment for handling ton containers is different from that used for cylinders and confusion can be avoided if the proper terms are used.

12 PAMPHLET 1

In this document, “container” will be used to refer to any vessel that holds chlorine for the purpose of transporting the product. This may include cylinders, ton-containers, cargo tanks, tank cars, and barges. If the information provided is specific to the type of container, it will be specified.

Site chlorine inventories exceeding the threshold quantity are subject to regulations such as as RMP and PSM. Check with federal, state, and provincial agencies for threshold requirements.

3.1.2 Cylinders

Chlorine cylinders are of seamless construction with a capacity of 1 to 150 lb (0.45 to 68 kg); those of 100 and 150 lb (45.4 and 68 kg) capacity predominate. The only opening in the cylinder is the valve connection at the top of the cylinder. The steel valve protective housing should be utilized to cover the valve during shipment and storage.

Care must be taken with the protective cap since the cylinder neck-ring to which it is attached is not physically welded to the cylinder.

Figure 3.1 – Chlorine Cylinder (Left – bump-bottom; Upper right – double-bottom; Lower right - foot ring)

3.1.3 Ton Containers

Ton containers are welded tanks having a capacity of one short ton, 2000 lb (907 kg), and a loaded weight of as much as 3650 lb (1655 kg). The sides are crimped inward at each end to form chimes which provide a substantial grip for lifting beams. The ton container valves are protected by a removable steel valve protective housing.

CHLORINE BASICS 13

Figure 3.2 – Chlorine Ton Container

3.2 CONTAINER VALVES

3.2.1 Cylinder Valves

The typical cylinder is equipped with one valve. The valve outlet threads are not standard pipe threads, but are special straight threads. These outlet threads are intended for securing the valve outlet cap and not for connecting unloading connections or other devices. Typical cylinder connections are made with a yoke and adapter. See CI Pamphlet 17 (11.1). The valve is also equipped with a fusible metal pressure relief device or, as more commonly named, a fusible plug.

Figure 3.3 – One Typical Style of a Cylinder Valve (Other designs may also be in use)

14 PAMPHLET 1

3.2.2 Ton Container Valves

Each ton container is equipped with two identical valves near the center of one end.

They are different from the typical cylinder valve in that they have no fusible metal plug and usually have a larger internal passage. Each valve connects to an internal eduction tube. See CI Pamphlet 17 (11.1).

Figure 3.4 – One Style of a Chlorine Ton Container Valve (Other designs may also be in use)

3.3 PRESSURE RELIEF DEVICES

3.3.1 General

Cylinders and ton containers are equipped with a metal relief device or fusible plug. The fusible metal is designed to comply with the requirements of 49 CFR Part 173.301(f), and therefore, will melt between 158°F and 165°F (70°C and 74°C). These devices will relieve pressure when subjected to temperatures at or above the melting point of the fusible metal. The devices will not function in the absence of high temperature.

3.3.2 Cylinders

Cylinder valves are equipped with one fusible metal relief device or fusible plug.

3.3.3 Ton Containers

Ton containers are equipped with fusible metal pressure relief devices. Most have six fusible metal plugs, three in each end.

3.4 CONTAINER SHIPPING

3.4.1 Cylinders

Cylinders may be shipped by highway, rail, or water. Suitable restraints are necessary to prevent cylinders from shifting during transportation. See CI Pamphlet 76 (11.1).

CHLORINE BASICS 15

Figure 3.5 – Lifting Beam for Handling Chlorine Ton Containers

3.4.2 Ton Containers

Most ton containers are shipped by highway. Trucks must have suitable hold-down devices to prevent the ton containers from shifting during transportation. Trucks are sometimes equipped with a crane and lifting beam to facilitate loading and unloading.

See CI Pamphlet 76 (11.1).

3.5 CONTAINER MARKING/LABELING AND VEHICLE PLACARDING

Containers in transportation must be marked and labeled and the vehicle placarded as required by regulations.

3.6 CONTAINER HANDLING

3.6.1 General

Chlorine containers must be handled with care. During shipment and storage, container valve protective housings should be in place. Containers should not be dropped and no object should be allowed to strike them with force. Containers should be secured to prevent them from rolling. See CI Pamphlet 76 (11.1).

3.6.2 Cylinders

Cylinders can be moved using a properly balanced hand truck. The hand truck should have a clamp or chain two-thirds of the way up the cylinder wall to hold the cylinder in place. If cylinders must be elevated by hoist, a specially designed cradle or carrier should be used. Slings and magnetic devices are unacceptable. Cylinders must not be lifted by the valve protective housing because the neck-ring to which the housing is attached is not designed to carry the weight of the cylinder.

