Pamphlet 94 - Edition 5 - January 2018

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THE CHLORINE INSTITUTE
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Pamphlet 94
Sodium Hydroxide
Solution and Potassium
Hydroxide Solution
(Caustic) Storage
Equipment and Piping
Systems
Edition 5
January 2018
Table of Contents
1. INTRODUCTION ................................................................................................................ 1
1.1 SCOPE ............................................................................................................................ 1
1.2 CHLORINE INSTITUTE STEWARDSHIP PROGRAM ................................................................. 1
1.3 DEFINITIONS AND ACRONYMS ........................................................................................... 1
1.4 SAFETY PROGRAMS ......................................................................................................... 3
1.5 DISCLAIMER ..................................................................................................................... 3
1.6 APPROVAL ....................................................................................................................... 3
1.7 REVISIONS ....................................................................................................................... 3
1.8 REPRODUCTION ............................................................................................................... 4
2. GENERAL INFORMATION................................................................................................ 4
2.1 PRODUCT DATA - SODIUM HYDROXIDE AND POTASSIUM HYDROXIDE SOLUTIONS (CAUSTIC) 4
2.2 CAUSTIC IN TRANSPORTATION .......................................................................................... 4
2.3 REACTIVITY AND COMPATIBILITY DATA .............................................................................. 5
2.4 PERSONAL PROTECTION INFORMATION ............................................................................. 5
2.5 SPILL PREVENTION PROGRAM .......................................................................................... 5
2.6 RELATED INSTITUTE PUBLICATIONS ................................................................................... 5
2.7 REGULATORY AND INSURANCE REQUIREMENTS ................................................................. 5
3. EMERGENCY RESPONSE ............................................................................................... 6
3.1 EMERGENCY PLANNING .................................................................................................... 6
3.2 CHEMTREC AND CANUTEC .......................................................................................... 6
3.3 REPORTING OF RELEASE .................................................................................................. 6
4. STORAGE TANKS ............................................................................................................ 8
4.1 GENERAL......................................................................................................................... 8
4.2 TANK CAPACITY ............................................................................................................... 9
4.3 SAFETY ..........................................................................................................................10
4.4 SECURITY .......................................................................................................................10
4.5 OPERATIONAL CONSIDERATIONS ......................................................................................11
4.6 DESIGN ..........................................................................................................................11
4.7 TANK ATTACHMENTS AND OPENINGS (APPURTENANCES) ..................................................17
4.8 SPILL CONTAINMENT .......................................................................................................18
4.9 INSPECTION AND MAINTENANCE .......................................................................................18
5. PIPING SYSTEMS ............................................................................................................20
5.1 GENERAL........................................................................................................................20
5.2 PIPING LAYOUT ...............................................................................................................20
5.3 PIPE AND PIPING COMPONENTS .......................................................................................22
5.4 VALVES ..........................................................................................................................32
5.5 OTHER COMPONENTS .....................................................................................................44
5.6 INSTRUMENTATION ..........................................................................................................45
5.7 INSPECTION AND MAINTENANCE .......................................................................................45
6. OTHER EQUIPMENT .......................................................................................................47
6.1 PUMPS ...........................................................................................................................47
6.2 HEAT EXCHANGERS ........................................................................................................48
6.3 AGITATORS AND MIXERS..................................................................................................48
7. REFERENCES ..................................................................................................................50
7.1 INSTITUTE PUBLICATIONS ................................................................................................50
i
7.2 API STANDARD SPECIFICATIONS ......................................................................................50
7.3 ASME CODES AND STANDARDS ......................................................................................51
7.4 NACE CORROSION DATA ................................................................................................51
7.5 OTHER REFERENCES ......................................................................................................51
7.6 OTHER RECOMMENDED READING AND VIEWING ...............................................................52
APPENDIX A – DATA SHEET – SODIUM HYDROXIDE SOLUTION ......................................55
APPENDIX B – DATA SHEET – POTASSIUM HYDROXIDE SOLUTION ...............................57
APPENDIX C – FREEZING POINT CURVE FOR CAUSTIC SODA SOLUTIONS ...................59
APPENDIX D – CAUSTIC SODA SERVICE GRAPH ...............................................................60
APPENDIX E – FREEZING POINTS OF AQUEOUS KOH SOLUTIONS .................................61
APPENDIX F – ALLOY SELECTION FOR CAUSTIC SODA SERVICE...................................62
APPENDIX G – PAMPHLET 94 CHECKLIST...........................................................................72
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SODIUM HYDROXIDE SOLUTION AND POTASSIUM HYDROXIDE SOLUTION
(CAUSTIC) STORAGE EQUIPMENT AND PIPING SYSTEM 1
1. INTRODUCTION
1.1 SCOPE
This publication is intended to provide useful information concerning the storage and
piping of sodium hydroxide and potassium hydroxide solutions. This pamphlet's
objective is to offer practical suggestions in the design, construction and operation of
systems suitable for 50% (and less) plus 73% solutions of sodium hydroxide, and for
50% (and less) solutions of potassium hydroxide. The requirements of anhydrous
sodium hydroxide and potassium hydroxide have not been considered.
1.2 CHLORINE INSTITUTE STEWARDSHIP PROGRAM
The Chlorine Institute exists to support the chlor-alkali industry in advancing safe,
secure, environmentally compatible, and sustainable production, distribution, and use of
its mission chemicals 1.
Chlorine Institute members are committed to adopting CI’s safety and stewardship
initiatives, including pamphlets, checklists, and incident sharing, that will assist members
in achieving measurable improvement. For more information on the Institute’s
stewardship program, visit CI’s website at www.chlorineinstitute.org.
1.3 DEFINITIONS AND ACRONYMS
In this pamphlet, the following meanings apply unless otherwise noted:
Alloy 20 (also known as Carpenter 20) one of the so-called “super”

stainless steels or nickel alloy that was designed for maximum
resistance to acid attack.
ANSI American National Standards Institute
API American Petroleum Institute
ASME American Society of Mechanical Engineers
ASTM ASTM International, formerly known as “The American Society

of Testing and Materials”.
CANUTEC Canadian Transport Emergency Centre
caustic generic term for either caustic soda or caustic potash
caustic a term that describes the stress corrosion cracking

embrittlement (intercrystalline cracking) of steel caused by exposure of caustic
solutions while under tensile stress.
1 CI’s mission chemicals: chlorine, sodium and potassium hydroxides, sodium hypochlorite, the
distribution of vinyl chloride monomer (VCM), and the distribution and use of hydrogen chloride.
2 PAMPHLET 94
caustic potash solutions of varying concentration of potassium hydroxide

(KOH)
caustic soda solutions of varying concentration of sodium hydroxide (NaOH)
CERCLA Comprehensive Environmental Response, Compensation and

Liability Act of 1980.
CFR Code of Federal Regulations (U.S.)
CHEMTREC Chemical Transportation Emergency Center
CPVC chlorinated polyvinyl chloride
DOT Department of Transportation (U.S)
ECTFE copolymer of ethylene and chlorotrifluoroethylene
EPDM ethylene propylene diene monomer or ethylene propylene diene

terpolymer
FEP fluorinated ethylene propylene
FRP fiberglass reinforced plastic
Hastelloy® a registered trademark of Haynes International, Inc.
HAZCOM Hazard Communication (refer to 29 CFR 1910.1200)
Inconel® a registered trademark of Special Metals Corporation
Institute The Chlorine Institute
kPa kilopascal
Monel® a registered trademark of Special Metals Corporation
OSHA Occupational Safety and Health Administration, under the U.S.

Department of Labor
OS&Y outside screw and yoke
PFA perfluoroalkoxy
psig pounds per square inch gauge

PTFE polytetrafluoroethylene
PVC polyvinyl chloride
release any loss of caustic to soil or water systems from the

containment (primary or secondary) vessel, pipe or equipment
SDS safety data sheet
SCC stress corrosion cracking
spill any loss of caustic from primary containment vessel, pipe or

equipment but not to soil or water systems
TC Transport Canada
transfer site any facility where product is loaded and/or unloaded
WHMIS Workplace Hazardous Material Information System (Canada)
1.4 SAFETY PROGRAMS
Every site handling caustic should have an ongoing safety program. Periodic training
sessions and safety inspections should be conducted in accordance with DOT and
OSHA regulations or equivalent local requirements. Special attention should be paid to
the appropriateness of emergency procedures and to equipment to be used in an
emergency. Additional information on safety programs is available from the Institute and
from caustic suppliers.
1.5 DISCLAIMER
The information in this pamphlet is drawn from sources believed to be reliable. The
Institute and its members, jointly and severally, make no guarantee, and assume no
liability, in connection with any of this information. Moreover, it should not be assumed
that every acceptable procedure is included, or that special circumstances may not
warrant modified or additional procedure. The user should be aware that changing
technology or regulations may require a change in the recommendations herein.
Appropriate steps should be taken to ensure that the information is current when used.
These recommendations should not be confused with federal, state, provincial,
municipal or insurance requirements, or with national safety codes.
1.6 APPROVAL
The Institute's Health, Environmental, Safety, and Security Issue Team approved Edition
5 of this pamphlet on January 31, 2018.
1.7 REVISIONS
Suggestions for revisions should be directed to the Secretary of the Institute.

4 PAMPHLET 94
1.7.1 Significant Revisions in Current Edition
Section 4.2 “Tank Capacity” was expanded to include considerations for the utilization of
used tanks for caustic service. Carbon steel construction considerations, previously
contained on Section 4.2, were moved to Section 4.6 “Design.”
Section 4.6.3 “Materials of Construction” was expanded to include considerations for use
of plastic materials, materials for tanks maintained at less than 120 °F (49 °C) and tank
liquid circulation.
Added the use of acetic solution for maintenance to Section 4.9.4.
1.8 REPRODUCTION
The contents of this pamphlet are not to be copied for publication, in whole or in part,
without prior Institute permission.
2. GENERAL INFORMATION
2.1 PRODUCT DATA - SODIUM HYDROXIDE AND POTASSIUM HYDROXIDE SOLUTIONS (CAUSTIC)
Sodium hydroxide solution and potassium hydroxide solution are the proper shipping
names for these products. However, this pamphlet will henceforth use the generic
product names caustic soda and caustic potash (or caustic to mean both).
Personnel handling caustic solutions should be thoroughly familiar with the chemical and
physical properties as well as the health hazards and first aid procedures appropriate for
these products. It is highly recommended that the reader review the safe handling
practices outlined in the data sheets found in Appendices A and B.
2.2 CAUSTIC IN TRANSPORTATION
Caustic soda and caustic potash are classified for transportation by DOT and TC as
Class 8 (corrosive materials). They are shipped as solutions in bulk containers.
However, due to relatively high freezing points (Appendices C and E) the materials may
solidify during transportation if shipping precautions are not taken into consideration.
Caustic soda is generally shipped as 50% concentration, while caustic potash is shipped
at a concentration of 45% to 50%. "Fifty-percent caustic soda" is the commercial
designation for caustic concentrations typically 48% to 52%. For purposes of
consistency, all references to 50% caustic in this pamphlet are intended to include
concentrations typically 48% to 52%. All persons handling bulk transports should be
familiar with all applicable regulations and safety procedures for the particular product
and its concentration. Higher concentrations of caustic soda, typically at 73%, are
generally shipped at elevated temperatures that require special handling.
Additional information on the transportation of, and handling practices for, caustic soda
and caustic potash can be found in CI Pamphlet 80 (for barges), CI Pamphlet 87 (for
tank cars) and CI pamphlet 88 (cargo tanks) (7.1).
2.3 REACTIVITY AND COMPATIBILITY DATA
Under normal use and conditions, caustic is generally regarded as stable. However,
caustic will rapidly attack and destroy such materials as leather, wool and the metals and
the alloys of aluminum, zinc, and tin. In addition, the reaction with these metals may
generate flammable hydrogen gas. The reaction of caustic with aluminum is particularly
vigorous and contact should be avoided. Both caustic soda and caustic potash are
strongly alkaline and may react violently with acidic solutions. These reactions will
generate heat and could cause splattering of the liquid. Caustic will also react vigorously
with many organic chemicals and due caution is required. Neither caustic soda nor
caustic potash form hazardous decomposition products nor contribute to hazardous
polymerization.
Considerable heat is generated when caustic is diluted with water. Proper handling
procedures must be followed to prevent vigorous boiling, spattering or violent eruption of
the diluted solution. Additional information can be found in CI Pamphlet 164 (7.1).
2.4 PERSONAL PROTECTION INFORMATION
Detailed requirements for personal protective equipment should be established on a site-

specific basis. Handling caustic requires adequate personal protective equipment to
protect the handler/user against product hazards. This topic is addressed in the
Occupational Safety and Health Standard in 29 CFR 1910 Subpart I – PPE. Users of
this pamphlet should be familiar with these regulations and incorporate their
requirements into the training of those involved in caustic handling.
Proper caustic compatible protective equipment (which may include hard hat, chemical
splash goggles, full face shields, gloves, rubber boots, etc.) should be worn when
handling caustic.
Safety showers and eye wash facilities should be located in the immediate work area.
Additional information about protective equipment for handling caustic can be found in CI
Pamphlet 65 (7.1).
2.5 SPILL PREVENTION PROGRAM
All transfer and handling facilities should have a documented spill prevention and
containment program for all hazardous materials. Refer to Section 4.8 for
recommendations on caustic spill containment. Consideration must be given to the
containment of caustic spills and leaks to comply with applicable federal, state and local
regulations (7.6 and Appendices A and B).
2.6 RELATED INSTITUTE PUBLICATIONS
For related information regarding physical properties, handling, protective equipment,

tank cars and tank motor vehicle the reader should refer to Section 7.1 and Appendices
A and B.
2.7 REGULATORY AND INSURANCE REQUIREMENTS
The location, capacity, design, maintenance and operation of caustic storage

installations may be subject to local, state or provincial regulations and to insurance
company requirements. Installations shall fully comply with all applicable requirements.
6 PAMPHLET 94
3. EMERGENCY RESPONSE
3.1 EMERGENCY PLANNING
Emergency/contingency plans should be in place for all areas of caustic handling and
transportation. These plans should identify hazards, develop systems for accident
prevention, and procedures for minimizing loss and damage resulting from accidents.
Copies of the plan should be on file as required by regulation.
Transfer Sites
All personnel responsible for transfer operations should be completely familiar with the
site emergency plan for handling spills and leaks of caustic. Refer to OSHA regulations
29 CFR 1910.120 for emergency response training. Each site should have proper
emergency response equipment on hand.
Transportation
The DOT and TC have specific training requirements applicable to handling of

hazardous materials. Shippers and consumers should familiarize themselves with these
specific requirements, and the emergency response communication standards and
OSHA/WHMIS requirements for off-site responder training.
3.2 CHEMTREC AND CANUTEC
For transportation-related incidents in the U.S., one should utilize CHEMTREC, the
Chemical Transportation Emergency Center in Falls Church, VA, as the dispatch
agency. CHEMTREC operates around the clock - 24 hours a day, seven days a week to
receive calls from any point in the United States and Canada at 800-424-9300.
CHEMTREC provides immediate advice for those at the scene of emergencies, then
promptly contacts the appropriate shipper and others as required. Registration with
CHEMTREC is provided through the American Chemistry Council. In Canada,
CANUTEC, the Canadian Transport Emergency Centre in Ottawa, should be used as
the dispatch agency. Their telephone number is 613-996-6666 (call collect) or *666 from
a mobile phone in Canada only. CANUTEC is administered by Transport Canada and
operates in a manner that is similar to CHEMTREC.
3.3 REPORTING OF RELEASE
Sodium hydroxide and potassium hydroxide are identified as hazardous substances in

Table 302.4 - List of Hazardous Substances and Reportable Quantities of 40 CFR 302.4.
CERCLA requires immediate notification of a release equal to or in excess of the
reportable quantity. The reportable quantity of both substances is currently 1,000
pounds (454 Kg). The 1,000-pound reportable quantity is based on a 100% basis (i.e. a
50% caustic soda solution contains 6.4 lbs. per U.S. gallon (766.9 kg/m3)).
Should a reportable release occur in the U.S., the law requires these agencies be
notified as soon as possible:
• National Response Center (1-800-424-8802)

• State Emergency Response Commission
• Local Emergency Planning Committee
In addition, state and local laws may require reporting to the appropriate state and/or
local environmental agencies.
While the laws/regulations do not require direct notification of the Coast Guard, many
facilities have found it mutually beneficial to directly notify the Coast Guard regarding
releases that might affect the use of a waterway.
In most cases, the initial report will be by telephone for expediency. A follow up written
report is also required. It is suggested that the following information be given during the
telephone report:
• Name of company involved

• Name of caller
• Plant location
• Chemical released
• Date, time, and duration of release
• Release quantity estimate
• Information as to whether or not the release is continuing or has been stopped
• The medium or media into which the release occurred (air, water, land)
• Any known or anticipated acute or chronic health risks associated with the
emergency and, where appropriate, advice regarding medical attention for
exposed individuals (Health Hazard Data and First Aid information from the
current caustic Safety Data Sheet (SDS) may be utilized.)
• Precautions taken as a result of the release
• Wind speed and direction
• Name and telephone number of person to contact for further information
If any agency notified has emergency response capabilities and/or responsibilities, you
should also inform them of any assistance you need.
A written follow-up emergency notice is required as soon as practicable after a

reportable release. This document should:
• Set forth and update the verbal information given previously
• Discuss actions taken to respond to and contain the release

• Discuss any known or anticipated acute or chronic health risks associated with
the release
• Where appropriate, give advice regarding medical attention for exposed
individuals.
8 PAMPHLET 94
It is also suggested, but not required, that the final report list the cause and corrective
actions, with a timetable if appropriate. If the report is mailed, it is recommended to be
sent by certified mail, return receipt requested.
3.3.1 Federal Reporting Requirements
In addition to reporting to the National Response Center, certain facilities are required to
make annual reports of hazardous substances and releases (refer to 40 CFR 370).
3.3.2 State Reporting Requirements
Varies from state to state, but usually includes:
• State Emergency Response Commission in addition to the immediate reporting

notification
Immediate notification required:
• State Environmental Department or environmentally responsible agency. This

may be more than one agency. Reporting time limits vary.
• State Police. Reporting time limits vary.
3.3.3 Local Reporting Requirements
In addition to reporting to the Local Emergency Planning Committee, immediate

notification may be required to the following. Reporting time limits vary.
• Town or city leadership groups

