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GEST 79/82
8th Edition
June 2004
Euro Chlor
Euro Chlor is the European federation which represents the producers of chlorine and its primary
derivatives.
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 authorisation of Euro Chlor.
Euro Chlor and its members make no guarantee and assume no liability whatsoever for the use or
the interpretation of any of the information in this document.
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.
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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 that its activities cause the minimum harm to 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 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 should be taken into account 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 Equipment Working Group to whom all
suggestions concerning possible revision should be addressed through the offices of Euro Chlor.
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GEST 79/82
8th Edition
Section Nature
3.1.1 The words degreased hydrocarbon were added at the end of the fourth
paragraph
3.1.1 Hydrocarbon based oils replaces oilsin the paragraph below the bullets
3.1.4 In the second paragraph, bursting disc was added
3.1.6 A more detail information is given: used in thin wall applications e.g. bursting
disks
3.2.2 At the end of this section, the following sentence was added: PVC and PVC/GRP
must not be used with liquid chlorine
3.2.5 It has been added that PTFE is not completely impervious to gaseous chlorine at
elevated temperatures
3.3.2 The exception of using graphite for pump bearing was deleted
7 In the second paragraph, water was added (reactive to chlorine)
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TABLE OF CONTENTS
1. INTRODUCTION 6
2. GENERAL COMMENTS 6
3. MATERIALS 7
3.1. Metallic Materials 7
3.1.1. Carbon Steel 7
3.1.2. Cast Iron 8
3.1.3. Ductile Iron 8
3.1.4. Stainless Steels 8
3.1.5. Alloyed Steels 8
3.1.6. High Nickel Alloys 8
3.1.7. Hastelloy C 9
3.1.8. Titanium 9
3.1.9. Tantalum 10
3.1.10. Copper 10
3.1.11. Silver, Gold 10
3.1.12. Lead 10
3.1.13. Zinc, Tin, Aluminium 10
3.2. Plastics 10
3.2.1. (GRP) Glass Fibre Reinforced Polyester 11
3.2.2. (PVC) Polyvinyl Chloride 11
3.2.3. C-PVC - Chlorinated PVC 11
3.2.4. PVDF (Poly Vinylidene Difluoride), PVDF/GRP 11
3.2.5. PTFE - PolyTetraFluoroEthylene 11
3.2.6. FEP, PFA, TFE/HFP-copolymer, Perfluoro-alkoxypolymer 12
3.2.7. Polypropylene, Polyethylene 12
3.2.8. Other Plastics 12
3.3. Other Materials 12
3.3.1. Rubber or Ebonite 12
3.3.2. Graphite 12
3.3.3. Stoneware, Glass, Enamel 12
3.3.4. Brickwork 13
4. CORROSION RESISTANCE OF VARIOUS MATERIALS 13
5. GASKETS 14
6. THIN SECTION APPLICATIONS 14
7. PRECAUTIONARY COMMENTS 14
8. REFERENCES 15
APPENDIX 1: REACTION TITANIUM CHLORINE WATER 16
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1. INTRODUCTION
2. GENERAL COMMENTS
Materials of construction must be chosen to suit the conditions under which chlorine is
being handled
* Wet or dry
* Gaseous or liquid chlorine
* Temperature
* Pressure
For dry chlorine gas, i.e. containing less than 20 mg H2O/kg chlorine, steel is the usual
material. For liquid chlorine and cold dry chlorine gas, fine grain carbon steel should be
used, taking into account the possibility of depressurizing the system.
For wet chlorine gas, the usual materials are titanium , rubber lined steel, Glass
Reinforced Polyester Resins (GRP), PTFE lined steel, PVC externally reinforced with
GRP (PVC/GRP) and PVDF.
Plastic materials must also be chosen taking account of their resistance to ageing and the
possibility of damage caused by external factors. A basic principle in chlorine safety is
to learn from previous experience. Caution is therefore necessary before any new
material is introduced and extensive testing may be required before any equipment is
built.
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3. MATERIALS
Carbon steel is the most commonly used material for handling liquid chlorine or dry gas.
A grade of steel must be chosen to suit the temperatures which can arise in each case.
