GEST 12 406 Edition 1

Best Practices in the Production and
Handling of Caustic Soda/Potash
GEST 12/406
Edition 1
April 2014
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 12/406
Edition 1
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 user’s 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 Chlor’s 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.
April 2014 Page 2 of 55

GEST 12/406
Edition 1
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 GEST (Storage,
Transport and Safety Working Group) to whom all suggestions concerning
possible revision should be addressed through the offices of Euro Chlor.

GEST 12/406
Edition 1
TABLE OF CONTENTS
1. INTRODUCTION ......................................................................... 6
2. PHYSICAL PROPERTIES OF CAUSTIC SODA/POTASH .............................. 6
3. PRODUCTION ............................................................................ 7
3.1 Generalities ........................................................................... 7

3.1.1. Mercury cell process ................................................................ 7
3.1.2. Diaphragm cell process ............................................................ 8
3.1.3. Membrane cell process ............................................................. 8
3.2. Concentration Processes ........................................................... 8
3.3. Solid caustic production ............................................................ 9
4. DESIGN & OPERATION OF CAUSTIC SODA INSTALLATIONS ...................... 9
4.1. Evaporators ........................................................................... 9
4.2. Heat exchangers .................................................................... 11
4.3. Pumps ................................................................................. 12
4.4. Filters ................................................................................. 13
4.5. Storage tanks ........................................................................ 14
4.6. Piping systems ....................................................................... 16
4.7. Dilution ............................................................................... 16
4.8. Instrumentation ..................................................................... 16
4.9. Valves ................................................................................. 16
4.10. Sampling Devices .................................................................... 16
4.11. Loading & unloading facilities .................................................... 17

4.11.1. General ............................................................................. 17
4.11.2. Truck loading ...................................................................... 18
4.11.3. Truck unloading ................................................................... 19
4.11.4. Railcar loading and unloading .................................................. 20
4.11.5. Ship loading ........................................................................ 21

GEST 12/406
Edition 1
5. SAFETY .................................................................................. 23
5.1. Safety (emergency) showers & eyewash fountains ........................... 23
5.2. Training ............................................................................... 24
6. MAINTENANCE ......................................................................... 24
6.1. Preparation for the maintenance ................................................ 24
6.2. Back into operation after maintenance ........................................ 25
7. APPENDICES ............................................................................ 25
8. REFERENCES ........................................................................... 25

GEST 12/406
Edition 1
1. INTRODUCTION
In the past, Euro Chlor was mainly focused on chlorine. In the production of
chlorine by the electrolysis of sodium chloride or potassium chloride, caustic
soda or caustic potash is co-produced. Caustic is very corrosive material to the
eyes and skin. It can cause severe burns, permanent injuries, lifelong scars and
even blindness. Therefore, safety in handling caustic soda/potash has a top
priority. While handling caustic, special care must be taken to protect yourself
and the recommended procedures for loading/unloading, maintenance and
inspection, Lock-out, Tag-out, Try-out (LoToTo), etc. must be followed. Based
on the fact that periodically incidents and accidents are reported, Euro Chlor
took the initiative to provide two documents describing the risk and the
precautions that can be taken to prevent incidents.
 This document describing the best practices in the production and
handling caustic soda and caustic potash.
 The Health 9 - Code of Practice-Control of Worker Exposure to Caustic
Soda in the Chlor-Alkali Industry.
The purposes of this document are:

 to have a best practice for the design, operation and maintenance of
caustic soda/potash installations
 to recommend procedures or checklists for employees who are handling
caustic.
For reasons of simplicity, the text in this document will mainly refer to
“caustic soda”, even if it can evenly be applied to caustic potash. The only
difference comes in appendices 1 and 2, dealing respectively with the
physical properties of caustic soda and caustic potash.
Remark: in this document, the concentration values of the caustic are expressed
in “weight” percentage.
2. Physical properties of caustic soda/potash

The main physical properties of caustic soda (solid-liquid equilibrium, density,
freezing and boiling points and enthalpy) are presented in appendix 1; those of
caustic potash are in appendix 2.

GEST 12/406
Edition 1
3. Production
3.1 Generalities
Caustic soda is one of the oldest man-made chemicals. Excavations in Egypt
show samples dating back to 3000 BC. In its solid form, caustic soda has a white,
crystalline appearance.
Caustic soda is a co-product in the production of chlorine, in a fixed ratio of

1.128 tons (as 100% NaOH) per ton of produced chlorine (1.577 as 100% KOH).
The caustic soda solution from the different processes is treated in slightly
different ways owing to the differences in composition and concentration.
Figure 1: Typical paths from raw brine to storage of caustic soda with
different processes
3.1.1. Mercury cell process
In the mercury process, the anode reaction involves chloride ions being
converted into chlorine gas. Mercury flows over the steel base of the cell and
acts as the cathode.
The sodium dissolves in the mercury and forms a sodium amalgam. This is
carried into the secondary cell where it reacts with water releasing sodium
hydroxide and hydrogen. To increase the rate of this reaction, the secondary
reactor contains carbon balls or plates, which catalyses the reaction. The
produced caustic soda solution contains about 50% NaOH. The free mercury is
returned to the electrolytic cell. The caustic soda solution is treated to remove

GEST 12/406
Edition 1
mercury and then stored in a storage tank. The solution is shipped to the
customers in cargo tanks, rail road tank cars, pipes and barges to the various
customers. For some uses, caustic soda can be diluted to 18-23% solution, which
can be handled without the risk of freezing.
3.1.2. Diaphragm cell process
A diaphragm is employed to separate the chlorine liberated at the anode from

the hydrogen and caustic soda produced directly at the cathode. Without the
diaphragm, the hydrogen and chlorine would form an explosive mixture, which
can easily ignite. Furthermore, the caustic soda and chlorine would react,
forming sodium hypochlorite (NaOCl), with further reaction to produce sodium
chlorate (NaClO3).
The diaphragm was made of asbestos, today mostly replaced by synthetic fibres,
and separates the feed brine (anolyte) from the caustic-containing catholyte.
Purified brine enters the anode compartment and percolates through the
diaphragm into the cathode chamber. The liquid leaving the cathode chamber
consists of a mixture of water, NaCl and NaOH. The composition of this solution
is approx. 12% NaOH and 14% NaCl in water. This solution is normally
concentrated to a 50% caustic solution by means of evaporation and the NaCl is
removed as a solid salt.
3.1.3. Membrane cell process
In this process a membrane is used instead of a diaphragm to separate the

chlorine from the hydrogen and the produced caustic. The membrane functions
completely differently compared with the diaphragm. Where the diaphragm is
permeable to sodium ions and chloride ions, the membrane is only permeable to
the sodium ions; the chloride ions are rejected almost completely. At the
cathode, a 32% NaOH solution is produced in modern systems. In some older
membrane processes, a 22-24% NaOH solution is produced. This solution is
normally concentrated to a 50% solution by means of evaporation.
3.2. Concentration Processes

Usually, the produced caustic solution by a membrane or diaphragm process is
further treated in an evaporation process to increase the concentration of the
solution.
In order to accomplish energy efficient use, a multi-effect evaporation is

generally used to concentrate the caustic from the starting concentration (for
instance 32%) to the desired usual commercial concentration of 50%.
For diaphragm process the produced caustic (approx. 12%) and salt solution
(approx. 14%) is generally also concentrated in multi-effect evaporators to a 50%
caustic solution. During the evaporation process the NaCl crystallizes as solid
salt and is removed from the caustic solution. The remaining caustic solution
normally contains less than 1% NaCl.

GEST 12/406
Edition 1
3.3. Solid caustic production

In some cases the caustic soda solution is further concentrated to solid material;
this can either be prills, flakes or drums.
The anhydrous forms are obtained through further concentration of 50% caustic
soda. Solid caustic soda results when hot molten caustic soda, from which all the
water has been evaporated, is allowed to cool and solidify. Flake caustic soda is
made by passing molten caustic soda over cooled flaking rolls or belts to form
flakes of uniform thickness. The flakes can be milled and screened into several
crystalline products with controlled particle size.
The manufacture of caustic soda beads involves feeding molten liquor into a
prilling tower under carefully controlled operating conditions, producing a
spherical bead.
In some cases the molten caustic is simply filled into drums where it solidifies.
4. Design & operation of caustic soda Installations
4.1. Evaporators
Design
In the membrane and diaphragm process, the concentration of the produced

caustic solution does not meet the usual commercially required concentration of
50%. Thus, the caustic solution is further treated in a multi-effects evaporation
process to concentrate it mainly to 50%.
Normally three types of evaporators are used:
 Shell and tubes falling film evaporators
 Shell and tubes rising film evaporators
 Plate type heat exchangers/evaporators
The number of effects strongly depends on the local conditions, operating
pressure, and cost of steam, cooling water temperatures and possibilities for
heat integration. More effects increase the energy efficiency, however at an
increase of investment cost. Normally up to 3 effects are used for membrane
caustic (up to 5 for diaphragm liquor).
In a multi-effect evaporator, the liquid is boiled in a series of heat exchangers,

each held at a lower pressure than the previous one. The caustic feed goes into
the heat exchanger with the lowest pressure. The vapour/liquid mixture is
separated in a chamber. Because of the boiling point elevation, the vapour is
flowing in counter flow to the liquid. Only the first heat exchanger (at the
highest pressure) requires an external heat source (steam).