• Local police or sheriff
• Local fire department(s)
• Local health department
4. STORAGE TANKS
4.1 GENERAL
The guidelines in this section are intended to provide sound engineering practices for the
design, fabrication, operation and maintenance of above ground caustic storage tanks.
Caustic storage tanks are available in several shapes, and in both a vertical and a
horizontal orientation. However, the most common design is a vertical cylindrical design,
using a flat bottom and a closed top. This pamphlet will concentrate its comments on
the vertical cylindrical design. The guidelines in this section can be considered
independent of the shape selected.
This pamphlet will address storage of caustic up to and including concentrations of 73%.
The storage of anhydrous caustic is not covered.
Prior to designing a safe, secure and reliable caustic storage facility the expected
service conditions, product quality, safety and security requirements should be
completely defined.
• Service conditions to be defined should include the capacity, temperature ranges

and pressure ranges.
• Product quality parameters to be defined should include caustic concentration,
product contamination, and dilution effects. These parameters provide the
information required for the selection of shape, and the materials of construction.
• Safety requirements that can affect the design include containment needs,
environmental protection, personnel safety, and local codes.
• Operational considerations to be defined should include utilities, loading and off-
loading, lighting, freeze protection, operation logic, and maintenance.
• Site assessment should include soil analysis, ambient conditions including wind,
snow, flood, and seismic rating for the area.
4.2 TANK CAPACITY
General
The caustic storage system capacity should be the minimum that satisfies:
• operation
• maintenance
• inspection
• inventory and shipping requirements of the facility
• environmental risks
Storage Capacity
It is suggested that the size of a consumer's storage tank be one and one half times the
size of the delivered transport container. This ratio is often reduced for large capacity
tanks.
If a continuous supply of caustic is being consumed at the site, at least two tanks should
be considered to facilitate filling and gauging for product transfer, inspection, and
maintenance.
10 PAMPHLET 94
As with any chemical application, the utilization of tanks for an application other than
their initial design basis should be carefully evaluated. Due to specific gravity
differences, the capacity calculations for a tank designed for water or equivalent may not
be applicable to caustic service. If planning to install a used tank, or any tank previously
designed for storage of a material other than caustic, the capacity limitations of the tank
in caustic service should be verified by either the tank manufacturer or a qualified
engineer. If necessary, the effective capacity of the tank should be de-rated to account
for the higher specific gravity of caustic.
4.3 SAFETY
Consideration should be given in locating the caustic tank to minimize the potential
exposure to workers. However, in locating the tank in a remote area of the facility,
security concerns may be elevated.
The tank area should be well-marked with the appropriate warning signs and labels, as
identified in the HAZCOM plans. If located in heavy traffic areas, consideration should
be given to controlled access.
In the U.S., the federal OSHA Hazard Communication regulations 29 CFR 1910.1200
requires all manufacturing plants to label “hazardous chemical” vessels and ensure that
all employees are trained concerning the hazards involved. State and local government
regulations may require more specific labeling. In Canada, federal regulation WHMIS
(Workplace Hazardous Material Information System) is applicable.
4.4 SECURITY
Security concerns should be addressed including potential for breach, consequences

and mitigation. As with the other components of a risk assessment, the community may
be asked to participate in the design process.
In identifying security requirements, potential methods of breaching security should be

identified, the consequences of sabotage and the methods to reduce these security risks
should be evaluated and where appropriate implemented into the design of the site.
Caustic storage facility security concerns should be considered by having the proposed
site and facility design reviewed by those having security expertise. Design issues
addressed should include:
• Physical location relative to other facility components and the surrounding

community
• Clear visibility; open/clear areas
• Lighting
• Surveillance including security personnel, motion detectors and cameras
• Locked compounds and equipment (valves, pumps, etc.)
• Fencing, bollards, trenches, entrance/exit points
• Access control system
4.5 OPERATIONAL CONSIDERATIONS
Essential utilities such as air, water, steam, and power should be considered in the
storage area.
A potable water supply should be included for eye wash fountains and safety showers.
Non-potable water can be used for flushing the tank, lines, etc.
A steam supply to the caustic tank area may be used for freeze protection by
maintaining the tank temperature above 60oF (15.6oC) and for thawing and transferring
caustic without the use of a pump from some types of railcars.
If loading or off-loading of tank trucks or railcars is considered, the tank site must be
sized large enough for safe maneuvering and positioning of the vehicles. The tank area
should have adequate lighting, even if night operations are not planned, to facilitate the
efficient management of a potential emergency that could occur day or night. An
automatically controlled lighting system is preferred and should include emergency
lighting in critical working areas such as pump rooms, valve areas, etc. in case of power
failure.
Because of the high freezing point of 50% caustic (refer to Appendices C and E), it is
desirable to locate these tanks in heated buildings maintained above 60oF (15.6oC).
However, this may not be practical for large storage facilities where the tank must be
placed outdoors with a source of heat supplied to prevent freezing and flow problems.
The tank layout and access should consider tank openings (inlet and outlet),
maintenance, instrumentation, logic such as level indication/controls and spill
containment.
All personnel responsible for operating the caustic storage facility should also be trained
on security issues protocol.
4.6 DESIGN
4.6.1 General
The storage tank design should be performed by persons experienced in the area of
storage tank design. All the user’s requirements including the location and security
(accessibility) assessment should provide the basis of the tank design.
4.6.2 Design Standard
The basis of the design for metallic vertical cylindrical tanks can be either API 12F,
or API 620, or API 650 standard (7.2). The design parameters will govern the
standard selected. ASME Section VIII is an appropriate design standard for metallic
horizontal tanks. ASME RTP-1 (7.3.1) is an appropriate design standard for reinforced
thermoset plastic vessels.
The design of the storage tank will require complete documentation. The documentation
should include the process description, piping and instrument design, definition of the
standards employed, design calculations, certified tank drawings, materials of
construction and record of proof testing.
12 PAMPHLET 94
If the storage tank has an internal supported roof, the open structural shapes are
preferred over pipe for the supports, because all surface areas can be visually inspected
for corrosion.
4.6.3 Materials of Construction
General
The selection of material or combination of materials should take into consideration the
caustic concentrations, temperature and purity control. Carbon steels, carbon steel with
protective coatings or linings, carbon steel with clad alloys, stainless steels, nickel, nickel
alloys, plastics, and dual laminates have all been successfully utilized as materials of
construction for storage tanks. Refer to Appendix D, Caustic Soda Service Graph.
Appendix D is also applicable to caustic potash based on membership experiences. CI
Pamphlet 164 (7.1) may also be used as a reference.
• Carbon steel is common at lower concentrations (≤ 51%) and temperatures (≤

120oF (48.9oC)) where iron contamination is not a concern. At higher
concentrations and temperatures over 120oF (48.9oC), carbon steel will
experience accelerated corrosion and stress corrosion cracking (sometimes
referred to as "caustic embrittlement").
• Carbon steel can be protected with the application of various lining or coating
systems. The success of the liners is typically a function of temperature. There
is a wide range of liners in service that include various rubbers, coating systems,
metal cladding and thermoplastic linings.
• Stainless steels have been used successfully, but possible failure from exterior
chloride cracking should be considered.
• Nickel and nickel alloys can be used at any combination of temperature and
concentration. The use of these materials is typically found in high temperature,
high concentrations, or critical purity applications. Acceptable alternatives also
include nickel or nickel alloy clad to the carbon steel. When this option is used,
additional precaution in the welding and joining of the dissimilar metals is
necessary.
• FRP and dual laminate fabricated storage tanks for caustic have been
successfully utilized but are not commonly used, and may be considered if metal
contamination of the caustic is a significant concern. Important parameters in
selection are structural strength, ability to heat trace as compared to metal
construction, and corrosion barrier. A manufacturer and designer with
adequate experience in the fabrication of FRP and dual laminate tanks
should be consulted. Because caustic can readily attack the glass
fibers, synthetic surfacing veils, with an appropriate corrosion barrier, should
be specified. The proper selection of a corrosion barrier is critical. Some of
the vinyl ester and epoxy resins have good resistance for caustic service within
certain temperature and concentration limits. The resin selection should be
carefully reviewed for any potential FRP applications, especially if the process
caustic concentration is greater than 20%. The resin manufacturer should be
contacted to determine the correct application of FRP resin for the service.
• Plastic materials of construction including cross-linked high density polyethylene,

polypropylene, PVC and CPVC have been used successfully for smaller capacity
caustic storage tanks. When considering the use of a plastic tank, it is important
to ensure the tank is rated for a specific gravity higher than that of caustic, which
is approximately 1.54. Many plastic tanks are available with a design specific
gravity of 1.9 for use in caustic storage service. It is also important to ensure that
the heat source provided (i.e. steam, indoor climate control, electrical heat
tracing, etc.) to prevent caustic from freezing is controlled such that the
temperature of the plastic tank does not exceed the design temperature and
weaken the structural integrity of the plastic tank or piping. Plastic materials of
construction have a higher coefficient of expansion when compared to other
materials like carbon steel. Therefore, tank and pipe anchoring designs should
account for the thermal expansion and contraction of plastic when there is
variation in product storage temperature, and flexible connections from fixed
piping systems should be considered. Safety provisions for metal tanks including
adequate tank venting, containment, and seismic restraints should also be
considered for plastic tanks.
• The selection of a corrosion allowance is very important. Steels and stainless
steels can be attacked from inside or outside the tank. For floors and walls, a
minimum corrosion allowance of 1/8 inch (3 mm) is typical for carbon steel.
Corrosion rates must be carefully considered for the tank roof, and for any
internal support system for the roof.
50% and Less Caustic Storage Tanks
Temperature below 120oF (49oC)
For caustic solutions maintained below 120oF (48.9oC), the most common material for
tank construction is carbon steel. The plate joints should be welded with appropriate
rods, such as those containing 1/2% molybdenum.
Temperature 120oF – 160oF (49oC – 71oC)
If service temperatures above 120oF (48.9oC) are expected, stress relieving of welds and
bends should be considered, refer to Appendix D. The potential for stress corrosion
cracking (SCC) can be minimized by reducing stresses in the steel.
Temperature above 160oF (71oC)
At temperatures above 160oF (71oC), more corrosion resistant materials such as alloys
of nickel should be considered.
• The austenitic stainless steels, primarily 304L and 316L have been used
successfully in caustic service. The low carbon content austenitic grade provides
improved protection of the weld area (heat affected zone) against corrosion.
However both general corrosion rates and the risk of stress corrosion cracking
increase at higher temperatures. Therefore, in the absence of specific
experience in a particular application, a general upper limit of 200oF (95oC)
should be observed, refer to Appendix D. Cracking may result from stress
corrosion cracking (generally internal to the equipment) or chloride attack
(generally external to the equipment).
14 PAMPHLET 94
73% Caustic Storage Tanks
From a corrosion point of view, nickel is the material of choice for 73% liquid caustic
storage. However, nickel clad or lined steel tanks have been used successfully.
Linings
Tank linings may be used to minimize corrosion and iron pick-up. Factors to consider for
lining selection are chemical compatibility, temperature resistance, and physical
properties such as thermal shock, impact resistance, permeability, and wear resistance.
Before selecting a lining material for a caustic environment, both the lining supplier and
the caustic supplier service representatives should be consulted.
Silica-containing materials such as glass, brick and tile are attacked by caustic liquors
and should not be used.
Nickel and Nickel Alloys
Nickel and nickel alloys are much more resistant to attack by caustic than carbon steels
and the extra cost may be justified.
Where high purity product must be maintained or a storage tank temperature in excess
of 160oF (71.1oC) is expected, nickel, nickel-clad, or nickel-lined tanks should be
considered.
Plastic Linings
Plastic materials can be used for lining of metal or FRP tank structures; lined equipment
can afford higher levels of structural integrity than unsupported plastic material. Many
plastics have chemical resistance to caustic solution, up to their temperature limits.
Materials such as PVC, CPVC, polypropylene, polysulfone and the fluorocarbon resins
(PFA, FEP, PTFE, and ECTFE) will normally not be degraded by 50% caustic soda.
Plastic liners can fail if maximum temperatures are exceeded. Therefore, design should
take into consideration the maximum process temperature.
Resins
Epoxy resins and some vinyl resins have been successfully used for tank linings. The
supplier of the resin should be asked about the suitability of a given material for a
specific service and requested to make recommendations for qualified applicators.
Elastomers
Certain rubbers, such as natural rubber, neoprene and chlorobutyl rubber have proven
successful in some applications at varying temperature limits. The manufacturer of the
elastomer should be consulted for a recommendation for a specific application.
Coating Systems
Selected coating systems have successfully been used as a barrier in preventing iron
contamination of the caustic. The manufacturer of the coating system should be
contacted for a recommendation for a specific application.
4.6.4 Foundations
The detailed design and construction of the tank foundation can only be done after
careful assessment of the site surface, subsurface, and climatic conditions to ensure
adequate tank support.
Foundations for vertical tanks should be a uniformly supporting design. A reinforced

concrete foundation or ring wall with an impervious material inside the wall should be
considered. Moisture intrusion beneath the tank can cause external corrosion.
Appropriate design to prevent moisture intrusion should be considered. A leak detection
system should also be considered.
4.6.5 Tank Heating and Insulation
Caustic storage tank heating requirements are determined by the caustic concentration
in storage and its corresponding freezing point. Refer to Appendices C and E.
It is desirable to place higher concentration caustic tanks (higher freezing points) in

heated buildings that are maintained at a temperature greater than 60oF (15.6oC).
However, this is usually only practical for smaller tanks.
Storage tanks located outdoors should be insulated and/or heated if sustained

temperatures below 60oF (15.6oC) are expected.
For internal tank heating, a nickel bayonet-type, or coil-type heat exchanger should be
considered.
Care must be taken to prevent overheating to temperatures above those recommended

for the materials of construction. Automatic temperature control or regulation of the
steam source within temperature and material limitations should be considered.
Circulation of the liquid in the tank can be an effective way to minimize “hot areas” with
too much localized heating.
A temperature controller including a high temperature alarm and a thermocouple at the

same liquid level as the steam coil should be considered. Field indication of temperature
is desirable.
If a source of steam is not available, the storage tank can be heated using an electrical
horizontal bayonet-type heat exchanger similar to the one described above.
Wall heating can be accomplished with steam coils or electrical heating tape. Wall
heating systems must be designed to avoid the creation of hot spots which can exceed
the design limits of the vessel. The temperature of the caustic solution can be
maintained or increased slowly using electrical heat-tracing tape attached to the outside
of the storage tank.
If electrical heat-tracing tape is the only source of heat, the storage tank should be well-
insulated to minimize heat loss from the caustic solution. Not as common but also used
are hot water circulation in external coils made of carbon steel separated from the tank
with spacers.
Temperatures of the storage tank can also be maintained by circulating the contents
through an external heat exchanger (Refer to Section 6.2).
16 PAMPHLET 94
4.6.6 Tank Exterior Painting
All carbon steel tanks, including insulated tanks, should have an appropriate paint
system to minimize corrosion of the vessel’s exterior.
4.6.7 Instrumentation
Appropriate instrumentation along with safe operating procedures will greatly reduce the
risks of overfilling as well as temperatures and pressure excursions.
All instrumentation should be routinely checked for reliability and accuracy.
Tank Level
Redundant liquid level indicators with audible and visible high level alarms should be
considered. The first stage alarm should provide adequate time for the operator to take
appropriate action before a second high level alarm or overflow is reached.
For the second stage (high high-level) alarm system, a sensor independent of the tank
level instrument should be considered. CAUTION: Due to specific gravity differences,
the level transmitters that measure liquid head will vary dramatically as the caustic
solution is diluted.
Consideration should be given to automatic shutdown of the tank fill operation if the
second stage alarm is activated. This alarm should be set far enough below the actual
tank overflow, giving the operator sufficient time to react.
The tank may also be provided with a low level alarm to prevent overheating if the liquid
level were to drop below the heat source, e.g., steam coil, or, if not heated, the pump
suction line.
Sight glasses should not be used on caustic storage tanks unless materials of
construction compatible with caustic are used and it is well protected. Glass materials
should be avoided.
Tank Temperature
For heated storage, the temperature of the caustic storage tank contents should be
controlled within the limitations of the materials of construction. Refer to Appendices C
and E. Automatic control is preferred. A local temperature indicator should also be
considered. Temperature sensors are typically installed in thermowells for ease of
maintenance.
4.6.8 Other Considerations
If carbon steel construction is used, the amount of iron pick-up can be minimized by
keeping the contact area of metal with the caustic solution to a minimum. From this
standpoint, a height to diameter ratio of 1:1 is optimal. In addition to minimal surface
area per unit volume, problems related to heating and insulation are minimized.
4.7 TANK ATTACHMENTS AND OPENINGS (APPURTENANCES)
4.7.1 General
All welding carried out on any attachment to the tank should be done by qualified
welders using proven welding procedures in accordance with Section IX of the ASME
Code.
Reinforcement requirements at attachments and openings should be determined by the

