Chlorine Reference Manual

THE CHLORINE REFERENCE MANUAL
GEST 06/317
1st Edition
July 2008
EURO CHLOR PUBLICATION
This document can be obtained from:

EURO CHLOR - Avenue E. Van Nieuwenhuyse 4, Box 2 - B-1160 BRUSSELS
Telephone: 32-(0)2-676 72 65 - Telefax: 32-(0)2-676 72 41
GEST 06/317
st
1 Edition
Euro Chlor
Euro Chlor is the European federation which represents the producers of chlorine
and its primary derivatives.
Euro Chlor is working to:
improve awareness and understanding of the contribution that chlorine

chemistry has made to the thousands of products, which have improved our
health, nutrition, standard of living and quality of life;
maintain open and timely dialogue with regulators, politicians, scientists, the
media and other interested stakeholders in the debate on chlorine;
ensure our industry contributes actively to any public, regulatory or scientific

debate and provides balanced and objective science-based information to
help answer questions about chlorine and its derivatives;
promote the best safety, health and environmental practices in the

manufacture, handling and use of chlor-alkali products in order to assist our
members in achieving continuous improvements (Responsible Care).
***********
This document has been produced by the members of Euro Chlor and should not be reproduced in
whole or in part without the prior written consent of Euro Chlor.
It is intended to give only guidelines and recommendations. The information is provided in good
faith and was based on the best information available at the time of publication. The information is
to be relied upon at the users own risk. Euro Chlor and its members make no guarantee and
assume no liability whatsoever for the use and the interpretation of or the reliance on any of the
information provided.
This document was originally prepared in English by our technical experts. For our members
convenience, it may have been translated into other EU languages by translators / Euro Chlor
members. Although every effort was made to ensure that the translations were accurate, Euro
Chlor shall not be liable for any losses of accuracy or information due to the translation process.
Prior to 1990, Euro Chlors technical activities took place under the name BITC (Bureau
International Technique du Chlore). References to BITC documents may be assumed to be to Euro
Chlor documents.
July 2008
Page 2 of 62
GEST 06/317
st
1 Edition
RESPONSIBLE CARE IN ACTION
Chlorine is essential in the chemical industry and consequently there is a need for
chlorine to be produced, stored, transported and used. The chlorine industry has
co-operated over many years to ensure the well-being of its employees, local
communities and the wider environment. This document is one in a series which
the European producers, acting through Euro Chlor, have drawn up to promote
continuous improvement in the general standards of health, safety and the
environment associated with chlorine manufacture in the spirit of Responsible
Care.
The voluntary recommendations, techniques and standards presented in these
documents are based on the experiences and best practices adopted by member
companies of Euro Chlor at their date of issue. They can be taken into account in
full or partly, whenever companies decide it individually, in the operation of existing
processes and in the design of new installations. They are in no way intended as a
substitute for the relevant national or international regulations which should be fully
complied with.
It has been assumed in the preparation of these publications that the users will
ensure that the contents are relevant to the application selected and are correctly
applied by appropriately qualified and experienced people for whose guidance they
have been prepared. The contents are based on the most authoritative information
available at the time of writing and on good engineering, medical or technical
practice but it is essential to take account of appropriate subsequent developments
or legislation. As a result, the text may be modified in the future to incorporate
evolution of these and other factors.
This edition of the document has been drawn up by the General Technical
Committee to whom all suggestions concerning possible revision should be
addressed through the offices of Euro Chlor.
July 2008
Page 3 of 62
GEST 06/317
st
1 Edition
TABLE OF CONTENTS
SCOPE
1 THE CHLORINE INDUSTRY
1.1
General Information
1.2
Economical Aspects
2 CHLORINE MANUFACTURE
2.1
Production of Chlorine
10
10
2.1.1
Mercury Technology
11
2.1.2
Diaphragm Technology
13
2.1.3
Membrane Technology
14
2.2
Chlorine Treatment
16
2.2.1
Cooling
16
2.2.2
Purification
16
2.2.3
Drying
16
2.2.4
Compression
17
2.2.5
Liquefaction
17
2.3
Products Usages
18
2.3.1
Chlorine
18
2.3.2
Sodium Hydroxide
18
2.3.3
Hydrogen
19
3 PROPERTIES AND HAZARDS OF CHLORINE
19
3.1
Physical Properties
19
3.2
Reactivity
19
3.3
Hazards
19
3.3.1
Chlorine and Explosion Risk
19
3.3.2
Construction Materials
20
4 PROPERTIES AND HAZARDS OF HYDROGEN
21
5 PROCESS SAFETY MANAGEMENT
21
5.1
Site Security
21
5.2
Process Safety Information
21
5.2.1
Process Design Information
22
5.2.2
Mechanical Design Information
22
5.3
Process Hazards Analysis
22
5.4
Management of Change
22
5.5
Operating Procedures
23
5.6
Safe Work Practices
23
5.7
Mechanical Integrity
23
July 2008
Page 4 of 62
GEST 06/317
st
1 Edition
5.8
Pre-Start-Up Safety Review
24
5.9
Emergency Response and Control
24
5.10
Investigation of Process Related Incidents
24
5.11
Audits of Process Hazards Management Systems
25
6 TRAINING
6.1
25
Personnel of the Facility
25
6.1.1
Topics covered
25
6.1.2
Initial Training
26
6.1.3
Refresher Training
26
6.1.4
Plant Modifications
26
Training of Road Tanker Drivers
26
6.2
7 SAFETY GUIDANCE
7.1
Chlorine Detection and Monitoring
26
26
7.1.1
Purpose of Chlorine Monitors
26
7.1.2
Chlorine Monitoring Systems
26
7.1.3
Arrangement
27
Preventing Major Hazards
27
7.2
7.2.1
Nitrogen Trichloride
27
7.2.2
Moisture
28
7.2.3
Hydrogen
28
7.3
Protective Equipment
8 HEALTH HAZARDS, TRAINING AND FIRST AID
29
30
8.1
Health Hazards and Toxicity of Chlorine
30
8.2
Monitoring Chlorine Exposure to Workers
31
8.3
Treatment of Chlorine Gassing
31
8.4
Exposition of workers to mercury
32
8.5
Electromagnetic Fields (EMF)
32
9 TECHNICAL GUIDANCE FOR THE FACILITY
33
9.1
Materials
33
9.1.1
Materials for Liquid Chlorine and Dry Chlorine Gas
33
9.1.2
Materials for Wet Chlorine Gas
33
9.2
Equipments
33
9.2.1
Piping
34
9.2.2
Valves
34
9.2.3
Bolts and Gaskets
37
9.2.4
Pumps
37
9.2.5
Instruments
37
July 2008
Page 5 of 62
GEST 06/317
st
1 Edition
9.2.6
Liquid Chlorine Quality
37
9.2.7
Pressure Relief Systems
38
9.2.7.1 General Policy
38
9.2.7.2 Requirements for Provision of Relief Systems
38
9.2.7.3 Design Criteria
38
9.2.7.4 Arrangement
38
9.2.7.5 Operation
39
9.2.8
Back Flow Prevention
39
9.2.9
Services
40
9.2.9.1 Instrument Air
40
9.2.9.2 Effluent Drains
40
9.3
Chlorine Transfer Compressors
40
9.4
Chlorine Storage
40
9.5
Loading and Off-loading
41
9.5.1
Introduction
41
9.5.2
Piping Connections
41
9.5.3
Padding Gas Used for the Transfer
41
9.5.4
Venting Arrangements
42
9.5.5
Choice of Flexible Connections to the Tanker
42
9.5.6
Location of the Loading or Off-loading Station
42
9.5.7
Loading and Off-loading Procedure
43
9.5.8
Emergency Planning
44
9.6
Chlorine Vaporisers
44
9.7
Absorption Systems
44
9.7.1
Chemical Principles
45
9.7.2
Disposal of Hypochlorite Solution
46
9.7.3
Technical Design of Absorption Systems
46
9.7.4
Materials of Construction
47
10 TECHNICAL GUIDANCE FOR TRANSPORT

10.1
47
DESIGN AND CONSTRUCTION OF TRANSPORT EQUIPMENT
47
10.1.1 Design and Construction of Rail Tank Wagons
48
10.1.2 Design and Construction of Road Tankers
48
10.1.3 Design and Construction of ISO Containers
48
10.1.4 Design and Construction of Drums and Cylinders
48
10.2
TRANSPORT OF CHLORINE BY RAIL
48
10.3
TRANSPORT OF CHLORINE BY ROAD
49
10.4
HANDLING OF CHLORINE IN SMALL CONTAINERS
49
July 2008
Page 6 of 62
GEST 06/317
st
1 Edition
10.4.1 Cylinders
50
10.4.2 Drums
50
10.4.3 Spheres
50
10.4.4 Drums and Transport Spheres Loading and Off-loading
50
10.5
MAINTENANCE OPERATIONS
11 CHLORINE ACCIDENTS
50
51
11.1
Emergency Assistance
51
11.2
Measures for Containing Chlorine Leaks
51
11.2.1 First Measures
51
11.2.2 Limiting a Chlorine Leak
51
11.2.3 Stopping a Chlorine Leak
52
11.2.4 Sealing
52
11.2.5 Containment
52
11.3
Learning from Experience
52
12 ENVIRONMENTAL PROTECTION
52
13 SWIMMING POOLS
54
14 REFERENCES
54
15 APPENDICES
57
APPENDIX 1: SAFE TRANSPORT OF LIQUID CHLORINE BY RAIL TANKER

VEHICLES - HIGHLIGHTS FROM GEST 80/89
58
1. Construction Code
58
2. Operation of Rail Tankers
58
3. Transport
59
APPENDIX 2: TRAINING OF CHLORINE ROAD TANKER DRIVERS HIGHLIGHTS FROM GEST 73/20
60
1. Driving Skills and Procedures
60
2. Properties of Chlorine
60
3. Equipment and Procedures for Handling Chlorine
60
4. Examples of Operating Hazards
61
TABLE OF FIGURES
Figure 1: Flow Diagram of the Three Main Chlor-Alkali Processes
11
Figure 2: Electrolyser and Decomposer of the Mercury Technology
12
Figure 3: Electrolyser of the Diaphragm Technology
13
Figure 4: Electrolyser of the Membrane Technology
15
July 2008
Page 7 of 62
GEST 06/317
st
1 Edition
SCOPE
The objective of this document is to give a brief overview of the chlorine industry
covering general information, some economical aspects, chlorine manufacture,
consumption of products, and will mainly focus on the European safety,
environmental protection and health aspects, referring to the Euro Chlor guidelines
and recommendations.
Safety aspects are of much concern in the chlor-alkali industry. Production,
storage, loading, transportation and use of chlorine require compliance with
certain provisions designed to minimise the possibility of incidents potentially
dangerous for operators, the public or the plant. A general policy for the prevention
of and response to industrial accidents is usually based on the prevention principle:
the plant is constructed and operated in such a way as to prevent any uncontrolled
development and to mitigate the consequences of accidents.
In the European Union, Member States agreed in 1982 on a Directive, the
SEVESO Directive (82/501/EEC), as a means of controlling major industrial
hazards connected with process and storage facilities where dangerous
substances are present. The principles of the Directive set out:
General requirements for industries which use dangerous substances to

take all preventive measures to reduce the risks and to inform neighbouring
populations of such hazards
Requirements for authorities to control the activities and prepare appropriate

emergency planning in the event of major accidents.
Since then, advancing knowledge and experience have provided new insights. The
"SEVESO II" Directive (96/82/EC) represents a fundamental revision of the
Directive. Storage and processes using chlorine are part of the scope of the
Directive starting from 10 tonnes, along with hydrogen starting from 5 tonnes, while
the alkali solutions are not covered.
Although chlorine is a hazardous material in terms of reactivity and toxicity, it can
be produced, distributed and handled safely provided that appropriate precautions
and measures are realised.
Since 1952, Euro Chlor, previously known as BITC, has been active in promoting
the safe handling of chlorine and has developed guidelines. This present manual is
a synthesis of papers already published dealing with chlorine production, handling,
loading and off loading, transportation and use. The appropriate Euro Chlor
recommendations are mentioned in each section and must be consulted for more
precise details.
These guidelines are not intended to replace existing relevant national or
international regulations, which must be fully complied with. They supplement
these regulations by drawing on the detailed experience of chlorine producers.
Reference to existing regulations is only made where it is considered necessary for
the purpose of clarification.
Euro Chlor recommends that these guidelines should be applied by all parties
involved in the chlorine activity (construction, production, maintenance, distribution
and use) and asks them to report all accidents and incidents in order to continue to
improve by learning from experience.
July 2008
Page 8 of 62
GEST 06/317
st
1 Edition
In order to facilitate effective management of safety in the overall process of

transportation, it is recommended that chlorine producers should check periodically
the transport arrangements.
The main goal of Health documents is to provide sufficient information to
managers, plant engineers and local occupational physicians to enable them to
protect the health of workers against harmful effects of chlorine and mercury;
electromagnetic fields is also a topic considered in a specific guideline.
Environmental protection is essentially mercury oriented. The many years
experience of the companies has allowed developing recommendations explaining
techniques that minimise any contamination in the final products and discharged
streams; wherever possible, the removed mercury within the process should also
be recycled.
1 THE CHLORINE INDUSTRY

1.1
General Information
The chlor-alkali industry is the industry that produces chlorine (Cl2) and alkali,
sodium hydroxide (NaOH) or potassium hydroxide (KOH), by electrolysis of a salt
solution. The main technologies applied for chlor-alkali production are mercury,
diaphragm and membrane cell electrolysis, mainly using sodium chloride (NaCl) as
feed or to a lesser extent using potassium chloride (KCl) for the production of
potassium hydroxide.
This co-production of 1 tonne of chlorine, 1.128 tonne of sodium hydroxide (or 1.58
tonne of potassium hydroxide) and 28 kg of hydrogen is usually referred to as ECU
(Electrochemical unit).
Other electrochemical processes in which chlorine is produced include the
electrolysis of hydrochloric acid and the electrolysis of molten alkali-metal and
alkaline-earth-metal chlorides, in which the chlorine is a by-product, but these
account for less than 5% of the total chlorine production capacity.
In 1800, Cruickshank was the first to prepare chlorine electrochemically. The
process was, however, of little significance until the development of a suitable
generator and of synthetic graphite for anodes in 1892. These two developments
made possible the electrolytic production of chlorine, the chlor-alkali process, on
an industrial scale. About the same time, both the diaphragm cell process
(Griesheim cell, 1885) and the mercury cell process (Castner-Kellner cell, 1892)
were introduced. The membrane cell process was developed much more recently
(1970). Currently, 95% of world chlorine production is obtained by the chlor-alkali
process.
Since 1970 graphite anodes have been largely superseded by activated titanium
anodes in the diaphragm and mercury cell processes. The newer membrane cell
process uses only activated titanium anodes.
1.2
Economical Aspects
Production of chlorine was very low in the 1800s and chlorine was only used for
bleaching. In 1887, annual world production was 115 tonnes. Chlorine production
since the 1940s has risen enormously, on the back of the burgeoning demand for
plastics, notably PVC, isocyanates and polycarbonates. The production of
July 2008
Page 9 of 62
GEST 06/317
st
1 Edition
chloroaromatics (e.g. chlorobenzene for phenol synthesis), propylene oxide