GEST 12/406
Edition 1
The appendix 3 shows the organisation of the different pieces of equipment in

the case of a double and of triple effects unit.
In the diaphragm caustic concentration unit, the precipitated salt is separated

via centrifuges and further cleaned in washing columns for recycling.
The materials of construction that can be used are depending on the caustic
concentrations and temperatures, for this see appendix 4.
Safety provisions
The separation chamber must have two independent level instruments against
overfilling and preventing the pump from dry running, especially if a magnetic
driven pump is used.
The vapour coming from the evaporator that receives caustic from the
electrolysis section will contain some hydrogen. In the design it should be
arranged that after condensation of the water vapour no explosive mixture can
be formed. An option could be to add some nitrogen gas.
Operation
Figure 2 shows a typical falling film evaporator. The caustic soda is sent to the
top of the heat exchangers from where it flows into the pipes. The pipes are
provided with special inlets to provide an even distribution of the liquid.
V-3
FC
Caustic
soda
V-1 V-2
V-4
Steam
Condensate
Vapors
PI
LC
H(A)
TI
LS
E-101
PI
M
V-9
V-5 V-8 Concentrated caustic soda
to Off-spec tank or
Another falling film
V-10 V-11
evaporator
V-12
V-6
P-101
Water
V-7
Drain
Figure 2: Falling film evaporator
A mixture of liquid and vapour leaves the exchanger at the bottom and is
separated in the chamber. The vapour flows through a demister or a separator

GEST 12/406
Edition 1
to the next evaporator or condenser. The caustic soda flows either to the next
evaporator or the storage.
On the shell, either steam or vapour from the previous evaporation step is
applied to drive the evaporation process. On the bottom and top of the shell, a
vent is connected to prevent build-up of inert gas. Special care should be taken
if NH3 is present in the steam as this can cause corrosion of the (Ni) piping.
To prevent encrustation, a minimum wetting rate must be applied. This can be

realized via the circulation line.
The steam flow to the first evaporator can be controlled via a concentration
(density) measurement or boiling point elevation calculation (based on
measured p, T values) of the produced caustic.
4.2. Heat exchangers

Design
The heat exchangers used for cooling and/or heating caustic soda are plate type
or shell and tube heat exchangers.
As a cooling medium, caustic soda of a lower temperature or cooling water can

be used. For heating normally steam, hot water or warmer caustic solution can
be used.
The materials of construction that can be used are depending on the caustic
concentrations and temperatures, for this see chapter 6.
Safety provisions
When the cold medium can be blocked in the heat exchanger it is required to
have a safety relief valve taking care of the expansion of the liquid when
heated.
Figure 3: Caustic heat exchanger for a cooling duty with water

GEST 12/406
Edition 1
For plate type heat exchangers normally splash protection sheets/covers are
installed.
4.3. Pumps
Design
Typically, magnetic driven pumps should be used to prevent spills to the

environment. Depending on the temperature and caustic concentration, the
pump can be SS-316, PFA lined or Ni see Chapter 6. As an alternative, pumps
with double mechanical seals can be used.
Sufficient drain and flush facilities should be installed to drain the remaining
caustic from the pump and piping connections and to have facilities to wash out
the remaining caustic after draining.
PI
Water
V-5
V-4
Caustic
V-6 soda
Caustic
soda
V-1
V-2 P-101
V-3
Drain
Figure 4: Caustic soda pump
Safety provisions
In case of large pump and/or long lines (i.e. for ship loading, transport pipelines
to consumers/customers), care must be taken to prevent water hammer e.g. by
using:
 Slow opening/closing valves
 Soft starter or frequency converter for pumps
The risk for water hammer should be checked by calculation. Especially if the
pipeline is empty, it has to be filled carefully before the full flow is applied.
Putting the whole capacity of the pump on an empty line can lead to severe
water hammer which makes damage on the line.

GEST 12/406
Edition 1
4.4. Filters
In the caustic processing unit, filters can be used on intermediate product
streams (e.g. caustic from the electrolysis to the evaporation unit) or on final
product (e.g. to storage or from storage to a transport loading station or
pipeline).
Design
In most cases candle type filters are used. The filters have a specific pore size
(e.g. 10 micron). Depending on the temperature and concentration the filter
can be insulated and/or traced in order to keep the temperature of caustic soda
solution above melting temperature.
Regarding the materials of construction, see Appendix 4.
Safety provisions
The filter should be ventilated properly to prevent build-up of inert gas. In the
loading filters, the inert gas cannot be sent to the air. Because of this, the vent
should be connected to the drain and the drain should be sent to a safe
location. In the filters on the caustic coming directly from the electrolysis, the
vent is connected to the H2 vent section due to the presence of H2 in 32% caustic
soda solution.
Figure 5: Caustic soda filters

GEST 12/406
Edition 1
Figure 6: Caustic soda filtration from caustic coming from the electrolysis
section
4.5. Storage tanks

Design
Normally 18 - 50% caustic soda solution is stored in a tank. Especially for the
higher concentrations (30 - 50%) it has to be ensured that the operating
temperature is kept above melting temperature of the solution to prevent
solidification. This can be achieved by feeding relatively hot caustic soda
continuously to the tank or the tank can be heated by an internal coil or by
external circulation over a heat exchanger. Additionally, the storage tanks can
be insulated.
The materials of construction depend on temperature and concentration of the

caustic to be stored, see chapter 6. In some cases the internal walls of the tank
are lined with a compatible coating to minimise corrosion and iron pick-up.
Safety provisions:
The storage tanks should have 2 independent level instruments with high alarms
against overfilling and of which at least one is acting as safety trip (e.g. closing
the inlet valve and or stopping the supply pump). By using two level indicators
(instead of one indicator and one switch), both measurements can be
continuously compared which allows a significant increase in reliability.
Besides this overfilling protection, the tank is protected with an overflow line.
The overflow line should reach close to the floor to minimize splashing.
Additionally, an independent vent is required to prevent over- and under-
pressure.
Depending on local regulations, the tank is protected against leakage to the

environment either by placing the tank in a second containment (bund), having

GEST 12/406
Edition 1
a double walled bottom, or a completely double walled tank. In all cases of

failure of the storage tank, it should be detected and alarmed automatically.
The bund containment capacity should correspond to the largest of the tanks it
protects. The floor and the wall of the bund should be coated with a caustic
resistant material.
The temperature of the tank must be safeguarded against a too low (to prevent
the solidification of the caustic soda) or too high temperature (to prevent
exceeding the design temperature of the tank), in general via a high and low
temperature alarm, independent from the control of the tank temperature.
When the caustic solution from the electrolysers is stored, since it contains
hydrogen, the tank must be vented to atmosphere to prevent build-up of an
explosive mixture in the tank. When nitrogen is used, special care has to be
taken when the tank is taken out of operation and inspected. In those cases it
has to be ensured that the nitrogen connection is removed and that the tank is
sufficiently purged with air to ensure safe working conditions.
Operation
At normal operation, caustic soda solution is stored in a storage tank before it is

sent to the loading section by a pump (P-101 in Figure 7). In order to maintain a
safe minimum flow through the pump, some amount of caustic solution is
recycled to the tank.
Figure 7: Representation of caustic storage tank

GEST 12/406
Edition 1
4.6. Piping systems

Design
Pipelines for 32-50% caustic can be traced and insulated to prevent freezing of
the caustic. In general, electrical tracing is used. The maximum temperature of
the tracing must be safeguarded in accordance with the design temperature. For
carbon steel piping, the temperature must stay below 50 oC for 50% caustic soda
solution to prevent stress corrosion (See Table 9 in Appendix 4).
Safety provisions
All non-insulated flange connections should be equipped with splash guards if

the risk of unprotected flanges is considered too high.
Control and block valves in long pipelines should have dedicated closure times to
prevent water hammer.
Pipelines should have sufficient connections for draining and cleaning the
pipelines before opening.
4.7. Dilution
In some cases, the caustic soda has to be diluted with water for use or
transportation to customers. Considerable heat is generated by this operation
and proper handling procedures must be followed (if necessary by cooling) to
prevent boiling or eruptions of the product. Also the compatibility with the
materials has to be checked for the increase of temperature.
If the dilution is realised in a tank, the caustic will systematically be added to

the water, with constant agitation, and not in the opposite way.
In-line dilution, with use of static mixers can also be applied at the inlet of
storage tanks or trucks.
4.8. Instrumentation
Instruments should be installed in a way allowing sufficient isolation and
decontamination for maintenance (see chapter 5).
4.9. Valves
When isolating a section, the design should allow for a slip plate or blind flange
to be used in addition to the closure of the manual valve. For the main isolation
valves, the installation of double block and bleed can be considered.
4.10. Sampling Devices

Since caustic soda is highly corrosive, exposure should be avoided by installing
proper safe sampling devices.