For liquid chlorine and cold dry chlorine gas, fine grain steel should be used, taking
into account the possibility of depressurizing the system (vaporisation of residual
liquid chlorine at minus 34C at atmospheric pressure or lower if pressure can go
subatmospheric).
All steel components must be thoroughly degreased, cleaned and dried to remove
surplus oxide, oil, hydrocarbons, moisture, etc, before coming into contact with
chlorine, see GEST 80/84 - Code of Good Practice for the Commissioning of
Installations for Dry Chlorine Gas and Liquid.
In contact with dry chlorine, carbon steels become covered by a layer of ferric
chloride. It is this layer that protects the underlaying carbon steel from further
attack1.. The iron chloride layer can be destroyed by:
High velocity (erosion)l
In order to avoid destruction of the protective layer of ferric chloride due to erosion,
the linear velocity of liquid chlorine at the vessel wall should be limited. The normal
practice for pipework is to limit liquid chlorine velocities to less than 2 m/sec.
Moisture (corrosion)
High temperature. The maximum temperature for carbon steel in presence of
dry chlorine should be below 120C.
In certain circumstances where there is a risk of traces of hydrocarbon based oils,
water or rust being present, reaction with chlorine can increase the temperature
sufficiently to lead to spontaneous ignition of steel.
The use of steel with a high specific surface area, such as steel wool, should be
avoided. When chlorine reacts with iron, the temperature can increase sufficiently to
cause ignition of steel.
Forged or cast steel can be used on condition that the mechanical property of the
fabricated components have been studied for the range of temperatures and stress
which might be encountered.
1
Hammink, M.W.J. and Westen, P.C. - Modern Chlor-Alkali Technology [3] 71-81
(1985)
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Not acceptable
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3.1.7. Hastelloy C
Hastelloy C-4 and Hastelloy C-276 are often used for components for dry
chlorine and chlorine with traces of moisture. The low temperature mechanical
properties are excellent.
They can be used up to 400C-500C.
3.1.8. Titanium
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- At higher temperatures (75C and up) exponentially more water is needed for safe
conditions (not flow rate dependant).
- The unstable transition area between safe and unsafe conditions is dependent on
mass transfer of water to the metal surface and should be avoided.
Care shall be taken of local situations e.g. depressurisation after a valve, erosion of
the titanium dioxide layer. ....
3.1.9. Tantalum
Tantalum is the only metal that can be used without restriction on wet and dry
chlorine. Because of its high price, however, it is used only for special equipment
parts such as transmitter membranes and bursting disks.
3.1.10. Copper
Copper is resistant to dry chlorine gas or liquid. The use of copper is restricted to
flexible connections for drums and cylinders filling, but it becomes embrittled by
frequent stressing and requires regularly stress relieving by moderate heat treatment.
Certain alloys of copper (such as brass or bronze), used in components that have been
proved by long service experience, are accepted for the manufacture of certain
cylinder valves because of the regular checks carried out on such equipment and their
frequent replacement.
3.1.12. Lead
Lead is resistant to dry chlorine and the rate of attack upon lead by moist chlorine is
low.
Lead can be used as a trapped gasket in some circumstances, but otherwise its use
with chlorine is not recommended on safety reasons because of its poor mechanical
properties.
Lead-antimony alloys are sometimes used for protective membranes, because they are
resistant in the presence of moisture.
3.2. Plastics
The following comments deal only with the use of the materials on construction duties
or as a lining. Their behaviour when used on specialised duties is dealt with in sections 5
and 6. Most of these plastics are slowly attacked by chlorine and require a schedule of
inspection and replacement before they become defective. Many of them are liable to
stress corrosion cracking and the fabrication of components or systems from plastics
should avoid regions of high stress during manufacture or service.
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PVDF has good resistance up to 140C on wet or dry chlorine gas. At higher
temperatures, it stands up better than PVC and polyesters, but is subject to a degree of
chlorination. Like most plastics already listed, the material is liable to stress corrosion
cracking.
The stress cracking problem for PVDF is caused by atomic chlorine radicals (for
example due to UV light or in certain chemical reaction conditions). PVDF qualities
specified as "Atomic chlorine resistant" should be used on chlorine duties. PVDF can
also be reinforced externally with GRP to give improved mechanical strength for
applications at higher temperatures or pressures.