(chlorohydrin process), solvents containing chlorinated hydrocarbons, and
inorganic chlorine compounds are also important factors behind the increased use
of chlorine after 1940.
After a fall at the beginning of the 1990s, production in Western Europe now
seems to be stabilised at around 10 millions tonnes per year. This placed it behind
the United States, with production a bit higher, but ahead of Japan. The global
demand for both chlorine and caustic has been forecast to increase, although
mainly in Latin America and Asia. In the recent years, the production of chlorine in
China has boomed. In 2005, Asia became the largest chlorine producer in the
world. The total world capacity was roughly split into Europe 26%, North America
23% Asia 43% and 8% for the other regions.
Euro Chlor estimates that there are 46000 employees involved in the direct
production of chlorine in the EU. When chlorine derivatives and chlorine-dependent
industry are included the number of employees is approximately two millions.
2 CHLORINE MANUFACTURE
Since 1975, the membrane cell process has been developed to a high degree of
sophistication. It has ecological advantages over the two older processes and has
become an economically advantageous process in recent years. Despite these
advantages, the change of technology to membrane cells has been slow in
Western Europe because most existing chlorine plants were installed in the 1970s
with a plant life of 40-60 years and there has been no need for new production
capacity.
The reference document on best available techniques in the chlor-alkali industry
reflects an information exchange carried out according to Article 16(2) of Council
Directive 96/61/EC. (See http://eippcb.jrc.es/pages/FActivities.htm).
Best available techniques for the production of chlor-alkali are considered to be
membrane or non asbestos diaphragm technologies.
During the remaining life of mercury and asbestos diaphragm cell plants, all
possible measures should be taken to protect the environment as a whole.
2.1
Production of Chlorine
The chlor-alkali industry produces chlorine and caustic solution (sodium or

potassium hydroxide see section 1.1) simultaneously by means of electrochemical
decomposition by direct current of a solution of salt in water. Along with the
chlorine and the caustic solution, hydrogen is produced. An industrial chlor-alkali
production unit comprises a series of operations, structured as shown in Figure 1
here below.
There are three basic processes for the electrolytic production of chlorine, the
nature of the cathode reaction depending on the specific process. These three
processes are the diaphragm cell process, the mercury cell process, and the
membrane cell process. Each process represents a different method of keeping
the chlorine produced at the anode separate from the caustic soda and hydrogen
produced, directly or indirectly, at the cathode.
July 2008
Page 10 of 62
GEST 06/317
st
1 Edition
Figure 1: Flow Diagram of the Three Main Chlor-Alkali Processes

The basic principle in the electrolysis of a sodium chloride solution is the following:
NaCl
Na Cl
At the anode, chloride ions are oxidised and chlorine (Cl2) is formed.
2 Cl (aq) Cl 2 ( g ) 2 e
At the cathode:
In the mercury process a sodium/mercury amalgam is formed and
transported to another equipment, the denuder, where hydrogen (H2)
and hydroxide ions (OH-) are formed by the reaction of the sodium of
the amalgam with water.
In membrane and diaphragm cells, water decomposes in a separate
compartment to form hydrogen (H2) and hydroxide ions (OH-).
The global cathode reaction is:

2 Na (aq ) 2 H 2 O 2e H 2 ( g ) 2 Na (aq ) 2 OH (aq )
The overall reaction is:
2 Na(aq) 2 Cl(aq) 2 H 2 O Cl 2 2 Na(aq) 2 OH (aq) H 2 ( g )
2.1.1 Mercury Technology

As shown in Figure 2 below, the mercury cell process involves two "cells".
July 2008
Page 11 of 62
GEST 06/317
st
1 Edition
Figure 2: Electrolyser and Decomposer of the Mercury Technology

In the primary electrolyser (brine cell) purified and saturated brine flows through an
elongated trough that is slightly inclined from the horizontal. In the bottom of this
trough a shallow film of mercury (Hg) flows along the brine cell co-currently with
the brine. Closely spaced above the cathode, an anode assembly is suspended.
Electric current flowing through the cell decomposes the brine passing through the
narrow space between the electrodes, liberating chlorine gas (Cl2) at the anode
and metallic sodium (Na) at the cathode. The chlorine gas is accumulated above
the anode assembly and discharged to the purification process.
As it is liberated at the surface of the mercury cathode, the sodium immediately
forms an amalgam. The liquid amalgam flows from the electrolytic cell to a
separate reactor, called decomposer or denuder, where it reacts with water in the
presence of a graphite catalyst to form sodium hydroxide and hydrogen gas. The
sodium-free mercury is fed back into the electrolyser and reused. The brine anolyte
leaving the cell is saturated with chlorine and must be dechlorinated before
resaturation with salt.
The sodium hydroxide is produced from the denuder at a concentration of about
50%; decomposer may be regarded as a short-circuited electrical cell in which the
graphite catalyst is the cathode and sodium amalgam the anode.
The steel base of the electrolyser is made as smooth as possible to ensure
mercury flow in an unbroken film. In the event of a break in the mercury surface,
caustic soda will be formed on the bare (steel) cathode, with simultaneous release
of hydrogen, which will mix with the chlorine. Because hydrogen and chlorine can
form a highly explosive mixture, great care is necessary to prevent hydrogen
formation in the cell.
The mercury process has the advantage over diaphragm and membrane cells that
it produces a chlorine gas with nearly no oxygen, and a 50% caustic soda solution
(usual commercial concentration). However, mercury cells operate at a higher
voltage than diaphragm and membrane cells and, therefore, use more electrical
energy (caustic soda concentration excluded). The process also requires a pure
brine solution with little or no metal contaminants to avoid the risk of explosion
through hydrogen generation in the cell. The amalgam process inherently gives
rise to some environmental releases of mercury.
July 2008
Page 12 of 62
GEST 06/317
st
1 Edition
2.1.2 Diaphragm Technology

The diaphragm process was the first commercial process used to produce chlorine
and caustic soda from brine. In North America, diaphragm cells are still the primary
technology. The process differs from the mercury cell process in that all reactions
take place within one cell and the cell effluent contains both salt and caustic soda.
A diaphragm is employed to separate the chlorine liberated at the anode, and the
hydrogen and caustic soda produced directly at the cathode. Without the
diaphragm to isolate them, the hydrogen and chlorine would spontaneously
combine to form an explosive mixture and the caustic soda and chlorine would
react to form sodium hypochlorite.
The diaphragm was made of asbestos (chrysotile asbestos called "white
asbestos") and separates the feed brine (anolyte) from the caustic-containing
catholyte. Due to the potential exposure of employees to asbestos and emissions
in the environment, replacement of asbestos by other diaphragm materials has
been considered.
Development of non-asbestos diaphragms started in the middle of the 1980s and
performances has improved during the last years. The basis of the material used is
the same in all diaphragms developed free of asbestos, i.e. a fluorocarbon
polymer, mainly PTFE (polytetrafluoroethylene). The differences lie in the fillers
used and the way the hydrophobic PTFE fibres are treated and deposited in order
to form a permeable and hydrophilic diaphragm.
As shown in the Figure 3 purified brine enters the anode compartment and
percolates through the diaphragm into the cathode chamber. The percolation rate
is controlled by maintaining a higher liquid level in the anode compartment to
establish a positive and carefully controlled hydrostatic head. The percolation rate
is determined as a compromise between a low rate that would produce a desirably
high concentration of caustic soda in the catholyte (which provides the cell effluent)
and a high rate to limit back-migration of hydroxyl ions from catholyte to anolyte,
which decreases cathode current efficiency.
Figure 3: Electrolyser of the Diaphragm Technology

In the diaphragm cell, saturated brine (about 25% NaCl) is decomposed to
approximately 50% of its original concentration in a pass through the electrolyser.
July 2008
Page 13 of 62
GEST 06/317
st
1 Edition
When graphite anodes were used, the diaphragm became rapidly inoperable due
to plugging of the diaphragm by particles of graphite. Nowadays, all plants in the
European Union use metal anodes.
Both diaphragm and membrane cells for the production of chlorine and sodium
hydroxide are classified as either monopolar or bipolar. The designation does rot
refer to the electrochemical reactions that take place, which of course require two
poles or electrodes for all cells, but to the electrolyser construction or assembly:
Monopolar electrolyser is assembled so that the anodes and cathodes are

arranged in parallel. As a result of this configuration, all cells have the same
voltage of about three to four volts; up to 200 cells can be constructed in
one circuit.
Bipolar electrolysers have unit assemblies of the anode of one cell unit
directly connected to the cathode of the next cell unit, thus minimising
intercell voltage loss. These units are assembled in series.
Many different types of activated cathodic coating can be used in order to reduce
the energy consumption of the cell. These have to be robust because the powerful
water jet used to remove the used diaphragm from the cathode mesh can
adversely affect the cathode. This activated coating is especially interesting with
long lifetime diaphragms.
All diaphragm cells produce that contains ca. 11% caustic soda and 18% sodium
chloride. This solution is evaporated with steam to 50% NaOH by weight, at which
point all of the salt, except a residual 1.0-1.5% by weight, precipitates out. The salt
generated is very pure. This high quality sodium chloride is sometimes used as a
raw material for an amalgam or membrane process.
Chlorine contains low concentrations of oxygen formed by electrolytic
decomposition of water; due to reaction of chlorine with water hypochlorous acid is
present in cell liquor.
2.1.3 Membrane Technology

In the 1970s, the development of ion-exchange membranes enabled a new
technology to produce chlorine: the membrane electrolysis process. The first ion
exchange membranes were developed at the beginning of the 1970s in the United
States, followed by Japan where the first industrial membrane plant was installed
in 1975, due to the pressure of Japanese environmental regulations: non-chloralkali related mercury pollution in Minamata drove the authorities to prohibit all
mercury processes and Japan was the first country to install the membrane
process on a massive scale in the mid-1980s.
Today, it is a promising and fast-developing state of the art technique for the
production of chlor-alkali and it will undoubtedly replace the other two techniques in
time. This can be deduced from the fact that since 1987 practically 100% of the
new chlor-alkali plants world-wide apply the membrane process. The replacement
of existing mercury and diaphragm cell capacity with membrane cells is taking
place at a much lower rate because of the long lifetime of the existing plants and
because of the high capital costs of conversion.
In this process, the anode and cathode are separated by a water-impermeable ionconducting membrane. Brine solution flows through the anode compartment where
chloride ions are oxidised to chlorine gas. The sodium ions migrate through the
membrane to the cathode compartment which contains flowing caustic soda
solution. The demineralised water added to the catholyte circuit is hydrolysed,
July 2008
Page 14 of 62
GEST 06/317
st
1 Edition
releasing hydrogen gas and hydroxide ions. The sodium and hydroxide ions
combine to produce caustic soda which is typically brought to a concentration of
32-35% by recirculating the solution before it is discharged from the cell (see
Figure 4).
The membrane prevents the migration of chloride ions from the anode
compartment to the cathode compartment; therefore, the caustic soda solution
produced does not contain salt as in the diaphragm cell process. Depleted brine is
discharged from the anode compartment and resaturated with salt. Usually, the
caustic liquor produced has to be concentrated by evaporation (using steam) to
reach a concentration of 50%.
The cathode material used in membrane cells is either stainless steel (older cells)
or nickel. The cathodes are often coated with a catalyst that is more stable than the
substrate and that increases surface area and reduces over-voltage. Coating
materials include Ni-S, Ni-Al, and Ni-NiO mixtures, as well as mixtures of nickel
and platinum group metals. The anodes used are metallic (titanium coated with
titanium/ruthenium/ oxides).
Figure 4: Electrolyser of the Membrane Technology

Membranes used in the Chlor-alkali industry are commonly made of perfluorinated
polymers. They generally consist of two layers. One of these layers consists of
perfluorinated polymer with substituted carboxylic groups and is adjacent to the
cathodic side. The other layer consists of perfluorinated polymer with substituted
sulphonic groups and is adjacent to the anodic side. To give the membrane
mechanical strength, the membrane is generally reinforced with PTFE fibres.
Membranes must remain stable while being exposed to chlorine on one side and a
strong caustic solution on the other.
As in the diaphragm technology membrane cells are classified as either monopolar
or bipolar, the latest being the today state of the art (See section 2.1.2).
July 2008
Page 15 of 62
GEST 06/317
st
1 Edition
Membrane cells have the advantage of producing a pure caustic soda solution and
of using less electrical electricity than the other processes. In addition, the
membrane process does not use toxic materials such as mercury and asbestos.
Disadvantages of the membrane process are that the caustic soda produced may
need to be evaporated to increase concentration and, for some applications, the
chlorine gas produced needs to be processed to remove the traces of oxygen.
Moreover brine entering a membrane cell must be of a very high purity, which often
requires costly additional purification steps prior to electrolyses.
2.2
Chlorine Treatment
Whatever the used technology is, the chlorine produced in the electrolysis cells is
saturated with water and may also contain brine mist, inert gases like nitrogen,
CO2 and some oxygen and traces of chlorinated hydrocarbons. Before the chlorine
can be used, it is usually cooled, dried, purified, compressed and where
necessary, (partially) liquefied and possibly vaporised.
2.2.1 Cooling
The gas is not cooled below 10C to avoid solid chlorine hydrate formation.
Cooling is accomplished in either one or two stages. Chilled water can be used in
the second stage.
The chlorine gas can be cooled indirectly in a tubular titanium heat exchanger so
that the cooling water is not contaminated. The resultant condensate can be fed
back into the brine system or into any other suitable recovery, or dechlorinated by
stripping.
The chlorine gas can also be cooled directly in packed towers. This treatment
thoroughly washes the chlorine, but the cooling water must be free of ammonium
salts traces to avoid the formation of nitrogen trichloride. The purge can be
recycled in the brine or dechlorinated.
2.2.2 Purification
Two techniques are generally used:
Water droplets and impurities such as brine mist are mechanically removed
by special filter elements with glass wool fillings or porous quartz granules,
or in electrostatic purification (chorine gas is passed between wire
electrodes in vertical tubes collecting the charged particles). The electrodes
are maintained at a direct current potential. Particular attention must be paid
to avoid too high hydrogen concentration (risk of explosion). Particles and
droplets in the chlorine become charged and are collected on the tube walls.
The resultant liquid is fed back into the brine system, or chemically treated
before disposal.
Scrubbing with liquid chlorine reduces the content of organic impurities,

carbon dioxide and bromine. Nitrogen trichloride can also be removed from
the gaseous chlorine by this method.
2.2.3 Drying
Drying chlorine is carried out with concentrated sulphuric acid. Depending on the
final concentration of the waste acid, drying can be a two to four stage process.
Acid and chlorine flow in counter current. The final moisture content depends on
the concentration and temperature of the acid in the final stage. Chlorine is
July 2008
Page 16 of 62
GEST 06/317
st
1 Edition
considered as dry when it contains less than 20 mg of water per kg. Molecular
sieves can be used to get lower moisture content.
After drying, chlorine gas is passed through a demister or a packed bed to remove
residual sulphuric acid mist.
2.2.4 Compression
Several types of compressors can be used depending on the amount and the
quality of chlorine to be treated, and the level of required pressure.
Wet chlorine gas can be compressed by a single-stage blower or fan with a rubberlined steel casing or titanium turbo compressor.
Several techniques can be used to compress dry chlorine:
Liquid ring compressors: sulphuric acid is used; the heat of compression is

removed by cooling the circulating liquid; the advantages are simplicity of
construction, strength, reliability, ability to compress gas containing inerts,
but the efficiency is low and the volume flow per equipment is limited.
Reciprocating compressors: formerly lubricated with sulphuric acid, they are

now available as dry-ring compressors (no lubrication); for high pressures
multi-stages equipments are used; the heat of compression of each stage is
removed by chlorine heat exchangers or by liquid chlorine injection; wellpurified chlorine gas is essential for trouble-free operation.
Turbo-compressors: they operate with large amount of chlorine. Labyrinth

seals are used on the high-speed shafts; requirements for cooling and gas
purity are similar to those of reciprocating compressors.
To avoid chlorine-iron fires, it is recommended the chlorine temperature at the

outlet of any stage of the compressor should never exceed 120C, unless the
compressor is manufactured using special material suitable for higher
temperatures.
Note: if necessary, the nitrogen trichloride present in the dry gaseous chlorine can
be destroyed by passing the compressed chlorine on active carbon bed, under
strict temperature control (exothermic reaction).
2.2.5 Liquefaction
Important factors are the composition of gaseous chlorine, the desired purity of
liquid chlorine, the desired yield and the pressure level of the liquid chlorine
storage. See GEST 72/10 - Pressure Storage of Liquid Chlorine and GEST
73/17 - Low Pressure Storage of Liquid Chlorine.
Any hydrogen is concentrated in the residual gas. To keep hydrogen concentration
below the explosive limit (see paragraph 7.2.3), conversion of gas to liquid should
be limited to a level depending on the initial gas purity, or dilution dry air (or
nitrogen) should be added. Continuous analysis of the content of hydrogen in
residual chlorine gas is recommended.
If the chlorine pressure is high enough, liquefaction can be achieved with water/air
cooling and does not require a refrigeration unit.
In the other cases, refrigerant compatible with chlorine must be used; attention
must be paid to the increased solubility in chlorine of other gases, especially
carbon dioxide. The process achieved at low temperature (less than minus 40C)
is advantageous when large amounts of chlorine must be liquefied as completely
July 2008
Page 17 of 62
GEST 06/317
st
1 Edition
as possible. Be aware of the increased concentration of hydrogen in the residual

gas, and the lower allowed water concentration in the dried chlorine gas (risk of
corrosion).
A process achieved at temperatures between minus 10C and minus 20C is
specially useful when only a part of the chlorine has to be liquefied and the
remaining gas is to be reacted at the liquefaction pressure, e.g., with ethylene to
produce ethylene dichloride. The residual gas can be fed into the compressor
suction system, provided that the increased inert gas content does not interfere
with the subsequent process (chlorine quality and explosive risk).
2.3
Products Usages
The co-production of chlorine and sodium hydroxide in fixed proportions (ECU),