tank design code used. If stress relieving is required it should be carried out in
accordance with the applicable code.
When possible, all connections at the top of the tank should be located to permit
servicing.
Flanged type connections are preferred. ASME flanges should be considered, if not
required, by the applicable code. Alloy construction should be considered for lap-joint
flanges.
All valves installed on the tank should be of a design that will allow secure locking of the
operating mechanism.
Specific considerations for certain tank openings are as follows:
Manways
A manway should be considered for entry for cleaning, washing, linings, coatings
inspection and bottom non-destructive examination testing and maintenance. Manway
diameter should be large enough to facilitate safe entry of personnel. For larger field
tank installation, top and bottom manways should be arranged to facilitate air circulation
for confined-space entry into the tank.
Vents
The tank vent, open to atmosphere at all times, should have a cross-sectional area
sufficient to prevent overpressure or vacuum. Valves should never be installed on the
vent line. When outdoor storage tanks are used, the design of vents should consider the
potential of plugging the vent with frozen caustic or other materials, especially with air
pad pressurized unloading processes.
Overflows
Overflow lines should extend from the top of the shell of the tank to an adequate
elevation above ground level. A dedicated overflow, routed safely to a containment
vessel should be installed. Flow detection instrumentation should be considered with
the installation of the overflow.
Inlet Fill Connection
Consideration should be given to locating the fill line connection above the tank overflow
level. An isolation valve should be installed in the nearest practical location. Material
and design of the valve should be in accordance with the recommendations in Section
5.4.
18 PAMPHLET 94
Outlet Connection
An isolation valve should be located at the tank’s outlet connection, or as close as

possible.
Drain Connection
A drain connection at the lowest point of the tank should be considered to facilitate
flushing and cleaning.
Spare Nozzles
Future welding on the tank after caustic is introduced is difficult, therefore, spare nozzles
should be considered in the initial design.
Access
Platforms, walkways, and access should be provided so routine operator and

maintenance activities at valves, connections, sample points, instrumentation, etc. can
be performed on items that are located above grade.
4.8 SPILL CONTAINMENT
As part of the risk assessment process, all new caustic storage facilities must comply
with local regulatory requirements for spill containment of storage tank systems.
Containment can be gained by use of sumps or reservoirs, double wall tankage, or by
diking. The containment system should not allow disposal of collected material without
prior confirmation of the contents.
If the material is recovered into the process, confirmation may not be required. All
existing systems should be evaluated on an individual basis with respect to industry best
practices.
Emergency provisions including the recovery and disposal of any caustic spilled should
be developed. Personnel should be thoroughly trained to handle emergencies
effectively.
Design layout in any containment area should consider the potential for mixing of
incompatible materials.
4.9 INSPECTION AND MAINTENANCE
4.9.1 General
A well-managed inspection and maintenance program for the caustic storage tank(s) will
ensure a safe and reliable operation.
Guidelines outlined in API Standard 653 - Tank Inspection, Repair, Alterations and
Reconstruction should be adopted where appropriate (7.2.6).
All repair work and inspections should be thoroughly documented for future reference.
4.9.2 Commissioning
Before a new caustic storage tank is put into service, its integrity must be proven through
an inspection and testing process. The tank should not be insulated until this process is
complete and the tank is accepted by the owner/operator.
Following a thorough cleaning of the tank, the floor and roof welds should be tested in
accordance with applicable codes. Next, the tank should be filled with water for leak
testing. For large outdoor tanks, its settling should be surveyed and documented as it
undergoes the initial water fill.
A carbon steel tank which has been exposed to a corrosive atmosphere for an extended
period may require descaling. It must be inspected to ensure integrity in caustic service.
Once descaled, it should be filled with caustic as soon as possible to passivate the
surface.
4.9.3 Inspection
A formal in-service and out-of-service inspection program should be well-established for

caustic storage tanks. The tank inspections should be carried out by certified inspectors.
The intervals between inspections can be determined by service history and corrosion
rates measured during previous inspections. Local regulatory requirements may also
dictate the frequency of inspections.
In addition to determining the integrity of the tank proper, the foundation structural
integrity, shell plumbness, appurtenances, heater, instruments, and dike’s drainage
system should be routinely inspected.
Visual
A good visual inspection can be a very effective component of the program. The wall
area next to the floor on large tanks can experience significant loads and should be
given special attention. Any white, crystallized residue on the tank may indicate
leakage.
Ultrasonic Thickness Check
Portable ultrasonic thickness gauges can be used during tank inspection to measure the
tank wall thickness. Measurement can be obtained without disturbing the tank contents.
Corrosion inspection points should be labeled and clearly identified.
Cracked Weld Areas (carbon steel and stainless steel tanks)
Weld areas that are not stress relieved become more susceptible to stress corrosion
cracking. If the service temperature is frequently above the 120oF (48.9oC) range, these
areas should be carefully inspected by proven crack detection techniques. Magnetic
particle and liquid penetrant tests can detect surface cracks very well.
4.9.4 Maintenance
A well-established preventive maintenance program will predict and minimize major

repair work and caustic tank outage.
20 PAMPHLET 94
The inspection program previously discussed in section 4.9.3 will play a key role in
determining the extent of repair work required on the tank.
All tank repair work should be done in accordance with the applicable code by qualified
personnel.
Cleaning and neutralizing of metal surfaces exposed to caustic in preparation for welding
is critical to prevent sensitizing the heat-affected zone. Common practice is to soak or
swab these areas with a 5-10% acetic acid solution and allow it to dwell on the metal
surface for 5-10 minutes. The surface should then be rinsed clean with water and a spot
test should be performed with pH paper to ensure that a surface pH is in an acceptable
range (6.0-8.0).
5. PIPING SYSTEMS
5.1 GENERAL
The guidelines in this section are intended to provide sound practices for the design and
construction of piping systems. In general, the industry follows the requirements
contained in the ASME B31.3 code (7.3.4).
Caustic is a hazardous material and therefore the piping systems for caustic service
should be designed carefully. The expected service conditions should be thoroughly
defined before a safe and reliable design can be engineered. The designer should
consider variability in operating conditions, including start-ups, shutdowns, process
upsets and system cleaning. Material selection should be based on expected service
temperatures, pressures, concentrations and intended caustic purity.
The piping systems for anhydrous caustic soda are not covered in this section. For
more information on storing and handling dry caustic soda, consult your supplier's
technical representative.
5.2 PIPING LAYOUT
Proper piping layout can enhance safety, reduce maintenance time and provide efficient
operations at effective costs. The following are several important considerations in
designing piping layout.
General Practices
• Avoid low point traps which will make clearing the line for maintenance or freeze
protection more difficult. If traps are unavoidable, drains should be provided or
procedures should be developed that will allow the line to be blown clear or
washed with the least amount of exposure to personnel and the environment.
• If pigging will be used to clear piping systems, proper components should be
used to allow passage of the pig. Long radius elbows, guide bars, and full port
valves are some of the components typically used in a piping system that will be
pigged.
• Pipe loops are preferred (horizontal plane) for lines requiring provision for linear
thermal expansion.
• Piping systems should be installed to allow complete drainage. High point vents
and low point drains should be provided. However, in some circumstances high
point vents collect oxygen, which leads to internal corrosion. Do not install more
high point vents than are required.
• Piping systems should include the appropriate number of fittings to facilitate
hydrotesting, clean-out, and maintenance. On flange connections, flange guards
may be considered in cases where there is risk of splashing personnel with
product.
• Caustic lines should be clearly identified.
• Pipe routing should be kept to a minimum, especially outdoors where the caustic
solutions can easily freeze if heating equipment malfunctions.
• Caustic (50%) freezes at temperatures below 60oF (15.5oC); therefore, all
associated process piping should be heat traced and insulated if caustic
temperatures are anticipated to be 60°F (15.5°C) or lower. For other caustic
concentrations, refer to Appendix C (NaOH) and Appendix E (KOH) to validate
the need for insulation and/or heat tracing.
• Electric heat tracing is strongly preferred to steam heat tracing. “Self-limiting”
electric tracing is preferred in those cases where it is practical to use it. In all
cases the heat input should be controlled to avoid high metal temperatures that
would result in caustic stress corrosion cracking, refer to Appendix D. Use
caution in the placement of the temperature measurement device so that it does
not indicate a false “low” reading if the layout of the piping system is such that the
pipeline may be hotter in some sections than it is in other sections.
Clearances
Road and walkway clearances should be set to minimize the possibility of impact
damage. Barriers or guard rails should be considered. Railroad and roadway
clearances may be regulated by federal, state, provincial, or local laws.
Supports
Piping should be designed with adequate support to avoid excessive deflection between
adjacent supports and not allow metal to metal wear or corrosion. If located in an area
where seismic activity can be significant, the local code requirements should be
reviewed. In general, pipes should be supported with hangers, shoes or saddles, pipe
clamps or U-bolts. Do not hang other piping from a caustic line and do not hang caustic
lines from other piping. For new construction “weld-on” shoes are preferred over “clamp-
on” shoes since metal to metal connections provide crevices that tend to corrode. This
is especially true in climates that have high humidity levels.
Routing
Aboveground installations are preferred for in-plant piping. When routing caustic piping
over equipment, the potential for caustic leaks should be considered. In general, caustic
lines should be routed on the lower elevation of the pipe rack.
22 PAMPHLET 94
Valves and Controls
Accessibility should be considered when locating all valves and controls to facilitate their
operation and maintenance.
Block valves should be located in branch lines, preferably at the main header. When
locating block valves, consider such factors as accessibility and the ability to isolate
piping equipment and tanks. Block valves located below the normal liquid level should
be close to or at the tank nozzles.
5.3 PIPE AND PIPING COMPONENTS
This section provides recommended minimum specifications for pipe and piping
components for caustic. All parts of this pamphlet should be consulted before deciding
on the components of a piping system.
5.3.1 Metallic Piping Systems
Piping systems, including pipe, fittings, gaskets, nuts and bolts, valves, and other items
have been organized into three groups (Tables 5.1, 5.2 and 5.3) according to the
following construction breakdown:
• Threaded construction
Threaded construction should be limited to pipe systems two inches in diameter

or less. Threaded construction reduces the wall thickness of the pipe and can
add stress points which may be a disadvantage. Threaded connections are
susceptible to leaks in caustic service due to the very low surface tension of
caustic soda solutions. Threaded joint leaks are especially prone to occur at line
pressures exceeding about 60 psig (414 kPa).
• Socket Weld Construction
Socket weld construction is sometimes used for pipe systems two inches in
diameter or less. However, failure can occur if proper fit-up and welding
procedures are not followed. Crevice corrosion is also cause for concern, and for
this reason the use of socket welded pipe construction is not recommended
choice for permanent systems that are expected to stay in service for long time
periods. Socket welded systems are more acceptable for piping systems that are
intended to be of a temporary nature.
• Butt Weld Construction
Butt welding and flanged joints are recommended for all sizes.
Within the three construction groups listed above, there are several material groups
which can be selected. The characteristics of the various materials of construction are
as follows:
• Carbon Steel
Carbon steel is a common material of construction within limited temperature and

caustic concentration ranges. At temperatures above 120oF (49oC) at 50%
caustic soda, carbon steel is susceptible to stress corrosion cracking. Refer to
Appendix D.
• Stainless
The austenitic low carbon stainless steels, primarily 304L and 316L have been
used successfully in caustic service. The low carbon content austenitic grades
provide improved protection of the weld area (heat affected zone) against
corrosion. However, both general corrosion rates and the risk of stress corrosion
cracking (SCC) increase at higher temperatures and concentrations. Therefore,
in the absence of specific experience in a particular application, a general upper
limit of 200oF (95oC) should be observed, refer to Appendix D. Cracking may
result from SCC (generally internal to the equipment) or chloride attack (generally
external to the equipment). Temperatures above 212°F (100oC) tend to create
product quality issues with both color and with high iron concentrations.
Temperatures above 248°F (120oC) are susceptible to caustic SCC. External
chloride SCC can occur at much lower temperatures (even at ambient
temperatures) if the atmosphere or the pipe insulation contains chlorides.
Chloride SCC is generally not a problem on the inside of the pipe due to the high
pH levels that are normally present.
• Monel
Monel is used in caustic applications up to 73% and is more resistant to stress

corrosion cracking than stainless steel. However, when compared to nickel,
Monel has a higher corrosion rate at elevated temperatures.
• Nickel
Nickel is the common material for caustic piping at high temperatures and
concentrations. It is resistant to stress corrosion cracking and has a very low
corrosion rate minimizing metal ion contamination. Nickel provides the greatest
corrosion resistance of the metallic materials listed in this section.
24 PAMPHLET 94
Table 5.1: Threaded Construction [See Note 7]

ITEM NOMINAL <=50% CAUSTIC <=50% CAUSTIC <=73% CAUSTIC <=73% CAUSTIC
PIPE SIZE <=120oF(48.9oC) <=200oF(95oC) <=260oF(126.7oC) <=350oF(176.7oC)
(NPS) [See Note 1] [See Note 1] [See Note 1] [See Note 1]
<=175 PSIG(1207 kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa)
CARBON STEEL STAINLESS STEEL MONEL NICKEL
[See Note 2] [See Notes 2, 3 and 8] [See Note 2] [See Notes 2 and 8]
PIPE See Material [Through 1-1/2"] [Through 2"] [Through 1"] [Through 1"]
Group ASTM A106 Grade B ASTM A312 ASTM B165 ASTM B161
Sch 80 Carbon Steel Grade TP304 UNS N04400, Annealed UNS N02200, Annealed
Seamless Sch 40S Stainless Steel Sch 40, Seamless or Sch 40 Seamless or
ASME B36.10 Seamless or Welded ASTM B725 ASTM B725
ASME B36.19 UNS N04400, Annealed UNS N02200, Annealed
[See Note 11] Sch 40 Welded Sch 40 Welded
ASME B36.19 ASME B36.19
[2"] [1-1/2" and Larger] [1-1/2" and Larger]

ASTM A53 Grade B Not Recommended Not Recommended
Sch 40 Carbon Steel [See Note 11] [See Note 11]
Seamless or Welded
ASME B36.10
FITTINGS Through 1" ASTM A105 ASTM A351 Grade CF8 ASTM A494 Grade M35-2 ASTM A494
Class 3000 Class 150 Cast SS or Class 150 Cast Monel or Grade CZ-100
Forged Carbon Steel ASTM A182 Grade F304 ASTM B366 (B564/B164) Class 150 Cast Nickel or
Threaded Ends Class 3000 Forged SS Grade WPNC ASTM B366 (B564/B160)
ANSI B16.11 Threaded Ends Class 3000 Grade WPN
ANSI B16.11 Forged Monel, Annealed Class 3000
[See Note 5] Threaded Ends Forged Nickel, Annealed
ANSI B16.11 Threaded Ends
[See Note 5] ANSI B16.11
[See Note 5]
1-1/2" to 2" ASTM A105 ASTM A351 Grade CF8 Not Recommended Not Recommended
Class 3000 Class 150 Cast SS or
Forged Carbon Steel ASTM A182 Grade F304
Threaded Ends Class 3000 Forged SS
ANSI B16.11 Threaded Ends
ANSI B16.11
[See Note 5]
UNIONS Through 1" ASTM A105 ASTM A351 Grade CF8 ASTM A494 Grade M35-2 ASTM A494
Ground Joint Seat Class 3000 Forged SS Grade WPNC ASTM B366 (B564/B160)
Threaded Ends Ground Joint Seat Class 3000 Grade WPN
Threaded Ends Forged Monel, Annealed Class 3000
[See Note 5] Ground Joint Seat Forged Nickel, Annealed
Threaded Ends Ground Joint Seat
[See Note 5] Threaded Ends
[See Note 5]
1-1/2" to 2" ASTM A105 ASTM A351 Grade CF8 Not Recommended Not Recommended
Class 3000 Class 150 Cast SS or
Forged Carbon Steel ASTM A182 Grade F304
Ground Joint Seat Class 3000 Forged SS
Threaded Ends Ground Joint Seat
Threaded Ends
[See Note 5]
Table 5.1: Threaded Construction [See Note 7]

[See Note 2] [See Notes 2, 3 and 8] [See Note 2] [See Notes 2 and 8]
FLANGES Through 1” ASTM A105 ASTM A182 Grade F304 ASTM B164/B564 ASTM B160/B564
Class 150 Class 150 UNS N04400 UNS N02200
Forged Carbon Steel Forged Stainless Steel Class 150 Class 150 or Class 300
Raised Face Raised Face Forged Monel, Annealed Forged Nickel, Annealed
Threaded Threaded Raised Face Raised Face
ASME B16.5 ASME B16.5 Threaded Threaded
[See Note 6]
1-1/2" to 2" ASTM A105 ASTM A182 Grade F304 Not Recommended Not Recommended
Class 150 Class 150
Forged Carbon Steel Forged Stainless Steel
Raised Face Raised Face
Threaded Threaded
GASKETS All Sizes PTFE Gasket With PTFE Gasket with Various PTFE Gasket with Various PTFE Gasket with Various
Various Fillers or EPDM Fillers or EPDM or Non- Fillers Non-Asbestos Fillers or Non-Asbestos
Non-Asbestos Asbestos [See Note 4] [See Note 4]
[See Note 4] [See Note 4 ]
BOLTS All Sizes ASTM A193 Grade B7 ASTM A193 Grade B7 ASTM A193 Grade B7 ASTM A193 Grade B7
Alloy Steel Alloy Steel Alloy Steel Alloy Steel
Quenched and Quenched and Tempered Quenched and Tempered Quenched and Tempered
Tempered Stud Bolts and Stud Bolts and Stud Bolts and
Stud Bolts and Cap Screws Cap Screws Cap Screws
Cap Screws ASME B18.2.1 ASME B18.2.1 ASME B18.2.1
ASME B18.2.1 [See Notes 9 and 10] [See Notes 9 and 10] [See Notes 9 and 10]
[See Notes 9 and 10]
NUTS All Sizes ASTM A194 Grade 2H ASTM A194 Grade 2H ASTM A194 Grade 2H ASTM A194 Grade 2H
Carbon Steel Carbon Steel Carbon Steel Carbon Steel
Heavy Hex Nuts Heavy Hex Nuts Heavy Hex Nuts Heavy Hex Nuts
ASME B18.2.2 ASME B18.2.2 ASME B18.2.2 ASME B18.2.2
[See Note 9] [See Note 9] [See Note 9] [See Note 9]
These notes correspond to Table 5.1
Note 1. Piping material selection should be based on a combination of caustic

concentration and temperature, refer to Appendix D for material selection.
Note 2. Higher pressures may be acceptable based on ANSI/ASME specifications for

the temperature - pressure application. The maximum listed are based on the
ANSI/ASME specifications and Appendix D.
Note 3. The specifications listed are typical for 304 stainless steel. Type 316 (regular
or low carbon grades) may be substituted, with corresponding appropriate
specifications or the “L” grades.
Note 4. PTFE gaskets with various fillers and expanded PTFE have been used
successfully.
26 PAMPHLET 94
Note 5. Fittings and unions in stainless steel, Monel and nickel can be Class 150 or
Class 3000. Selection of the proper fitting should be based on design
parameters of application.
Note 6. Check pressure-temperature ratings of flanges.
Note 7. The pressures and temperatures listed in the table are based on current
applications of caustic suppliers and users.
Note 8. Stainless steel and nickel threads are susceptible to galling.
Note 9. Threads shall be to ASME B1.1. Bolts shall have a Class 2A fit and nuts shall
have a Class 2B fit.
Note 10. Stud bolts are preferred on in-line piping components that do not have tapped
threads. Cap screws may be used for tapped piping components and
instrumentation.
Note 11. Welded pipe has increased susceptibility to galling when threaded.
Table 5.2: Socket Weld Construction [See Note 7]