3.6.3 Ton Containers

Ton containers are typically moved using a monorail or crane with a lifting beam (see Drawing 122). They can be rolled on rails or roller conveyors designed for this purpose.

If a forklift truck is used, the ton container must be adequately restrained to prevent it from falling off, particularly when the truck changes direction. The forklift truck must be rated to handle the gross weight of the ton container.

16 PAMPHLET 1

3.7 CONTAINER STORAGE

Containers may be stored indoors or outdoors. The storage area should comply with federal and state regulations.

If stored outdoors, the storage area should be clean so that accumulated trash or other combustible material does not present a fire hazard. Containers should not be stored near elevators or ventilating systems because dangerous concentrations of gas may spread rapidly if a leak occurs. All containers should be stored to minimize external corrosion.

Exposure of containers to flame, intense radiant heat or to steam lines must be avoided.

If the metal in the vicinity of the fusible plug reaches approximately 158°F (70°C), the fusible metal plug is designed to melt and chlorine will be released.

See CI Pamphlets 17 and 155 (11.1) for more detail on storage considerations.

3.8 CONTAINER USE

3.8.1 General

Before connecting or disconnecting a container, the operator should make sure that all safety and emergency equipment is available and operable. Containers and valves must not be modified, altered, or repaired by anyone other than the owner.

3.8.2 Gas Discharge

Chlorine gas discharge rates vary significantly because of local ambient temperature, humidity and air circulation, as well as the variations in the piping system and feeding equipment connected to the container. See CI Pamphlet 155 for details (11.1).

If the gas discharge rate from a single container will not meet the flow requirements, two or more may be connected to a manifold. Alternately, liquid from one or more containers may be sent to a vaporizer for increasing the chlorine gas delivery rate (see Section 3.8.3).

When discharging through a gas manifold, all containers should be at the same temperature to prevent transfer of gas from a warm container to a cool container.

3.8.3 Liquid Discharge

Discharging liquid chlorine has special design requirements. See CI Pamphlet 6 (11.1).

Liquid chlorine is delivered from the lower valve of a ton container. See the picture of eductor tubes in Figure 3.2. Very high liquid withdrawal rates can be obtained. The rate depends on the temperature of the chlorine in the ton container and on the backpressure. The dependable continuous discharge rate of liquid chlorine under normal temperature conditions and against a pressure of 35 psig (241 kPa gauge) is at least 400 lb/hr (181 kg/hr) for ton containers. When connected to a manifold, ton containers discharging liquid chlorine should include precautions to equalize the pressure. Drawing 183 depicts a system for equalizing pressures for gas valves

CHLORINE BASICS 17

connected to a manifold. It is not sufficient to depend on ton containers reaching the same pressure merely by storing them in the same working area. Piping evacuation procedures should be established so liquid chlorine is not trapped in the system.

3.8.4 Weighing

Because chlorine is shipped as a compressed liquefied gas, the pressure in a container depends on the temperature of the chlorine (Figure 10.1). The pressure is not related to the amount of chlorine in the container. Container contents can be determined accurately only by weighing.

3.8.5 Connections

A chlorine compatible flexible connection must be used between the container and a pressurized piping system. Copper tubing with a diameter of 1/4-inch or 3/8-inch is recommended. Flexible metallic hoses or fluoroplastic hoses as described in CI Pamphlet 6 (11.1) are also acceptable materials. If a system is to remain in operation while containers are being connected or disconnected, auxiliary (isolating) container valves must be used. Flexible connections should be inspected and replaced on a regular basis. A flat gasket on the face of the valve is part of the connection. A new gasket should be used each time a connection is made (see CI Pamphlets 6 and 155 (11.1) and Drawing 189).

3.8.6 Opening Valves

The container valve is opened by turning the valve stem in a counter-clockwise direction.

One full turn of the stem typically permits an appropriate feed rate. More stem turns should not be made unless recommended by the supplier. A wrench (50 ft/lbs maximum torque), no longer than 8 inches, should be used. Never use a wrench extension (cheater bar) as the valve may be damaged preventing gas-tight shutoff. Once the valve is opened, the wrench should be left in place so that the valve can be closed quickly. Do not loosen the packing nut unless authorized by the supplier.

To connect a line to the container, ensure the valve is closed. Make certain that the packing nut is at least hand tight; if it is not, contact your supplier for advice. Remove the valve outlet cap and attach the line to the valve with a yoke. Use a new gasket each time a connection is made. Make sure connections are tight.

Figure 3.6 – Open Yoke Adapter – Type Connector

Provided by S&P Global under license with The Chlorine Institute

18 PAMPHLET 1

Once connections have been made, pressurize the system with a small amount of chlorine, and check for leaks. If a leak is found, it must be remedied before proceeding (see CI Pamphlet 155 (11.1)).