1.128 tonnes of caustic soda (as 100% NaOH) per tonne chlorine produced, has
always been a challenge for the chlor-alkali industry. Both products are used for
very different end uses with differing market dynamics and it is only by rare chance
that demand is balanced for the two. Depending on which demand is dominant,
either can be regarded as a by-product and the price varies accordingly.
The hydrogen produced is always considered as a by-product.
2.3.1 Chlorine
Chlorine is largely used in the synthesis of chlorinated organic compounds. Vinyl
chloride monomer (VCM) for the synthesis of PVC still remains the driver of chloralkali production in most European countries (see (http://www.eurochlor.org/uses).
For safety, practical and economical reasons, chlorine is generally produced close
to the consumers. More than 90% of the chlorine produced in EU is used on the
same or adjacent sites (local pipeline transport). A general way to transport
chlorine is to produce ethylene dichloride, a precursor of PVC. When required,
liquid chlorine can be transported by rail, road or sometimes by ship.
The chlorine consumption can be divided into several types of uses (see also
http://www.eurochlor.org/applications):
Organic uses, which account for about 80% of consumption: synthesis of

VCM, chloromethanes, phosgene, organic chlorinated solvents such as
trichloro-ethylene, tetrachloro-ethylene, oxygenated derivatives, precursors
or intermediates for the synthesis of pesticides or pharmaceutical products.
Inorganic uses, which account for about 15% of consumption (synthesis of

sodium hypochlorite, hydrochloric acid, metal chlorides, bromine).
Direct uses, which account for less than 4% of consumption (water

treatment, pulp and paper).
More detailed uses are

http://www.eurochlor.org/tree.
also
shown
on
the
Euro
Chlor
website:
2.3.2 Sodium Hydroxide

Sodium hydroxide is usually supplied as a 50% aqueous solution and can be
stored for long periods and easily transported (rail, road and ship). The main areas
of application of sodium hydroxide are:
Chemicals: synthesis of organic or inorganic compounds
Metallurgy, alumina/aluminium
July 2008
Page 18 of 62
GEST 06/317
st
1 Edition
Pulp and paper - textile
Soaps, surfactants
Water treatment.
(See also http://www.eurochlor.org/causticsodaapplications).
2.3.3 Hydrogen
As sodium hydroxide, hydrogen is a co-product of the electrolysis of brine (28 kg
for 1 tonne of chlorine). Hydrogen is generally used as a combustible on integrated
sites or transported via high pressure pipelines; it can be also used for certain
chemical applications, in particular due to its high purity: synthesis of ammonia,
methanol, hydrochloric acid, hydrogen peroxide, sulphur removal from petroleum,
etc.
3 PROPERTIES AND HAZARDS OF CHLORINE

3.1
Physical Properties
Density gaseous (1.013 bar, 0C)
3.21
Relative to air (1.013 bar, 0C)
2.49
Boiling point (1.013 bar)

Heat of vaporisation (at 34C)
-34.05
-101
1 litre of liquid chlorine liberates

about (25C, 1.013 bar)
Solubility in water (25C, 1.013 bar)
Liquid chlorine thermal expansion
coeff. Vt2 = Vt1 1 + (t2-t1)
463
6
kg/m
C
kJ/kg
Litre of chlorine gas
kg/m
= 2.10-3 C-1
For a more detailed list of properties see GEST 91/168 Physical,

Thermodynamic and Selected Chemical Properties of Chlorine.
3.2
Reactivity
Chlorine is not flammable but strongly oxidising; it is one of the most reactive
elements and can combine with many substances elements at ambient
temperature. With many organic and inorganic compounds the reaction can be
violent and possibly even explosive.
3.3
Hazards
3.3.1 Chlorine and Explosion Risk

Chlorine is an oxidising agent and can form explosive gaseous mixtures with
organic and inorganic compounds such as hydrogen, ammonia, methane and
methyl chloride. In general, the flammability and detonation limits with these
compounds are comparable with those with oxygen. The auto ignition temperature
July 2008
Page 19 of 62
GEST 06/317
st
1 Edition
of organic compounds in chlorine is usually around 200C lower than the

corresponding value in air, meaning that thermal ignition is easier.
Chlorine reacts with almost every organic compound containing hydrogen and/or
nitrogen. The simple chlorination reaction:
RH Cl 2 RCl HCl
takes place very easily and in some cases at an explosive rate even at ambient
temperature. When both the combustible and the chlorine are in the liquid phase,
the explosion can be much more serious than in the case of a gaseous system.
Organic compounds which can react explosively with gaseous or liquid chlorine
are, for example, alcohols, esters, oils, solvents, silicone oils and silicone rubber.
This applies especially to lubricating oils, greases and cleaning solvents.
Components which require to be lubricated shall be treated with chlorine
compatible chloro-fluorinated grease.
Ammonia and some other nitrogen compounds may form nitrogen trichloride, a
very unstable explosive compound detonating very easily, both in the gaseous and
in the liquid phase.
Low levels of nitrogen trichloride are normally present in liquid chlorine and one
should avoid a situation of accumulation due to vaporisation of chlorine with
concentration of the higher boiling temperature of nitrogen trichloride in the liquid
phase residue. (See also section 7.2.1).
This is of concern in all situations where chlorine gas is withdrawn from liquid
chlorine, for example:
in a storage system, if it is being emptied by venting off gas (not

recommended by Euro Chlor),
with transport containers, if the chlorine is withdrawn from the gaseous

phase (not recommended by Euro Chlor), and
in vaporisers.
Suitable precautions must be taken to ensure that the NCl 3 content is maintained
at a safe level (cf. GEST 76/55 - Maximum Levels of Nitrogen Trichloride in
Liquid Chlorine).
3.3.2 Construction Materials

The choice of materials depends on the state of the chlorine (wet or dry, gas or
liquid, level of pressure and temperature) and must be adapted to the intended
use.
For dry liquid or gaseous chlorine, carbon steel can normally be used. But the
temperature has to be limited to 120C to avoid any risk of iron-chlorine fire.
Titanium must never be used with dry or insufficiently wet chlorine. Selected plastic
materials may be used on low pressure gaseous systems only.
Rubber gaskets must never be used with dry gas or liquid chlorine. (See section
9.2.3).
Because of safety implication of materials selection it is important to consult a
chlorine producer and to follow GEST 79/82 - Materials of Construction for Use
in Contact with Chlorine.
July 2008
Page 20 of 62
GEST 06/317
st
1 Edition
4 PROPERTIES AND HAZARDS OF HYDROGEN

Due to the fact that hydrogen, generated as a co-product, is a flammable gas and
may form explosive mixtures with ambient air (or chlorine), the two ATEX
Directives (Directive 1999/92/EC of 16 December 1999 and 94/9/EC of 23 March
1994) are applicable to electrolysis units. ATEX is the French abbreviation for
ATmosphres EXplosives.
The Position Paper X - Explosion Protection Considerations Regarding the
Cell room of a Chlor - Alkali Electrolysis Unit constitutes the ATEX evaluation
for the cell room and in the low pressure hydrogen circuit downstream of the cell
rooms. This document describes under which conditions electrolysis rooms may
usually be classified as non-dangerous zones according to Directive 1999/92/EC.
From the risk analysis, it can be stated that,
there is no risk of formation of an explosive atmosphere within the cell room

in normal operating conditions,
a hydrogen leak is highly unlikely - or would be detected very quickly - in all

foreseeable conditions (including process deviations),
even in the case of a hydrogen leak, the consequences would be very

limited, with a risk of flame but no explosion, and there would be very little or
no exposure to employees.
Taking all these items into consideration, it can be concluded that:
Cell rooms may be considered as non hazardous, with respect to the risk of
exposing employees to explosive atmospheres as defined by Directive
1999/92/EC).
Based on the preceding risk analysis and on norm EN 60079-10, cell rooms
can be classified as non dangerous zones according to Directive
1999/92/EC.
5 PROCESS SAFETY MANAGEMENT

5.1
Site Security
Guidance to assist facilities producing chlorine in implementing site security

measures to reduce the facilitys vulnerability to external threats and internal acts
of sabotage is described in GEST 05/316 Guideline for Site Security of
Chlorine Production Facilities.
5.2
Process Safety Information
Documented information should be developed and maintained. This information

will provide the foundation for identifying and understanding the hazards involved
in the process.
The basic references are the National/International Codes and Regulations, the
Euro Chlor recommendations, the Company Procedures. The information should
include two parts.
July 2008
Page 21 of 62
GEST 06/317
st
1 Edition
5.2.1 Process Design Information

This information includes:
Process chemistry
Flow diagram
Maximum intended inventory
Acceptable upper and lower limits for temperature, pressure, flow-rate,

concentration.
5.2.2 Mechanical Design Information

This information includes:
The materials of construction
The Piping and Instrument diagrams (P&ID)
The electrical areas classification
The design and basis of the pressure relief systems
The design of the ventilation system
The equipment and piping specifications
The description of shutdown and interlock systems
The design codes employed.
5.3
Process Hazards Analysis
A process hazards analysis must be performed for any facility. The purpose of this
analysis is to minimise the probability and consequences of any accident.
The analysis should take account of consequences of deviation from the operating
limits, of the steps required to correct or avoid deviation, and justify safety systems
and their functions.
5.4
Management of Change
The company should establish written procedures to review all changes in process
technology and changes to the facility.
Such procedures should address:
Technical basis for the proposed change
Safety, health and environmental considerations
Risk analysis of the modified (part of) installation
Modification to operating procedures
Proof-testing of critical instrumentation
Documentation of physical changes
Appropriate management approval
Communication and training of personnel involved
Documentation of training (and periodic retraining).
July 2008
Page 22 of 62
GEST 06/317
st
1 Edition
5.5
Operating Procedures
Written operating procedures should specify the following information:
Clear instructions for the safe operation, that are consistent with the process
safety information
Operating conditions and steps for the following phases of operation:

Initial start-up
Normal operation
Temporary operations as the need arises
Emergency operations, including emergency shutdown
Normal shutdown
Normal start-up.
The operating limits and the steps to maintain the system within the limits or
to bring it to a safe position
Occupational safety and health considerations including the following:

The properties of and hazards presented by the materials used in the
process
The special precautions required to prevent exposure, including
engineering controls and personal protective equipment
The control measures to be taken if physical contact or airborne
exposure occurs
Any special or unique hazard.
For new and modified facilities, the operating procedures should be in place before
start-up.
Operating procedures should be reviewed periodically, with typical review intervals
range between 3 to 5 years.
The operating procedures should be readily accessible to operating personnel. It is
also essential to check that the procedures are well known.
5.6
Safe Work Practices
For the safe conduct of operation, maintenance and modification activities,

especially including the opening of process equipment or piping, lock out and tag
out of electrical and mechanical energy sources, safe work practices should
provide procedures that involve ignition sources, entry into confined spaces and
the use of cranes and similar equipment.
A work authorisation system must be an element of the safe work practices,
including detailed written communication between the different team involved. Hot
work permits, when necessary, must be systematically used.
5.7
Mechanical Integrity
Assuring the quality and mechanical integrity of critical equipment is addressed in

the technical guidance part of these guidelines (see section 9).
July 2008
Page 23 of 62
GEST 06/317
st
1 Edition
Procedures could be briefly summarised:
Written quality control procedures for critical equipment during all stages of
fabrication should be implemented
Appropriate checks and inspection procedures should be implemented

before start-up
Maintenance systems that include appropriate inspection and testing should

be implemented to ensure ongoing mechanical integrity.
5.8
Pre-Start-Up Safety Review
The pre-start-up safety review should confirm prior to the introduction of chlorine
that:
Construction or major maintenance are in accordance with specifications
Safety, operating, maintenance and emergency procedures are in place and

adequate
Process hazard analysis recommendations have been addressed and

actions required for the start-up have been completed
Operating procedures are in place and training of operators has been

successfully completed
A physical inspection of the facilities has taken place and appropriate followup of findings addressed
Instrumentation has been functionally checked
Chlorine containing lines and equipment have been properly cleaned and
dried for dry chlorine service
Personal and collective protective equipment are available.
5.9
Emergency Response and Control
The measures to be taken in the event of chlorine accidents should be carefully

prepared. Their adequateness should be regularly checked and updated.
They should include:
An alarm plan for events without consequences outside of the factory limits
An alert plan for accidents with potential consequences outside of the

factory limits. This plan has to be developed in co-operation with the local
authorities, fire brigade, etc
All personnel involved should be regularly trained in emergency response.
5.10 Investigation of Process Related Incidents

The company should investigate every incident which either resulted in or could
reasonably have resulted in an uncontrolled chlorine release.
Investigations should be initiated as promptly as possible. An investigation team
should be established and a report should be prepared, including:
description of the incident and cause(s)
factors contributing to the incident
July 2008
Page 24 of 62
GEST 06/317
st
1 Edition
actions foreseen or taken to avoid repetition of the incident
description of any changes in process hazard management recommended

to prevent recurrence.
The report should be reviewed by the management responsible for safety

standards in the plant.
A Euro Chlor accident report should be systematically completed and sent for
discussion by the GEST Group, to allow improving the recommendations.
5.11 Audits of Process Hazards Management Systems

Audits should be completed periodically by a qualified audit team. A frequency of
every three years is recommended. The team should include persons
knowledgeable of the process used.
On a voluntary basis, companies may request a Euro Chlor selected audit team
consisting of member company and/or Euro Chlor staff representatives. An audit
report should be prepared.
The company should establish a system to determine and document the
appropriate response to each of the findings of the audit report and ensure actions
are completed on a timely and efficient basis.
To ensure high standards of safety are achieved, it is recommended that chlorine
users should seek the help of the chlorine producers to check their premises. See
GEST 92/175 - A Scheme for Safety Visits to Chlorine Customers' Plants.
6 TRAINING
In all cases, it is essential that the training is carefully validated to ensure a full
understanding of all aspects of the job, including items which would only be
expected to occur infrequently.
Any training should be documented and include means to verify that the employee
understood the training.
6.1
Personnel of the Facility
The health condition of employees with a potential for occupational exposure to

chlorine should be periodically checked; they should be trained to act quickly in
case of emergency and should be aware at all times of the wind direction and
escape routes.
In mercury plants, a special dedicated monitoring programme has to be setup.
6.1.1 Topics covered

The company should provide training for personnel responsible for operating and
maintaining the facility. The training should address the following:
Proper use and care of personal safety equipment
Proper use of emergency equipment
Operating procedures
Changes in process technology or facilities
July 2008
Page 25 of 62
GEST 06/317
st
1 Edition
Training in emergency operating and emergency shutdown procedures,

taking into account the local requirements of the authorities.
6.1.2 Initial Training

The company should ensure that any employee possesses the required
knowledge, skills and abilities before operating the process.
6.1.3 Refresher Training

Periodic training should occur at fixed intervals, not bigger than three years and
should be documented.
6.1.4 Plant Modifications

Whenever a change is made, operating personnel should be informed and
specifically trained.
6.2
Training of Road Tanker Drivers
A specific training is necessary for the road tanker drivers, as their role would be
crucial in case of an emergency (a rapid intervention can drastically reduce the
consequences of an accident).
Beside their driving skill, they must be informed of the properties of chlorine and
must be trained on the way to use the first intervention equipment that must be
available in the truck.
A check list is detailed in below, and more information is available in the GEST
73/20 - Code of Good Practice for Safe Transport of Bulk Liquid Chlorine by
Road Tanker Vehicles.
7 SAFETY GUIDANCE
7.1
Chlorine Detection and Monitoring
7.1.1 Purpose of Chlorine Monitors

A chlorine monitoring system may be installed to warn the operators about a
possible chlorine leakage in a production installation, a storage area or a
loading/off-loading area, enabling them to rapidly take corrective action.
A monitoring system may also be used in a storage area or a loading/off-loading
station for the automatic closing of valves to isolate chlorine-containing equipment.
However, this integration of chlorine that monitors the protective systems of the
plant should be carefully considered to ensure that automatic closure of valves,
independently of the operator's judgement, will not lead to dangerous situations.
7.1.2 Chlorine Monitoring Systems