GEST 12/406
Edition 1
4.11. Loading & unloading facilities

4.11.1. General
Caustic soda is usually transported by railcars, trucks, pipes and ships.
Due to the relatively high freezing point of the usual 50% commercial grade,
precautions have to be taken to avoid that the material solidifies during
transportation; in some cases the vessels will be equipped with heating coils and
steam connections.
Design, operation, maintenance and safety provisions of loading and unloading

facilities are described below.
Consideration must be given to the containment of caustic spills and leaks

(including from transfer connections); emergency procedures need to be
developed, communicated and the operators trained to remove these spills as
soon as possible; particular precaution is necessary when using a weak acid for
neutralisation.
Before loading activities can start a check which contains at least the following
items should be executed:
 Wear the required personal protective equipment before starting the
loading/unloading (see GEST 92/171 and Health 9)
 Switch off the vehicle and prevent movement (rail and road tank-cars,
ships)
 Fill in the shipping paper with the required information such as:
o Customer references
o Concentration of the solution
o Amount (every country has different regulations for the amount
loaded to the vehicle)
 Check the following:
o Be sure that the tank is appropriate for the product that has to be
loaded
o Cleanliness of the tank. If the tank was used before for other goods
a cleaning certificate must be available
o The vehicle is immobilised in proper position
o Capacity of the tank is appropriate for the amount to be loaded
(not greater than the maximum and not lower than the minimum)
o All connected piping, fittings, gaskets and covers are in good
condition
o All outlet valves are closed
During loading, check will be performed for possible leaks on the filling system.

GEST 12/406
Edition 1
After loading check all valves and covers for transport; check also the gross
weight does not exceed the permitted maximum.
Regulations
The loading, transport and unloading has to comply with the relevant legal
requirements. Specific regulations apply for the various transport options.
 For road transport the ADR (Accord européen relatif au transport
international des marchandises Dangereuses par Route)
 For rail transport the RID (Regulations concerning the International
carriage of Dangerous goods by rail)
 Inland waterway the ADN (Accord européen relative au transport
international des marchandises Dangereuses par voies de
Navigation intérieures)
 For ocean/sea the IMDG (International Maritime Dangerous Goods)
code
4.11.2. Truck loading
Design
The truck is connected to the loading section via a loading arm. A position
switch or restraining mechanism ensures that the loading arm is correctly
mounted. If the arm is not in the right position, loading cannot start. The truck
loading facilities are normally placed on a liquid tight floor with drain
connections to a dedicated collection facility where the dripped caustic can be
collected and neutralised.
Safety provisions
The access to the top of the tank should be safeguarded against possible fall.
The loading equipment should have one level instrument with high alarm against
overfilling of the truck. Besides, as another safety consideration, the truck can
be loaded on a weighbridge. The flow to the loading arm can be controlled by a
flow controller. In case of overfilling, loading must be stopped by closing the
valve in the supply line to the loading arm or stopping the loading pump.
After filling, wash the area of the tank around the loading point to remove
possible caustic drops.
Operation
Caustic soda is pumped (P-101 in figure 8) to the truck through a loading arm.
Minimum flow by-pass back to V-101 is ensured to protect the pump from
heating up.

GEST 12/406
Edition 1
4.11.3. Truck unloading
Design
The truck is normally connected via hoses to the unloading pump or unloading
vessel via the on-board pump. The unloading place should be located on a liquid
tight floor with drain connections to a dedicated collection facility where the
dripped caustic can be collected and neutralised. In the unloading connection or
vessel a detector is placed detecting no flow in order to stop the pump.
As an alternative to a pump, unloading of a truck can be performed by using air

pressure. Plant air is applied on the truck, and pushes its content to a storage
vessel.
Safety measures
Open the cover of the tank car before unloading to prevent under-pressure.
Level switch alarm on the receiving vessel (V-102 in figure 8) in order to prevent
overfilling.
In case of unloading by air pressure, the pressure has to be limited to a value

consistent with the truck maximum working pressure.
If the top of the tank has to be accessed, safeguard against possible fall should
be provided.

GEST 12/406
Edition 1
Figure 8: Truck loading and unloading
4.11.4. Railcar loading and unloading
For the design, operation and safety measures, see Truck Loading and Truck
unloading here above.

GEST 12/406
Edition 1
4.11.5. Ship loading
General design
The ship is connected to the loading line via a loading arm or hose. A position
switch or restraining mechanism ensures that the loading arm or hose is
correctly mounted. If the arm or hose is not in the right position, loading cannot
start. The loading arm or hose should be provided with breakaway couplings,
allowing the connection to be broken at pre-defined spots and triggering shut-
down of the caustic flow if the ship moves too much away from the platform
during loading; this should take into account the risk of high surge pressure in
the pipe due to fast shut-down. The overall process is shown in Figure 9.
Safety measures
There must be two walkways between the ship and the platform to guarantee an
escape route at all times. If it is not possible to set-up two walkways, the ship’s
crew should be able to leave the ship via a small boat on the side.
The safety of the ship loading on the platform is usually provided via 2 signal
cables. One is the emergency cable which can be used by the ship’s crew to
trigger the emergency stop. The other cable is for overfilling cases. If either
cable breaks, the filling is automatically stopped.
There are several chambers on the ship to store the caustic soda. When one of
those chambers is filled, ship’s crew is responsible to change the loading route
to another chamber. However in case of overfilling or triggering the emergency
button because of other unexpected situations, loading is automatically
stopped. Loading can also be stopped by an emergency button on the loading
platform and one in the control room.
Precautions have to be taken to avoid liquid hammer due to too rapid closing of
the valve or stopping the pump.
Be aware that rapid closure of a valve on board the ship could also result in
liquid hammer and the ship’s crew should be informed and trained.

GEST 12/406
Edition 1
Figure 9: Caustic soda shipping by ship

GEST 12/406
Edition 1
5. Safety
5.1. Safety (emergency) showers & eyewash fountains

The first seconds after exposure to caustic soda are very critical. Following skin
or eye contact, washing with water must be started immediately to prevent slow
healing chemical burns (see Health 9).
The safety showers and eyewash fountains should be installed in safe easily
accessible locations, for example near any acid or caustic handling area, to
allow for a rapid intervention.
It should be remembered that a caustic splash is to be rinsed for a minimum of

30 minutes but at least until health professionals take over treatment.
The system is simply activated by pressing foot pedal or pulling the handle; it is
recommended that this activation would trigger an alarm in the control room.
Figure 10: Combination of an emergency shower and an eyewash station

GEST 12/406
Edition 1
5.2. Training
Al workers, including contractors, that could be involved in handling caustic
should be made aware of its dangerous properties and trained on the best
operating practices and use of the protective equipment.
The training should include the following items.

 Physical and chemical properties of caustic (and how to rapidly
differentiate from water with Litmus paper)
 Potential health damages following exposition to caustic
 Description of specific personal protective equipment, safety showers,
eyewash fountains and exercises to use them (see GEST 92/171)
 Emergency intervention in case of contact with caustic (by the worker or
by a colleague)
As for all training, refreshing class room and field sessions should be organised
periodically.
6. Maintenance
All maintenance personnel, company or contractors, need to be thoroughly

trained with respect to the risk of caustic soda burns.
6.1. Preparation for the maintenance

Before starting with the activities, the equipment, pipeline and/or systems
should be taken out of operation. For this, a detailed shut-down procedure
should be available and followed. After the item is taken out of operation it
should be cleaned in order to remove the remaining caustic.
Note: where there has been a leak of caustic from the equipment, the
equipment should be washed externally to remove contamination before
maintenance; particular care must be taken with insulation that could be
heavily contaminated with caustic,
Normally the following actions take place:

 Where the equipment is insulated, the risk of caustic freezing after
removal of the insulation should be considered.
 Draining the caustic solution to a collection facility from where it can be
reworked or neutralised.
 Ensure that the item that has to be maintained is completely isolated
from the caustic system (and/or nitrogen, steam … systems) by using a
block and bleed arrangement, blind flanges or slip plates. For this step in
the process a LoToTo procedure should be in place.

GEST 12/406
Edition 1
 When the equipment, instrumentation or pipeline is isolated from the

caustic system, flushing can start. This can be done by spraying water (in
vessels) or filling up with water. The washing with water has to be
continued until the wash water has reached a pH of around 9 (checked
with pH paper or analysis by the laboratory). Special care has to be taken
when the equipment contains all kind of internals or dead spots where
caustic can remain after flushing the equipment. In this case, a good
solution could be filling up with water and draining several times. Some
equipment will need to be dismantled in a decontamination area to
ensure all caustic is removed. The wash water should be collected and
reworked in a later stage or neutralised and purged.
 If the system is connected to a nitrogen purge system to prevent the
formation of explosive mixtures of hydrogen (which can be present in the
caustic soda and the condensates from the concentration unit) one has to
ensure that before entering the equipment the nitrogen atmosphere has
been replaced by normal air and that the oxygen level is at the desired
concentration of approx. 20 vol%.
 After checking that the equipment or other parts are clean, the
maintenance activities can be executed.
6.2. Back into operation after maintenance

After maintenance, the drain and washing connection can be dismantled or
closed and the connection with the caustic systems can be opened or re-
installed. When the caustic connections are in place, the system will be tested
for possible leaks and then the installation can be taken back into operation.
Any removed insulation should be reinstated as soon as possible to avoid the risk
of caustic freezing.
A detailed start-up description should be available.
7. Appendices
Appendix 1: Physical properties of caustic soda
Appendix 2: Physical properties of caustic potash
Appendix 3: Schematic installation diagrams for a caustic concentration unit
Appendix 4: Materials selection for equipment, piping, etc. based on the
concentration and temperature of caustic soda
8. References
GEST 92/171 – Personal Protective Equipment in the Chlorine Industry
Health 9 - Code of Practice-Control of Worker Exposure to Caustic Soda in
the Chlor-Alkali Industry