<=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa)
[See Note 2] [See Notes 2 and 3] [See Note 2] [See Note 2]
PIPE See Material [Through 1-1/2"] [Through 1"] [Through 1"] [Through 1"]
Sch 40 Welded Sch 40 Welded
[2"] [1-1/2" and Larger] [1-1/2" and Larger] [1-1/2" and Larger]
ASTM A53 Grade B Not Recommended Not Recommended Not Recommended
Sch 40 Carbon Steel
Seamless or Welded
ASME B36.10
FITTINGS Through 1” ASTM A105 ASTM A351 Grade CF8 ASTM A494 Grade M35-2 ASTM A494
Socket Weld Ends Class 3000 Forged SS Grade WPNC ASTM B366 (B564/B160)
ANSI B16.11 Socket Weld Ends Class 3000 Grade WPN
ANSI B16.11 Forged Monel, Annealed Class 3000
[See Note 5] Socket Weld Ends Forged Nickel, Annealed
ANSI B16.11 Socket Weld Ends
[See Note 5] ANSI B16.11
[See Note 5]
1-1/2" to 2" ASTM A105 Not Recommended Not Recommended Not Recommended
Class 3000
Forged Carbon Steel
Socket Weld Ends
ANSI B16.11
UNIONS Through 1” ASTM A105 ASTM A351 Grade CF8 ASTM A494 Grade M35-2 ASTM A494
Class 3000 Class 150 Cast SS or ASTM Class 150 Cast Monel or Grade CZ-100
Forged Carbon Steel A182 Grade F304 ASTM B366 (B564/B164) Class 150 Cast Nickel or
Ground Joint Seat Class 3000 Forged SS Grade WPNC ASTM B366 (B564/B160)
Socket Weld Ends Ground Joint Seat Class 3000 Grade WPN
Socket Weld Ends Forged Monel, Annealed Class 3000
[See Note 5] Ground Joint Seat Forged Nickel, Annealed
Socket Weld Ends Ground Joint Seat
[See Note 5] Socket Weld Ends
[See Note 5]
Class 3000
Forged Carbon Steel
Ground Joint Seat
Socket Weld Ends
28 PAMPHLET 94
Table 5.2: Socket Weld Construction [See Note 7]

[See Note 2] [See Notes 2 and 3] [See Note 2] [See Note 2]
FLANGES Through 1” ASTM A105 ASTM A182 Grade F304 ASTM B164/B564 ASTM B160/B564
Socket Weld Socket Weld Raised Face Raised Face
ASME B16.5 ASME B16.5 Socket Weld Socket Weld
(See Note 6)
Class 150
Forged Carbon Steel
Raised Face
Socket Weld
ASME B16.5
GASKETS All Sizes PTFE Gasket With PTFE Gasket With PTFE Gasket With PTFE Gasket With
Various Fillers or Various Fillers or Various Fillers or Non- Various Fillers or Non-
EPDM or Non- EPDM or Non- Asbestos Asbestos
Asbestos Asbestos [See Note 4] [See Note 4]
[See Note 4] [See Note 4]
Quenched and Quenched and Tempered Quenched and Tempered Quenched and Tempered
Tempered Stud Bolts and Stud Bolts and Stud Bolts and
Stud Bolts and Cap Screws Cap Screws Cap Screws
Cap Screws ASME B18.2.1 ASME B18.2.1 ASME B18.2.1
ASME B18.2.1 (See Notes 8 and 9) (See Notes 8 and 9) (See Notes 8 and 9)
(See Notes 8 and 9)
(See Note 8) (See Note 8) (See Note 8) (See Note 8)

Note 2. Higher pressures may be acceptable based on ANSI/ASME specifications for the
temperature - pressure application. The maximum listed are based on the ANSI
specifications and Appendix D.
Note 3. The specifications listed are typical for 304 stainless steel. Type 316 (regular or
low carbon grades) may be substituted, with corresponding appropriate
successfully.
Note 5. Fittings and unions in stainless steel, Monel and nickel can be Class 150 or Class
3000. Selection of the proper fitting should be based on design parameters of
application.
Note 7. The pressures and temperatures listed in the table are based on current
applications of caustic suppliers and users.
Note 8. Threads shall be to ASME B1.1. Bolts shall have a Class 2A fit and nuts shall have
a Class 2B fit.
instrumentation.
30 PAMPHLET 94
Table 5.3: Butt Weld Construction [See Note 6]

PIPE <=120oF(48.9oC) <=200oF(95oC) <=260oF(126.7oC) <=350oF(176.7oC)
SIZE [See Note 1] [See Note 1] [See Note 1] [See Note 1]
(NPS) <=175 PSIG(1207 kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa)
[See Note 2] [See Notes 2 and 3) [See Note 2] [See Note 2]
PIPE See Material [Through 1-1/2"] [Through 3/4"] [Through 3/4"] [Through 3/4"]
[2" to 10"] [1" and Larger] [1" to 4"] [1" to 4"]

ASTM A53 Grade B ASTM A312 ASTM B165 ASTM B161
Seamless or Welded Sch 10S Stainless Steel Sch 10, Seamless or Sch 10 Seamless or
[12" and Larger] ASME B36.19 ASME B36.19

ASTM A53 Grade B [6" and Larger] [6" and Larger]
Std Wt Carbon Steel Monel UNS N04400 Nickel UNS N02200
Seamless or Welded ASTM and Thickness ASTM and Thickness
ASME B36.10 Per Application Per Application
FITTINGS Through 4" ASTM A234 Grade ASTM A403 Grade ASTM B366 Grade ASTM B366 Grade
Wrought WPB or WPB-W WP304 or WP304-W WPNC or WPNC-W WPN or WPN-W
Carbon Steel 304 SS Monel, Annealed Nickel, Annealed
Seamless or Welded Seamless or Welded Seamless or Welded Seamless or Welded
(bore to match pipe) (bore to match pipe) (bore to match pipe) (bore to match pipe)
ASME B16.9 ASME B16.9 ASME B16.9 ASME B16.9
6" and Larger ASTM A234 Grade ASTM A403 Grade Monel UNS N04400 Nickel UNS N02200
WPB or WPB-W WP304 or WP304-W ASTM Per Application ASTM Per Application
Carbon Steel 304 SS (bore to match pipe) (bore to match pipe)
Seamless or Welded Seamless or Welded
(bore to match pipe) (bore to match pipe)
FITTINGS All Sizes ASTM A105 ASTM A182 ASTM B564 ASTM B160/B564
Forged Forged Carbon Steel Grade F304 UNS N04400 UNS N02200
(bore to match pipe) Forged Stainless Steel Forged Monel Forged Nickel
(bore to match pipe) (bore to match pipe) (bore to match pipe
FLANGES All Sizes ASTM A105 ASTM A182 Grade F304 ASTM B164/B564 ASTM B160/B564
Weldneck or Slip-on (bore to match pipe) Raised Face Raised Face
(bore to match pipe) Weldneck or Slip-on Weldneck or Slip-on Weldneck or Slip-on
ASME B16.5 ASME B16.5 (bore to match pipe) (bore to match pipe)
[See Note 5]
Table 5.3: Butt Weld Construction [See Note 6]

PIPE <=120oF(48.9oC) <=200oF(95oC) <=260oF(126.7oC) <=350oF(176.7oC)
SIZE [See Note 1] [See Note 1] [See Note 1] [See Note 1]
[See Note 2] [See Notes 2 and 3) [See Note 2] [See Note 2]
GASKETS All Sizes PTFE Gasket With PTFE Gasket With PTFE Gasket With PTFE Gasket With
Various Fillers or Various Fillers or Various Fillers or Various Fillers or
EPDM or Non- EPDM or Non- EPDM or Non- EPDM or Non-
Asbestos Asbestos Asbestos Asbestos
[See Note 4] [See Note 4] [See Note 4] [See Note 4]
Quenched and Quenched and Quenched and Tempered Quenched and Tempered
Tempered Tempered Stud Bolts and Stud Bolts and
Stud Bolts and Stud Bolts and Cap Screws Cap Screws
Cap Screws Cap Screws ASME B18.2.1 ASME B18.2.1
ASME B18.2.1 ASME B18.2.1 (See Notes 7 and 8) (See Notes 7 and 8)
(See Notes 7 and 8) (See Notes 7 and 8)
(See Note 7) (See Note 7) (See Note 7) (See Note 7)

Note 2. Higher pressures may be acceptable based on ANSI/ASME specifications for

the temperature - pressure application. The maximum listed are based on the
ANSI/ASME specifications and Appendix D.
Note 3. The specifications listed are typical for 304 stainless steel. Type 316 (regular or
low carbon grades) may be substituted, with corresponding appropriate
successfully.
Note 6. The pressure and temperatures listed in table one based on current applications
of caustic suppliers and users.
Note 7. Threads shall be to ASME B1.1. Bolts shall have a Class 2A fit and nuts shall
have a Class 2B fit.
instrumentation.
32 PAMPHLET 94
5.3.2 Other Piping Systems
Nonmetallic piping systems including lined pipe, FRP, dual laminate FRP, PVC, CPVC,
polypropylene and other materials have been successfully used for many applications at
varying concentrations. The quality of the design and manufacture of dual laminate
piping is highly dependent on the utilization of a designer and manufacturer with
adequate expertise, therefore references and past experience should be strongly
considered when selecting a nonmetallic piping contractor.
Each application is unique and therefore the conditions (temperature, pressure, caustic
concentration, etc.) should be carefully considered before selection of the material of
construction.
5.4 VALVES
Valving for caustic service requires special attention by all associated with the
application, including the manufacturer, the supplier, the installer, the operator, and the
maintainer. An understanding by all involved of the following subsections will provide for
a successful application.
This section will discuss the types of valves currently in service, the criteria for selection
of valve features, valve selection tables and materials of construction tables. The
information presented is based on experience of the Institute’s membership and relevant
information furnished by valve manufacturers. There is no intention to exclude the use
of other valve types or materials provided there is adequate experience and sufficient
testing to ensure their safe operation.
5.4.1 General Caustic Service Valves
The types of valves commonly employed in caustic service are the globe, ball, plug,
gate, butterfly and diaphragm. Each type is available in several basic body patterns and
with different design features often unique to a particular service and/or installation.
Specific advantages and disadvantages are listed in the following section.
Globe Valves
Globe valves offer several important safety features, including tight shut off in both
directions (bidirectional seating) without trapping liquid inside cavities, multi-turn
operation that prevents quick (and sometimes accidental) opening and closing, and a
positive means to verify valve position (open or closed).
The recommended configuration includes a blow-out proof stem, a bolted bonnet

employing four bolts minimum, and a gland with outside screw and yoke (OS&Y) for
external packing gland adjustment. Either metal-to-metal seating employing hard-facing,
or soft-seating using a fluoropolymer insert will provide satisfactory service.
A bellows seal can be chosen for extended service life. Similar results may be achieved
with special stuffing box designs incorporating a live-loaded packing gland.
Ball Valves
Ball valves can provide tight shutoff with minimum resistance to flow when fully open.
They are generally easier to operate than plug valves of equal size. The 1/4-turn stem
movement lends itself to an inherently more reliable stem seal design than the rising
stem valve. Ball valves should incorporate a blow-out proof stem design and a means to
externally adjust the stem seal. The sealing material generally is a fluoropolymer resin,
although fluoroelastomer O-rings are sometimes employed as the outer secondary seal.
Glass reinforced fluoropolymer seals should not be used in caustic service.
Ball valves may be furnished either full-bore or reduced-bore. Flanged valves may have
either a long (standard) or short body pattern. Full-bore ball valves have openings
throughout the length of the valve with a diameter equal to their nominal pipe size. If the
ball valves are to be insulated, the stem should be extended to accommodate the
thickness of the insulation.
Two designs of ball valves generally used are the metal bodied type with fluoropolymer
resin seats and the fully lined type utilizing a fluoropolymer resin-lined body and
overmolded ball. Selection should be based on a complete understanding of the
pressure, temperature, and concentration of the application.
Plug Valves
Plug valves can be used for caustic service and have generally provided satisfactory
service. Their primary drawback is a need to balance turning torque and shutoff sealing
capability. Like the ball valve, this valve can provide tight shutoff and, with the 1/4-turn
stem movement, lends itself to an inherently more reliable stem seal design than the
rising stem valve and if insulated, the stem should be extended to accommodate the
thickness of the insulation.
Plug valves have an inherent blow-out proof stem design and should be provided with a
means to externally adjust the stem seal. The sealing material generally employed is a
fluoropolymer resin. Two designs of plug valves generally used are the metal type with
a fluoropolymer resin sleeve body and metal plug, and the fully lined type, utilizing a
fluoropolymer resin-lined body and overmolded plug.
While these valves provide good shutoff sealing, they require substantial torques to
operate them. This torque requirement tends to increase as the valve liner ages or
deforms. The use of gear operators on 4 inch (10.2 cm) valves and larger is strongly
recommended. In some cases, gear operators may be needed on 3 inch (7.6 cm)
valves, as well.
Gate Valves
Gate valves have provided satisfactory service in caustic applications. Gate valves
utilizing a rising stem design may require additional maintenance and packing
adjustments to avoid shaft leakage.
Material selection should be based on the specific application, with regards to the
concentration and temperature. Metal-to-metal seating or soft-seating using a
fluoropolymer resin insert will provide satisfactory service.
34 PAMPHLET 94
Rubber-Lined Butterfly Valves
Rubber-lined butterfly valves have been used in caustic applications employing

elastomers such as EPDM or chlorosulphonated-polyethylene for the body liner (seat).
Commonly supplied with a metal disc overmolded with these same rubber materials or a
fluoropolymer resin may also be used. An advantage of this type of valve is that the
body, shafts, bearings, and packing are non-wetted parts. In certain applications, these
valves may not provide adequate shutoff sealing. In those cases where positive shut off
is important, other valve choices should be considered.
Fluorocarbon Resin-Lined Butterfly Valves
Fluorocarbon resin-lined butterfly valves can provide tight shutoff in both directions
without trapping fluid, and with the 1/4-turn stem movement, lends itself to an inherently
more reliable stem seal design than the rising stem valve. It should incorporate a blow-
out proof stem design.
Soft-Seated "High-Performance" Butterfly Valves
Soft-seated, high-performance butterfly valves have been used in caustic applications,

particularly in larger pipe sizes. These valves are distinguished from rubber and
fluoropolymer-lined butterfly valves by their ANSI rated pressure capability. With these
valves, the metal body and disc come in contact with the media; hence, material
selection should be made with regards to concentration and temperature of the caustic.
Most soft-seated high-performance butterfly valves use an adjustable packing design, a

wetted shaft/disc arrangement and a one-piece soft-lip seal. Soft-seated high
performance butterfly valves can provide tight shut-off, and with the 1/4-turn stem
movement, lends itself to an inherently more reliable stem seal design than the rising
stem valve. If the butterfly valves are to be insulated, the stem should be extended to
accommodate the thickness of the insulation.
Diaphragm Valves
Diaphragm valves have been used in caustic applications. This type of valve employs a
variety of body materials (unlined metal and plastic or elastomer and plastic-lined) in
conjunction with an elastomer or fluoropolymer diaphragm. The body and diaphragm
are the only parts exposed to the media. Diaphragm valves can provide tight shut-off in
both directions without trapping fluid, multi-turn operation that prevents quick (sometimes
accidental) opening and closing, and can be provided with a positive means to verify
position (open or closed).
5.4.2 Valve Selection Guide
A valve selection guide is provided in Tables 5.4 through 5.11. These tables are
intended for use in selecting various types of valves that have been found satisfactory in
caustic service. It is not intended to prevent the use of valve types other than those
designated as "satisfactory" in a particular service class. However, the user is cautioned
against such practice unless ample testing (with documentation) has been conducted, to
assure safe operation.
Table 5.4: Globe Valves
NOMINAL COMMON PRIMARY <=50% CAUSTIC <=50% CAUSTIC <=73% CAUSTIC <=73% CAUSTIC
PIPE SIZE END FORM AND <=120oF(48.9oC) <=200oF(95oC) <=260oF(126.7oC) <=350oF(176.7oC)
(NPS) CONNECT MINIMUM <=175 PSIG (1207 <=175 PSIG (1207 <=175 PSIG (1207 <=175 PSIG (1207 kPa)
RATING kPa) kPa) kPa) NICKEL
CARBON STEEL STAINLESS STEEL MONEL [See Note 2]
Through 1" Threaded Forged API

[See Note 1] Class 800 or
Satisfactory Satisfactory Satisfactory Satisfactory
Cast ASME
Class 150
1-1/2" to 2" Threaded Forged API

[See Note 1] Class 800 or
Satisfactory Satisfactory Not Recommended Not Recommended
Cast ASME
Class 150
Through 1" Socket Forged API