3.8.7 Closing Valves

Apply 25-30 foot-pounds to the valve stem. Check for leaks. If any leaks still exist, the torque may be increased up to 40 foot-pounds. If the leak has not stopped at 40 foot-pounds, increase the torque on the valve stem to 50 foot-pounds. Foreign objects such as rust flakes or other debris can prevent positive shutoff of chlorine valves. If the container remains connected to the process and it is safe to do so, a complete cycling of the valve may dislodge the foreign material and allow positive valve shutoff. Always verify the valve is being turned clockwise for closing. If this fails to work, contact your supplier.

3.8.8 Disconnecting Containers

As soon as a container is empty, the valve should be closed (see Section 3.7.7). Prior to disconnecting, reconfirm that the valve is closed and provide a means of removing the chlorine trapped in the flexible connecting line. This can be accomplished by either purging the line with dry air or nitrogen with a dew point of -40°F (-40°C) or lower or by applying a vacuum. Personal Protective Equipment should be used as appropriate for the task. See CI Pamphlet 65 (11.1). 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.

4. BULK SHIPPING CONTAINER

4.1 GENERAL

Bulk chlorine is shipped by pipeline, tank cars, tank motor vehicles, portable tanks, and barge tanks.

4.2 TANK CARS

4.2.1 General

The following is generalized information on chlorine tank cars. See CI Pamphlet 66 (11.1).

4.2.2 Specifications

The most commonly used tank cars have a chlorine capacity of 90 tons. By regulation, tank cars may not be loaded with chlorine in excess of the nominal weight.

Table 4.1 Key Government Specifications

United States 49 CFR 179.102-2 49 CFR 176-314 (c) note 12 Transport Canada 79.102-2 73.314 (c) note 12

CHLORINE BASICS 19

The regulations require tank cars to be equipped with a pressure relief device whose setting is stenciled on the side of the car. Tank cars must be thermally protected with four inches of insulating material.

4.2.3 Manway Arrangement

The only opening into a chlorine tank car is through a manway on top, where the valves are enclosed with a steel cover.

Most chlorine tank cars have four angle valves. They also have one pressure relief device designed to release excess pressure buildup within the tank. Two of the angle valves are located on the longitudinal center of the car. These valves are connected to eduction pipes that run to the bottom of the tank and are used to unload liquid chlorine.

Two angle valves are located on a line perpendicular to the car's length and are connected to the vapor phase. These valves should never be used for gas withdrawal, but can be used to pressurize the car when needed to increase the rate of liquid withdrawal. In cars built prior to 2009, the liquid valves are equipped with excess flow valves designed to close at flow rates of 7,000, 15,000 or 32,000 lb per hour. The flow rate is usually stenciled on the side of the car. Unstenciled cars have 7,000-lb-per-hour valves.

Starting in 2009, chlorine tank cars began to be equipped with an alternate valve design. The primary feature that is different on the alternate design is that a check valve is used in place of an excess flow valve. The check valve is designed to remain closed during transport, so in the unlikely event of a rollover where valves shear off, the valve port remains closed and prevents an accidental release. Arrangements consisting of the alternate design may have wider bases and can consist of either 3 or 4 liquid/vapor valves and one pressure relief device.

The CI Emergency Kit C is designed to be used for stopping leaks on chlorine tank cars.

See CI Pamphlet 66 (11.1). It is important to know if an alternate valve design or the traditional valve design is used on a tank car because the C-Kit will need to be applied differently, depending on the valve design encountered.

For additional guidelines, recommended practices, and other useful information concerning chlorine tank cars, refer to CI Pamphlets 66, 166 and 168 (11.1).

4.2.4 Transfer Operations

The following is general information. See CI Pamphlet 66 (11.1).

Precautions

Every site handling chlorine in bulk containers should have RMP and PSM programs.

Special attention should be directed to the appropriateness of emergency procedures and to equipment to be used in an emergency.

Chlorine transfer operations must be performed only by personnel who are trained as required by applicable hazardous material regulations.

20 PAMPHLET 1

DOT (49 CFR), OSHA (29 CFR) and TC (Sec. 10.2) have specific training requirements applicable to handling of hazardous materials.

All personnel responsible for transfer operations should be knowledgeable about the facility’s emergency response plan for handling spills and leaks of products. See CI Pamphlet 66 (11.1).