GEST 12/406
Edition 1
Appendix 1 – Physical properties of caustic soda
Figure 11: Solid-liquid equilibrium data reference 1,2,3,4, 5 and 6
Table 1: Solid-liquid equilibrium data reference 1, 2, 3, 4, 5 and 6

GEST 12/406
Edition 1
Table 2: Density of caustic soda solution data ref 7, 8, 9, 10, 11 and 12

GEST 12/406
Edition 1
freezing point boiling point freezing point boiling point

dens
dens (Tm) dens(Tb) dens(Tb)
gNaOH [wt%] Tm [°C] Tb [°C] gNaOH [wt%] Tm [°C] (Tm) Tb [°C]
[kg/m3] [kg/m3] [kg/m3]
[kg/m3]
0% 0.0 1000.2 100.0 958.4 40% 15.5 1432.1 128.7 1354.8
1% -0.9 1012.5 100.1 968.6 41% 15.1 1442.3 130.3 1363.2
2% -1.7 1024.7 100.3 978.9 42% 14.4 1452.7 132.0 1371.4
3% -2.6 1037.0 100.5 989.2 43% 13.2 1463.4 133.7 1379.6
4% -3.6 1049.3 100.7 999.6 44% 11.3 1474.5 135.4 1387.6
5% -4.5 1061.6 100.9 1010.0 45% 8.6 1486.2 137.3 1395.6
6% -5.5 1073.9 101.1 1020.4 46% 5.4 1498.2 139.2 1403.5
7% -6.6 1086.2 101.4 1030.9 47% 7.5 1505.9 141.1 1411.3
8% -7.8 1098.6 101.6 1041.4 48% 9.2 1513.8 143.2 1419.0
9% -9.0 1111.0 101.9 1051.9 49% 10.6 1521.9 145.2 1426.7
10% -10.3 1123.5 102.3 1062.4 50% 11.6 1530.1 147.4 1434.3
11% -11.7 1136.0 102.6 1072.9 51% 13.3 1537.6 149.6 1441.8
12% -13.2 1148.7 103.0 1083.4 52% 18.9 1542.0 151.9 1449.3
13% -14.9 1161.4 103.4 1093.9 53% 24.1 1546.7 154.3 1456.7
14% -16.7 1174.3 103.8 1104.4 54% 29.0 1551.5 156.7 1464.1
15% -18.7 1187.3 104.3 1114.9 55% 33.6 1556.4 159.2 1471.4
16% -20.8 1200.5 104.8 1125.3 56% 37.9 1561.6 161.7 1478.8
17% -23.2 1213.9 105.3 1135.7 57% 41.9 1566.9 164.4 1486.1
18% -25.7 1227.6 105.9 1146.1 58% 45.5 1572.4 167.1 1493.4
19% -28.3 1241.3 106.5 1156.4 59% 48.8 1578.1 169.9 1500.7
20% -26.1 1250.6 107.1 1166.6 60% 51.8 1583.9 172.7 1508.0
21% -24.9 1260.6 107.8 1176.9 61% 54.5 1589.9 175.7 1515.3
22% -24.2 1271.2 108.5 1187.0 62% 56.8 1596.1 178.7 1522.7
23% -22.0 1280.3 109.3 1197.1 63% 58.8 1602.4 181.8 1530.1
24% -19.6 1289.2 110.0 1207.1 64% 60.5 1608.9 184.9 1537.5
25% -16.5 1297.6 110.9 1217.0 65% 61.8 1615.6 188.2 1545.0
26% -12.0 1304.8 111.7 1226.9 66% 62.9 1622.3 191.5 1552.5
27% -8.0 1312.5 112.6 1236.7 67% 63.6 1629.1 194.9 1560.0
28% -4.5 1320.7 113.6 1246.3 68% 64.1 1636.1 198.4 1567.7
29% -1.4 1329.2 114.6 1255.9 69% 64.3 1643.0 202.0 1575.4
30% 1.2 1338.1 115.6 1265.4 70% 64.2 1650.0 205.7 1583.2
31% 3.3 1347.2 116.7 1274.8 71% 63.8 1657.0 209.4 1591.0
32% 5.0 1356.6 117.8 1284.1 72% 63.3 1663.9 213.3 1599.0
33% 7.6 1365.4 119.0 1293.3 73% 62.8 1670.6 217.2 1607.0
34% 10.2 1374.1 120.2 1302.4 74% 62.4 1677.2 221.2 1615.1
35% 12.2 1383.2 121.5 1311.4 75% 72.6 1682.3 225.3 1623.4
36% 13.8 1392.5 122.8 1320.3 76% 87.0 1687.2 229.5 1631.7
37% 14.9 1402.0 124.2 1329.1 77% 101.1 1692.4 233.8 1640.2
38% 15.4 1411.9 125.7 1337.8 78% 114.9 1697.7 238.2 1648.8
39% 15.5 1421.9 127.1 1346.3 79% 128.3 1702.9 242.7 1657.5
80% 141.4 1708.0 247.3 1666.4
Table 3: Freezing and boiling points data ref. 1, 2, 3, 4, 5 and 6

GEST 12/406
Edition 1
Table 4: Enthalpy of caustic soda solution in kJ/kg references
For the references, see end of appendix 2

GEST 12/406
Edition 1
Appendix 2 – Physical properties of caustic potash
Figure 12: Solid-liquid equilibrium for caustic potash (data reference 17)
Phase Diagram - Composition of Solids

Maximums Transition Points
Concentration Temperature Concentration Temperature

Compounds (wt%) (°C) (wt%) (°C)
A Ice 0.0 0.0 A to B 30.8 * -65.2
B KOH•4H2O 43.8 -32.9 B to C 44.8 -33.0
C KOH•2H2O 60.9 75.3 C to D 57.4 33.0
D KOH•H2O 75.7 147.2 D to E 87.0 * 99.0
E KOH 100.0 406.0
* - Eutectic
Table 5: Solid-liquid equilibrium for caustic potash (data reference 17)

GEST 12/406
Edition 1
Tem perature(º C) at 0 º C at 10 º C at 20 º C at 30 º C at 40 º C at 50 º C at 60 º C at 70 º C
Density Concentration Concentration Concentration Concentration Concentration Concentration Concentration Concentration
(g/l) (%) (g/l) (%) (g/l) (%) (g/l) (%) g/l (%) g/l (%) g/l (%) g/l (%) g/l
1,200 20,5 245,5 20,9 251,2 21,4 256,6 21,9 262,3 22,4 268,3 22,9 274,3 23,4 281,0 24,0 288,4
1,210 21,5 259,7 21,9 265,4 22,4 270,8 22,9 276,4 23,4 282,7 23,9 288,7 24,4 295,5 25,0 302,7
1,220 22,5 274,0 22,9 279,6 23,4 285,2 23,9 291,1 24,3 297,0 24,8 303,1 25,4 310,3 26,0 317,4
1,230 23,4 288,3 23,9 294,2 24,4 299,9 24,8 305,5 25,3 311,7 25,8 317,8 26,4 325,0 27,0 332,1
1,240 24,4 302,7 24,9 308,6 25,4 314,5 25,8 320,4 26,3 326,5 26,8 332,6 27,4 339,8 28,0 347,2
1,250 25,4 317,1 25,8 322,9 26,3 329,3 26,8 335,0 27,3 341,5 27,8 347,8 28,4 354,8 29,0 362,0
1,260 26,3 331,9 26,8 337,7 27,3 343,9 27,8 350,0 28,3 356,6 28,8 362,9 29,4 370,1 29,9 377,0
1,270 27,3 346,7 27,8 352,7 28,3 359,2 28,8 365,4 29,3 371,7 29,8 378,2 30,3 385,2 30,9 392,4
1,280 28,2 361,3 28,7 367,6 29,2 374,1 29,7 380,7 30,2 386,9 30,8 393,6 31,3 400,6 31,9 407,8
1,290 29,2 376,4 29,7 383,0 30,2 389,2 30,7 396,0 31,2 402,1 31,7 409,1 32,3 416,2 32,8 423,3
1,300 30,1 391,8 30,6 398,2 31,1 404,7 31,7 411,5 32,2 418,0 32,7 424,6 33,2 431,5 33,8 439,1
1,310 31,1 407,3 31,6 413,8 32,1 420,0 32,6 428,8 33,1 433,2 33,6 440,0 34,1 446,8 34,7 454,7
1,320 32,0 422,8 32,5 429,4 33,0 435,6 33,5 442,2 34,0 448,9 34,5 455,7 35,1 462,9 35,7 470,7
1,330 32,9 438,1 33,5 445,2 33,9 451,4 34,4 457,9 34,9 464,6 35,5 471,6 36,0 479,1 36,6 486,5
1,340 33,9 453,6 34,4 460,6 34,9 467,0 35,4 473,8 35,9 480,5 36,4 487,5 36,9 495,4 37,5 502,5
1,350 34,8 469,4 35,3 476,6 35,8 482,8 36,3 490,2 36,8 496,5 37,3 503,6 37,9 511,0 38,4 518,7
1,360 35,7 485,3 36,2 492,5 36,7 499,1 37,2 506,2 37,7 512,7 38,2 519,2 38,8 527,3 39,3 534,9
1,370 36,6 501,6 37,1 508,5 37,6 512,3 38,1 522,4 38,6 529,1 39,1 536,2 39,7 543,6 40,2 551,9
1,380 37,6 518,3 38,0 524,8 38,5 531,4 39,0 538,8 39,5 545,4 40,1 552,7 40,6 560,0 41,1 567,7
1,390 38,4 534,0 38,9 541,0 39,4 547,8 39,9 555,0 40,4 561,7 41,0 569,2 41,5 576,7 42,0 584,1
1,400 39,3 550,6 39,8 557,5 40,3 564,3 40,8 571,5 41,3 578,5 41,9 586,0 42,4 593,3 42,9 601,2
1,410 40,2 567,0 40,7 574,0 41,2 581,1 41,7 588,1 42,2 595,3 42,7 602,6 43,3 610,1 43,8 618,0
1,420 41,1 583,3 41,6 590,4 42,1 597,5 42,6 604,6 43,1 611,7 43,6 619,3 44,1 626,8 44,7 634,9
1,430 41,9 599,7 42,5 607,2 43,0 614,5 43,5 621,8 44,0 628,8 44,5 636,1 45,0 643,8 45,6 651,9
1,440 42,8 616,6 43,3 623,7 43,8 631,2 44,4 638,9 44,9 645,8 45,4 653,3 45,9 660,8 46,5 669,2
1,450 43,6 632,8 44,2 641,1 44,7 648,4 45,2 656,0 45,7 662,8 46,2 670,3 46,8 678,0 47,3 686,1
1,460 44,5 650,1 45,1 658,0 45,6 665,5 46,1 673,2 46,6 679,9 47,1 687,5 47,6 695,1 48,2 703,3
1,470 45,4 667,4 45,9 675,2 46,5 682,8 46,9 689,9 47,4 697,2 47,9 704,7 48,5 712,4 49,0 720,5
1,480 46,3 684,5 46,8 692,3 47,3 700,0 47,8 707,3 48,3 714,7 48,8 721,9 49,3 729,6 49,9 737,9
1,490 47,1 701,6 47,6 709,4 48,1 717,1 48,6 724,6 49,1 732,0 49,6 739,5 50,1 747,1 50,7 755,3
1,500 47,9 718,8 48,5 726,8 49,0 734,7 49,5 742,1 50,0 749,9 50,5 757,1 51,0 764,6 51,5 773,0
1,510 48,7 735,8 49,3 744,0 49,8 752,4 50,3 759,8 50,8 767,5 51,3 774,8
1,520 50,1 761,4 50,7 770,2 51,2 777,5
Table 6: Density of potash caustic solution (data reference 16)