The monitoring system may consist of a single stand-alone sensor unit installed at
a critical point in a plant, or a number of sensor units surrounding a production
plant, a storage area etc.
Another option is a multipoint sampling system connected to a central sensor unit
measuring an average value at all sampling points, or measuring in sequence the
value at the individual sampling points (scanning system).
July 2008
Page 26 of 62
GEST 06/317
st
1 Edition
The sensor is in principle an electrochemical cell with a transmitter. Threshold is

typically close to 1 ppm by volume, or higher depending of the conditions. The
sensor should preferably be self-calibrating and suitable for continuous operation.
7.1.3 Arrangement
It is not possible to give specific recommendations for the arrangement of a
monitoring system. This must be considered for each individual case, since the
layout of the plant and its buildings, and the location of neighbouring installations,
will be important factors in deciding the performance required from the monitoring
system.
As general guidelines, it is recommended that:
Automatic actuation of valves should take place only if more than one
chlorine detector (sensor) gives an alarm signal
The alarm should not be set at an unnecessary low value to avoid shutdown
of the storage unit or loading/off-loading due to traces of chorine.
See also GEST 94/213 - Guidelines for the Selection and the Use of Fixed
Chlorine Detection Systems in Chlorine Plants.
7.2
Preventing Major Hazards
7.2.1 Nitrogen Trichloride

Nitrogen trichloride is a potentially explosive material which may be formed in small
quantities during chlorine production. The principal cause is reaction between
chlorine and the nitrogen compounds which are naturally present in brine used for
electrolysis. Nitrogen trichloride has a boiling point higher than that of chlorine. It
will therefore tend to condense preferentially during chlorine liquefaction. When
chlorine is subsequently vaporised, it will remain in the liquid phase and, if no
precautions are taken, could reach concentrations at which explosion would cause
serious damage to equipment.
The most important means of controlling this risk is removal of nitrogen trichloride
at source by the chlorine producer. GEST 76/55 Maximum Levels of Nitrogen
Trichloride in Liquid Chlorine states that liquid chlorine supplied to users should
contain less than 20 mg/kg for capacity less than 1000 kg and 10 mg/kg for bigger
ones (2 mg/kg is recommended for capacities larger than 300 t). A variety of
techniques are used to achieve this.
Chlorine users should be aware of any part of their process in which chlorine
evaporates and which therefore has the potential for nitrogen trichloride to
accumulate. This may include:
Mobile containers, particularly if chlorine is withdrawn as a gas rather than

as a liquid (not recommended by Euro chlor)
Chlorine storage tanks, if these are operated at low pressure with continual
loss of contents by evaporation, or if they are emptied by being vented to
dryness
Chlorine vaporisers, particularly the kettle type, holding a significant volume

of liquid chlorine in which nitrogen trichloride can accumulate.
GEST 76/55 - Maximum Levels of Nitrogen Trichloride in Liquid Chlorine

gives guidance on the levels to which nitrogen trichloride can be allowed to
July 2008
Page 27 of 62
GEST 06/317
st
1 Edition
accumulate safely. Analytical methods to monitor this are given in Anal 2 Determination of Nitrogen Trichloride in Liquid Chlorine.
However, any chlorine user, particularly if they are modifying their process or
equipment, is strongly advised to seek the expert help of a chlorine producer.
7.2.2 Moisture
Chlorine is dried to less than 20 mg water content per kg of chlorine during
manufacturing. Any subsequent equipment downstream in the producer plant, or at
the user, will normally use materials of construction appropriate for dry chlorine. To
prevent corrosion, it is vital that ingress of moisture is prevented. This can be
achieved by ensuring that:
Before coming into contact with chlorine, all new equipment is thoroughly
dried by heating, possibly under vacuum, by purging with dry gas, etc.
Equipment which has become wet due to washing in preparation for

maintenance, or due to pressure testing, must be thoroughly dried
Any inert gas used to transfer chlorine, to purge equipment before

maintenance of for drying after maintenance, has a dew point lower than
minus 40C
Any gasket which becomes wet during maintenance is replaced
Bellows in valves have to be dried by heating, possibly under vacuum
Precautions are taken to avoid backflow from any installation using chlorine
into a unit or equipment where water or moisture is present.
GEST 80/84 Code of Good Practice for the Commissioning of Installations

for Dry Chlorine Gas and Liquid should be consulted for further details.
Particular attention must be paid to flexible connections used for loading and offloading mobile containers. To avoid corrosion due to atmospheric moisture, these
should be purged free of chlorine after use and stored with the ends sealed. A new
gasket should be used each time the flexible is connected to the mobile container.
GEST 78/73 Design Principles and Operational Procedures for Loading/OffLoading Liquid Chlorine Road and Rail Tankers and ISO-Containers should
be consulted for further details.
7.2.3 Hydrogen
Small quantities of hydrogen are present in the chlorine gas produced. Normally,
the concentration will be below 1% from the cells until the chlorine compression.
The concentration will increase either as a result of chlorine liquefaction, or could
happen due to condensation in a pipeline operating under high pressure in cold
weather. If the hydrogen concentration exceeds certain limits in chlorine or air (see
table below), the gas mixture is potentially explosive. A similar problem can arise in
a chlorine absorption system where explosive hydrogen in air mixtures can arise
when the diluted chlorine is absorbed in sodium hydroxide.
The current information relating to the flammable limits of hydrogen in chlorine is
presented in the table below, with the effect of the initial temperature.
July 2008
Page 28 of 62
GEST 06/317
st
1 Edition
Temp (C)
H2-Air (vol % H2)
H2-Oxygen (vol % H2)
H2-Chlorine (vol % H2)
-60
4.0 - 69
4.0 - 96
5.0 - 90
-40
4.0 - 71
4.0 - 96
4.0 - 90.5
-20
4.0 - 72
4.0 - 96
4.0 - 91.5
4.0 - 73
4.0 - 96
3.5 - 92
20 - 25
4.0 - 75
4.0 - 96
3 - 92.5
50
3.7 - 76
4.0 - 96
3 - 93
100
3.0 - 80
4.0 - 97
3 - 93
The influence of the initial pressure is relatively small between 0.25 and 11.5 bara.
It is recommended that experimental measurements are undertaken if operating at
higher pressure.
The practical operating conditions in the production lines and equipments will be
chosen to work with a suitable safety margin with respect to these limits, taking into
account the fact that pressure increase widens the flammability zone.
In-line analysers will be used to check that one always remains below the low limit
of the table.
The possible dilution effect of water vapour will not be taken into consideration for
wet chlorine.
In very special cases, and after thorough calculations and risk assessment, it can
be acceptable to exceed the low limit by using pressure resistant equipment
(possible inflammation tolerated but pressure increase contained).
Depending on the process used, chlorine producers must monitor their brine to
ensure adequate sodium chloride content and acceptable levels of impurities such
as calcium, magnesium and heavy metals which can promote hydrogen formation.
Hydrogen in chlorine levels should be monitored continuously in the gas leaving
the cell room and after liquefaction. If a dangerous limit is approached, the gas
stream should be diluted by admitting dry air or nitrogen or the plant operating rate
reduced and the gas stream sent to absorption system until the cause of the
excess hydrogen has been identified and corrected. In serious cases, it may be
necessary to shut down the plant.
7.3
Protective Equipment
Information on most types of personal protective equipment used in the

manufacturing and handling of chlorine is given in GEST 92/171 Personnel
Protective Equipment for Use with Chlorine.
It is recommended that all persons, whether workers or visitors, entering a chlorine
plant, should be informed and provided with an escape mask.
Depending on the work to be carried out or on the conditions which exist at the
time, either breathing apparatus with filter or self-contained breathing apparatus
should be used (not escape mask).
July 2008
Page 29 of 62
GEST 06/317
st
1 Edition
With this type of equipment, protection is obtained only if the four following
conditions are met:
Filter or cartridge suitable for chlorine
Oxygen content at least 19% volume (make sure oxygen content is

sufficient)
Chlorine content under 0.5% volume
No other toxic substances (including CO) above the occupational exposure

level.
For all other situations or for extended use, self-contained breathing apparatus
should be worn.
In case of higher exposition risk, full protective clothing will protect the skin; the
decision to wear them will be taken by the intervention team leader, based on his
assessment of the situation.
Important remark: the filter mask must never be used inside vessels, reservoirs or
confined space without very careful testing of the oxygen content and the level of
contamination of the atmosphere, which should be very low (much lower than 0.5
% volume).
8 HEALTH HAZARDS, TRAINING AND FIRST AID

8.1
Health Hazards and Toxicity of Chlorine
The injurious effects of chlorine gas are due to its strongly oxidative properties. It
mainly causes damage to the mucous membranes of the larger airways, because
of the action of hydrochloric acid and hydrochlorous acid which are formed, and
chlorine itself.
Symptoms appear immediately after the start of the exposure. After cessation of
exposure the process stops and thus shortly after exposure, the level of severity of
the effects is evident.
The general effects of various levels of chlorine inhalation (depending on the
physical condition of the person involved and also on the duration of the exposure)
are as follows:
Exposure level
Effects
Less than 1 ppm
Threshold of odour perception for the average person
1 30 ppm
Symptoms in increasing order of severity: immediate

irritation of eyes, nose and upper airways, intense cough,
shortness of breath, chest pain, choking and vomiting
Above 30 ppm
Development of chemical tracheo-bronchitis, severe

bronchospasm, bronchial oedema or oedema of the glottis.
Prolonged exposure time at high concentration will cause
unconsciousness and finally death.
Determination of Chlorine in Workplace Air is described in the document Anal 8 Determination of Chlorine in Workplace Air.
July 2008
Page 30 of 62
GEST 06/317
st
1 Edition
Individuals suffering from asthma or chronic bronchitis and also heavy smokers are
particularly susceptible.
A study of chlorine toxicity carried out by the Dutch TNO-CIVO Toxicology and
Nutrition Institute at the request of Euro Chlor, has been published in Journal of
Hazardous Materials, 19 (1988) 195-208.
Toxicity of chlorine under emergency conditions has been published in HEALTH
7 - Code of Practice: Control of Workers Exposure to Chlorine in the ChlorAlkali Industry.
8.2
Monitoring Chlorine Exposure to Workers
A code of practice (HEALTH 7 - Code of Practice: Control of Workers

Exposure to Chlorine in the Chlor-Alkali Industry) defines:
a monitoring strategy
advice about monitoring equipment
insight into the costs of the proposed monitoring strategy.
The purpose of the document HEALTH 5 - Audit Questionnaire Chlorine is to

produce a self-assessment guideline to evaluate the health risk management
performance of a Chlor-Alkali plant with regard to chlorine.
8.3
Treatment of Chlorine Gassing
Warning: rescuers should always take care of avoiding intoxicating themselves.

ACTIONS TO BE TAKEN BY FIRST AIDERS
Use individual protective equipment to rescue casualties
Remove casualty to fresh air, in quiet area, in a half seated position
Remove contaminated clothing
If breathing has ceased, let the patient sit in a half seated position or lie
comfortably, start artificial respiration, avoiding contamination
Administer oxygen as soon as possible. Let the patient sit in a half seated
position or lie comfortably
In case of skin and/or eye contamination irrigate with water for at least 15
minutes
Avoid unnecessary exercise
Keep the casualty warm
Transport the casualty to the factory medical centre
All cases of chlorine gassing should be referred to the factory medical

department.
Euro Chlor has developed a document on this subject: HEALTH 7 - Code of

Practice: Control of Workers Exposure to Chlorine in the Chlor-Alkali
Industry.
July 2008
Page 31 of 62
GEST 06/317
st
1 Edition
8.4
Exposition of workers to mercury
In electrolysis units based on the mercury technology, workers are potentially

exposed to mercury and the toxicity of this product imposes to proactively take
protective measures.
HEALTH 2 - Code of Practice: Control of Worker Exposure to Mercury in the
Chlor-Alkali Industry provides information on the health hazards of mercury and
advices for the personal hygiene of the workers to reduce the risk of exposure to
mercury The document gives also recommendations for the bio-monitoring of the
workers. The document Analytical 6 - Determination of Mercury in Gasses
indicates the recommended methods for sampling and analysing mercury in the
cell room air.
The guideline Analytical 11 - Determination of mercury and creatinine in urine
recommends the methods for analysis of workers urine to determine their level of
exposition to mercury.
The purpose of HEALTH 6 - Audit Questionnaire Mercury is to produce a selfassessment guideline to evaluate the health risk management performance of a
Chlor-Alkali plant with regard to mercury. This paper can be also used for external
audits.
In case of plant dismantling, the risk of exposure can be higher and the specific
aspects are treated in a dedicated chapter of the guideline Env Prot 3 Decommissioning of Mercury Chlor Alkali Plants.
8.5
Electromagnetic Fields (EMF)
Referring to the Directive 2004/40/EC published on this subject, the Euro Chlor
document HEALTH 3 - Electromagnetic Fields in the Chlorine Electrolyses:
Effects on Health and Recommended Limits describes the electromagnetic
fields present in a chlorine cell-room and examines the medical evidence for direct
and indirect effects to human health. The document also provides guidance on
measurement and practical solutions to consider in electrolysis units.
The two main issues of concern are:
The direct effect of static magnetic fields greater than 0.5 mT on

pacemakers and other medical implants.
This effect has been known for many years and requires control over the access of
personnel fitted with pacemakers and others medical implants to plant areas where
the static field exceeds 0.5 mT. This field, which can extend beyond the boundary
of the cell-room building, is usually marked with signs and hazard warnings.
The estimation of multi-frequencies time-varying magnetic fields effect in

electrolysis units that needs to take into account the phase coherence, as a
simple summation formula on the different frequencies will lead to
overestimation of the exposure.
Euro Chlor has proposed to the Cenelec (the European Committee for
Electrotechnical Standardisation that has been charged by the European
Commission to prepare the measurement standards for applying the Directive) an
measurement standard to apply in our particular case.
It must be pointed out that the application of the directive has been postponed for
till 2012 for further analysis of its socio-economical implications and to taken into
account a scientific update of the proposed limits.
July 2008
Page 32 of 62
GEST 06/317
st
1 Edition
9 TECHNICAL GUIDANCE FOR THE FACILITY

9.1
Materials
Materials of constructions must be chosen to suit the conditions under which

chlorine is being handled:
Wet or dry
Gaseous or liquid
Temperature
Pressure.
Plastic materials must also be chosen taking account of their resistance to ageing
and to external factors. A basic principle in chlorine safety is to learn from previous
experience. Caution is therefore necessary before any new materials are
introduced. This may require extensive testing before any equipment is built.
General advice on the suitability of various materials for use with dry and wet
chlorine is given in Euro Chlor publication GEST 79/82 - Materials of
Construction for Use in Contact with Chlorine.
The principal materials are summarised below.
9.1.1 Materials for Liquid Chlorine and Dry Chlorine Gas

For dry chlorine gas, carbon steel is the usual material. For liquid chlorine and cold
dry chlorine gas, fine grain carbon steel, showing low temperature impact strength
should be used, to take account of low temperature (till minus 40C) arising when
depressurising the system.
In view of the reactivity of chlorine with carbon steel at elevated temperatures, a
chlorine temperature of 120C should not be exceeded. If higher temperatures are
unavoidable for process reasons, special materials (e.g. nickel, nickel alloys or
stainless steel) must always be used.
Under no circumstances may zinc, tin, aluminium, titanium and alloys based on
these be used for dry chlorine gas and liquid chlorine, as these metals react
spontaneously with dry chlorine.
9.1.2 Materials for Wet Chlorine Gas

Wet chlorine gas reacts with virtually all metals, with the exception of titanium and
tantalum that are successfully used. Attention has to be paid to the use of titanium
with wet chlorine gas that requires the respect of a minimum water content (see
GEST 79/82 Materials of Construction for Use in Contact with Chlorine).
Other suitable materials are carbon steel lined with rubber, enamel or chlorineresistant plastics, e.g. GRP (Glass Reinforced Polyester), PVC-GRP or PVDF.
9.2
Equipments
All equipment should be robust and protected against mechanical damage and
external corrosion. All precautions must be taken to avoid the entry of moisture into
the chlorine system, especially in the loading/off-loading connections.
July 2008
Page 33 of 62
GEST 06/317
st
1 Edition
9.2.1 Piping
Chlorine can be transported safely by pipeline either in the gaseous or liquid
phase. The design of the pipeline must take account of the problems associated
with the chosen phase. Piping must be carefully specified to ensure it meets the
specific requirements of each situation. All precautions should be taken to prevent
the accidental formation of liquid in a pipeline designed for chlorine gas.
The material used should be suitable for operations at minus 40C. Euro Chlor has
therefore drawn up two recommendations, which specify the criteria to be used in
the design, construction and operation of piping systems for a nominal pressure of
25/40 bars, or equivalent ASA classification.. One deals with inside plants piping
systems: GEST 79/81 Liquid and Dry Gaseous Chlorine Piping Systems
Located Inside Producer's or Consumer's Plants. Detailed information
concerning the transport of chlorine by pipeline (often longer than 1000 m) passing
outside the limits of the factory producing or using chlorine, is given in GEST 73/25
- Transport of Chlorine by Pipeline outside Site Boundaries.
The piping system must be designed to meet the most severe condition of internal
or external pressure and temperature variations to which it can be subjected during
service. The most severe condition is that which results in the greatest component
thickness and the highest component rating.
The design pressure for liquid chlorine service should be based on the vapour
pressure of chlorine at the chosen maximum design temperature and allowing for
any pressure surge conditions which may arise as a result of abnormal
circumstances, e.g. pump start-up.
It is also recommended that a 20% safety margin be allowed between the
maximum operating pressure of the system and its design pressure, i.e.:
PN 25 for 20 barg
PN 40 for 32 barg
PN 64 for 52 barg.
PN 25 should be the minimum design pressure.