Welded Class 800 or
Cast ASME
Class 150
1-1/2" to 2" Socket Forged API

Welded Class 800 or
Satisfactory Not Recommended Not Recommended Not Recommended
Cast ASME
Class 150
All Sizes Flanged Forged or

Cast ASME Satisfactory Satisfactory Satisfactory Satisfactory
Class 150
Note 1. Except for connections to transportation equipment, specific instruments,

and special process equipment, flanged valves are recommended.
Note 2. An ASME Class 150 nickel valve has a rating of 140 psig (965 kPa) at 350oF
(176.7oC) and an ASME Class 300 nickel valve has a rating 360 psig (2,482
kPa) at 350oF (176.7oC). When using a nickel system, caution should be
taken in selecting the correct valve rating.
36 PAMPHLET 94
Table 5.5: Ball Valves
(NPS) CONNECT MINIMUM <=175PSIG(1207kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa)
RATING CARBON STEEL STAINLESS STEEL MONEL NICKEL
[See Note 2]
Through 1" Threaded Forged or Satisfactory under

[See Note 1] Cast ASME specific conditions,
Satisfactory Satisfactory Satisfactory
Class 150 consult manufacturer
for details
1-1/2" to 2" Threaded Forged or

[See Note 1] Cast ASME Satisfactory Satisfactory Not Recommended Not Recommended
Class 150
Through 1" Socket Forged or Satisfactory under

Welded Cast ASME specific conditions,
for details
1-1/2" to 2" Socket Forged or

Welded Cast ASME Satisfactory Not Recommended Not Recommended Not Recommended
Class 150
All Sizes Flanged Forged or Satisfactory under

Cast ASME specific conditions,
[See Note 3] for details
Note 1. Except for connections to transportation equipment, specific instruments, and

special process equipment, flanged valves are recommended.
(176.7oC) and an ASME Class 300 nickel valve has a rating of 360 psig (2,481
kPa) at 350oF (176.7oC). When using a nickel system, caution should be taken
in selecting the correct valve rating.
Note 3. Fluoroplastic lined ball valves are satisfactory only under specific conditions.
Consult the manufacturer for details.
Table 5.6: Plug Valves
(NPS) CONNECT MINIMUM <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa) <=175 PSIG (1207 kPa)
[See Note 2]
Through 1" Threaded Cast ASME

[See Note 1] Class 150
1-1/2" to 2" Threaded Cast ASME

Satisfactory Satisfactory Not Recommended Not Recommended
[See Note 1] Class 150
Through 1" Socket Cast ASME Satisfactory under

Welded Class 150 specific conditions,
consult manufacturer for
details
1-1/2" to 2" Socket Cast ASME

Satisfactory Not Recommended Not Recommended Not Recommended
Welded Class 150
All Sizes Flanged Cast ASME

Class 150 Satisfactory Satisfactory Satisfactory Satisfactory
[See Note 3]

Note 3. Fluoroplastic lined plug valves are satisfactory only under specific conditions.
Consult the manufacturer for details.
38 PAMPHLET 94
Table 5.7: Gate Valves
NOMINAL COMMON PRIMARY FORM <=50% CAUSTIC <=50% CAUSTIC <=73% CAUSTIC <=73% CAUSTIC
PIPE SIZE END AND MINIMUM <=120oF(48.9oC) <=200oF(95oC) <=260oF(126.7oC) <=350oF(176.7oC)
(NPS) CONNECT RATING <=175 PSIG <=175 PSIG <=175 PSIG <=175 PSIG
(1207 kPa) (1207 kPa) (1207 kPa) (1207 kPa)
[See Note 2]
Through 1" Threaded Forged API

[See Note 1] Class 800 or Cast Satisfactory Satisfactory Satisfactory Satisfactory
ASME Class 150
1-1/2" to 2" Threaded Forged API

[See Note 1] Class 800 or Cast Satisfactory Satisfactory Not Recommended Not Recommended
ASME Class 150
Through 1" Socket Forged API

Welded Class 800 or Cast Satisfactory Satisfactory Satisfactory Satisfactory
ASME Class 150
1-1/2" to 2" Socket Forged API

Welded Class 800 or Cast Satisfactory Not Recommended Not Recommended Not Recommended
ASME Class 150
All Sizes Flanged Forged or Cast

ASME Class 150

Table 5.8: Rubber Lined Butterfly Valves
2" and Wafer Cast Satisfactory under Satisfactory under Not Recommended Not Recommended
Larger 150 psig specific conditions. specific conditions.
Consult manufacturer for Consult manufacturer for
details details
2" and Lug Cast Satisfactory under Satisfactory under Not Recommended Not Recommended
Larger 150 psig specific conditions. specific conditions.
details details
Table 5.9: Fluoropolymer Lined Butterfly Valves
2" and Wafer Cast Satisfactory under Satisfactory under Satisfactory under Satisfactory under specific
Larger 150 psig specific conditions. specific conditions. specific conditions. conditions. Consult
Consult manufacturer for Consult manufacturer for Consult manufacturer for manufacturer for details
details details details
2" and Lug Cast Satisfactory under Satisfactory under Satisfactory under Satisfactory under specific
Larger 150 psig specific conditions. specific conditions. specific conditions. conditions. Consult
Consult manufacturer for Consult manufacturer for Consult manufacturer for manufacturer for details
details details details
Table 5.10: High Performance Butterfly Valves
[See Note 1]
2" and Wafer Cast ASME Satisfactory Satisfactory Satisfactory Satisfactory under
Larger Class 150 specific conditions.
Consult manufacturer for
details
2" and Lug Cast ASME Satisfactory Satisfactory Satisfactory Satisfactory under
Larger Class 150 specific conditions.
details
(176.7oC) and an ASME Class 300 nickel valve has a rating of 360 psig (2,482 kPa)
at 350oF (176.7oC). When using a nickel system, caution should be taken in
selecting the correct valve rating.
40 PAMPHLET 94
Table 5.11: Diaphragm Valves
(See Note 2)
Through 1" Threaded Cast 150 psig Satisfactory under Satisfactory under Satisfactory under Satisfactory under
(See Note 1) specific conditions. specific conditions. specific conditions. specific conditions.
Consult manufacturer for Consult manufacturer for Consult manufacturer for Consult manufacturer for
details details details details
1-1/2" to 2" Threaded Cast 150 psig Satisfactory under Satisfactory under Not Recommended Not Recommended
(See Note 1) specific conditions. specific conditions.
details details
Through 1" Socket Cast 150 psig Satisfactory under Satisfactory under Satisfactory under Satisfactory under
Welded specific conditions. specific conditions. specific conditions. specific conditions.
Consult manufacturer for Consult manufacturer for Consult manufacturer for Consult manufacturer for
1-1/2" to 2" Socket Cast 150 psig Satisfactory under Not Recommended Not Recommended Not Recommended
Welded specific conditions.
details
All Sizes Flanged Cast ASME Satisfactory under Satisfactory under Satisfactory under Satisfactory under
Class 150 specific conditions. specific conditions. specific conditions. specific conditions.
[See Note 3] Consult manufacturer for Consult manufacturer for Consult manufacturer for Consult manufacturer for
Note 1. Except for connections to transportation equipment, specific instruments and

Note 3. Ratings for diaphragm valves are dependent upon size and materials of
construction. Consult manufacturer for specific applications.
5.4.3 Valve Material Selection Guide
Table 5.12 lists materials that have proven to be suitable for valve parts in caustic
service. Materials are listed by the applicable standard/material designations. This
guide is not intended to prevent the substitution of other materials known to be suited for
the specific service as agreed upon between the manufacturer and purchaser.
Table 5.12: Valve Material Selection Guide
PRODUCT VALVE PART <=50% CAUSTIC <=50% CAUSTIC <=73% CAUSTIC <=73% CAUSTIC
FORM <=120oF(48.9oC) <=200oF(95oC) <=260oF(126.7oC) <=350oF(176.7oC)
Castings Bodies, ASTM A216 ASTM A351 ASTM A494 ASTM A494
[See Note 8] Bonnets and Grade WCB Grade CF8 Grade M-30-2 Grade CZ-100
Covers ASTM A395 ASTM A395 ASTM A395 [See Note 9]
[See Notes 1 and 8] [See Note 1] [See Note 1] ASTM A395
ASTM A126 [See Note 1]
[See Note 1]
Forgings Bodies, ASTM A105, ASTM ASTM A182 ASTM B164/B564 ASTM B160/B564
Bonnets and A182 Grade F1 Grade F304 Grade N04400 Grade N02200
Covers [See Note 2] [See Note 8]
Rolled Plates Bodies, ASTM A516 ASTM A240 ASTM B127 ASTM B162
and Shapes Bonnets and Grade 70 Type 304 Grade UNS N04400 Grade UNS N02200
Covers [See Note 2] [See Note 8]
Body, Bonnet Machine Bolts ASTM A307 ASTM A307 ASTM A307 ASTM A307
and Cover and Stud Grade B (See Note 9) Grade B (See Note 9) Grade B,(See Note 9) Grade B,(See Note 9)
Bolting Bolts ASTM A193 ASTM A193 Grade B7 ASTM A193 Grade B7 ASTM A193
[See Note 6] [See Note 9] Grade B7 Grade B7
Nuts ASTM A563 ASTM A563 ASTM A563 ASTM A563

ASTM A194 ASTM A194 ASTM A194 ASTM A194
Grade 2H Grade 2H Grade 2H Grade 2H
Other Metal Stems 316 Stainless Steel, 316 Stainless Steel, Monel 400 and 405 Nickel 200
Parts (Shafts) Alloy 20, Alloy 20, (UNS N04400 and (UNS N02200)
[See Note 4] Monel 400 and 405 Monel 400 and 405 UNS N04405),
(UNS N04400 and UNS (UNS N04400 and UNS Hastelloy B and C,
N04405), Hastelloy B N04405), Inconel, Nickel 200
and C Hastelloy B and C, (UNS N02200)
Inconel, Nickel 200
(UNS N02200)
Balls, Discs 316 Stainless Steel, 316 Stainless Steel, Monel 400 and 405 Nickel 200
and Tapered Alloy 20, Monel 400 Alloy 20, Monel 400 and (UNS N04400 and UNS (UNS N02200)
Plugs and 405 (UNS N04400 405 (UNS N04400 and N04405), [See Note 2]
and UNS N04405), UNS N04405), Hastelloy B and C,
Hastelloy B and C Hastelloy B and C, Inconel, Nickel 200
[See Note 2] Inconel, Nickel 200 (UNS N02200)
(UNS N02200) [See Note 2]
[See Note 2]
Bellows Monel 400 and 405 Monel 400 and 405 Monel 400 and 405 (UNS Nickel Alloy [See Note 8]
(UNS N04400 and UNS (UNS N04400 and UNS N04400 and UNS N04405),
N04405), N04405), Hastelloy B and C
Hastelloy B and C Hastelloy B and C
Seats, Discs Hard Faced Hard Faced Hard Faced Hard Faced
and Wedge [See Note 3] [See Note 3] [See Note 3] [See Note 3]
Facings
Other Parts [See Note 4] [See Note 4] [See Note 4] [See Note 4]
42 PAMPHLET 94
Table 5.12: Valve Material Selection Guide
PRODUCT VALVE PART <=50% CAUSTIC <=50% CAUSTIC <=73% CAUSTIC <=73% CAUSTIC
FORM <=120oF(48.9oC) <=200oF(95oC) <=260oF(126.7oC) <=350oF(176.7oC)
Non-metallic Seats, EPDM, Chlorosulphonated Virgin or Reinforced Virgin or Reinforced
Parts Sleeves, Chlorosulphonated Polyethylene, Virgin or PTFE, PFA PTFE, PFA
Diaphragms Polyethylene, Virgin Reinforced PTFE, PFA
and Seals or Reinforced PTFE,
PFA
Fluoro- PTFE, PFA, FEP, PTFE, PFA, FEP, ETFE, PTFE, PFA, FEP, ETFE, PTFE, PFA, FEP, ETFE,
polymer ETFE, ECTFE ECTFE ECTFE ECTFE
Linings
Packing PTFE, Graphite, PTFE, Graphite, PTFE, Graphite, PTFE, Graphite,

Graphite Filled PTFE, Graphite Filled PTFE, Graphite Filled PTFE, Non- Graphite Filled PTFE,
Non-Asbestos Non-Asbestos Asbestos Non-Asbestos
Gasketing PTFE, Graphite, PTFE, Graphite, PTFE, Graphite, PTFE, Graphite,

Graphite Filled PTFE, Graphite Filled PTFE, Graphite Filled PTFE, Non- Graphite Filled PTFE,
Non-Asbestos Non-Asbestos Asbestos Non-Asbestos
The complete titles of specifications are listed in Section 7.
Note 1. Ductile Iron to ASTM A395 and Cast Iron to A126 may be lined for use as
rubber lined butterfly and diaphragm valves; fluoropolymer resin ball, plug,
butterfly, and diaphragm valves; and fluoropolymer resin sleeved plug valves.
Note 2. Use annealed Monel 400 per ASTM B564 Grade N04400 for forgings and
ASTM B127 Grade N04400 for plates.
Note 3. Hard-faced seating surfaces of Stellite 6, 12 and/or 21 are recommended for

metal seating surfaces prone to the combined effects of corrosion and
erosion. Monel K500 (UNS NO5500) also possesses good hard-facing
properties.
Note 4. Various metals are used as base materials for over molded parts such as
plugs, balls, and discs.
Note 5. The specifications listed are typical for 304 stainless steel. Type 316 may be
substituted, with corresponding appropriate specifications or the “L” grades of
304 and 316.
Note 6. Other parts (such as yokes, yoke nuts, glands, gland bushings, studs, and
handwheels) should be constructed of a material suitable for the service and
as agreed upon between manufacturer and purchaser. If environmental
conditions are such that chloride stress corrosion cracking is possible, then
Series 300 stainless steels should be avoided for bolts, studs and nuts.
Generally, Series 300 stainless steel bolts, studs, and nuts should be
avoided, as chloride stress cracking can occur as a result of “seep leaks” as
well as from chlorides in the atmosphere. These piping components are very
highly stressed during their fabrication, making them especially subject to
stress corrosion cracking from both chlorides and from caustic (even at
ambient temperatures).
Note 7. Ductile Iron to ASTM A395 and Cast Iron to A126 may be used for pressure
reducing valves and for fluorocarbon resin sleeved plug valves within this
system.
Note 8. The valve manufacturer should be consulted on the appropriate nickel alloy
for use in this system.
Note 9. ASTM A307 Grade B bolting on valves shall be restricted to bonnet or cover
bolting only for Class 300 and lower rated valves provided the service
o o
temperature is limited to 400 F (204 C). When required, ASTM A563 nuts
shall be used with ASTM A307 Grade B bolts and ASTM A194 Grade 2H
nuts shall be used with ASTM A193 Grade B7 bolts.
5.4.4 Check Valves
All of the standard types of check valves are suitable for caustic service. The body and
trim material should be consistent with the general piping specifications. For check
valves that utilize springs, Monel or Inconel should be specified for the spring material.
5.4.5 Pressure Relief Valves
Caustic systems should be designed to avoid the use of pressure relief valves if at all
possible. If the use of a pressure relief device is unavoidable, the materials of
construction of the device should be consistent with those of the piping system. For
temperatures above 140oF (60oC), Monel or Inconel springs should be specified.
The pressure relief valve vent system should be adequately sized and piped to a
containment system. The relief device and its associated piping should be protected
from freezing. Both caustic soda and caustic potash will become very viscous at 80oF
(26.7oC) and will freeze at temperatures below 60oF (15.6oC).
44 PAMPHLET 94
5.5 OTHER COMPONENTS
Expansion Joints
Caustic piping systems should have sufficient flexibility to prevent failure of the piping
system due to thermal expansion or contraction. When flexibility cannot be introduced
into the system through pipe routing, bellows expansion joints can be employed to
absorb the differential expansion while containing the system pressure.
These joints are engineered products which should not be purchased and used as
commodity items. Expansion joints should be kept to a minimum, but when required
should be metallic with minimum bellows metallurgy of Monel alloys 400 and R405 (UNS
N04400 and N04405) nickel or PTFE and should comply with ASME B31.3 (7.3.4).
The expansion joint in piping between the storage tank and its transfer pump should
always be located downstream of the first storage tank block valve. This allows isolation
of the storage tank in case of an expansion joint failure.
Hoses
Hoses are utilized for temporary connections in caustic service. Hose should be
selected based on chemical compatibility and mechanical integrity.
Loading Arms
Loading arms are utilized for loading and unloading caustic. Piping and joints should be
selected based on chemical compatibility and technical integrity.
Insulation and Heat Tracing
Caustic solutions, dependent on concentration, freeze at temperatures below 60oF