Before beginning transfer operations, a number of things should be considered. Details can be found in CI Pamphlet 66. A partial list of topics includes:

Connections

Pressure padding

Monitoring

Disconnecting

4.3 CARGO TANK MOTOR VEHICLES

4.3.1 General

The following is generalized information on chlorine cargo tank motor vehicles. See CI Pamphlet 49 (11.1). In North America, they usually have a capacity ranging from 15 to 22 tons (13,600 kg to 20,000 kg) with certain exceptions. DOT specifications apply only to the tank.

4.3.2 Manway Arrangement

The manway arrangement is the same as that on chlorine tank cars (see Section 4.2.3) except that special excess-flow valves are required under the gas valves.

4.3.3 Transfer Operations

Procedures for transferring chlorine to/from cargo tanks are essentially the same as for tank cars. There is, however, more variation in facilities and conditions at customers’ plants, and these may require modifications of methods and equipment.

4.3.4 Precautions

The engine should be shut off, hand brakes must be set, and wheel chocks must be in place during transfer. The tank motor vehicle must be attended at all times. The tank motor vehicle must not be moved when loading or unloading connections are attached to the vehicle (see discussion of tank car transfer, Section 4.2.40, for additional, applicable precautions).

4.3.5 Emergency Equipment

Approved respiratory equipment is required on the transport vehicle. An Emergency Kit “C” must be on the transport vehicle. Proper training on the use of emergency equipment is required (OSHA 29 CFR 1910.134).

CHLORINE BASICS 21

It also is required that the transport vehicle have 2-way communication such as a cell phone or radio.

4.3.6 Connections/Disconnecting

See discussion for tank cars (Section 4.2.4).

The driver should recheck all equipment by a visual inspection before starting the vehicle.

4.3.7 Pressure Padding

See discussion for tank cars (Section 4.2.4).

4.4 PORTABLE TANKS

Tanks suitable for multi-modal transportation (road, rail, and water) of chlorine should be built under the provisions of DOT 51 and special provisions for chlorine. See CI Pamphlet 49 (11.1).

4.5 TANK BARGES

Consult your supplier for information on chlorine barges.

5. EMERGENCY MEASURES

5.1 GENERAL

A chlorine emergency may occur during manufacture, use, or transportation. Trained employees, along with a comprehensive, written emergency response plan are necessary to mitigate the consequences of the emergency. Regular drills and reviews of emergency response plans with all involved organizations are encouraged. See CI Pamphlet 64 (11.1). Federal, state and provincial regulations, as well as various local fire and building codes, regulate chemical emergency preparedness and response. All persons responsible for the handling of chlorine must be familiar with those requirements. Regulatory requirements deal generally with preparation and response to chemical and other emergencies. See CI Pamphlet 64 (11.1). Help is also available from CHLOREP (see Sections 5.5.1 to 5.5.3) which can be accessed through CHEMTREC (U.S.). In Canada, CANUTEC may provide advice, as well as contact information for the appropriate CHLOREP Team.

5.2 RESPONSE TO A CHLORINE RELEASE

As soon as there is any indication of a chlorine release, immediate steps must be taken to correct the condition. Chlorine leaks always get worse if they are not promptly corrected. When a chlorine leak occurs, authorized, trained personnel equipped with respiratory and appropriate other PPE should investigate and take proper action.

Personnel should not enter into atmospheres containing concentrations of chlorine in excess of the IDLH Concentration of 10 ppm without appropriate personal protective equipment and backup personnel.

22 PAMPHLET 1

CI Pamphlet 65 (11.1) provides PPE recommendations for responders to a chlorine release. Keep unnecessary personnel away and isolate the hazard area. Persons potentially affected by a chlorine release should be evacuated or sheltered-in-place as circumstances warrant.

Area chlorine monitors and wind direction indicators can supply timely information (e.g., escape routes) to help determine whether personnel are to be evacuated or sheltered in place.

When evacuation is necessary, potentially exposed persons should move to a point upwind of the leak. To escape in the shortest time, persons already in a contaminated area should move crosswind. Because chlorine is heavier than air, higher elevations are preferable.

When inside a building and sheltering-in-place is selected, shelter by closing all windows, doors and other openings, and turning off air conditioners and air intake systems. Personnel should move to the side of the building furthest from the release.

Care must be taken not to position personnel without an escape route. A safe position may be made hazardous by a change in wind direction. New leaks may occur or the existing leak may get larger.

If notification of local authorities is required, the following information should be provided:

Company name, address, telephone number and the name of the person(s) to contact for further information

Description of the emergency

Travel directions to the site

Type and size of container involved

Corrective measure being applied

Other pertinent information, i.e., weather conditions, injuries, etc.

There are specific government requirements for reporting a hazardous chemical release.

Releases must be reported in a timely manner.

This is the start of the file's text. The full file is on GovTribe.

File details come from the government source that posted it. Updated Jun 27, 2025.