PVDF and PVDF/GRP must not be used with liquid chlorine.
2
Bergman G. and Petersson K. - Brittle Behaviour of PVC-lined FRP structures. Swedish Corrosion
Institute, Project report 66 226:2
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permeability can be reduced by using greater material thicknesses. Where PTFE is used
as a protective layer, the integrity of the supporting material must be regularly inspected.
3.3.2. Graphite
In spite of the strong oxidising properties of wet chlorine, impregnated graphite (to
avoid problems with its porosity) can be used with wet chlorine gas at temperatures up
to 80C. However, the impregnating resin (such as PTFE) must be confirmed as chlorine
resistant. It is frequently used on certain wet chlorination systems but above this
temperature of 80C there is a greater rate of oxidation. Corrosion rates are also greater
at pH values higher than 2, i.e. in the presence of hypochloride ions. It may also be used
in dry chlorine where there is a risk of moisture being present.
Graphite must not be used on liquid chlorine.
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3.3.4. Brickwork
Anti-acid bricks are used for lining of wet chlorine towers. A cement should be chosen
with good chemical resistance to all the chemicals which are present. An impervious
lining should be used between the brickwork and the steel vessel.
The table below gives general information on the corrosion resistance of various
materials for contact with chlorine. Corrosion resistance is not the only factor in
selecting the materials and therefore the table should only be used in conjunction with
the comments which follow in the rest of the note.
CONDITIONS OF SERVICE
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Key behaviour
G = Good A = Acceptable
P = Poor N = Must not be used
XX only taking into account corrosion resistance, is not a construction material
Comments:
Temperatures stated above give an indication of the maximum value, without safety
allowance.
The above table refers to the non-reinforced plastics without any plasticiser.
5. GASKETS
For gas containing systems (wet or dry), a certain amount of corrosive attack on rubber
based on a synthetic elastomer is acceptable so long as the jointing system retains the
necessary seal under service conditions. However, for liquid chlorine systems, whatever
the pressure, reactive gasket materials such as rubber must not be used. In these
circumstances, a gasket material specifically proven on chlorine duty. See GEST 94/216
- Experience of Non-Asbestos Gaskets on Liquid and Dry Chlorine Gas Service.
Certain duties such as flexible bellows, bursting discs, etc., demand the use of thin cross
section components. In these circumstances the material must be effectively non-
reactive to chlorine and not rely on a protective ferric chloride surface layer.
The most commonly used materials are :
. for dry chlorine : nickel, tantalum, Monel , Hastelloy C
. for chlorine with traces of moisture : Hastelloy C, tantalum, PTFE
. for wet chlorine : tantalum, PTFE, graphite
7. PRECAUTIONARY COMMENTS
The above comments under sections 3.1, 3.2 and 3.3 concern the pure materials, without
plasticisers, fillers, coatings, greases or other potentially reactive ingredients. Therefore
the choice of materials of construction for many systems must be controlled to avoid the
introduction of materials which could react with chlorine.
It is also important when using any component (which is itself made from a satisfactory
material for use with chlorine) to separate chlorine from other fluids, that account is
taken of the potential for leakage occurring between two fluids. This could occur in
components associated with heat transfer or hydraulic systems, where it is important to
make sure that the fluid is not reactive with chlorine and to avoid products such as
water, silicone fluids, hydrocarbon oils, etc. Suitable materials for lubrication or
hydraulic or heat transfer fluids are fully chlorofluorinated fluids which are non-reactive
to chlorine gas or liquid. Perchloroethylene may be used for heat transfer fluid.
All ancillary equipment (instruments, sealing arrangements, etc.) should always be
checked as made from materials which are compatible with chlorine. Materials used for
thermal insulation should also be selected from those, which do not react readily with
chlorine or generate corrosive products under service conditions.
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8. REFERENCES
GEST 80/84 - Code of Good Practice for the Commissioning of Installations for Dry
Chlorine Gas and Liquid
GEST 94/216 - Experience of Non-Asbestos Gaskets on Liquid and Dry Chlorine Gas
Service
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Appendix 1 Page 1 of 1
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8th 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.
Euro Chlor
Avenue E Van Nieuwenhuyse 4
Box 2
B-1160 Brussels
Belgium
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