(15.5oC) and therefore the piping system should be heat traced and insulated when
these conditions are anticipated. Self-regulating electric tracing is recommended over
steam tracing which can in turn result in stress cracking and ultimately premature pipe
failure. The following should be considered when designing the heat trace/insulation
system:
• If the material of construction of the piping system is carbon steel, the heat
tracing should not allow the piping temperature to exceed 120oF (48.9oC) as
corrosion rates are elevated at this temperature resulting in iron contamination of
the caustic and susceptibility to stress corrosion cracking.
• If the material of construction of the piping system is stainless steel (type 304L or
316L), the heat tracing should not allow the piping temperature to exceed 200oF
(95oC). At temperatures above 200oF (95oC) type 304L and 316L stainless steel
in caustic service experience increased general corrosion rates and higher
susceptibility to stress cracking.
• Steam tracing of caustic piping is not generally recommended, however, in
situations where it is used, standoffs should be employed to prevent hot tubing
from direct contact with the pipe and in case the pipe material temperature limit is
reached.
• Some insulation materials, if high in chloride content, can promote external stress
corrosion cracking of stainless steel at elevated temperatures. Use of alternate
insulation systems or protection of the stainless-steel surface is necessary.
5.6 INSTRUMENTATION
Proper instrumentation can be a key factor in safe operations of caustic piping systems.
Isolation of instrument devices from the process may be accomplished by materials of
construction or diaphragm protection.
• If direct reading pressure sensing devices are used, they should be equipped
with Alloy 20, Monel, nickel, or Hastelloy C bourdon tubes.
• Pressure sensing instruments may be protected from the caustic process by a
liquid-filled seal. The process connection can be carbon steel, Monel, Alloy 20,
nickel, or Hastelloy C. The diaphragm should be Monel, Alloy 20, nickel, or
Hastelloy C.
• Temperature sensing devices should be equipped with thermowells of suitable
material, such as Monel, Alloy 20, nickel, or Hastelloy C, to permit replacement of
the temperature element without a shutdown.
• Many types of level devices including pressure, displacement, proximity, and
capacitance types can be used if designed for caustic service. Glass devices are
attacked by caustic. Differential pressure sensing devices must be calibrated to
the correct caustic concentration. If not, the measured level will be incorrect.
• Many types of flow devices including orifice flanges, magmeters, vortex shedding
meters, turbine meters, coreolis meters, etc., can be used if designed for caustic
service. Flow devices should be made of corrosion resistant materials such as
stainless steel, Alloy 20, Monel, nickel, or Hastelloy C.
• Control valve materials and design should follow guidelines presented in Section
5.4. Due to cycling, stem sealing is a more important consideration than with
manual valves and care must be exercised in seal selection.
• Aluminum, magnesium, zinc, brass, copper, and tantalum are materials that are
attacked by caustic and must be avoided.
• Shutoff or isolation valves are recommended to permit service of the instruments
while in use.
5.7 INSPECTION AND MAINTENANCE
Routine Maintenance
Written procedures specific to caustic piping maintenance should be used to ensure long
term integrity of the system. Personnel that work on caustic piping systems should be
trained in the proper maintenance procedures. After maintenance, the affected area of
piping should be checked for leaks.
46 PAMPHLET 94
Cleaning and neutralizing of metal surfaces exposed to caustic in preparation for welding
is critical in order to avoid caustic SCC of the welded heat-affected zone.
Periodic Inspections
Caustic piping systems should be inspected on a regular basis. The inspections will
help to find problems prior to failure. Criteria for initiating replacement or repair should
be developed for each facility. There are multiple ways to inspect these systems.
Useful methods include visual inspections and nondestructive test checks. A visual
inspection is by far the most important inspection that can be done. Other methods can
be used as a supplement. Nondestructive testing can be used in measuring corrosion
rates. The results of all inspections should be well documented.
Preventive Maintenance
As part of a good overall preventive maintenance program, consideration should be

given to ensuring that the following items be checked periodically and corrected as
needed:
• flange bolt condition and tightness

• valve packing adjustment
• valve operation
• condition of supports
• paint condition
• heat tracing functionality
• insulation condition
• Transfer hoses and connections should be inspected each time they are going to
be used. These are non-repairable items and should be replaced any time there
is leakage, fraying, deformation, or corrosion.
Consideration should be given to repainting on a regular basis, with timing determined

by individual site conditions.
Visual
A visual inspection should include a leak check of all flanges, valves and other fittings
and attachments. Particular areas of concern should include such things as pipe
supports and areas with paint or insulation damage. Where insulation is damaged
further inspection is warranted. Special note should be taken of weld areas, as these
areas corrode most quickly. Any significant observed pitting or wall loss should be
investigated further, and should be corrected as necessary.
Nondestructive Testing
Nondestructive testing methods detect pipe wall thickness, pit depths, and internal and
external erosion/corrosion. These methods include ultrasonic thickness measurements
and radiographic measurements.
Due to normal variations in pipe dimensions, it is important that the same points be
measured each time they are tested. This can be accomplished by developing "maps"
or isometric sketches of the system, with test points clearly identified and marked.
Routine testing will show the corrosion rates typical for the system, so that predictive
maintenance can be estimated. Consideration should be given to checking areas of
high fluid velocity more frequently due to possible internal erosion.
Radiographic techniques are available to check pipe wall thickness through insulation.
This permits checking piping systems without breaking the vapor barrier of the
insulation. If test methods are used which require the removal of insulation, care must
be taken to restore the insulation vapor barrier integrity.
Inspection Records
Written records should be maintained. These records should include the initial
inspection report, as well as recommended further inspections and corrective actions.
Documentation of all follow-up actions should be appended to the initial original report.
6. OTHER EQUIPMENT
6.1 PUMPS
Centrifugal pumps are recommended for transferring caustic solutions from storage to
the point of use, however, positive displacement and other types of pumps are used for
specific conditions.
• Ductile iron pumps or stainless steel may be used for caustic solutions below
120oF (49oC). Alloy 20, CD4M, Monel or other nickel alloy pumps will provide a
longer service life at temperatures above 120oF (49oC).
• Caustic transfer pumps may be equipped with a high pressure/low pressure
switch or low flow switch cutoff to prevent continued operation when the pump is
dead-headed or running dry. A minimum flow recycle line will also help to
prevent pump damage from dead-heading.
• The centrifugal pump shaft seal can be a packing gland, a mechanical seal
and/or a repeller equipped seal-less pump. If dilution of caustic is a concern,
double mechanical seal or repeller equipped seal-less pump should be
considered. The gland area of the pump should be shielded for personnel
protection. A magnetically-coupled pump eliminates the need for seals.
• Aluminum, magnesium, zinc, brass, copper, and tantalum are materials that are
attacked by caustic and are to be avoided in pump construction.
• Piping connections for washing and draining for pump maintenance should be
provided.
48 PAMPHLET 94
• Pump location should receive careful consideration. The pump should be easily
accessible for operation and maintenance. The area adjacent to the pump
should be designed to minimize personnel exposure and environmental
contamination should the pump develop a leak.
For pumps in 50% caustic service where ambient temperatures are below 60oF (15.6oC),
the pump casing may be heat traced and insulated to prevent caustic freezing.
6.2 HEAT EXCHANGERS
Heat exchangers are used either to remove the heat of dilution from caustic (usually to
permit storage in carbon steel tanks) or to add heat to caustic to prevent it from freezing.
Two types of heat exchangers are commonly used, shell and tube, and plate and frame
type.
For the shell and tube heat exchanger, steam is normally introduced to the shell side for
heating while cooling water is introduced to either the shell or tube side for cooling. Use
of cooling water on the tube side has the advantage of easy access for cleaning.
The shell and tube heat exchanger can be installed either vertically or horizontally for
either heating or cooling.
As an alternative to internal heating of caustic storage tank (4.6.5), the heat exchanger is
used for heating externally. External heating has the advantage of easy inspection and
maintenance of the heat exchanger, and minimizes the possibility of local hot spots on
the tank. The latter is especially important for lined or coated storage tank.
In selecting the heat exchanger materials of construction, the maximum temperature of

the heating medium must be considered. Typically, nickel 200 is used on the process
(caustic) side of the heat exchanger. Steam pressure of 15 psig (103 kPa) is typically
used for heating. The 15 psig steam is to minimize the potential of boiling caustic in the
heat exchangers.
The plate and frame type heat exchanger is commonly used for removing heat from
caustic dilution rather than the shell and tube type. Stainless steel plates such as 304
and 316 has been used successfully. However, increased general corrosion rates at the
higher temperatures generally limit the practical upper temperature to 140oF (60oC), as
the plates typically have minimal corrosion allowance. Above 140oF (60oC), Monel 400
or nickel 200 should be considered. Rubber gaskets have been successfully used.
Contact the heat exchange manufacturer for alternative gasket materials.
All plate and frame heat exchangers should be equipped with an OSHA approved safety
shroud to protect operating personnel against being sprayed if there is gasket leak.
6.3 AGITATORS AND MIXERS
Agitation is needed to maintain a uniform concentration during caustic dilution. The

normal practice of agitation and mixing is by an in-line static mixer, an internal tank
mixing eductor or a circulation loop from the diluted caustic transfer pump. (For
additional precautions when diluting caustic soda, refer to Appendices A and B.)
The 316 stainless steel in-line static mixer is suitable for temperatures below 140oF
(60oC). For temperatures above 140oF (60oC) nickel or nickel alloy or fluorocarbon
resin-lined static mixer, should be considered due to induced stresses which may be
present in fabricated stainless mixers.
Internal tank mixing eductors have proven very effective for mixing. They require an
external recirculation pump. However, this can be combined with an external heating or
cooling system or the diluted caustic transfer pump. For a properly sized system, the
eductors can completely mix a storage tank in two to four hours following receiving new
material into the tank. The eductors are normally of stainless or CPVC construction
depending on the temperature.
A recirculation loop from the diluted caustic transfer pump can also be used for mixing.
The recirculation line should be routed to the tank 180o from the pump suction nozzle for
better mixing.
50 PAMPHLET 94
7. REFERENCES
7.1 INSTITUTE PUBLICATIONS
The following publication is specifically referenced in CI Pamphlet 94. The latest

editions of CI publications may be obtained at http://www.chlorineinstitute.org.
Pamphlet # Title
65 Personal Protective Equipment for Chlor-Alkali Chemicals, ed.
6; Pamphlet 65; The Chlorine Institute: Arlington, VA, 2015.
80 Recommended Practices for Handling Sodium Hydroxide

Solution Potassium Hydroxide Solution (Caustic) Barges, ed. 4;
Pamphlet 80; The Chlorine Institute: Arlington, VA, 2014.

Solution Potassium Hydroxide Solution (Caustic) Tank Cars,
ed. 4; Pamphlet 87; The Chlorine Institute: Arlington, VA, 2012.

Solution Potassium Hydroxide Solution (Caustic) Cargo Tanks,
ed. 4; Pamphlet 88; The Chlorine Institute: Arlington, VA, 2016.
164 Reactivity and Compatibility of Chlorine and Sodium Hydroxide

with Various Materials, ed. 3; Pamphlet 164; The Chlorine
Institute: Arlington, VA, 2017.
7.2 API STANDARD SPECIFICATIONS
7.2.1 Specification for Shop Welded Tanks for Storage of Production Liquids, API 12F; The
American Petroleum Institute: Washington, DC, 2008.
7.2.2 Valve Inspection And Testing, API 598; The American Petroleum Institute: Washington,
DC, 2016.
7.2.3 Butterfly Valves: Double Flanged, Lug, and Wafer Type; API 609; The American
Petroleum Institute: Washington, DC, 2016.
7.2.4 Design and Construction of Large, Welded, Low-Pressure Storage Tanks, API 620; The
American Petroleum Institute: Washington, DC, 2013.
7.2.5 Welded Steel Tanks for Oil Storage, ed. 12; API 650; The American Petroleum Institute:
Washington, DC, 2013.
7.2.6 Tank Inspection, Repair, Alteration, And Reconstruction, API 653; The American
Petroleum Institute: Washington, DC, 2014.
7.3 ASME CODES AND STANDARDS
7.3.1 Reinforced Thermoset Plastic Corrosion-Resistant Equipment, (Fiberglass

Construction); ASME RTP-1; American Society of Mechanical Engineers: New York, NY,
2015.
7.3.2 Rules for Construction of Pressure Vessels - Section VIII, Division I, ASME Boiler and
Pressure Vessel Code, ASME BPVC-VIII-I; The American Society of Mechanical
Engineers: New York, NY, 2015.
7.3.3 Welding And Brazing Qualifications, Section IX, ASME Boiler and Pressure Vessel
Code, ASME BPVC-IX; The American Society of Mechanical Engineers: New York, NY,
2017.
7.3.4 Process Piping, ASME Code for Pressure Piping, ANSI/ASME B 31.3; The American
Society of Mechanical Engineers: New York, NY, 2016.
7.3.5 Pipe Flanges and Flanged Fittings, ASME B16.5, an ANSI Standard; The American
Society of Mechanical Engineers: New York, NY 2013.
7.3.6 Face-to-Face And End-to-End Dimensions of Valves, ASME B16.10; an ANSI Standard;
The American Standard of Mechanical Engineers: New York, NY 2009.
7.3.7 Valves - Flanged Threaded and Welding End, ASME B16.34, an ANSI Standard; The
American Standard of Mechanical Engineers: New York, NY 2013.
7.4 NACE CORROSION DATA
7.4.1 Corrosion, Data Survey, Metals Section; Ed. 6, National Association of Corrosion
Engineers: Houston, TX.
7.5 OTHER REFERENCES
7.5.1 U.S. Code of Federal Regulations, Title 49. Parts 100-185. Office of the Federal
Register National Archives and Records Administration. U.S. Government Printing
Office: Washington, DC, (revised annually).
7.5.2 North American Emergency Response Guidebook, Office of Hazardous Material

Transportation: Washington, DC, 2016.
7.5.3 U.S. Code of Federal Regulations, Title 40. Part 150. Office of the Federal Register
National Archives and Records Administration. U.S. Government Printing Office:
Washington, DC, (revised annually).
52 PAMPHLET 94
7.6 OTHER RECOMMENDED READING AND VIEWING
The following Chlorine Institute pamphlets and other documents, though not specifically
referenced in Pamphlet 94, may be of additional help to the reader. These CI
documents as well as the complete CI catalog may be obtained at
http://www.chlorineinstitute.org/.
Pamphlet
Title
& DVD #
64 Emergency Response Plans for Chlor-Alkali, Sodium Hypochlorite, and

Hydrogen Chloride Facilites, ed. 7; Pamphlet 64; The Chlorine Institute:
Arlington, VA, 2014.
139 Electrical Safety in Chlor-Alkali Cell Facilities, ed. 5; Pamphlet 139; The
Chlorine Institute: Arlington, VA, 2012.
For further assistance and information on items referenced, contact:
American Chemistry Council American National Standards Institute

700 2nd Street, NE (ANSI)
Washington, DC 20002 1899 L Street, NW
202-249-7000 11th Floor
202-249-6100 (Fax) Washington, DC 20036
http://www.AmericanChemistry.com 202-293-8020
202-293-9287 (Fax)
http://www.ansi.org
American Petroleum Institute (API) American Society of Mechanical Engineers

1220 L Street, NW (ASME)
Washington, DC 20005-4070 Two Park Avenue
202-682-8000 New York, NY 10016-5990
800-854-7179 (Order Desk) 800-843-2763
http://www.api.org http://www.asme.org
American Society of Testing and Materials Association of American Railroads (AAR)

(ASTM) 425 Third Street, SW
100 Barr Harbor Drive Washington, DC 20024
West Conshohocken, PA 19428-2959 202-639-2100
610-832-9500 http://www.aar.org
610-832-9555 (Fax)
http://www.astm.org
Chemistry Industry Association of Canada Canadian General Standards Board

350 Sparks Street, Suite 805 Place du Portage
Ottawa, Ontario K1R 7S8 (CANADA) Phase III, 6B1, 11 Laurier Street
613-237-6215 Gatineau, Quebec K1A0S5 (CANADA)
613-237-4061 (Fax) http://www.pwgsc.gc.ca/cgsb
http://www.canadianchemistry.ca
(Regulation Purchases)
819-956-0425
819-956-5740 (Fax)
http://publications.pwgsc.gc.ca
Canadian Transport Emergency Centre Chemical Transportation Emergency Center

(CANUTEC) (CHEMTREC)
330 Sparks Street 2900 Fairview Drive
Office 1415 Falls Church, VA 22042-4513
Ottawa, Ontario K1A 0N5 (CANADA) 800-262-8200, 703-741-5525 (Information)
613-990-4624 (Information) 703-741-6037 (Fax)
613-954-5101 (Fax) http://www.chemtrec.org
http://www.tc.gc.ca/canutec
Compressed Gas Association CSA Group

14501 George Carter Way, Ste. 103 178 Rexdale Boulevard
Chantilly, VA 20151 Toronto, Ontario M9W 1R3 (CANADA)
703-788-2700 416-747-4000
703-961-1831(Fax) 1-800-463-6727
http://www.cganet.com 416-747-4149 (Fax)
416-747-4044 (Standard Purchases)
http://www.csagroup.org/
ICC International Compliance Center Ltd. National Archives and Records Admin.
205 Matheson Boulevard, East, Unit 7 Director, Office of the Federal Register
Mississauga, Ontario L4Z 1X8 (CANADA) 8601 Adelphi Road
888-977-4834 (Canada) College Park, MD 20740-6001
888-442-9628 (U.S.) 1-866-272-6272
866-821-0735 (Fax) 301-837-0483 (Fax)
http://www.cganet.com https://www.federalregister.gov/
National Association of Corrosion Engineers National Board of Boiler and Pressure

NACE International Vessel Inspectors
15835 Park Ten Place 1055 Crupper Avenue
Houston, TX 77084 Columbus, OH 43229-1183
281-228-6200 614-888-8320
281-228-6300 (Fax) 614-888-0750 (Fax)
http://www.nace.org http://www.nationalboard.org
54 PAMPHLET 94
National Fire Protection Association National Tank Truck Carriers, Inc.