GEST 12/406
Edition 1
400
350
300
Temperature ª C
250
200
150
100
0 10 20 30 40 50 60 70 80 90 100
Concentration % KOH
Figure 13: Boiling point for aqueous solutions of KOH at atmospheric pressure
(data reference 18)

GEST 12/406
Edition 1
Temp.(ºc) 30% KOH 40% KOH 50%KOH

20
25 4,10 0,62 2,61
30 7,33 3,95 5,51
35 10,58 7,29 8,43
40 13,85 10,62 11,35
45 17,14 13,96 14,28
50 20,45 17,29 17,22
55 23,77 20,63 20,17
60 27,11 23,96 23,13
65 30,48 27,30 26,10
70 33,86 30,63 29,08
75 37,26 33,96 32,06
80 40,67 37,30 35,06
85 44,11 40,63 38,07
90 47,56 43,97 41,09
95 51,03 47,30 44,11
100 54,52 50,64 47,15
105 58,03 53,97 50,19
110 61,56 57,31 53,25
115 65,11 60,64 56,31
120 68,67 63,97 59,39
125 72,25 67,31 62,47
130 75,85 70,64 65,56
135 79,47 73,98 68,66
140 83,11 77,31 71,77
145 86,77 80,65 74,90
150 90,44 83,98 78,03
155 94,14 87,32 81,17
160 97,85 90,65 84,32
165 101,58 93,98 87,47
170 105,33 97,32 90,64
175 109,09 100,65 93,82
180 112,88 103,99 97,01
185 116,68 107,32 100,21
190 120,50 110,66 103,41
Table 7: Enthalpy for aqueous solutions of KOH (data reference 17)

GEST 12/406
Edition 1
Table 8: Viscosity for aqueous solutions of KOH (data reference 17)

GEST 12/406
Edition 1
References for appendices 1 and 2

(1) Int. Crit. Tables, vol IV (1928), 235, 247
(2) J. Timmermans, The Physico-chemical Constants of Binary Systems in
Concentrated Solutions, vol 3 (1960), 367-368
(3) Gmelin's Handbuch der Anorganische Chemie, Natrium, vol 21 (1928),
212-216
(4) Gmelin's Handbuch der Anorganische Chemie, Natrium, erg. 2, vol 21
(1965), 847-849
(5) W.F. Linke, Solubilities - Inorganic and Metal-organic Compounds, K-Z,
4th ed., vol II (1965), 1084
(6) D.R. Lide, CRC Handbook of Chemistry and Physics, 79th ed (1998) 6-119
(7) Int. Crit. Tables, vol III (1928), 79
(8) J. Timmermans, The Physico-chemical Constants of Binary Systems in
Concentrated Solutions, vol 3 (1960), 369-373
(9) Gmelin's Handbuch der Anorganische Chemie, Natrium, vol 21 (1928),
218-220
(1965), 861-862
(11) Perry's Chemical Engineers' Handbook, 7th ed. (1997), 2-105
(12) J. Krey, Z. Phys. Chem. (NF) 81 (1972) p. 252-273
(1965), 871-873
(14) H.R. Wilson and W.L. McCabe, Specific Heats and Heats of Dilution of
Concentrated Sodium Hydroxide Solutions Ing. Eng. Chem. 34 (1942) p.
565-566
(15) Table in Solvay brochure: Liquid Caustic Soda - Enthalpy of aqueous
solutions of NaOH
(16) Akerlof and Bender, Journal American Chemical Society, 63, April 1941.
(17) https://koh.olinchloralkali.com/TechnicalInformation/Phase%20Diagram%
200-80.pdf
(18) http://www.oxy.com/OurBusinesses/Chemicals/Products/Documents/Cau
sticPotash/kohhandb.pdf

GEST 12/406
Edition 1
Appendix 3: Schematic installation diagrams for a caustic

concentration unit
Two effects installation

GEST 12/406
Edition 1
Three effects installation

GEST 12/406
Edition 1
Appendix 4 - Materials selection for equipment, piping, etc. based

on the concentration and temperature of caustic soda/potash
1. General
In this chapter, various materials of constructions (MOC) are discussed regarding

their corrosion behaviour in the caustic production facilities. In Table 9, an
overview of the operating temperature limits and possible degradation
phenomena of the commonly used materials is given. This table can be used for
a first selection of materials of construction for piping and tanks but it is not
valid for heat exchangers, castings, velocities >2 m/s, two phase flow streams
(e.g. flashing conditions), highly diluted and highly contaminated NaOH/KOH.
It must be reminded that caustic reacts violently with many organic materials
(greases and oils …).
Glass is usually not recommended (sight-glass and sometimes also present in

measuring instruments) due to its severe corrosion by caustic.
2. Influencing factors for metals and alloys
A range of engineering materials can be used for the production and handling of
caustic. Their selection for a specific application depends on:
 the concentration of the solution

 the temperature
 the presence of impurities (e.g. hydrogen, oxygen, chlorate, sulphur
compounds)
 mechanical stress level (residual and applied operational stress)
 alloy composition and microstructure
 construction aspects (e.g. weldability, formability, castability)
 NaOH/KOH product quality demands on impurity levels (release of
undesired corrosion products)
 economical aspects and commercial availability
2.1 Concentration
For carbon steel and stainless steel, dependency of uniform corrosion rate on
caustic soda concentration is not very strong. In general, 50% caustic is
somewhat more corrosive than 24% caustic at the same temperature.
2.2 Temperature
Especially for stainless steels, the uniform corrosion rates show a very strong
dependency on temperature if passivity is lost above the indicated temperature.
For heat exchangers, maximum occurring wall skin temperatures should be used