Small branches on vessels and in piping are potential weak points in the system.
For liquid chlorine a minimum wall thickness should be selected to ensure
resistance to mechanical impact. Thus, for example, for the frequently used pipe of
2 inches or 50 mm diameter, the wall thickness should be 4 mm instead of 1 or
2 mm as indicated by calculation.
The corrosion resistance of steel in contact with liquid chlorine is due to a thin layer
of ferric chloride formed on the internal surface. In order to avoid destruction of this
protective layer by erosion, the linear velocity of chlorine at the wall should be
limited. The normal practice for pipework is to limit liquid chlorine velocities to
2m/s; for gas-piping the practical experience shows that a maximum velocity of 20
m/s is acceptable when liquid entrainment is excluded.
9.2.2 Valves
To ensure safe handling of liquid chlorine it is essential that suitable valves are
used.
Euro Chlor has published specifications or recommendations which define the
requirements for each type of valve.
July 2008
Page 34 of 62
GEST 06/317
st
1 Edition
Criteria for design, construction, testing and inspection on dispatch or receipt of

valves for use with liquid chlorine are explained in following Euro Chlor documents:
For flanged globe valves see GEST 90/150 Specification for Flanged
Steel Globe Valves -Packed Gland- for Use on Liquid Chlorine.
For quarter turn, self lubricating straight through ball valves, see GEST
93/180 Specification for Flanged Steel Ball Valves -Packed Gland- for
Use on Liquid Chlorine.
For control valves (either with double packed gland or with bellows and
packed gland) see GEST 98/245 - Specification for Process Control
Valves -Bellows Sealed- for Use on Liquid Chlorine.
For remotely operable globe shut off valves (including quick-closing valves),
it is recommended that the criteria given in GEST 89/140 Specification
for Flanged Steel Globe Valves -Bellows Sealed- for Use on Liquid
Chlorine and GEST 90/150 Specification for Flanged Steel Globe
Valves -Packed Gland- for Use on Liquid Chlorine are followed.
Manual valves should be in accordance with GEST 89/140 - Specification

for Flanged Steel Globe Valves -Bellows Sealed- for Use on Liquid
Chlorine or GEST 90/150 - Specification for Flanged Steel Globe Valves
-Packed Gland- for Use on Liquid Chlorine.
A remotely operated valve is recommended in the fixed liquid chlorine pipework

connected to the loading or off-loading point. This valve should be sufficiently close
to the flexible connection to limit the emission in the event of an accident.
The operation of this valve and of the automatic valves on the transport tanker
should be linked. These valves should be fail-closed.
Opening of the pneumatic valves should be linked to the interlock system.
Provision should be made for operation from at least two alternative locations.
GEST 98/247 - Specification for Remotely Operable Shut-Off Valves Bellows
Sealed for Use on Liquid Chlorine gives requirements for this type of forged and
cast steel flanged valves used at temperatures between minus 40C and plus
120C.
The same valves are recommended for use with dry gas under pressure (more
than 4 barg).
It should be noted that valves are available from several suppliers with the
designation Euro Chlor approval.
This is issued by Euro Chlor to confirm that the concerned valves have been
approved according to GEST 86/128 - Procedure for Approval of Valves for Use
on Liquid and Dry Gaseous Chlorine, tested according to GEST 86/129 Procedure for an Independent Assessment of Valves for Use on Liquid and
Dry Gaseous Chlorine, Prior to Consideration for Euro Chlor Approval and
respect the specifications defined in the corresponding Euro Chlor
recommendation.
The purchase of suitable valves by itself will not guarantee a high safety standard.
It is also necessary to ensure correct installation, operation and maintenance, as
outlined in Code of good practice GEST 80/84 Code of Good Practice for the
Commissioning of Installations for Dry Chlorine Gas and Liquid.
The content of the previous paragraph is also applicable for tanker valves.
July 2008
Page 35 of 62
GEST 06/317
st
1 Edition
Practical experience has shown that the installation of dry gaseous and liquid
chlorine valves necessitates specific precautions to avoid their deterioration and
consequent loss of gas tightness. GEST 80/85 - Code of Good Practice for
Installation Removal and Maintenance of Manually Operated Chlorine Valves
has been written to provide a number of simple rules that will help avoid
deterioration of such valves; the guidance is applicable:
During initial installation or following replacement on an operating

installation.
In the course of maintenance to or inspection of the installation.
During repairs to or overhaul of such types of valve.
Pneumatically operated valves for use on storage tanks for liquid chlorine need to
satisfy a number of basic functions and technical characteristics different from
other types of valves. The functions and characteristics necessary to satisfy the
Euro Chlor safety criteria are described in GEST 94/204 - Pneumatically
Operated Valves for Use on Storage Tanks for Liquid Chlorine which covers
design, manufacture, materials, examination, testing and verification.
GEST 94/201 - Procedure for Verification of Pneumatically Operated Valves
for Use on Rail and Road Tankers and ISO-Containers for Liquid Chlorine
gives a procedure that relates to the Euro Chlor verification of pneumatically
operated valves for use on rail and road tankers and ISO containers for liquid
chlorine. The procedure, whose objective is to promote the safe transport of liquid
chlorine, covers the assessment of the valve's design, which needs to satisfy a
number of basic functions and technical characteristics unique to the particular
type of valve, the valve's manufacture and its performance. The valves to which
this procedure applies are covered by GEST 75/46 - Pneumatically Operated
Valves for Use on Rail and Road Tankers and ISO-Containers for Liquid
Chlorine, a document which is based on a limited number of valve proven
designs, manufacture and development.
GEST 76/53 Code of Good Practice for Installation, Removal and
Maintenance of Pneumatic Valves on Road and Rail Tankers and ISOContainers for Liquid Chlorine provides simple rules that will minimise any
deterioration of pneumatic valves; it is applicable:
For the first installation on a new vessel (road and rail tankers, ISOcontainers)
For the inspection and testing of the vessel.
Repair weld procedures shall be in accordance with European Regulation.

Production weld repairs refers to the repair by welding of valves to be used for dry
gaseous or liquid chlorine duty, during the casting, and subsequent machining
procedures, prior to assembling of the finished product. GEST 96/220 Specification for Weld Repairs during Manufacturing of Cast Valves for
Liquid and Dry Gaseous Chlorine relates to the weld repairs referenced in
relevant Euro Chlor valve standards. The specification includes the requirements
for the welding methods, standards to be followed, locations on the valve which
may be repaired, and inspection procedures to be employed to ensure defect free
weld repairs. The individual valve specifications define the acceptable defects for
that type of valve.
July 2008
Page 36 of 62
GEST 06/317
st
1 Edition
9.2.3 Bolts and Gaskets

For liquid chlorine service stud bolts (threaded studs with nuts) or hexagonal heads
bolts with nuts should be used. See GEST 88/134 Stud Bolts, Hexagon Head
Bolts and Nuts for Liquid Chlorine.
The jointing material should be suitable for the style and rating of the flanges.
Experience with these materials is given in GEST 94/216 Experience of NonAsbestos Gaskets on Liquid and Dry Chlorine Gas Service.
Procedures must ensure that gaskets are never used twice.
9.2.4 Pumps
For continuous or semi-continuous processes, pumps may be used to transfer
liquid chlorine. Canned pumps or submerged pumps are recommended.
For canned pumps, the pump and motor are built together as one unit, in which all
lubrication is made by liquid chlorine recycled from the delivery side to the pump
suction side through the space between the stator and rotor.
For safety and design principles, materials of construction and other particulars of
the pumping system, see GEST 83/119 Canned Pump for Use with Liquid
Chlorine.
For submerged pumps, special measures have to be taken to ensure no leakage
takes place along the shaft even in case of mechanical seal failure.
9.2.5 Instruments
The purpose of the code GEST 94/210 - Code of Practice for the Installation of
Flow Measuring Devices on Dry Gaseous and Liquid Chlorine Applications is
to provide advice on the installation of flow measuring instruments used on dry
gaseous and liquid chlorine applications. This code does not advise the selection
of equipment; however, installation related selection criteria are mentioned.
Advice on the installation of pressure measuring and detection instrumentation on
dry compressed gaseous and liquid chlorine applications are described in GEST
94/207 - Code of Practice for the Installation of Pressure Sensing Devices on
Dry Gaseous and Liquid Chlorine Applications.
In the two previous cases, an important factor is the correct choice of intermediate
fluid, if used: a complete compatibility with chlorine is required (fully halogenated
liquid)
Sampling and transfer equipment for wet or dry gaseous and liquid chlorine
towards an analyser must be carefully designed to eliminate the effect of certain
chemical or physical factors which may affect the analysis. Precautions must be
taken to ensure safety during installation, operation and maintenance of the
analytical equipment.
9.2.6 Liquid Chlorine Quality

Methods for liquid chlorine analysis are described in Anal 9 - Methods for the
Analysis of Liquid Chlorine.
July 2008
Page 37 of 62
GEST 06/317
st
1 Edition
9.2.7 Pressure Relief Systems

9.2.7.1 General Policy
Pressure relief systems introduce potential hazards and should therefore be
avoided wherever this can be done by design.
Where a pressure relief system is necessary on chlorine under pressure, it must
never vent directly to atmosphere, but to an absorption system (See section 9.7). It
should be designed to be as simple as possible, consistent with minimising the
risks of installation, maintenance or operating errors. Sufficient instrumentation
should be provided to permit system fault finding.
9.2.7.2 Requirements for Provision of Relief Systems
A relief system is required on each pressure storage tank. For low pressure
storage, protection against under-pressure as well as over-pressure needs to be
provided.
The installation of relief systems on transport containers is mandatory for sea
transport, but forbidden for rail and road. For more details, see GEST 80/92 Installation of Relief Valves on Road and Rail Tankers and ISO-Containers for
the Transport of Liquid Chlorine.
Relief systems are also normally required:
With positive displacement compressors or pumps
With liquid vaporisers
On the ends of long distance pipelines (protection against thermal

expansion and surge in case of liquid chlorine)
To allow for thermal expansion of trapped liquid chlorine.

9.2.7.3 Design Criteria
The pressure relief system should be sized to handle all credible over-pressure
scenarios, which will normally include:
Excess pressure of liquid in a pump system
Over-pressure due to gas transfer system
Over-pressure due to inert gas and increase of temperature
Thermal expansion of liquid chlorine following over-filling or trapped within a

closed system
Increase of temperature in a low pressure liquid chlorine system.
As storage systems must be installed to avoid any risk from fire or external source
of radiation, risk of fire is not included in the design hypothesis.
All pressure relief systems should vent to an absorption system.
The possibility of two phase flow should be allowed for the design, if necessary.
9.2.7.4 Arrangement
A relief system will discharge to an absorption system, which will typically be
designed to handle chlorine gas only. Where a relief could contain liquid, it is
therefore necessary to install a liquid/gas separator, adequately sized to hold the
maximum foreseeable quantity of liquid and to prevent the carry over of liquid
July 2008
Page 38 of 62
GEST 06/317
st
1 Edition
droplets. The vessel should be fitted with a level and/or temperature alarm to
indicate the presence of liquid.
It is also necessary to ensure that the maximum relief flow is compatible with the
capacity of the absorption plant. A buffer vessel of suitable capacity may be
provided to absorb a possible pressure wave.
Relief into a closed tank may also be considered. Closed expansion tanks should
be provided on the downstream side of a pressure relief system intended to protect
a liquid chlorine installation from thermal expansion. These vessels should always
be of adequate dimensions and equipped with alarm systems.
The relief system may consist of either a bursting disc or a relief valve; these will
preferably be protected by a rupture disc upstream, with pressure detection
between the two equipments.
A pressure relief valve must be protected against deterioration:
A bursting disc is usually fitted upstream of the pressure relief valve to

prevent contact with chlorine during normal operation
A high pressure alarm should be installed between disk and valve
A protective diaphragm may be used downstream to prevent return of

moisture from the vent system
Controlled purging by dry inert gas may achieve the same result of keeping
the moisture out.
In any case, flushing with dry gas downstream of the relief system must be
possible.
9.2.7.5 Operation
Correct operating and maintenance procedures are essential.
For all details, refer to:
GEST 76/64 Relief Valves for Use on Dry Gas or Liquid Chlorine
GEST 87/133 Over Pressure Relief of Liquid Chlorine Installations.
9.2.8 Back Flow Prevention

When using chlorine, all precautions have to be taken in order to prevent any
unwanted mixture of chlorine with any chemical product or any reactive material,
which can lead to violent reactions. It is also necessary to prevent chlorine entering
utility systems like dry air or nitrogen.
In order to avoid these dangerous mixtures, preventive measures are necessary to
detect and prevent "back flow".
Different recommendations to address this problem have been given: GEST 75/47
Design and Operation of Chlorine Vaporisers and GEST 78/73 Design
Principles and Operational Procedures for Loading/Off-Loading Liquid
Chlorine Road and Rail Tankers and ISO-Containers.
Back flow from a reactor into the chlorine supply line should be prevented by either
a barometric leg for reactors operating close to atmospheric pressure, or by a
safety valve actuated by a low differential pressure detection device. The piping of
the barometric leg and the safety valve should be made from materials suitable for
both chemicals to be separated.
July 2008
Page 39 of 62
GEST 06/317
st
1 Edition
An automatic shut-off valve, based on a low differential pressure or no-flow

detection, should be used to prevent back-flow at compression, evaporation, or offloading station units; check valves are not considered as sufficiently reliable.
The same principle can also be used to prevent flow of chlorine into air or nitrogen
systems which are connected to pipework or equipment containing chlorine.
9.2.9 Services
9.2.9.1 Instrument Air
All instrumentation and control equipment should be installed so that there is no
direct connection between the air supply and chlorine. Therefore, instrument air
must never be used for purging or padding.
9.2.9.2 Effluent Drains
In all cases where there are effluent streams, these must comply with the relevant
legislation. Effluent drainage systems should be arranged so as to prevent any
mixing of acidic effluents with hypochlorite solutions.
9.3
Chlorine Transfer Compressors
Liquid chlorine can also be transferred from one container to another by

compression of the gaseous phase in the container being emptied, using the
chlorine gas extracted from the container being filled. This operation can be carried
out using a transfer compressor with the advantage of avoiding the use of an inert
gas, which necessitates a subsequent venting and absorption operation to avoid
any risk of excess of pressure in the container being emptied.
For advice on choice of compressor, installation, operation and on problems to be
avoided, see GEST 79/79 Transfer of Liquid Chlorine by Padding with a
Chlorine Compressor.
9.4
Chlorine Storage
According to local needs, liquid chlorine may be stored in a low-pressure storage

vessel at low temperature or in a under pressure storage at ambient temperature.
Basis for choice between storage of high or low pressure are summarised here
below.
A low pressure storage system is basically unsuitable for factories which are not
chlorine producers because of the chlorine compression and absorption systems
which are needed and because of the complexities of this type of storage.
Recommendations concerning the low pressure storage are given in GEST 73/17
Low Pressure Storage of Liquid Chlorine.
For pressure storage of liquid chlorine see GEST 72/10 - Pressure Storage of
Liquid Chlorine.
Storage tanks for liquid chlorine should be situated away from any risk from fire
and possible thermal radiation. Welding or any other form of hot work should only
be permitted if stock tanks and pipework are protected from heating (safe distance
or adequate protection).
The maximum permissible filling weight is 1.25 kg/dm (filling factor). This applies
to storage containers, cylinders, drums and tankers-containers. This means e.g.
July 2008
Page 40 of 62
GEST 06/317
st
1 Edition
that storage containers for liquid chlorine may only be filled to less than 95% of
their volume for a maximum temperature of 50C.
Storage vessels for liquid chlorine can be installed inside a building or in the open
air. The advantages and disadvantages of these alterations are discussed in GEST
88/135 Memorandum on Confinement of Liquid Chlorine plants.
Recommendations on confinement are given in GEST 94/215 - Confinement of
Units Containing Liquid Chlorine.
9.5
Loading and Off-loading
9.5.1 Introduction
Bulk loading and off-loading of chlorine is an activity outside of the main production
business. Nevertheless it is of fundamental importance to the safety of the plant
operation and of the transport itself.
At the loading station several sources of risk coincide: on one hand, there are high
quantities of chlorine at a comparatively high pressure. On the other hand, the
tankers connection between the mobile and the stationary loading facility must be
made by mechanical opening and closing of a flexible piping system. So to avoid
any risk of chlorine release or damage to the installation or tanker, special care
must be taken with equipment and procedures for the emptying and filling of
chlorine tankers,
9.5.2 Piping Connections