1 Batterymarch Park 950 N. Glebe Road, Ste. 520
Quincy, MA 02169-7471 Arlington, VA 22203-4183
617-770-3000 703-838-1960
508-895-8301 (Fax) 703-838-8860 (Fax)
http://www.nfpa.org http://www.tanktruck.org
Occupational Safety and Health Ministry of Transportation &

Administration (OSHA) Communications
U.S. Department of Labor Land Transport Directorate
200 Constitution Avenue, NW Hazardous Materials & Waste Directorate
Washington, DC 20210 Avenida Xola, esquina con Eje Central
800-321-6742 S/N, Col. Narvarte
http://www.osha.gov Del. Benito Juarez, MEXICO
52-55-572-39300
Society of Automotive Engineers Superintendent of Documents

(SAE) 400 Commonwealth Drive Government Printing Office
Warrendale, PA 15096-0001 732 North Capitol Street, NW
724-776-4841 Washington, DC 20401
724-776-0790 (Fax) 202-589-0249 (Sales)
https://www.sae.org/ http://www.access.gpo.gov
Transport Canada The Chlorine Institute

330 Sparks Street 1300 Wilson Boulevard, Ste. 525
Ottawa, Ontario K1A ON5 (CANADA) Arlington, VA 22209
613-990-2309 703-894-4140
613-954-4731 (Fax) 703-894-4130 (Fax)
http://www.tc.gc.ca http://www.chlorineinstitute.org
APPENDIX A – DATA SHEET – SODIUM HYDROXIDE SOLUTION

This information provides basic chemical properties and other information based on industry-wide data for the reader’s general
understanding of the product. Because of the variances in production and shipment methods throughout industry, this information
may not necessarily reflect the specific chemical information included in a particular company’s product Safety Data Sheet (SDS).
Consult your supplier to request an SDS for their product specific information and considerations.
NAME: Sodium Hydroxide Solution CHEMICAL FORMULA: NaOH
TRADE NAME: Caustic Soda
SYNONYMS: Liquid Caustic, Lye Solution, Caustic, Lye, Soda Lye
PHYSICAL DATA
Boiling Point: 288oF (142oC) 50% Solution Vapor Pressure: Per producer data
371oF (189oC) 73% Solution
Solution in water: 100% Vapor Density: Per producer data
Sp. 1.53 @ 60oF (15.6oC) 50% Solution Appearance: Colorless or slightly

Gravity: 1.706 @ 194oF (90oC) 73% Solution colored, clear or
opaque
Odor: Odorless Molecular Weight: 40.0 g/mol
FIRE AND EXPLOSION HAZARD DATA
Flash Point: None Flammable Limits: LFL: N/A

UFL: N/A
Fire and Explosion In water solution caustic can react with amphoteric metals (such
Hazards: as aluminum) generating hydrogen which is flammable and/or
explosive when ignited.
REACTIVITY DATA
Stability: Product absorbs water and carbon dioxide from the air.
INCOMPATIBILITY
Hazardous Material Dilution with water evolves large amount of heat. Product is
Decomposition: strong caustic alkali. May react violently with acid and a number
of organic compounds. Caustic reacts rapidly with aluminum,
tin, and zinc. It will also react with bronze and brass.
HEALTH HAZARDS
Eye: May cause severe irritation with corneal injury and result in
permanent impairment of vision, even blindness. Dusts may
irritate eyes.
Skin Contact: Short single exposure may cause severe skin burns.
56 PAMPHLET 94
Ingestion: May cause gastrointestinal irritation or ulceration and severe

burns of the mouth and throat.
Inhalation: Dusts or mists may cause severe irritation to upper respiratory

tract.
HANDLING AND STORAGE PRECAUTIONS
Ventilation: Control airborne concentrations below the exposure guideline.

Good general ventilation sufficient for most operations.
Respiratory Protection: In misty atmospheres, use an approved mist respirator. If

respiratory irritation is experienced, use an approved air-
purifying respirator.
Skin Protection: Use protective clothing impervious to this material. Selection of

specific items such as gloves, boots, apron, hard hat with face
shield, or full-body suit will depend on operation. Remove
contaminated clothing immediately, wash skin area with soap
and water, and launder clothing before reuse.
Eye Protection; Use chemical goggles. Full-face shield in addition to goggles

may be desirable to protect face. Maintain eye wash fountain
and safety shower at or near work area.
ADDITIONAL INFORMATION:
Special Precautions to be Taken in Handling and Storage:
Prevent eye and skin contact. Do not breathe dusts or mists.
Avoid storing next to strong acids. Caustic should be stored in clean, dry areas. Do not store in
underground tanks. Product absorbs water and CO2 from air. Keep containers closed and
sealed.
Special Precautions for Diluting Caustic Soda Solution:

ALWAYS add caustic soda solution to water with constant agitation.
NEVER add water to the caustic soda solution.

The water should be lukewarm (80-100oF) (27-38oC). NEVER start with hot or cold water.
The addition of caustic soda to liquid will cause a rise in temperature. If caustic soda becomes
concentrated in one area, or is added too rapidly, or is added to hot or cold liquid, a rapid
temperature increase can result in DANGEROUS mists or boiling or spattering which
may cause immediate VIOLENT ERUPTION.
APPENDIX B– DATA SHEET – POTASSIUM HYDROXIDE SOLUTION
This information provides basic chemical properties and other information based on industry-wide data for the reader’s general
understanding of the product. Because of the variances in production and shipment methods throughout industry, this information
may not necessarily reflect the specific chemical information included in a particular company’s product Safety Data Sheet (SDS).
Consult your supplier to request an SDS for their product specific information and considerations.
NAME: Potassium Hydroxide Solution CHEMICAL FORMULA: KOH
TRADE NAME: Caustic Potash
SYNONYMS:
PHYSICAL DATA
Boiling Point: 290oF (143oC) Vapor Pressure: Per producer data
Solution in water: 100% Vapor Density: Per producer data
Sp. 1.53 @ 60oF (15.6oC) 50% Solution Appearance: Clear liquid

Gravity: 1.706 @ 194oF (90oC) 73% Solution
Odor: Odorless Molecular Weight: 56.1 g/mol
FIRE AND EXPLOSION HAZARD DATA
Flash Point: None Flammable Limits: LFL: N/A

UFL: N/A
Fire and Explosion Hazards:
REACTIVITY DATA
Stability: Under normal conditions, the material is stable.
INCOMPATIBILITY
Hazardous Material Avoid direct contact with water. This product may be added slowly
Decomposition: to water or acids with dilution and agitation to avoid a violent
exothermic reaction. Avoid contact with aluminum, tin, zinc, and
alloys containing these metals. Avoid contact with leather, organic
halogen compounds, organic nitre compounds, acid, and wool.
HEALTH HAZARDS
Eye: Is destructive to eye tissues on contact. Will cause severe burns

that result in damage to the eyes and even blindness.
Skin Contact: Is destructive to tissues contacted and produces severe burns. A

latent period may exist between exposure and sense of irritation.
58 PAMPHLET 94
Ingestion: May cause severe burns and complete tissue perforation of

mucous membranes of the mouth, throat, esophagus, and
stomach.
Inhalation: Mists or spray may cause damage to the upper respiratory tract
and even to the lung tissue proper which could produce chemical
pneumonia, depending on severity of exposure.
HANDLING AND STORAGE PRECAUTIONS
Ventilation: Use with adequate ventilation.
Respiratory Protection: When exposure to dust, mist or spray is possible, employ

respiratory protection.
Skin Protection: Use protective clothing impervious to this material. Selection of

specific items such as gloves, boots, apron, hard hat with face
shield or full-body suit will depend on operation. Remove
contaminated clothing immediately, wash skin area with soap and
water, and launder clothing before reuse.
Eye Protection: Use chemical goggles. Full-face shield in addition to goggles may
be desirable to protect face. Maintain eye wash fountain and
safety shower at or near work area.
ADDITIONAL INFORMATION:
Special Precautions to be Taken in Handling and Storage:
Prevent eye and skin contact. Do not breathe dusts or mists.
Avoid storing next to strong acids. Caustic should be stored in clean, dry areas. Do not store in
underground tanks. Product absorbs water and CO2 from air. Keep containers closed and
sealed.
Special Precautions for Diluting Caustic Soda Solution:

ALWAYS add caustic potash solution to water with constant agitation.
NEVER add water to the caustic potash solution.

The water should be lukewarm (80-100oF) (27-38oC). NEVER start with hot or cold water.
The addition of caustic potash to liquid will cause a rise in temperature. If caustic potash
becomes concentrated in one area, or is added to rapidly, or is added to hot or cold liquid, a
rapid temperature increase can result in DANGEROUS mists or boiling or spattering which may
cause immediate VIOLENT ERUPTION.
APPENDIX C – FREEZING POINT CURVE FOR CAUSTIC SODA SOLUTIONS
Note: The curve indicates the point at which crystals exist in contact with solution. From T.P. Hou, Manufacture of Soda Ash, 2nd
A - ICE
B - ICE + NaOH7 H2O
C - NaOH7 H2O
D - NaOH7 H2O + NaOH5 H2O
E - NaOH5 H2O
F - NaOH5 H2O + NaOH4 H2O
G - NaOH4 H2O
H - NaOH4 H2O +NaOH3 ½ H2O
I - NaOH3 ½ H2O
J - NaOH3 ½ H2O + NaOH2 H2O
K - NaOH2 H2O
L - NaOH2 H2O + NaOH H2O
M - NaOH H2O
TEMPERATURE, °c
TEMPERATURE,
N - NaOH H2O + NaOH
P - NaOH
°F
NaOH, % BY WEIGHT
Ed. N.Y., Reinhold Publishing Corp., 1942. From Industrial Engineering Chemistry, Vol. 46, No. 11, p. 2401.
60 PAMPHLET 94
APPENDIX D – CAUSTIC SODA SERVICE GRAPH

Reprinted from Corrosion Data Survey - Metals Section, Sixth Edition. Copyright 1985 by
NACE International. All Rights Reserved by NACE; reprinted with permission.
AREA “C”
APPLICATION OF NICKEL ALLOYS TO BE CONSIDERED IN THIS AREA
NICKEL ALLOY TRIM FOR VALVES

IN AREAS “B” & “C”
AREA “B”
CARBON STEEL
STRESS RELIEVE WELDS & BENDS
TEMPERATURE, °c
TEMPERATURE, °F
AREA “A”
CARBON STEEL
NO STRESS REILEF NESCESSARY
CONCENTRATION NaOH, % BY WEIGHT

APPENDIX E – FREEZING POINTS OF AQUEOUS KOH SOLUTIONS

Reprinted from Occidental Chemical Corporation Caustic Potash Handbook,
Reprinted with permission.
Chart 1- Freezing Points of Aqueous KOH
Roman numerals represent the following:

I H2O (Ice)
II H2O · 4H2O
III KOH · 2H2O
IV KOH · H2O
The more important transition points:
I to II -85.4°F 30.83% KOH
II to III -27.4°F 44.29% KOH
III to IV +90.5°F 56.82% KOH
IV
TEMPERATURE, °F
III
44.3% KOH, -27.4°F

I
II
30.8% KOH, -85.4°F
Concentration, % KOH
62 PAMPHLET 94
APPENDIX F – ALLOY SELECTION FOR CAUSTIC SODA SERVICE

by C.M. Schillmoller
NiDI Technical Series No10 019
Reprinted with permission from the Nickel Development Institute
Alloy selection for caustic

soda service
by C.M. Schillmoller*
Caustic soda (i.e., sodium hydroxide, NaOH) and chlo process variables involved.
rine are oo-produced by the electrolysis of a sodium chloride In general, factors to be considered in materials selec
solution. Both chemicals find world-wide application in the tion include practicality, availability, mechanical properties,
chemical and related process industries. (Alloy selection for corrosion resistance, risk/benefit considerations and eco
Chlorine is discussed in the NiDI publication #10020, nomics.
"Alloys to Resist Chlorine, Hydrogen Chloride and Critical factors in caustic service include:
Hydrochloric Acid.") Caustic soda ranks third in tonnage 1. The concentration of the caustic solution.
production among the inorganic chemicals; some 13.2 2. The temperatures to be encountered (including pos
million tons were used in the USA alone in 1986. sible excursions).
Roughly half of all caustic produced is used in the 3. The presence of other chemicals which may be
manufacture of other chemicals. Another 16% is consumed present in the caustic, as contaminants or additives.
by the pulp and paper industry. Other important uses are 4. Tolerance limits for metallic ion contamination of the
in the production of rayon, cellulose, textiles, petroleum caustic itself (or of the process end-product).
products, soaps and the refining of Bauxite ore in the 5. Residual or applied tensile stresses, which may affect
production of aluminum. corrosion resistance.
6. The economics of cosUlife considerations.
CRITERIA FOR MATERIALS SELECTION Metals and alloys most frequently considered for use in
A number of materials of construction may be used to caustic soda are carbon steel, stainless steels, nickel and
produce and handle caustic solutions. Their suitability for high-nickel alloys. Some alloys, with their generic names,
specific applications will depend upon factors associated common trade-names, UNS numbers and nominal com
with the concentration and use of the caustic and the positions are given in Table I.
Table 1
Alloys commonly used in caustic soda systems
Reference Nominal Composition, % ASTM UNS Most Common

Materials In text Ni Cr Fe Mo Cu TI B Numbers Tradenames
Nickel
Nickel Alloy 200 99.6 161-163 N02200 Nickel 200
Low-carbon Nickel Alloy 201 99.6 161-163 N02201 Nickel 201
Nickel-Copper Alloys
Nickel-copper alloy Alloy 400 67 1.5 31 163-165 N04400 Mone!' 400
Nickel-Chromium-Iron Alloys
Nickel-chromium alloy Alloy 600 76 15 8 163-168 N06600 lnconel' 600
Nickel-iron-chromium alloy Alloy 800 32 21 46 163-407 N08800 lncoloy• 800
Nickel-iron-chromium-
moly-copper alloy Alloy 825 42 21 30 3 2.3 163-423 N08825 lncoloy• 825
Nickel-iron-chromium-
moly-copper alloy Alloy 20 34 20 39 2.5 3.3 464-468 N08020 Carpenter••
20 Cb-3° •
Stainless Steels
Chromium-nickel stainless Type 304 10 18 72 S30400 Type 304
Chromium-nickel-moly stainless Type 316L 12 18 70 S31603 Type 316L
Chromium stainless Type 430 17 83 $43000 Type 430
Chromium-moly stainless 26-1 26 73 1 EB 26-1
Titanium
Titanium, grade 2 Titanium Gr2 99+ 338 Titanium Gr2
'Mone/, lnconel and lncoloy are tradenames of the International Nickel Co.
• 'Carpenter and 20 Cb-3 are tradenames of CARTECH
*Schillmoller Associates, Houston, TX; Consultant to NiDI

64 PAMPHLET 94
As these represent a considerable variation in first costs, nickel cast irons, such as Ni-Resists (UNS• F4INNN and
the final choice for a specific service will depend on an anal F43NNN series) are even more corrosion-resistant.
ysis of all of the above factors.
Austenitlc Stainless Steels

MATERIALS OF CONSTRUCTION The "18-8"-type stainless steels, exemplified by Types 304
(S30400) and 316 (S31600), have a usefully low corrosion
Steel and Cast Irons rate in caustic at up to 50% concentration to about 70 °C
Carbon steel is useful for handling sodium hydroxide up (160 °F).
to about 50% concentration, where iron contamination is Note that Figure 2, based on Copson's work (5) on SCC
not a problem, to moderate temperatures, e.g., 85 ° C of stainless steels, is somewhat more optimistic, showing
(185 ° F). However, steels are subject to an anodic form of less than I mpy up to about 93 °C (200 ° F). This is prob
environmental cracking [i.e., stress-corrosion cracking ably due to dissolved oxygen or traces of oxidizing species,
(SCC)], often called "caustic embrittlement," in hot caustic. because it is known that Type 304 can go active in 40%
The relation of temperature and concentration in caustic at about 80 ° C (175 ° F) and in 50% caustic at 70 °C
promoting cracking is shown in Figure 1. ( l 60 ° F). In the active state, the 18-8 alloys corrode faster
Because of the effect of residual stress in promoting this than carbon steel.
type of attack, both welded and cold-worked (i.e., flared, Table 2 shows the results of a study by NACE Task
bent) fabricated steel equipment must be thermally stress Group T5A-3D (4) to assess the relative corrosivity of
relieved to extend its life in caustic service. diaphragm-cell caustic vs. mercury-cell caustic. The results
For services where iron pick-up is undesired, steel tanks indicate no significant difference between Types 304
are frequently coated with an organic paint system to (S30400) and 316 (S31600) in 50% caustic, nor in 73%
minimize iron contamination. concentration in which both materials suffered active cor
Cast iron is not usually used in caustic service, because rosion as well as some pitting attack. It seems probable that
of the safety problems caused by its inherent brittleness. these products contained unknown amounts of chlorates,
However, ductile cast iron is permissible, and the high- as produced.
OF oc °F °C
300.----r---,----.--�.---��---,150 500.---------,-----.------,
300
Boiling Point Curve
Stress Cracking Zone

250 125 500
250
'
Apparent Stress-Corrosion
', ' '

100 Cracking Boundary
200 400 200
I / Atmospheric
''
'{"' Boiling Point Curve
!!' \ >30mpy
75 ::,
1ii
, Danger Zone � 300 150
,
E 110 , .....
{!; 50mpy -
Cracking Reported/' ' - _ 50
Above Curve 100
100 200
25 <1mpy
50
50 100
0
0
OL---'----'---�---''-----'---'
10 20 30 40 50 60 20 40 60 80
Sodium Hydroxide. wt % Sodium Hydroxide, wt %
Figure 1 Figure 2
Relation of temperature and concentration of sodium lsocorrosion chart for AISI 304 and 316 stainless steels
hydroxide to cause stress cracking of carbon steel. in sodium hydroxide, with stress cracking boundary
superimposed.
•'ll1rouih<>ut this publication. UrtiflOd Numbering S"""1 (UNS) d<sisnatioos have been included
for alloy identification.
2
Table 2
"Round Robin" test program by four caustic soda producers-comparison of corrosiveness of diaphragm cell vs.
mercury cell caustic (conducted by NACE Committee TSA-30)
Company Company
2 3 4 2 3 4
Ave,- Temperature Corrosion Rate, mpy

Material Corrodent •c Of •c 'f •c 'F •c 'f
Nickel 200 50% NaOH-Diaphragm Cell
50% NaOH-Diaphragm Cell
35 95
40 104 - -
29 85
- -
88 190 54 130
Ambient
<0.1
<0.1
1<0.1 <0.1 <0.1
<0.1
50% NaOH-Mercury Cell 38 100 105 221 82 180 .so 140 <0.1 <0.1 1.0 <0.1
- -
50% NaOH-Mercury Cell
- - - -
37 98 45 113
- - Ambient <0.1 <0.1 <0.1
-- -- - - --- ---
50% NaOH-Mercury Cell Ambient Ambient <0.1 <0.1
73% NaOH-Diaphragm Cell 119 246 99 210 <0.1 0.2
73% NaOH-Diaphragm Cell 125 257 - - 0.2
73% NaOH-Mercury Cell 114 236 0.3
lnconel alloy 600 50% NaOH-Diaphragm Cell