GEST 12/406
Edition 1
to evaluate corrosion risks. Table 9 is not valid for selecting MOC’s for heat
exchangers.
2.3 Velocity
Austenitic stainless steels and nickel alloys develop a protective Ni-NiO layer in
caustic applications. This black layer becomes thicker, less protective and less
adherent (brittle) with increasing temperature. Based on experience, it is quite
well known that high velocities can result in high degradation rates due to
erosion-corrosion effects. The temperature limits mentioned in Table 9 are valid
up to approximately 2.0 m/s. Table 9 is not valid for two phase (liquid-gas) flow;
impingement of droplets can easily disturb protective oxide layers. Extreme
care should be taken in case of plate heat exchangers in caustic service. Plates
tend to rub each other at the contact points. Because of the thick brittle oxide
layers formed, wear may easily occur at the contact points leading to premature
failure of the plates. Therefore, Table 9 is not valid for plate heat exchangers.
Erosion due to the presence of solids is normally not encountered in membrane

caustic evaporation units (diaphragm caustic soda contains solid salt particles
during evaporation).
2.4 Oxygen
The oxygen content in the catholyte, heat medium circuit and caustic
evaporation section of membrane electrolysis plants is normally very low (ppb
range). Oxygen is an important factor in almost every electrochemical corrosion
process. It can show a positive (passivation) or negative (intensifying
degradation) effect depending on the conditions and alloy used. This is also the
case for stainless steels and nickel alloys in caustic applications. However the
precise influence of oxygen is not well established under the various conditions.
The temperature limits given in Table 9 for austenitic stainless steels will shift
to somewhat lower values with increasing oxygen level. If these limits are
exceeded, corrosion rates increase quite strongly with the oxygen level.
Corrosion rate of carbon steel also increases with oxygen content below the
limiting temperature indicated. Presence of oxygen can result in increased
corrosion rates on Ni-200/Ni-201 in evaporator units producing 73- 100% caustic.
2.5 Chlorate
Caustic from membrane plants contains usually 10 to 60 mg/kg chlorate in 50%
solution. Although chlorate is thermodynamically an oxidizing agent, the kinetics
of its reduction is quite low in highly alkaline media. Therefore, the
temperature limits given in Table 9 can be regarded as virtually independent of
chlorate levels in the range of 0 – 100 mg/kg. Only at substantial higher levels
and temperatures higher than 160ºC chlorate can have a negative effect on the
corrosion behaviour. Presence of chlorate can result in increased corrosion rates
on Ni-200/Ni-201 in evaporator units producing 73- 100% caustic.

GEST 12/406
Edition 1
2.6 Mechanical stress

Cyclic or fluctuating stress/strains may cause localized crack nucleation and
propagation referred to as fatigue. Fatigue life is influenced by a variety of
factors as: type of alloy, stress level, number of cycles, temperature and surface
geometry like notches, scratches, surface roughness which may cause stress
concentration or provide crack nucleation sites.
Corrosion fatigue is a localized degradation phenomenon of a construction under

the joint action of corrosion and cyclic loading. In general, this results in shorter
service life compared to cyclic loading of the same construction in an inert
environment. Prediction of service life for a specific situation is difficult without
prior accurate testing due to the variety of influencing factors. Corrosion fatigue
may under certain specific situations also arise in caustic installations.
In caustic applications, many MOC’s can suffer from stress corrosion cracking
(SCC) if loaded with residual and/or applied tensile stress. Susceptibility is often
noticed above certain temperature limits depending on type of alloy and caustic
concentration. The temperature limits given in Table 9 are based on experience
within the industry and corrosion literature. These limits for carbon steel and
nickel alloys are quite well established (Figure 12). The same is true to a lesser
extent for the 300 series stainless steel (Figure 13).
Stress relief treatment can be applied to minimize the risk of cracking. In the
following Figure 12, three areas can be distinguished: in area “A” no stress
relief is necessary, in “B” stress relief treatment of welds and cold worked parts
is deemed necessary, whereas in “C” stress relief treatment is ineffective and
other MOC’s should be selected.

GEST 12/406
Edition 1
Figure 12. Caustic soda service chart (carbon steel and nickel alloys)
Figure 13. Susceptibility to SCC of AISI 304L and AISI 316L

GEST 12/406
Edition 1
The temperature limits to avoid SCC of higher alloyed stainless steel types and
nickel alloys cannot be presented in simple way; besides temperature there is
also a strong dependency on stress level, alloy structure, heat treatment (e.g.
stress relief) and presence of contaminants.
Although the temperature limits for carbon steel and stainless steel 300 series in
Table 9 (and also in Figures 12 and 13) present good engineering practice, it
should be noticed that these limits are not guaranteed. In constructions with
extremely high (internal) stress levels (e.g. due to heavy cold forming or
welding) susceptibility to SCC may already arise below these limits. It has been
observed at temperature well below 100°C (drain plugs and pipes).
This is especially true for threaded connections and their applicability should be
carefully evaluated in caustic service. These connections may contain highly
stressed roots that can serve as stress corrosion cracking initiation points.
Local evaporation of small caustic leaks at the outer surface of flange or

threaded connections may occur which will increase the caustic concentration.
Risk of SCC is further increased due to contact with oxygen from the
atmosphere.
3. Metals and alloys
3.1 Aluminium
Aluminium is rapidly attacked by even dilute solutions of caustic at all
temperatures. In the corrosion reaction with caustic, hydrogen is formed due to
the reduction of water. At pH=9 or less, the corrosion rate is low at ambient
temperatures (<0.05 mm/y) but at higher pH, the protective oxide layer breaks
down locally and pitting occurs. At pH 12 and higher, severe localized corrosion
and at higher caustic concentrations severe general corrosion occurs. Corrosion
rate of aluminium in 20% NaOH at 20ºC is >>100 mm/y. Aluminium has to be
avoided for any application where there is contact with caustic even for a very
short exposure time (e.g. due to spills).
3.2 Titanium
Titanium is widely used in chlorine absorption system containing chlorinated
caustic soda. However it is unsuitable for use in pure caustic solutions and
requires a minimum level of chlorination to maintain the passive layer
protection.
3.3 Unalloyed and low alloyed steel

At ambient temperature, carbon steel is not attacked by caustic. Caustic
concentration has a small effect on the carbon steel corrosion rate. At a
temperature up to 45ºC in 50% NaOH, corrosion rate is typically <0.02 mm/y due

GEST 12/406
Edition 1
to the presence of a passive iron oxide layer. At higher temperatures, this oxide
layer provides less effective protection and corrosion rates increase.
Although corrosion rates are low up to about 45 ºC, the use of carbon steel
equipment may cause too much iron pick-up. In order to minimize iron
contamination a suitable liner or coating or an alternative material of
construction like FRP-PP, FRP-PVC or stainless steel can be considered. To avoid
excessive iron pick-up of the first NaOH batches in a carbon steel tank which has
been newly constructed, modified or out of service during a long period of time,
a passivation treatment of the tank is advised.
If tensile stresses are present, as from cold work, welding or internal pressure,
carbon steel equipment or piping is vulnerable to caustic stress corrosion
cracking (SCC) depending on temperature and concentration. This failure
mechanism is commonly referred to as caustic embrittlement. Caustic SCC is
typically intergranular, although transgranular cracking can also occur
depending on metal structure. The majority of the industrial cases of caustic
SCC in carbon steel equipment are associated with non stress-relieved welds,
typically in the heat-affected zone (HAZ) and adjacent base metal. Cracking
rate is highly unpredictable; however it steeply increases with stress level and
temperature.
Special attention should be given to proper temperature control of tracings

(both in and out of service situation) to avoid temperatures outside area “A” of
graph 6-1 of the previous section.
3.4 Austenitic stainless steel

General
Due to their good mechanical properties, weldability and corrosion resistance,

austenitic stainless steel types are widely used in both equipment and piping for
production, storage and shipping of caustic. It is widely accepted that corrosion
resistance of austenitic stainless steel types in caustic increases with nickel
content. Corrosion behaviour of stainless steel in caustic strongly depends on
the corrosion potential; behaviour under deaerated conditions (hydrogen
overpressure) can differ strongly from aerated conditions:
 At low potential, protection is provided mainly by Ni whereas Mo and Fe

are detrimental.
 At high potential, under oxygen overpressure, Ni along with Fe is
protective. Mo is detrimental if the Ni content is not high enough (>20%
Ni).
These conclusions should be considered as general guidelines. It cannot be

concluded that molybdenum containing alloys perform less in general since the
resistance of a specific alloy depends on the combination of alloying elements,
the percentage of the elements and their ratio.

GEST 12/406
Edition 1
To ensure reliable results when testing new or alternative alloys, it is strongly

preferred to test in situ under plant condition above lab experiments due to the
strong dependence of corrosion behaviour on corrosion potential.
Uniform corrosion
In an extensive survey of caustic soda producers, no difference in corrosion

behaviour was found of types AISI 304L and AISI 316L up to about 100 oC. If
atmospheric corrosion resistance is an issue (corrosion under insulation or
proximity of salt unloading units) Mo containing types like AISI 316L should be
preferred over Mo free types.
Corrosion resistance of austenitic stainless steel in hot deaerated caustic soda is

by the formation of a NiO-Ni black surface layer. Chromium and iron are
preferentially leached leaving behind a nickel rich surface layer. At lower
temperatures this layer is dense and well adherent providing excellent
resistance to both corrosion and erosion. As temperature increases this layer
becomes thicker, increasingly porous, less well adherent and brittle. Because of
this, the surface layer becomes increasingly susceptible to erosion (high flow
rates, local turbulences), temperature changes (start up – shut down), and
change in reducing – oxidizing conditions in time (certain H 2 pressure during
operation, aerated rinsing water during turnarounds), etc. The presence of such
an unprotective NiO-Ni layer is highly undesired: NiO spalled-off particles may
cause clogging or fouling (frequent filter cleaning), impair caustic soda product
quality and/or result in premature failure due to locally high corrosion rates.
Note: be aware that NiO is carcinogen by oral intake and precautions need to be
taken when coming in contact with it (maintenance work …).
Stress corrosion cracking
As carbon steel, stainless steel types may lead to stress corrosion cracking in hot
caustic however at clearly higher temperatures. Susceptibility depends on: alloy
composition, metallurgical structure, mechanical tensile stress level,
concentration, temperature and contaminants (e.g. oxygen, sulphur
compounds). In general the risk of cracking decreases with increasing nickel
content whereas the presence of oxidizing species or sulphur compounds
promote this form of failure.
In Figure 13 above, the range of susceptibility to SCC of 300 series stainless steel
types depending on NaOH concentration and temperature is shown. It should be
noticed that in this figure the influence of mechanical stress and contaminants
like dissolved oxygen is not shown. In general, susceptibility to SCC of these
stainless steel types can occur at concentration >20% and at temperatures
>100ºC. At concentrations <20%, the temperature for SCC susceptibility
increases with decreasing concentration.