Beside for the instrument air, the usual connections are for:
Pad gas
Gaseous chlorine
Liquid chlorine.
The filling of tankers may be done by a pump or by pressure padding. It is possible

to raise the pressure by dry air, nitrogen or chlorine provided these gasses are
exempt of hazardous impurities such as grease, hydrogen, organics, water etc.
The emptying of a container is usually done by padding.
The use of inert gas to enable the transfer of liquid chlorine necessitates a unit for
the absorption of diluted chlorine from venting-down operations.
Discharge in the liquid phase is the normal procedure. Euro Chlor do not
recommend discharge in the gaseous phase except for fairly small discharge rates
and from small containers; furthermore the method involves several safety aspects
which need careful study to avoid problems, mainly the NCl3 concentration
increase. See GEST 78/73 - Design Principles and Operational Procedures for
Loading/ Off-Loading Liquid Chlorine Road and Rail Tankers and ISOContainers.
9.5.3 Padding Gas Used for the Transfer

For purging and padding on a chlorine system, a gas which is inert to chlorine,
such as dry air or nitrogen, should be used. The transfer gas should have a dew
point lower than minus 40C at atmospheric pressure (minus 40C corresponds to
146 ppm volume or about 90 mg/kg water in gas). It should be clean and contain
no impurities such as dust or oil. Its pressure should be at least 1.5-2 bars greater
July 2008
Page 41 of 62
GEST 06/317
st
1 Edition
than that which exists in the chlorine system, and all precautions must be taken to
ensure that this differential pressure is permanently maintained. It is also important
to ensure that the inert gas pressure remains less than the design pressure of the
tanker (or the storage).
To avoid any risk of contamination by other materials or products which could react
with the chlorine, the inert gas system used for the pressurisation of the tanker (or
the storage) should not be linked to any other installation.
In addition, in order to avoid the risk of chlorine contaminating the rest of the
system, it is prohibited to use instrument air for pressurisation of a chlorine tanker.
9.5.4 Venting Arrangements

The use of padding gas for pressurising the container makes it necessary to
provide means for venting-down the tankers at the end of the operation.
Therefore an absorption system is required. It should also be possible, in the event
of an incident involving the tanker, to be able to reduce the pressure in the tanker
via the chlorine venting system.
The venting-down of tankers and connections leads to the possibility of liquid
chlorine being transferred with the padding gas, either during the venting-down of
the liquid chlorine pipework, or following a wrong operation. A knockout pot should
therefore be installed in the purge gas line, which should contain a temperature
or/and level alarm to indicate to the operating personnel the presence of liquid
chlorine.
It is necessary to ensure that all valves are in the right position before the chlorine
transfer. In particular, the connection between the liquid (or gaseous) chlorine
piping system and the vent gas absorption system must have been closed before
filling or emptying.
9.5.5 Choice of Flexible Connections to the Tanker

Design construction and operations of the flexible connections are especially
important for safety.
The following alternatives may be used:
Flexible hoses: GEST 75/43 - Flexible Steel pipes, Flexible Monel and
Hastelloy Hoses for the Transfer of Dry Gaseous or Liquid Chlorine
Articulated arms: GEST 75/44 - Articulated Arms for the Transfer of Dry
Gaseous or Liquid Chlorine.
A visual examination of the flexible connections of the flanges before each use,
and their preventive replacement, are essential. A leak test is mandatory.
9.5.6 Location of the Loading or Off-loading Station

It is recommended to perform the loading operation on a weighbridge.
The tanker, pipework, valves, accessories and other equipment should be located
and protected in such a manner that it cannot be subjected to risk of fire, corrosion
or mechanical damage due to impact from vehicles, falling objects, etc.
The station should not have a slope. Furthermore, it is important to prevent
uncontrolled movement of the tanker during filling or emptying, for example by the
use of wheel chocks.
July 2008
Page 42 of 62
GEST 06/317
st
1 Edition
The station should be adequately separated from traffic and exclusively used for
chlorine. The approach of any other vehicle should be prevented by an efficient
system, for example by the use of rigid barriers which should be locked into
position.
A warning visible sign should be provided to show that liquid chlorine transfer is
taking place.
The lay out should be such that during any movement of the tanker (even with the
valve dome open), it cannot come into physical contact with any part of the station.
9.5.7 Loading and Off-loading Procedure

All operations should be carried out by personnel who have been specifically
trained for this work. The operations should be in accordance with GEST 78/73 Design Principles and Operational Procedures for Loading/ Off-Loading
Liquid Chlorine Road and Rail Tankers and ISO-Containers.
A typical sequence of operation for off-loading would include the following:
Check that absorption system is available with sufficient absorption capacity
Set interlocks
Connect up using new gaskets
Test newly made connections with gas before admitting liquid
Check that valves on fixed pipework are correctly set, in particular that vent
valve is closed
Open to tanker so that pressure in tanker can be checked
Check that padding pressure is higher than tanker pressure
Active chlorine monitoring system during all the operation
Open padding and liquid connections and check that discharge is

happening correctly
Continue transfer until the liquid chlorine has been removed from tanker
Isolate and drain pipework, taking particular care not to trap liquid between
closed valves
Purge chlorine from flexible pipes and disconnect
Cap off flexible pipes and, preferably, leave them under a dry air purge to
prevent any ingress of moisture
Cap off valves on tanker and double check before despatching.
Similar procedures are applied to loading operations, but for these additional
checks must be made, as describe below.
It is important to ensure that, if there is a separate inert gas phase in the tanker at
the end of the loading operation, the maximum pressure which may be reached
during transport (due to temperature increase of the chlorine) will under no
circumstances exceed the maximum operating pressure of the container. The total
amount of chlorine loaded into the tanker must be carefully monitored to ensure
that, even under the worst conditions, it will not become liquid full: the maximum
filling ratio is usually fixed in Europe to 1.25 kg/dm. As an added precaution, the
tanker must be subjected to a second weighing on an independent weighbridge
prior to dispatch.
July 2008
Page 43 of 62
GEST 06/317
st
1 Edition
9.5.8 Emergency Planning

All personnel who enter the area of a chlorine discharge installation should have
personal protective equipment available.
An emergency plan and precise instructions in case of emergency should be
permanently available and brought to the knowledge of the personnel involved.
The operator should be able to rapidly deploy fixed or mobile water sprays in order
to help the dispersion of a gas cloud, and should avoid the discharge of water on to
liquid chlorine or on to the actual area of leakage.
Self-contained breathing apparatus and protective clothing suitable for dealing with
a chlorine leak should be available in lockers located not too far from the discharge
point and be accessible at all times in case of emergency. It should be noted that
the use of filter masks is not suitable where there is a risk of a high concentration
of chlorine.
Means of indicating the wind direction should be installed in order to inform the
operating personnel of the direction of dispersion of gas which might occur in the
event of an accident.
All personnel should be specifically instructed in the means for dealing with
leakages of chlorine and periodical training exercises should be organised.
9.6
Chlorine Vaporisers
Chlorine is usually delivered to customers as a liquid and the user will usually
vaporise the chlorine before it is used.
About 250 kJ (60 kcal) is needed to vaporise one kg of chlorine. Additional energy
is required to heat the liquid to boiling point and for super-heating the gas. For
smaller quantities of chlorine, gas can be taken directly from cylinders or drums,
since the necessary heat is transmitted to the chlorine through the walls of the
container. As first approximation, 5 kg per hour per square meter of surface of
container at an ambient temperature of 20C is the maximum amount of chlorine
which can be vaporised by natural convection.
For higher flow rates, it is necessary to use a chlorine vaporiser. For advice on the
design, construction, operation and maintenance of chlorine vaporisers and for a
review of typical advantages and disadvantages for each type of vaporiser, see
GEST 75/47 Design and Operation of Chlorine Vaporisers.
9.7
Absorption Systems
In chlorine producers' premises an absorption system is essential for containment

and treatment of gaseous chlorine effluents, and the same applies for consumers
handling liquid chlorine. Normally caustic soda of 18-22% is used as absorption
liquor which is converted to sodium hypochlorite/chloride solution when absorption
of chlorine takes place.
This may arise as:
A continuous or intermittent flow of residual gases containing chlorine (e.g.

coming from on-line analytical units)
Vent gas coming from chlorine containing systems such as containers,

flexible connections, pipework before maintenance or during offloading
Depressurisation vent of chlorine system for safety reasons
July 2008
Page 44 of 62
GEST 06/317
st
1 Edition
Plant or cell start up and shut down.
The absorption reactor is generally designed as a packed column or as a liquid

ejector system, although combined units are also in use.
The first priority for the design of an absorption system is to specify carefully:
The maximum quantity of chlorine
The composition of the gas stream
The maximum instantaneous flow
to be absorbed in emergency conditions.

A choice also has to be made between continuous or batch operation regarding
caustic soda solution supply, since this will influence the size of the unit, the
storage capacity for caustic soda and hypochlorite solution as well as the need for
coolers, back-up systems or emergency supply for electricity and services. It
should be noted that caustic supply to the absorption system is also necessary
during power failure (caustic pumps with emergency power supply, caustic head
tank on the roof ).
For more detailed information see GEST 76/52 - Equipment for the Treatment of
Gaseous Effluents Containing Chlorine.
9.7.1 Chemical Principles

Chlorine reacts with caustic soda solution forming sodium hypochlorite and sodium
chloride, according to the following reaction:
Cl2 + 2 NaOH NaOCl + NaCl +H2O
H = -108 kJ/mole NaOCl = -365 kcal/kg Cl2
(1kg Cl2 forms 1.049 kg NaOCl)
The heat of reaction causes a rise of temperature in the solution. Over-chlorination
occurs when there is no longer an excess of NaOH. In this situation, the reaction of
chlorine with hypochlorite takes place with, in parallel, some dissolution of chlorine
in water (which generates acid):
depletion of hypochlorite
NaOCl + Cl2 + H2O 2 HOCl + NaCl
dissolution of chlorine in water
Cl2 + H2O HOCl + HCl
As there is no alkaline medium remaining to absorb the chlorine, a gas emission to

the atmosphere may take place.
The generation of additional sodium chloride within the absorption medium by the
production of chlorate (see below) may lead to salt precipitation with the risk of
blockage of equipment.
A high rate of chlorine absorption may cause the temperature of the solution to rise
above 55C, accelerating the conversion of hypochlorite into sodium chlorate
according to the following overall reaction:
3 NaOCl NaClO3 + 2 NaCl
H = -38 kJ/mole = -121 kcal/kg NaOCl
This reaction also produces heat and therefore decomposition is self-accelerating.
This has to be prevented by cooling.
July 2008
Page 45 of 62
GEST 06/317
st
1 Edition
In cases only small quantities of chlorine have to be absorbed, the cooler can be
omitted, provided there is sufficient caustic soda solution inventory in the system.
Precautions must also be taken at all times to avoid uncontrolled acidification of
any liquor containing hypochlorite.
Generally the absorbed gas stream contains air which means carbon dioxide,
(CO2). Its concentration in air is only 0,033% by volume but it cannot be neglected
as it consumes caustic soda according to the equation:
2 NaOH + CO2 Na2CO3 + H2O
Although sodium carbonate solution absorbs chlorine, too, this reaction is less
complete and the chlorine level in the vent gas will rise. Furthermore, the risk of
solid salt formation has to be regarded, which can block the absorber.
9.7.2 Disposal of Hypochlorite Solution

The design of the absorption system will be influenced by the method used for the
disposal of the hypochlorite solution. This can be e.g.
Further chlorination to commercial grade hypochlorite solution
Thermal decomposition to NaClO3
Decomposition in presence of heavy metal ions with release of oxygen and

formation of sodium chloride according to the following reaction:
Catalyst
2 NaClO
NaCl O2
H = - 61 kJ/mole NaClO = - 196 kcal/kg NaClO
Decomposition by acidification with release of chlorine
Reduction with e.g. NaHSO3, Na2SO3, Na2S2O3, H2O2.
Note that in all cases where there are liquid wastes, care must be taken that these
comply with relevant legislation.
9.7.3 Technical Design of Absorption Systems

Generally, the absorption system should generate slight suction on all the chlorine
venting system.
An absorption system is designed to handle gaseous chlorine, usually at ambient
pressure, but not liquid. Where it is used for safety relief from liquid chlorine
systems or when there is a risk of liquid chlorine entrainment into the vent, the
absorption must be protected by a knock out pot (fitted with a low temperature or
level alarm) from which liquid chlorine is allowed to vaporise at a controlled rate.
Careful study should be made of the whole system to ensure that sufficient
integrity is maintained at all times.
The chlorine content of eventual gas discharge from the unit is usually limited by
official regulations. As a general rule during routine operation, the design figure is
less than 5 mg/m. During emergency conditions, this figure can slightly increase
for short periods.
The suction can be achieved by ventilators or using an ejector system based on
the Venturi principle. This construction is relatively simple and a single pump
provides both caustic circulation and suction. The ejector must be designed by an
experienced supplier.
July 2008
Page 46 of 62
GEST 06/317
st
1 Edition
Packed columns are more complex, needing a pump for caustic circulation and a
fan for suction. However, they offer a buffer effect giving a better reaction to surges
in chlorine quantity to be absorbed, and offer a better protection if electricity supply
fails, since they can continue to absorb chlorine from a pressure relief system
using caustic soda stored in a head tank.
In some cases, a double effect system is required which can be e.g. a combination
of an ejector system as first step and a packed column as second absorber, which
takes care of the risk of decomposition or failure of the first step.
Temperature control of the absorption liquor is essential: a cooler may be
necessary (see section 9.7.1).
Sufficient caustic soda must be maintained at all times. A redox-measurement to
prevent over-chlorination is usually used. Nevertheless regular checks by titration
have to be made to confirm there is still enough unreacted caustic in the system.
Over-chlorination combined with high temperature in the absorption area can
destroy the construction or packing material of the absorber and cause an
unacceptable emission of chlorine to the atmosphere.
On the other hand, care must be taken that no moisture from the absorber can flow
back into the dry chlorine area.
9.7.4 Materials of Construction

Materials of construction in an absorption system have to withstand extremely
corrosive conditions. They will be exposed to caustic soda, moist chlorine, sodium
hypochlorite, hypochlorous acid and chlorate. Acidic conditions will arise in the
event of over-chlorination according to the reactions described in 9.7.1 here above
(depletion of hypochlorite and reaction of chlorine with water).
NaOCl + 2 Cl2 + 2 H2O 3 HOCl + HCl + NaCl
Overal
ClO 2 HOCl ClO3 2 H 2 Cl
This reaction gives rise to species that are particularly corrosive to some nonmetallic materials, which on the other hand withstand hypochlorite well.
Hence careful choice of material for equipment or coating (potentially) in contact
with the absorption liquor is necessary. Typical materials are:
For absorption systems: GRP - reinforced PVC, PVDF and titanium
For internals: C-PVC, PVC, PVDF or titanium
For packing: PP, C-PVC, PVC or PVDF.
Titanium should be the first choice for pumps and coolers where there is no risk of
a contact with dry chlorine.
10 TECHNICAL GUIDANCE FOR TRANSPORT