GEST 12/406
Edition 1
3.5 Duplex stainless steel

Duplex stainless steel (DSS) types like Alloy 2205 (1.4462) and Alloy LDX 2101
(1.4162) have approximately twice the yield strength of austenitic types.
Besides, they offer a far higher resistance to chloride induced stress corrosion
cracking which offers clear benefits when corrosion under insulation is a point of
concern. Due to their low nickel content, the DSS grades can be a cost effective
alternative to comparable austenitic types. For instance if its corrosion
resistance is proven, LDX 2101 may offer clear cost benefits for use in caustic
storage tanks compared to AISI 304L or 316L. Alloy 2205 shows a uniform
corrosion resistance in caustic comparable to stainless steel 316L. In general,
the DSS grades show a clear lower susceptibility to SCC in caustic than the
austenitic grades. For the higher alloyed DSS grade SAF 2906, it is reported that
it has a clear higher corrosion resistance than AISI 316L. However, little
experience with DSS from practical applications has been reported so far.
Therefore, DSS types should be used with caution, unless good operational
experience is available.
3.6 Nickel and nickel alloys

At higher temperatures, typically above approximately 100oC, commercially pure
nickel (Ni-200 or Ni-201) is normally the preferred material of construction. It is
highly resistant to both uniform and stress corrosion cracking up to very high
temperatures. At T>315oC, Ni-201 (low carbon grade commercially pure nickel)
is recommended to avoid embrittlement due to graphite enrichment on the
grain boundaries. At very high temperatures, nickel may suffer from some
corrosion due to presence of oxidizing agents (e.g. oxygen and chlorate).
Reductive agents (e.g. sugar) are sometimes used to lower corrosion rates of
nickel in 73 - 100% NaOH. It is reported that the presence of sulphur compounds
in molten NaOH may result in cracking of Ni200/Ni201 due to formation of low
melting nickel sulphide (a cracking mechanism similar to liquid metal
embrittlement).
A disadvantage of Ni-200 and Ni-201 is the low mechanical strength. For this
reason nickel equipment often uses backing flanges of stronger materials such as
carbon steel or stainless steel. Care must be taken in the event of leaks as rapid
SCC damage can occur to the backing flanges.
Alloy 600 and Alloy 400 show high corrosion resistance to hot caustic soda. Due
to their higher strength compared to Ni-200, they are sometimes preferred, for
instance for tube sheets. At temperatures >160 oC, these alloys may be
susceptible to stress corrosion cracking and intergranular corrosion, depending
on the corrosion potential, microstructure (heat treatment) and mechanical
stress levels. In hot caustic facilities, applicability of Alloy 600 and Alloy 400
should be carefully evaluated for each specific situation. Due to its high copper
content, application of Alloy 400 can result in highly undesired pick up of
copper.

GEST 12/406
Edition 1
At normal operation, there is little incentive to use NiCrMo alloys like Alloy 625,
Alloy C-276, Alloy C-22, Alloy 59 and Hastelloy C-2000 in hot caustic. Mo free
alloys like Alloy 600, Alloy 800, Monel 400 or Ni-200 should be preferred. Alloy
625 may be used for plate heat exchangers (PHE) as an alternative for Ni-200 up
to about 115oC. Only for PHE coolers for hot caustic soda using oxidizing chloride
containing cooling water, NiCrMo alloys are used, because Mo free alloys would
suffer from crevice or pitting corrosion due to the aggressive cooling water. Mo
is in general detrimental to corrosion resistance in hot caustic and this effect
becomes dominant above 100ºC with increasing Mo content. NiCrMo alloys may
suffer from caustic de-alloying; especially chromium, molybdenum and
tungsten are leached out leaving behind an almost pure layer of metallic nickel
on the surface. This layer is porous and not protective. Additions of iron (if
>15%) appear to decrease the susceptibility to this form of attack. Caustic de-
alloying is rarely observed below 100oC; however susceptibility strongly increases
with the temperature above 100oC. Also oxidizing (oxygen) conditions stimulate
this kind of failure. NiCrMo alloys are sometimes used in PHE's to cool down 50%
NaOH from temperatures above 100ºC using chloride containing cooling water.
Service life time of Inconel 625 is about 6 years. Hastelloy C-2000 may offer
improved service life but experience is limited. Applicability of NiCrMo alloys
(“Hastelloy C types”) in hot caustic should be carefully evaluated for each
specific situation.
3.7 Copper and copper alloys

Copper and copper alloys are rarely used in caustic soda applications; under
oxidizing conditions, these alloys may result in undesired pick-up of copper ions.
However under deaerated conditions copper-nickel alloy UNS C71500 (70%Cu,
30%Ni) performs very well in a shell and tube coolers. The limiting temperature
for this alloy is not well established. Due to its nickel content, it is estimated at
approximately 110oC.
4. PLASTICS
4.1 Polypropylene (PP)

PP is available in three different types, namely PP-Homopolymer (PP-H), PP
Random-copolymer (PP-R) and PP Block-copolymer (PP-B) which are
discriminated on the basis of their polymer backbone structure.
Because of its higher stiffness and strength, PP-H is the preferred material for
pressure piping. Although PP-B was always preferred for low temperature
applications because of its lower modulus and better impact properties; modern
types of PP-H have almost matched these properties.
In general, all PP types have a good chemical resistance against caustic soda in
all concentrations up to approximately 80 to 90°C. Contaminations with
chloride, chlorate or oxygen have no influence on this.

GEST 12/406
Edition 1
In caustic soda, PP is normally used as a liner in fibre reinforced

polyester/vinylester (also known as FRP), to be able to reach the desired
mechanical properties.
When manufacturing PP lined FRP for hot caustic soda, extra attention should be
given to weld quality (high strength, low stress) and liner adhesion. Weld quality
is crucial as any weld leakage will lead to strong FRP attack and loss of
containment on a short time scale. Liner adhesion is important as thermal
cycling of lined FRP puts high stress on the bond between liner and FRP and may
cause de-bonding in case of inadequate initial adhesion.
When manufactured correctly, expected life time of FRP piping with this type of
liner in 32% NaOH at about 88°C (membrane cell temperature) is currently
estimated as approximately 15 years. Crack formation around the welds is the
life time determining factor.
For higher operating temperatures, up to approximately 100°C, certain specific

grades of PP are available. These are block-copolymers with a good history in
hot caustic soda applications in chlorine plants.
4.2 Polyethylene (PE 100)

PE is somewhat similar to PP in chemical resistance against caustic soda, but is
limited to a maximum temperature of approximately 60°C, even when
reinforced with FRP. Application for hot caustic soda is therefore limited.
4.3 Polyvinylchloride (PVC-U)

PVC-U, without plasticisers (U = Unplastised) can be used up to approximately
40°C in all caustic soda concentrations, usually reinforced with FRP to improve
mechanical properties (and impact resistance).
4.4 Polyvinylidenefluoride (PVDF)

PVDF is highly susceptible to stress corrosion cracking (SCC) in caustic soda at
approximately pH >12 and temperature >40°C, preventing its use in caustic soda
service in chlorine plants.
4.5 Perfluoralkoxyl (PFA) / Polytetrafluorethylene (PTFE) /

Fluorinated ethylene propylene (FEP)
These fully fluorinated plastics have complete chemical resistance against all
caustics to at least 150°C and are used as liners in valves, pipes and pumps.
They may be suited for temperatures above 150°C as well, but experience in
this range is scattered.