10.1 DESIGN AND CONSTRUCTION OF TRANSPORT
EQUIPMENT
The transport of liquid chlorine under pressure in tank wagons may take place only
if it satisfies the conditions laid down in the national and international regulations.
July 2008
Page 47 of 62
GEST 06/317
st
1 Edition
10.1.1
Design and Construction of Rail Tank Wagons
The wagons must meet the design and construction requirements of the RID
(International Regulations for the Transport of Dangerous Goods by Rail). These
statutory provisions are completed by the Euro Chlor recommendation GEST
78/72 Rail Tank Wagons for the Transport of Liquid Chlorine under
Pressure.
10.1.2
Design and Construction of Road Tankers
The tankers must meet the design and construction requirements of the ADR
(European Agreement concerning the International Carriage of Dangerous Goods
by Road).
These statutory provisions are completed by the Euro Chlor recommendation
GEST 79/76 Design and Construction of fixed Tanks and Tank containers
for the Transport of Liquid Chlorine by Road.
10.1.3
Design and Construction of ISO Containers
The tanks must meet the design and construction requirements of one or more of
the following regulations:
The ISO international recommendations and standards
The RID International Regulations concerning the transport of dangerous

goods by rail
The ADR European Agreement concerning the international carriage of

dangerous goods by road
The IMDG International Maritime Dangerous Goods Code.
These statutory provisions are completed by the Euro Chlor recommendation

GEST 74/31 Regulation for Tank Containers for the Transport of Liquid
Chlorine under Pressure.
10.1.4
Design and Construction of Drums and Cylinders
In addition to the existing regulations, the drums and cylinders must meet the
design and construction requirements of the Euro Chlor recommendation GEST
88/138 - Small Chlorine Containers Construction and Handling.
Remark: GEST 98/249 - Code of Good Practice: Construction and Operation
of Tank Containers for Transport of Liquid Chlorine under Pressure is drawn
up from the information based on the safe transport of chlorine experience already
listed in other Euro Chlor recommendations.
10.2 TRANSPORT OF CHLORINE BY RAIL

Notwithstanding an excellent safety record for more than 50 years, the chlorine
industry, under the aegis of Euro Chlor, is aware of the continuing necessity to
improve the safety of such transport.
GEST 80/89 - Code of Good Practice for Safe Transport of Liquid Chlorine by
Rail Tanker gives the various safety measures adopted by member companies of
Euro Chlor taking into account the experience of chlorine producers in the different
countries. The main features of this document are summarised in below.
July 2008
Page 48 of 62
GEST 06/317
st
1 Edition
RID ask for an increased protection of rail tankers, and several alternatives are
proposed; between them, and based on practical experience and field tests, Euro
Chlor recommends the use of shields or buffer override protections.
10.3 TRANSPORT OF CHLORINE BY ROAD

Notwithstanding an excellent safety record for more than 50 years, the chlorine
industry, under the aegis of Euro Chlor, is aware of the continuing necessity to
improve the safety of such transport.
Euro Chlor has issued the recommendations GEST 73/20 - Code of Good
Practice for Safe Transport of Bulk Liquid Chlorine by Road Tanker Vehicles
and GEST 79/76 Design and Construction of fixed Tanks and Tank
containers for the Transport of Liquid Chlorine by Road.
GEST 73/20 gives the various safety measures adopted by member companies of
Euro Chlor taking into account the experience of the chlorine producers in the
different countries.
Road tankers and vehicles conveying tank containers should be equipped with
safety equipment which, as a minimum, is in line with ADR requirements as
follows:
Safety goggles
Butyl rubber gloves
Suitable respiratory protective device specifically approved for chlorine
Communication equipment and emergency telephone numbers readily

available, since rapid communication in case of emergency is an important
safety feature
Fire extinguishers
2 orange flash lights
Wheel blocks of size suited to the vehicle and to the diameter of the wheels
General first aid and emergency equipment of chlorine transportation.
GEST 79/76 Design and Construction of fixed Tanks and Tank containers
for the Transport of Liquid Chlorine by Road and GEST 96/221 - Protection of
Road Tankers for the Carriage of Chlorine give also details of the systems
recommended by Euro Chlor to provide protection of the chlorine vessel in the
event of a road incident.
A road tanker and its protection must be an integrated system and the external
protection recommended cannot compensate for a weak road tanker design.
10.4 HANDLING OF CHLORINE IN SMALL CONTAINERS

Euro Chlor, aware of the continuing necessity to improve safety, has drawn up
recommendation GEST 88/138 - Small Chlorine Containers Construction and
Handling for the construction and handling of liquid chlorine drums, cylinders and
transport spheres.
Liquid chlorine is a toxic dangerous substance, which can however be handled in a
safe fashion if personnel are properly trained. The main specific precautions for
transport are listed here below.
July 2008
Page 49 of 62
GEST 06/317
st
1 Edition
10.4.1
Cylinders
Care must be taken to ensure that cylinders are securely anchored for transport.
Vertical loading has the advantage that the valve is in the gaseous phase, which
reduces the emission in case of a valve leak. However, because of the shape of
the cylinders, special provisions are necessary for anchoring them.
Cylinders may be strapped or chained to rings securely attached to the vehicle.
Palletisation of cylinders is also widely used where the proper loading and offloading equipment is available.
10.4.2
Drums
The preferred methods of securing drums are to use fixed chocks or purpose made
cradles.
These can be used where the customer has suitable lifting equipment or with selfoff-loading trucks.
If there is a need to roll the container to the rear of the truck for offloading, a
recommended method of containment in transit is to use chains with front and rear
blocking. Straps should be limited to securing individual ton containers. Wooden
chocks or wedges should be placed under each container as an additional
safeguard. The front bulkhead should be reinforced.
Rear roll-off protection must be provided. A reinforced removable guard rail or a
contour fitting steel chock anchored behind the rearmost containers to the truck
bed with pins or chains is an effective restraint.
10.4.3
Spheres
Spheres should only be transported on dedicated low bed trucks with special fixing
or clamping systems for the spheres on the bed of the trucks.
10.4.4
Drums and Transport Spheres Loading and Offloading
Lifting beams, travelling electric hoists or fork lift trucks are usually employed by
shipper and customer. Proper design of the lifting beam is essential. Extreme care
must be exercised when operating fork lift trucks. The preferred method is to use a
purpose made lifting beam attachment on the forks.
10.5 MAINTENANCE OPERATIONS

GEST 79/78 Code of Good Practice for the Operations to be Carried out
before and after Maintenance on Road and Rail Tankers and ISO-Containers
of Liquid Chlorine concerns the operations which need to be carried out on road
tankers, rail tankers and ISO-Containers:
Before beginning any maintenance operation which necessitates entry into

the vessel and/or pressure testing.
After such operations, in order to put the barrel back into the required
condition for service, minimising any risk of deterioration in the materials of
construction or external safety.
This code attempts to define the operating standards and safety requirements, so
that incidents can be avoided during maintenance and after being put back into
service. It is, however, understood that establishments carrying out these
July 2008
Page 50 of 62
GEST 06/317
st
1 Edition
operations, particularly if they are external organisations, must have a thorough

understanding of the requirements for dealing with chlorine.
11 CHLORINE ACCIDENTS
11.1 Emergency Assistance
Together with the competent local authorities, the European chlorine producers
have set up organisations to intervene in case of an accident in which chlorine is
involved (see http://www.eurochlor.org/transportation). The main production units
have an emergency team and equipment permanently available for going out to
the scene of an accident. Personnel are specifically trained in dealing with such
emergencies and are available at the request of local authorities within their zone
of operation.
Vehicles and relevant safety and work equipment are available in most countries.
To take full benefit of this aid scheme, it is necessary that all responsible
authorities (police, fire brigade, civil protection ) and notably key personnel of the
railway system continue to be actively involved in the organisation of these
emergency plans in order to be able to call for their application as soon as an
accident or incident involving chlorine occurs.
11.2 Measures for Containing Chlorine Leaks

Occasionally, a leak might occur in the equipment used for producing, consuming
or transporting chlorine.
A leak resulting from corrosion generally starts as a small leak with a limited
emission impact. Due to atmospheric conditions (moisture) such a small leak will
always become worse, sometimes very rapidly. It is therefore of paramount
importance to intervene without delay to solve the problem.
11.2.1
First Measures
Take proper personal protective measures before approaching the area of

the leak, depending on the situation (inside a building or in the open air)
Locate the leak
Check if isolation of the leak by closing valves (controlled or by hand) is

possible
Depending on the size of the leak (emission) initiation of the emergency

plan must be considered
Cover the leak by a plastic sheet and blow with dry gas.
Water should never be sprayed on or in the vicinity of the leak since it would
aggravate it by severe corrosion.
After these first measures, and based on an estimate of the size of the leak, further
action can be taken to limit and, if possible, stop the leak.
11.2.2
Limiting a Chlorine Leak
If the leak is on the liquid side of a transport vessel, a repositioning, if possible,

should be carried out, in such a way that the leak is situated in the gas phase.
July 2008
Page 51 of 62
GEST 06/317
st
1 Edition
Wherever possible, pressure in the equipment should be lowered to reduce the

leak before attempting to seal it.
Cooling with a cooling agent such as liquid nitrogen reduces the chlorine pressure,
limiting in this manner the amount of chlorine escaping from the leak.
Water curtains can be used to limit locally the strength of the chlorine cloud,
providing that no water will come close to the leaking point.
11.2.3
Stopping a Chlorine Leak
This can be realised either by sealing or by containment of the leak.
11.2.4
Sealing
Sealing of the leak can be done with a wooden, copper, lead or brass peg.
Depending on the location of the leak e.g. plain or convex wall, pipeline with small
diameter or weld, other methods can be applied such as:
Rubber sheet with clamps or pipe clips
Inflatable rubber cushion
Mastic or quick setting cement held in place, if necessary, by some support.
11.2.5
Containment
Containment of a leak can be considered if a bottle, cylinder or drum is leaking.

Whether the leak is sealed or not by the above mentioned methods, the leaking
vessel can be locked away in a tailor made sealed container. See also GEST
92/176 Chlorine Emergency Equipment and GEST 93/179 Emergency
Intervention in Case of Chlorine Leaks.
In case of an accident involving a liquid chlorine vessel or pipe, it may be
necessary to transfer the chlorine into an empty vessel. Various considerations
necessary to achieve this are described in GEST 90/162 - Emergency Transfer of
Liquid Chlorine.
11.3 Learning from Experience

In order to continue to improve learning from experience, a document is published
on a periodic basis in collaboration with the other chlorine producers associations
of the World Chlorine Council, outlining significant chlorine accidents with causes
and possible solutions to avoid reoccurrence. Although some statistical data can
be included, the main purpose is to identify the lessons to be learnt from the
accidents, so that they can be prevented in other plants. If appropriate, Euro Chlor
Recommendations will be revised to take account of the lessons (see: GEST AP 1
- Learning from Accidents and GEST AP 2 - Learning from Experience).
12 ENVIRONMENTAL PROTECTION
In the electrolysis of brine for the production of chlorine the mercury process is still
one of the most used in Europe, even if the membrane process has now a bigger
share of the global installed capacity.
The mercury is in intimate contact with the raw materials (brine) and the final
products, hydrogen and caustic soda (or caustic potash). It is thus inevitable that
the untreated process streams contain mercury. Therefore a key element of
July 2008
Page 52 of 62
GEST 06/317
st
1 Edition
operating this technology is to apply techniques that minimise any contamination in

the final discharged or sold streams and that, wherever possible, recycle the
mercury within the process.
The chlorine industry in Europe puts a great deal of effort into minimising the
mercury emissions from the amalgam process. For the last two decades European
chlorine producers have been successful in reducing their overall mercury
emissions via products, waste water and process air. Based on the practical
experience of Euro Chlor members, the guideline Env Prot 13 Guideline for the
Minimisation of Mercury Emissions and Wastes from Mercury Chlor-Alkali
Plants describes the best available techniques used for this purpose.
The mercury losses by the cell room ventilation air remain the highest figures in the
average European Emission Data of amalgam plants. Env Prot 5 Guideline for
the Measurement of Air Flow and Mercury in Cell Room Ventilation presents a
summary and evaluation of the present Euro Chlor knowledge on the
measurement of this kind of emissions. The principle of all techniques is to
measure the mercury concentration of the cell room outlet air and simultaneously
the air flow rate to obtain the mercury emission rate.
The Good Housekeeping Practices detailed in Env Prot 11 - Code of Practice Mercury Housekeeping results from more than 50 years operating experience
from the European chlorine plants.
The first step to improve is to measure: methods for the Determination of Traces of
Mercury are described in the document Anal 3-7 - Standardization of Methods
for the Determination of Traces of Mercury while Analytical 6 - Determination
of Mercury in Gasses specifically recommends the measurement methods in air.
With the same principle, Euro Chlor members compile each year a mercury
balance of their plants, and the corresponding data are reported to the local
authorities and to OSPAR administration for the concerned sites (voluntary
commitment of the industry). The importance of accurate, complete and consistent
data for this compilation cannot be overstated.
Making a mercury balance in a chlorine plant is described in the Euro Chlor
recommendation Env Prot 12 - Guidelines for Making a Mercury Balance in a
Chlorine Plant. The calculation process is based on data obtained from:
Mercury emissions in products, to water and gaseous streams
Mercury in wastes
Mercury inventories.
The guideline Anal 10 - Determination of the Total Weight of Mercury in the

Electrolysis Cells by Radioisotopes precises the procedures for a good
inventory of the mercury contained in the cells.
Results are open to audit by the competent national authorities through a
designated independent third party. For plants with ISO or similar certification, the
best way is to include, as a whole, in the plant quality system, the document Env.
Prot. 12, with all the associated requirements. For the others, Env Prot 17 - Audit
Guideline for Preparing an Audit of the Mercury Balance in a Chlorine Plant is
a guideline to check the compliance with the mercury balance audit; it includes
requirements both for calculation procedure and used data.
Env Prot 15 - Management of Mercury Contaminated Sites aims to give a state
of the art of the management of mercury contaminated sites showing which
possible techniques have to be developed and/or confirmed by the practice.
July 2008
Page 53 of 62
GEST 06/317
st
1 Edition
It must be emphasized that the purpose of this document is not the creation of a
contaminated site management guide, but to provide managers with a relevant and
up-dated review of techniques and trends in site characterisation, risk assessment
and subsequent contaminated site management, including monitoring and
remediation. Thereby the reader will find there a useful toolbox from which to
select, with the aid of qualified environmental professionals, and in respect with
specific local, regional and national regulations, the techniques and technologies
which best suit each individual case, and which will undoubtedly be modulated by
socio-economic and political considerations.
Many chlor-alkali cell rooms using mercury cell technology will be shut down over
the next years (Industry committed for 2020 at the latest). Env Prot 3 Decommissioning of Mercury Chlor Alkali Plants has been drawn up as a
reference document for Euro Chlor members on the best experienced techniques
for health, safety and environment protection during all stages of plant shut down
from initial decontamination materials through to final disposal. It is based on the
experience of member companies in shutting down cell rooms in the last 20 years.
For the elimination of the mercury recovered after the shut down of the plants, the
documents Env Prot 19 - Guideline for the preparation for permanent storage
of metallic mercury above ground or in underground mines gives a guidance
on the safe handling method proposed by the industry to comply with the
requirements of the European Regulation.
13 SWIMMING POOLS
GEST 94/206 - Safe Use of Chlorine at Swimming Pools recommends the best
practices for liquid chlorine delivered in cylinders to non domestic swimming pools.
It is not the purpose of this recommendation to address swimming pool chemistry
and to define the optimum chlorine content needed to maintain adequate water
quality. The objective is to eliminate any risk to the public at the swimming pool
due to use of chlorine gas.
The European chlorine producers have also drawn up a document to promote
continuous improvement in the general standards of safety associated with the use
of sodium hypochlorite solution delivered in bulk or in ISO-containers to nondomestic swimming pools (GEST 96/218 - Safe Use of Sodium Hypochlorite at
Swimming Pools). Although it is recognised that some smaller and older
installations use drums or plastic containers for storage of disinfection chemicals,
this is not recommended and thus is not covered in this document.
14 REFERENCES
Reference Document on Best Available Techniques in the Chlor-Alkali
Manufacturing industry (BREF Document) October 2000
Anal 2 - Determination of Nitrogen Trichloride in Liquid Chlorine
Anal 3-7 - Standardization of Methods for the Determination of Traces of
Mercury
Analytical 6 - Determination of Mercury in Gasses
Anal 8 - Determination of Chlorine in Workplace Air
Anal 9 - Method for the Analysis of Liquid Chlorine
July 2008
Page 54 of 62
GEST 06/317
st
1 Edition
Anal 10 - Determination of the Total Weight of Mercury in the Electrolysis