GEST 12/406
Edition 1
4.6 Fibre reinforced polyester (FRP)

FRP is the combination of a thermoset resin with glass fibre mats, fabrics and/or
rovings. The glass fibre reinforcement is protected from chemical attack by
either a barrier layer with high resin / low glass content or by a thermoplastic
liner. The type of FRP resin is selected on the basis of the design temperature
and expected chemical load.
Three main groups of resins are available:
 Polyester resins are the most economical resins, but have very limited
chemical resistance against caustic soda and should always be protected
from direct contact.
 Vinylester resins have much better caustic soda resistance than
polyesters, but direct contact is still limited to maximum temperatures of
approximately 50°C, with increasing corrosion and penetration rates at
increasing temperatures
 Epoxy resins have relatively good caustic soda resistance, but are more
difficult to process and have limited applications in piping and equipment
in chemical environments.
Because of the limited chemical resistance against hot caustic soda, FRP is
normally used only in combination with a thermoplastic liner, e.g. PP-FRP or
PVC-FRP. Vinylester resin is preferred for these FRP applications, in view of the
much better barrier function in case of liner leakage, at an only slightly higher
cost than polyester.
5. Gaskets
The choice of gaskets strongly depends on process temperature and material of

construction and a table has been included in the GEST 94/216 – Experience of
Gaskets in Chlorine and Liquid Caustic Service to summarises the chemical
resistance of various gasket materials.
For plastic equipment with low process pressure various rubber gaskets can be
used. Often EPDM is used but depending on process temperature also other
rubbers are available. However fluorine elastomers like Viton cannot be used. If
the process pressure is above 5 bar then a reinforced rubber gasket should be
used.
For metals at a temperature <100°C graphite gaskets with stainless steel

reinforcement or PTFE based gaskets can be used. For a process temperature
>100oC graphite with nickel reinforcement or PTFE based gasket with stainless
steel or nickel insert can be used.
For all gaskets, it is important to achieve the optimum sealing pressure. The
sealing pressure depends on the combination of material of construction, flange
design, the used gaskets and the used bolts. Gasket calculations have to be

GEST 12/406
Edition 1
made to calculate the optimum bolt torque. Qualified mechanics are used to
place the gaskets.
Other factors like creep (PTFE) need to be considered when selecting a gasket.

GEST 12/406
Edition 1
Limiting
Material of
≦ 25% NaOH ≦ 32% NaOH ≦50% NaOH 72% NaOH 100% NaOH degradation Remarks
Construction
mechanism
SCC (Stress
Use of carbon steel results
relief heat
in pick-up of iron. Each
treatment may
Carbon steel 60oC 55oC 50oC not resistant not resistant application is evaluated
increase
separately on
limiting
contamination risk
temperature)
(1) SCC at T> 100°C. (2)

AISI 304L
Above limiting
(1.4306 and Uniform
85oC 80oC 70oC 70oC not resistant temperatures, corrosion
equivalent Corrosion
rates steeply increase with
with > 10% Ni)
temperature
(1) SCC at T> 100°C
(2) Above limiting
AISI 316L temperatures, corrosion
(1.4404, Uniform rates steeply increase with
85oC 80oC 70oC 70oC not resistant
1.4571 and Corrosion temperature
equivalent)
(3) 60°C is the maximum
recommended for KOH
>40%

GEST 12/406
Edition 1
Limiting
Material of
Construction
mechanism
(1) SCC at T> 115°C.

(2) Above limiting
temperatures, corrosion
AISI 310S or rates steeply increase with
100oC Uniform
AISI 310L 105oC 105oC 100oC not resistant temperature
(estimated) Corrosion
(1.4335)
(3) nickel alloys
recommended above 32%
and temperature above
60°C
(1) SCC at T> 115°C
(estimated)
Alloy 904L
100oC Uniform (2) Above limiting
(UNS 08904, 105oC 105oC 100oC not resistant
(estimated) Corrosion temperatures, corrosion
W.NR. 1.4539)
rates steeply increase with
temperature
Useful up to
Useful up to Useful up to atmospheric
Risk on SCC at
atmospheric atmospheric boiling point Application at higher
Alloy 400 T>180°C. In
boiling point. boiling point. however may temperatures may result in
(UNS04400. general, not not resistant SCC
However, it However, it suffer from SCC. highly undesired copper
W.Nr 2.4360 ) recommended
may result in may result in Each application pick up
in hot 72% NaOH
copper pick up copper pick up is evaluated
separately

GEST 12/406
Edition 1
Limiting
Material of
Construction
mechanism
Useful up to
Useful up to atmospheric
Useful up to Useful up to atmospheric boiling point. SCC Condition
atmospheric atmospheric boiling point. However, it In general, not and heat
Alloy 600 At high temperatures,
boiling point. boiling point. However, it may may suffer recommended treatment
(UNS06600, only to be used in stress
However, Ni However. Ni suffer from SCC from SCC. due to high strongly
W.Nr 2.4816) relieved condition
200 is 200 is Each application Each risk on SCC influences
preferred preferred is evaluated application is susceptibility
separately evaluated
separately
Preferred
material in
boiling 72%
Sulphur contaminants at
NaOH. at T > 315°C
Fully resistant Fully resistant high temperatures may
Nickel 200 Fully resistant up However, it embrittlement
up to up to result in cracking due to
(UNS N02200, to atmospheric may suffer 315°C due to graphite
atmospheric atmospheric formation of a low
W. Nr 2.4060) boiling point from corrosion precipitation at
boiling point boiling point melting nickel sulphide
due to grain boundaries
compound
presence of
oxidizing
contaminants

GEST 12/406
Edition 1
Limiting
Material of
Construction
mechanism
Preferred Preferred
material in material in
boiling 72% molten 100%
Sulphur contaminants at
NaOH. NaOH.
Fully resistant Fully resistant high temperatures may
Nickel 201 Fully resistant up However, it However, it
up to up to Uniform result in cracking due to
(UNS N02201 , to atmospheric may suffer may suffer
atmospheric atmospheric corrosion formation of a low
W.Nr. 2.4061) boiling point from corrosion from corrosion
boiling point boiling point melting nickel sulphide
due to due to
compound
presence of presence of
oxidizing oxidizing
contaminants contaminant
In 60% NaOH,
Resistant up to Resistant up to Resistant up to
PE resistant up to no data
60°C 60°C 60°C
40°C
In 60% NaOH, SCC at welds,

PP resistant up to no data debonding of
100°C 100°C 80°C
60°C liner in PP-FRP
In 60% NaOH,
PVC resistant up to no data SCC
60°C 40°C 40°C
40°C
PVDF Not resistant Not resistant Not resistant Not resistant Not resistant SCC

GEST 12/406
Edition 1
Limiting
Material of
Construction
mechanism
SCC in hot
ECTFE not applicable not applicable concentrated
100°C 100°C 80°C
NaOH
Resistant up to Resistant up to Resistant up to Resistant up to Possibly also resistant to

PFA, PTFE not applicable
150°C 150°C 150°C 150°C higher temperatures,
Uniform
corrosion,
Bisphenol-A Resistant up to Resistant up to Resistant up to Detailed FRP
not applicable not applicable attack of glass
vinylester FRP 65°C 65°C 65°C specification needed
fibre
reinforcement
Table 9: Materials of construction for different concentrations of caustic soda

GEST 12/406
Edition 1
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

GEST 12 406 Edition 1

Uploaded by

Copyright:

Available Formats

You might also like

GEST 12 406 Edition 1

Uploaded by

Document Information

Original Description:

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

GEST 12 406 Edition 1

Uploaded by

Copyright:

Available Formats

Best Practices in the Production and

Handling of Caustic Soda/Potash

EURO CHLOR PUBLICATION

This document can be obtained from:

EURO CHLOR - Avenue E. Van Nieuwenhuyse 4, Box 2 - B-1160 BRUSSELS

Euro Chlor is the European federation which represents the producers of

Euro Chlor is working to:

 improve awareness and understanding of the contribution that chlorine

 maintain open and timely dialogue with regulators, politicians,

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

 Promote the best safety, health and environmental practices in the

April 2014 Page 2 of 55

RESPONSIBLE CARE IN ACTION

Chlorine is essential in the chemical industry and consequently there is a need

The voluntary recommendations, techniques and standards presented in these

April 2014 Page 3 of 55

2. PHYSICAL PROPERTIES OF CAUSTIC SODA/POTASH .............................. 6

3.1 Generalities ........................................................................... 7

3.2. Concentration Processes ........................................................... 8

3.3. Solid caustic production ............................................................ 9

4. DESIGN & OPERATION OF CAUSTIC SODA INSTALLATIONS ...................... 9

4.1. Evaporators ........................................................................... 9

4.2. Heat exchangers .................................................................... 11

4.3. Pumps ................................................................................. 12

4.4. Filters ................................................................................. 13

4.5. Storage tanks ........................................................................ 14

4.6. Piping systems ....................................................................... 16

4.7. Dilution ............................................................................... 16

4.8. Instrumentation ..................................................................... 16

4.9. Valves ................................................................................. 16

4.10. Sampling Devices .................................................................... 16

4.11. Loading & unloading facilities .................................................... 17

April 2014 Page 4 of 55

5.1. Safety (emergency) showers & eyewash fountains ........................... 23

5.2. Training ............................................................................... 24

6.1. Preparation for the maintenance ................................................ 24

6.2. Back into operation after maintenance ........................................ 25

April 2014 Page 5 of 55

The purposes of this document are:

2. Physical properties of caustic soda/potash

April 2014 Page 6 of 55

Caustic soda is a co-product in the production of chlorine, in a fixed ratio of

3.1.1. Mercury cell process

April 2014 Page 7 of 55

3.1.2. Diaphragm cell process

A diaphragm is employed to separate the chlorine liberated at the anode from

3.1.3. Membrane cell process

In this process a membrane is used instead of a diaphragm to separate the

3.2. Concentration Processes

In order to accomplish energy efficient use, a multi-effect evaporation is

April 2014 Page 8 of 55

3.3. Solid caustic production

4. Design & operation of caustic soda Installations

In the membrane and diaphragm process, the concentration of the produced

In a multi-effect evaporator, the liquid is boiled in a series of heat exchangers,

April 2014 Page 9 of 55

The appendix 3 shows the organisation of the different pieces of equipment in

In the diaphragm caustic concentration unit, the precipitated salt is separated