Cells by Radioisotopes
Analytical 11 - Determination of mercury and creatinine in urine
Env Prot 3 - Decommissioning of Mercury Chlor-Alkali Plants
Env Prot 5 - Guideline for the Measurement of Air Flow and Mercury in Cell
Room Ventilation
Env Prot 11 - Code of Practice - Mercury Housekeeping
Env Prot 12 - Guidelines for Making a Mercury Balance in a Chlorine Plant
Env Prot 13 - Guideline for the Minimisation of Mercury Emissions and
Wastes from Mercury Chlor-Alkali Plants
Env Prot 15 - Management of Mercury Contaminated Sites
Env Prot 17 - Audit Guideline for Preparing an Audit of the Mercury Balance
in a Chlorine Plant
Env Prot 19 - Guideline for the preparation for permanent storage of metallic
mercury above ground or in underground mines
GEST 72/10 - Pressure Storage of Liquid Chlorine
GEST 73/17 - Low Pressure Storage of Liquid Chlorine
GEST 73/20 - Code of Good Practice for Safe Transport of Bulk Liquid
Chlorine by Road Tanker Vehicles
GEST 73/25 - Transport of Chlorine by Pipeline outside Site Boundaries
GEST 74/31 - Regulation for Tank Containers for the Transport of Liquid
Chlorine under Pressure
GEST 75/43 - Flexible Steel Pipes, Flexible Monel and Hastelloy Hoses for the
Transfer of Dry Gaseous or Liquid Chlorine
GEST 75/44 - Articulated Arms for the Transfer of Dry Gaseous or Liquid
Chlorine
GEST 75/46 - Pneumatically Operated Valves for Use on Rail and Road
Tankers and ISO-Containers for Liquid Chlorine
GEST 75/47 - Design and Operation of Chlorine Vaporisers
GEST 76/52 - Equipment for the Treatment of Gaseous Effluents Containing
Chlorine
GEST 76/53 - Code of Good Practice for Installation, Removal and
Maintenance of Pneumatic Valves on Road and Rail Tankers and ISOContainers for Liquid Chlorine
GEST 76/55 - Maximum Levels of Nitrogen Trichloride in Liquid Chlorine
GEST 76/64 - Relief Valves for Use on Dry Gas or Liquid Chlorine
GEST 78/72 - Rail Tank Wagons for the Transport of Liquid Chlorine under
Pressure
GEST 78/73 - Design Principles and Operational Procedures for Loading/OffLoading Liquid Chlorine Road and Rail Tankers and ISO-Containers
GEST 79/76 - Design and Construction of fixed Tanks and Tank containers
for the Transport of Liquid Chlorine by Road
July 2008
Page 55 of 62
GEST 06/317
st
1 Edition
GEST 79/78 - Code of Good Practice for the Operations to be Carried out
before and after Maintenance on Road and Rail Tankers and ISO-Containers
of Liquid Chlorine
GEST 79/79 - Transfer of Liquid Chlorine by Padding with a Chlorine
Compressors
GEST 79/81 - Liquid and Dry Gaseous Chlorine Piping Systems Located
Inside Producer's or Consumer's Plants
GEST 79/82 - Materials of Construction for Use in Contact with Chlorine
GEST 80/84 - Code of Good Practice for the Commissioning of Installations
for Dry Chlorine Gas and Liquid
GEST 80/85 - Code of Good Practice for Installation, Removal and
Maintenance of Manually Operated Chlorine Valves
GEST 80/89 - Code of Good Practice for Safe Transport of Liquid Chlorine by
Rail Tanker
GEST 80/92 - Installation of Relief Valves on Road and Rail Tankers and ISOContainers for the Transport of Liquid Chlorine
GEST 83/119 - Canned Pump for Use with Liquid Chlorine
GEST 86/128 - Procedure for Approval of Valves for Use on Liquid and Dry
Gaseous Chlorine
GEST 86/129 - Procedure for an Independent Assessment of Valves for Use
on Liquid Chlorine, prior to Consideration for Euro Chlor Approval
GEST 87/133 - Over Pressure Relief of Liquid Chlorine Installations
GEST 88/134 - Stud Bolts, Hexagon Head Bolts and Nuts for Liquid Chlorine
GEST 88/135 - Memorandum on Confinement of Liquid Chlorine plants
GEST 88/138 - Small Chlorine Containers Construction and Handling
GEST 89/140 - Specification for Flanged Steel Globe Valves - Bellows Sealed
- for Use on Liquid Chlorine
GEST 90/150 - Specification for Flanged Steel Globe Valves -Packed Glandfor Use on Liquid Chlorine
GEST 90/162 - Emergency Transfer of Liquid Chlorine
GEST 91/168 - Physical, Thermodynamic and Selected Chemical Properties
of Chlorine
GEST 92/171 - Personnel Protective Equipment for Use with Chlorine
GEST 92/175 - A Scheme for Safety Visits to Chlorine Customers' Plants
GEST 92/176 - Chlorine Emergency Equipment
GEST 93/179 - Emergency Intervention in Case of Chlorine Leaks
GEST 93/180 - Specification for Flanged Steel Ball Valves -Packed Gland- for
Use on Liquid Chlorine
GEST 94/201 - Procedure for Verification of Pneumatically Operated Valves
for Use on Rail and Road Tankers and ISO-Containers for Liquid Chlorine
GEST 94/204 - Pneumatically Operated Valves for Use on Storage Tanks for
Liquid Chlorine
July 2008
Page 56 of 62
GEST 06/317
st
1 Edition
GEST 94/206 - Safe Use of Chlorine at Swimming Pools

GEST 94/207 - Code of Practice for the Installation of Pressure Sensing
Devices on Dry Gaseous and Liquid Chlorine Applications
GEST 94/210 - Code of Practice for the Installation of Flow Measuring
Devices on Dry Gaseous and Liquid Chlorine Applications
GEST 94/213 - Guidelines for the Selection and Use of Fixed Chlorine
Detection Systems in Chlorine Plants
GEST 94/215 - Confinement of Units Containing Liquid Chlorine
GEST 94/216 - Experience of Non-Asbestos Gaskets on Liquid and Dry
Chlorine Gas Service
GEST 96/218 - Safe Use of Sodium Hypochlorite at Swimming Pools
GEST 96/220 - Specification for Weld Repairs during Manufacturing of Cast
Valves for Liquid and Dry Gaseous Chlorine
GEST 96/221 - Protection of Road Tankers for the Carriage of Chlorine
GEST 98/245 - Specification for Process Control Valves -Bellows Sealed- for
Use on Liquid Chlorine
GEST 98/247 - Specification for Remotely Operable Shut-Off Valves Bellows
Sealed for Use with Liquid Chlorine
GEST 98/249 - Code of Good Practice: Construction and Operation of Tank
Containers for Transport of Liquid Chlorine under Pressure
GEST 05/316 - Guideline for Site Security of Chlorine Production Facilities
GEST AP 1 - Learning from Accidents
GEST AP 2 - Learning from Experience
HEALTH 2 - Code of Practice: Control of Worker Exposure to Mercury in the
Chlor-Alkali Industry
HEALTH 3 - Electromagnetic Fields in the Chlorine Electrolyses: Effects on
Health and Recommended Limits
HEALTH 5 - Audit Questionnaire Chlorine
HEALTH 6 - Audit Questionnaire Mercury
HEALTH 7 - Code of Practice: Control of Workers Exposure to Chlorine in the
Chlor-Alkali Industry
Position Paper X - Explosion Protection Considerations Regarding the Cell
room of a Chlor - Alkali Electrolysis Unit
15 APPENDICES
Appendix 1: SAFE TRANSPORT OF LIQUID CHLORINE BY RAIL TANKER
VEHICLES - HIGHLIGHTS FROM GEST 80/89
Appendix 2: TRAINING OF CHLORINE
HIGHLIGHTS FROM GEST 73/20
July 2008
ROAD TANKER DRIVERS
Page 57 of 62
GEST 06/317
st
1 Edition
APPENDIX 1: SAFE TRANSPORT OF LIQUID CHLORINE

BY RAIL TANKER VEHICLES - HIGHLIGHTS FROM GEST
80/89
1. Construction Code
(See GEST 80/89 - Code of Good Practice for Safe Transport of Liquid
Chlorine by Rail Tanker).
The design pressure is based on a test pressure at 22 barg.
The steel should be non-alloyed fine grain steel to meet the impact strength
requirements laid down by RID at the temperature of minus 40C.
Preferably, the steel should have an ultimate tensile strength at rupture Rm 560
N/mm and a minimum elongation at fracture of 20%.
Welds should be examined 100% by radiography.
There should be only one manhole in the centre of the upper cylindrical sector of
the vessel and there must be no other branch on the vessel. The manlid should
have three flanged branches for the valves according to the layout of UIC 573 and
EN 12561.
The valves:
Should consist of two sections:

An internal to the tanker security ball or disc, situated below the valve
plate and spring loaded to close automatically
A standard valve, fixed to the valve plate above the disc
Should be capable of remote rapid operation(air actuated motor)
Should be of a type agreed by Euro Chlor (see recommendation GEST

75/46 - Pneumatically Operated Valves for Use on Rail and Road
Tankers and ISO-Containers for Liquid Chlorine).
No relief valves should be used for rail tanker, the reasons are given in GEST
80/92 - Installation of Relief Valves on Road and Rail Tankers and ISOContainers for the Transport of Liquid Chlorine.
2. Operation of Rail Tankers

(See GEST 80/89 - Code of Good Practice for Safe Transport of Liquid
Chlorine by Rail Tanker).
Chlorine producers receiving a rail tanker from fabrication, maintenance or tests,
should carry out an inspection of the vessel and of the fittings.
The vessel and the fittings should be dried until a dew point less than minus 40C
(at atmospheric pressure) has been obtained on the exit gas from both available
valves, after allowing sufficient delay for mixing of the gas within the vessel.
Complete leak tightness should be checked.
July 2008
page 58 of 62
GEST 06/317
st
1 Edition
After drying, the vessel should be maintained under an overpressure of 0.2 barg
minimum dry gas to avoid ingress of moisture.
The vessel should be filled at a filling installation which meets the requirements laid
down in recommendation GEST 78/73 - Design Principles and Operational
Procedures for Loading/Off-Loading Liquid Chlorine Road and Rail Tankers
and ISO-Containers.
The first filling with chlorine after commissioning or after test should be made with
gas before the introduction of liquid.
Specific attention is drawn to the control of the total weight: the total load must not
exceed 1.25 kg of chlorine per dm of capacity within the vessel (filling ratio defined
for most international transport of chlorine within Europe).
The recommended method to achieve this is by filling of the tanker on a
weighbridge. Whatever method of control is used during loading, the container
must be subjected to a second weight check on an independent weighbridge.
If necessary, the vessels should be vented down so that the maximum allowable
concentration of inert gas is not exceeded, to avoid that the maximum operating
pressure of the container is not exceeded during the journey.
After filling, the tightness of the valves should be checked and the blank flanges on
the valves should be put in place with new gaskets.
Before dispatch, one should make a final check on leak tightness and a check on
the labelling.
3. Transport
(See chapter 5 of GEST 80/89 - Code of Good Practice for Safe Transport of
Liquid Chlorine by Rail Tanker).
On leaving the factory, handling of the rail tanker is the responsibility of the rail
company. Special attention is to be given to:
The method of marshalling of the trains
The make up of the train.
Whenever possible, dedicated trains are preferred.
July 2008
page 59 of 62
GEST 06/317
st
1 Edition
APPENDIX 2: TRAINING OF CHLORINE ROAD TANKER

DRIVERS - HIGHLIGHTS FROM GEST 73/20
The following checklists outline the scope of the training and experience necessary
for drivers of road tankers.
1. Driving Skills and Procedures
Valid licence
Roadworthiness checks prior to loading
Routes to be followed
Road closures/diversions
Bad weather procedures
Security: parking/attendance
Emergency procedures
Check that tractor and trailer are correctly coupled.
2. Properties of Chlorine
Toxicity
Physical properties: gas density, typical vapour pressures
Effect of presence of inert gases
Effects of trapped liquid in pipeline or overfilled vessels
Reactions with oils and greases: use only specially approved lubricants
Reactions with unsuitable materials such as rubber gaskets, titanium,

plastics
Corrosion of steel in moist chlorine: need to keep connections dry
Reaction with ammonia: use of ammonia bottle
Chlorine iron fire
Frosting and ice formation.
3. Equipment and Procedures

Chlorine
Personal protective equipment and its use
Details of tankers, valves and other fittings
Details of equipment at customer installations
Off-loading procedures and split of responsibilities
Checks prior to leaving loading point
July 2008
for Handling
page 60 of 62
GEST 06/317
st
1 Edition
Checks at customers prior to offloading
Checks at customers prior to leaving
Emergency procedures.
4. Examples of Operating Hazards

These examples have to be considered for cases where the driver takes part in the
offloading process:
Reverses flow of chlorine into pad gas system
Liquid chlorine into vent system
Too many people in vicinity of offloading
Insufficient flexibility in offloading pipework
Passing valves
Leaking joints
Instruments not working correctly
Blocked pipes
Leaking valves or internal sealings
Fire.
July 2008
page 61 of 62
GEST 06/317
st
1 Edition
Industrial consumers of chlorine, engineering and equipment supply companies

worldwide and chlorine producers outside Europe may establish a permanent
relationship with Euro Chlor by becoming Associate Members or Technical
Correspondents.
Details of membership categories and fees are available from:
Euro Chlor
Avenue E Van Nieuwenhuyse 4
Box 2
B-1160 Brussels
Belgium
Tel: +32 2 676 7211
Fax: +32 2 676 7241
e-mail:
eurochlor@cefic.be
Internet:
http://www.eurochlor.org
July 2008
page 62 of 62

Chlorine Reference Manual

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chlorine Reference Manual

Uploaded by

Copyright:

Available Formats

THE CHLORINE REFERENCE MANUAL

EURO CHLOR PUBLICATION

This document can be obtained from:

improve awareness and understanding of the contribution that chlorine

ensure our industry contributes actively to any public, regulatory or scientific

promote the best safety, health and environmental practices in the

RESPONSIBLE CARE IN ACTION

1 THE CHLORINE INDUSTRY

3 PROPERTIES AND HAZARDS OF CHLORINE

Chlorine and Explosion Risk

4 PROPERTIES AND HAZARDS OF HYDROGEN

5 PROCESS SAFETY MANAGEMENT

Process Safety Information

Process Design Information

Mechanical Design Information

Process Hazards Analysis

Safe Work Practices

Pre-Start-Up Safety Review

Emergency Response and Control

Investigation of Process Related Incidents

Audits of Process Hazards Management Systems

Personnel of the Facility

Training of Road Tanker Drivers

Chlorine Detection and Monitoring

Purpose of Chlorine Monitors

Chlorine Monitoring Systems

Preventing Major Hazards

8 HEALTH HAZARDS, TRAINING AND FIRST AID

Health Hazards and Toxicity of Chlorine

Monitoring Chlorine Exposure to Workers

Treatment of Chlorine Gassing

Exposition of workers to mercury

Electromagnetic Fields (EMF)

9 TECHNICAL GUIDANCE FOR THE FACILITY

Materials for Liquid Chlorine and Dry Chlorine Gas

Materials for Wet Chlorine Gas

Bolts and Gaskets

Liquid Chlorine Quality

Pressure Relief Systems

9.2.7.1 General Policy

9.2.7.2 Requirements for Provision of Relief Systems

9.2.7.3 Design Criteria

Back Flow Prevention

9.2.9.1 Instrument Air

9.2.9.2 Effluent Drains

Chlorine Transfer Compressors

Loading and Off-loading

Padding Gas Used for the Transfer

Choice of Flexible Connections to the Tanker

Location of the Loading or Off-loading Station

Loading and Off-loading Procedure

Disposal of Hypochlorite Solution

Technical Design of Absorption Systems

10 TECHNICAL GUIDANCE FOR TRANSPORT

DESIGN AND CONSTRUCTION OF TRANSPORT EQUIPMENT

10.1.1 Design and Construction of Rail Tank Wagons

10.1.2 Design and Construction of Road Tankers

10.1.3 Design and Construction of ISO Containers

10.1.4 Design and Construction of Drums and Cylinders

TRANSPORT OF CHLORINE BY RAIL

TRANSPORT OF CHLORINE BY ROAD

HANDLING OF CHLORINE IN SMALL CONTAINERS

10.4.4 Drums and Transport Spheres Loading and Off-loading

Measures for Containing Chlorine Leaks