35 95
40 104 -29 -85 88- 190- Ambient
54 130 <0.1 (1)
<0.1
<0.1 <0.1 <0.1
<0.1
50% NaOH-Mercury Cell 38 100 105 221 82 180 60 140 <0.1 <0.1 <0.1 <0.1
50% NaOH-Mercury Cell 37 98 45 113 - - Ambient <0.1 <0.1 <0.1
- - - -
73% NaOH-Diaphragm Cell 119 246
Ambient
- -
- - - 99 210 - -
Ambient
- - <0.1
<0.1
0.2
<0.1
- -- -
73% NaOH-Diaphragm Cell 125 257 - 0.3
73% NaOH-Mercury Cell 114 236 - - 0.2
Monet alloy 400 50% NaOH-Diaphragm Cell

35 95
40 104 -29 85- 88- 190- 54 130
Ambient
<0.1
<0.1
<0.1 <0.1 <0.1
<0.1
50% NaOH-Mercury Cell 38 100 105 221 82 180 60 140 <0.1 0.1 0.2 <0.1
- -
- - Ambient
37 98 45 113
- - Ambient <0.1 <0.1 <0.1
73% NaOH-Diaphragm Cell 119 246 - - 99 210
-- -- -- -- - -
Ambient
- - <0.1
<0.1
0.8
<0.1
73% NaOH-Diaphragm Cell 125 257 0.4

73% NaOH-Mercury Cell 114 236 - - 0.5
lncoloy alloy 800 50% NaOH-Dlaphragm Cell 35 95 29 85 88 190 54 130 <0.1 <0.1 <0.1 <0.1
50% NaOH-Diaphragm Cell 40 104 - - - - Ambient <0.1 <0.1
- -
50% NaOH-Mercury Cell - - - -
37 98 45 113
Ambient - -
Ambient
-- --
Ambient
<0.1 <0.1
<0.1
<0.1
<0.1
73% NaOH-Diaphragm Cell 119 246 99 210 0.1 4.1 (2)
- - - -
125 257
114 236 - - - - - - 0.5
0.3 (1)
carpenter alloy 20 Cb-3 50% NaOH-Diaphragm Cell

35 95
40 104 - - 88- 190-
29 85 54 130
Ambient
<0.1
<0.1
<0.1 <0.1 <0.1
<0.1
- -
50% NaOH-Mercury Cell 37 98 45 113
- - Ambient - - Ambient <0.1 <0.1 <0.1
- - 99 210 - -
Ambient <0.1 <0.1
- -
73% NaOH-Diaphragm Cell 119 246 0.4 1.5 (3)
- - - -
125 257
114 236 - - - - - - 0.5
0.4
Type 316 Stainless Steel 50% NaOH-Diaphragm Cell 35 95 2985 88 190 54 130 <0.1 <0.1 3.3 <0.1
50% NaOH-Diaphragm Cell 40 104 - - - - Ambient 0.2 <0.1
50% NaOH-Mercury Cell 38 100 105 221 82 180 60 140 <0.1 <0.1 0.2 <0.1
- -
37 98
- - 45 113
Ambient
- -
- - Ambient
Ambient
- -
<0.1 0.1
<0.1
0.3
<0.1
- - -- --
73% NaOH-Diaphragm Cell 119 246 99 210 6 (4) 8.7
- -
125 257
114 236 - - - - 13.1 (5)
10 (4)
Type 304 Stainless Steel 50% NaOH-Diaphragm Cell

35 95
40 104
2985
- - --
88 190 54 130
Ambient
<"0.1
<0.1
<0.1 1.1 <0.1
<0.1
50% NaOH-Mercury Cell 38 100 105 221 82 180 60 140 <0.1 0.1 (1,6) 0.3 <0.1
50% NaOH-Mercury Cell 37

-
- 98 45 113 - -
- - Ambient <0.1
11.0
<0.1 0.4
73% NaOH-Diaphragm Cell 119 246
Ambient
- -
- -
99 210 - --
Ambient
15 (4)
<0.1
13 (7)
<0.1

125 257
114 236 - - -- -
-
-
- - 19.4 (5)
15 (4)
(1) Pitted to a maximum depth of 1 mil. (5) Pitted to a maximum depth of 3 mils. (7) Pitted to a maximum depth of 8 mils.
(2) Pitted to a maximum depth of 4 mils. (6) Mercury droplets in tank 2 rates shown are for
(3) Pitted to a maximum depth of 5 mils. the duplicate specimens (not averaged).
(4) Stress corrosion crack through one of the iden Specimen with high rate showed stress
tifying punch marks. accelerated local attack.
3
66 PAMPHLET 94
As indicated in Figure 2, I8-8 stainless is susceptible to dehydrating amines with hot 70% caustic, in the total
SCC in hot caustic, e.g., 15% NaOH at about 150° C absence of oxygen or oxidizing agents.
(300 °F). In practice, this is most often encountered in Aluminum bronzes may be subject to dealuminification,
caustic-contaminated steam (e.g., Oxycat units, expansion due to the amphoteric nature of the aluminum constituent.
joints in 400 psi steam). Caustic cracking of stainless is
characterized by a gun-metal bluing effect, quite striking
on visual examination. High-Nickel Alloys
An additional consideration is chloride contamination The nickel-chromium-iron alloys, with and without
in the caustic. Mercury cell production yields caustic with molybdenum, e.g., Alloy 800 (N08800), Alloy 825
low amounts of chloride, typically 20-30 ppm. Diaphragm (N08825), Alloy 20 Cb-3 (N08020) have useful resistance
cell production, on the other hand, yields caustic of con to caustic soda solutions at concentrations up to 73%, as
siderable chloride, e.g., up to I% sodium chloride (6000 shown in Table 2, up to approximately 120° C (250°F).
ppm Ci-). Unfortunately, they are susceptible to caustic cracking,
The effect of chloride in caustic is moot (some Russian certainly around 150° C (300°F). In materials selection to
researchers have claimed it inhibits caustic sec of I 8-8). prevent stress-corrosion cracking, it is therefore essential
However, if the sodium hydroxide is used in a process in to determine whether the responsible species are chlorides,
which it is consumed or otherwise converted to a different in which case these are acceptable alternative alloys, or
compound, its chloride content remains as a potential caustic, which calls for nickel-base alloy replacement.
haz.ard for chloride sec. Use of mercury-cell caustic dimin
ishes this risk (6).
Nickel-Base Alloys
Ferritic Stainless Steels These are the alloys having more than 50% nickel, and
can be conveniently divided into two groups; those that
Traditional ferritic stainless steels, such as Type 430 do not contain chromium, and those that do.
(S43000), have lower temperature limits in caustic than do
the I8-8 austenitic stainless steels. They are considered sus CHROMIUM-FREE ALLOYS
ceptible to caustic cracking, as well.
In recent years, there has been wide-spread application These comprise a group of three generic types, nickel
of extra-low interstitial, molybdenum-bearing ferritics, such itself, nickel-copper and nickel-molybdenum alloys.
as Alloy 26-1 (S44626), in evaporator tubing. Performance
has ranged from good to poor. Nickel
Good performance is probably associated with oxidizing Nickel is available in two alloys, Alloy 200 (N02200),
contaminants, such as chlorates, which tend to enhance and a low-carbon variant Alloy 201 (N02201), both of
passivity. which have excellent resistance to caustic, even as the hot
Failures, due to either localized or general corrosion, anhydrous form, as shown in Figure 3. Except for silver,
have been associated with one or more of the following nickel is the· most resistant metal for high caustic concen
factors: trations at the elevated temperatures which generally
I. Contamination of the tubes with minute amounts of prevail. At concentrations up to 73% caustic, the corro
oil, grease or other hydrocarbons in the production, heat sion rate is generally less than I mpy (.025 mm/yr.). The
treatment or fabrication. The superferritic grades readily rates increase slightly above 73%, as shown.
absorb carbon under such conditions, obviating the low Nickel 200 contains up to 0.10..% carbon, which can
interstitial controls. precipitate as graphitic carbon on heating above 425° C
2. High temperatures in the first effect evaporator, i.e., (800°F), which reduces ductility of the alloy. This may also
in excess of 150° C (300° F). occur upon prolonged heating at temperatures as low as
3. Blockage of tubes with insoluble salts, creating locally 315°C (600 °F). Above 300° C (570°F), e.g., in molten
high skin temperatures. anhydrous caustic, the low-carbon Alloy 201 (N02201) is
preferred.
Behavior of these nickel alloys in caustic solutions is
Copper Alloys apparently unaffected by stress. Prior to development of
the low-carbon variant, a few failures of nickel were
It is sometimes mistakenly assumed that copper alloys reported in high-temperature service in concentrated
are unsuitable for caustic service. This is probably due to caustic, with an intergranular.mode of attack thought to
the dearth of data available. Copper alloys are not, in fact, be caustic cracking. These are now believed to have been
used in contact with caustic to be employed in the rayon cases of embrittlement due to graphite precipitation.
industry (because of color problems) or soap industry
(because of rancidity). Nickel-Copper Alloys
On the other hand, except for the yellow brasses (which
are susceptible to dezincification), coppers, phosphor (tin) Alloy 400 (N04400) has corrosion resistance quite similar
bronzes and cupronickels may be used for up to 70% to nickel for concentrations up to 73%, although it is sus
caustic unless powerful oxidants (e.g., chlorates) are present. ceptible to caustic cracking in severe service. At higher
A conventional bronze valve or pump is eminently satis concentrations, the corrosion rate is somewhat greater than
factory to handle 25% caustic, for example, for pH control. nickel. In lower concentrations, and for service conditions
Copper alloys have given good life in processes for where contamination by small amounts of copper and
4
nickel is not detrimental, Alloy 400 {N04400) can be useful Nickel-Chromium-Iron Alloys
for caustic service at a somewhat lower cost than pure Alloy 600 {N06600) exhibits resistance similar to nickel
nickel. up to and including the anhydrous product. It is favored
Alloy 400 {N04400) is subject to caustic cracking at for heating coils, because of higher strength at tempera
elevated temperatures (e.g., in caustic-contaminated ture than the pure nickel alloys. It may cause a small
3()().400 psi steam). It is also subject to liquid metal cracking amount of contamination from Cr VI ions.
(LMC) by mercury and its salts. There have been instances It is subject to caustic cracking under severe conditions
of LMC with Alloy 400 {N04400) components used in han in prolonged exposure, and should be used in the stress
dling mercury-cell caustic prior to final separation of relieved condition.
mercury and its salts from the product. Alloy 600 {N06600) offers an advantage, compared to
The solution-hardening variants of Alloy 400 (e.g., Alloy 201 {N0220I) when a sulfur-bearing contaminant
N04404 and N04405),and the age-hardening variants (e.g., may be present, in being less susceptible to nickel sulfide
Alloy K500 or N05500 and N05502) have substantially eutectic formation (a low-melting nickel-nickel sulfide com
the same corrosion characteristics. pound causes intergranular penetration analogous. to
LMC). It has been used for the production of anhydrous
Nickel-Molybdenum Alloys caustic where a sulfur-containing chemical must be toler
ated as a contaminant in the heating medium. It has also
There is little occasion to use Alloy B-2 {NI0665) in been used where sulfur has been present in one of the
caustic service. Published data indicate that it has excel process reactants.
lent resistance, at least in lower concentrations in the Alloy 600 {N06600) has also replaced Type 316 (S31600)
absence of powerful oxidants. Individual applications stainless heat exchangers in a high-temperature process for
would have to be explored. the recovery and reuse of chloride-bearing caustic (the stain
less having failed by chloride stress-corrosion cracking).
CHROMIUM-BEARING ALLOYS Alloy 600 {N06600) can also offer an advantage over
Alloy 200 {N02200) in caustic from the diaphragm-cell
This group comprises Alloy 600 {N06600) and its var process, in which chlorates and hypochlorites are present.
iants and the molybdenum-bearing grades, Alloy 625 Being oxidizing in nature, these accelerate corrosion of
{N06625) and Alloy C276 {NI0276) and its variants. Alloy 200 (N02200), as shown in Figure 4, whereas the
mpy mm/yr
soo'F 100 2.5
No Sodium
Corrosion Rates for 300
Chlorates Chiorates
Alloy 200 and Alloy 201 1.0
500
250 20 0.5
10 0.25
� 400
::, 200 ., 5
�., �
a. 0.10
E
C:
0
150 "iii
f': 300
g2 0.05
0
(.)
1 0.025
100
200
0.010
50
< 0.1 mpy
100 0.2 0.005
0 0.1 0.0025
20 40 60 80 100 8
"' " "' 0
....J I() 0
"' "
....J
"'
I()
8
� CX) � �
0 0
Sodium Hydroxide, wt %
0 CX)
m
Sodium Hydroxide, 50 wt%, 300'F (150'Cl
Figure 3 Figure 4
Corrosion rates for Nickel Alloy 200 and low carbon Typical comparative corrosion rates for several alloys in
Nickel Alloy 201 in sodium hydroxide. sodium hydroxide in the presence of sodium chlorates.
5
68 PAMPHLET 94
resistance of the chromium-bearing alloy is not greatly processes, to alleviate accelerated corrosion which would
affected. otherwise occur at elevated temperatures.
Nickel-Chromium-Molybdenum Alloys SODIUM CHLORIDE REMOVAL
Such alloys, exemplified by Alloy 625 (N06625) and Residual sodium chloride, which concentrates during the
Alloy C276 (Nl0276) and its variants, are intended for acid evaporation process and crystallizes out, must be removed
service, little being published about caustic resistance. Of by settling and filtration. Much of the crystallized salt is
course, their higher cost, as compared with Alloys 200 or recycled in the cell-feed liquor, the balance being purged
600, practically excludes them from consideration. by blow-down from the circuit to control build-up of sul
There is one notable exception. Alloy 625 (N06625) has fates and other undesirable constituents in the cell liquor.
become the material of choice for corrugated metal expan
sion joints in high pressure steam, where environmental SPECIFIC EQUIPMENT
cracking of austenitic stainless steels occurs due to caustic
carry-over while chloride carry-over may cause pitting of 50% Caustic
Alloy 600 (N06600), for example. These alloys are practi
cally unaffected by hot caustic up to at least 320 °C Evaporators
(600 °F). The multiple-effect evaporators required for concentra
tion employ Alloy 200 (N02200) tubing, tube-sheets,
circulation piping, and the wetted surfaces of the evapo
ALLOYS IN CAUSTIC SODA PRODUCTION rator bodies. A triple-effect evaporator for the production
Caustic soda and its co-product, chlorine, are made by of 50% caustic is shown in Figure 6, while alloy selection
electrolysis of a sodium chloride solution. Sodium for specific areas is indicated in Figure 7. Also, Table 3
hydroxide is produced at the cathode, while chlorine is provides information on various applications of nickel-base
evolved at the anode. alloys and nickel cast irons in caustic soda equipment.
Mercury Cell Caustic

Table 3
Carbon steel has been the conventional material of con Applications of nickel alloys in caustic soda equipment
struction for mercury-cell caustic, resisting caustic up to (typical examples, courtesy INCO Alloys International)
70% to about 93° C (200 °F). Small amounts of other alloys
are used for specific areas in the process.
Subterranean brines used as feedstock for electrolytic Brine Pumps.. ....................Ni-Resist and alloy 400
processes must be heated and chemically treated to remove Brine Heaters .... Nickel 200 and alloy 400
calcium, iron, manganese and sulfates. A simplified process Evaporators
flow diagram of the brine processing and chlorine handling Bodies ....... Nickel-clad steel or lined with Nickel 200 sheet
in an electrolytic brine-processing circuit is shown in Steam Chests .Nickel 200 or alloy 400 tube sheets
Figure 5. Nickel 200, alloy 400 or nickel-clad steel
downtakes
For the brine heaters, both Alloy 400 (N04400) and Nickel 200 or alloy 400 tubes
titanium (R50400) or its variants) have been used. Titanium Anhydrous ....Nickel 201 or alloy 600 tubes
alloys are preferred, because of the problem of LMC of Heat Exchangers . ... Nickel 200 or alloy 400
the nickel-base alloy by entrained mercury, as well as cor Pumps
rosion by small amounts of chlorine or hypochlorites. Bodies . ..Nickel 200, alloy 400 or Ni-Resist
Shafts. ...........Nickel 200 or alloy 400
Impellers ...Nickel 200, alloy 400 or Ni-Resist
Diaphragm Cell Caustic Valves & Fittings . ...Nickel 200, alloy 400 or Ni-Resist
This electrolytic process produces about 75% of present Pipe Lines ... ..... Nickel 200, alloy 400 or Ni-Resist
day production of sodium hydroxide. The initial product, Filters
the cell liquor leaving the electrolysis cell bank, contains Bodies & Drums .... Nickel 200 or nickel-clad steel
only about 10-12% caustic. The other constituents are Filter Cloth
Backing Wire } ...Alloy 400 or Nickel 200
unreacted sodium chloride, sodium chlorate plus traces of Winding Wire
dissolved chlorine (both powerful oxidants) and sodium Piping, Valves and Fittings .. Nickel 200, alloy 400 or Ni-Resist
sulfate. Settling Tanks. .Nickel-clad steel or lined with nickel sheet
This cell liquor must be concentrated to 50% or 73%,
Storage Tanks ...... Nickel-clad steel or lined with nickel sheet
or to the anhydrous grade for commercial use. Multiple
effect evaporators are utilized to achieve these higher con Crystallizers
Bodies . Nickel-clad steel or lined with nickel sheet
centrations. Shafts & Agitators. . ...... : .. Nickel 200 or alloy 400
Centrifugals ..Alloy 400 baskets and wire cloth liners
CHLORATE REMOVAL
Tank Cars
Sodium chlorate, being both an oxidizing agent and a Bodies... . ........ Nickel-clad steel
source of more chloride upon decomposition, is an objec Coils ... . . ...... Nickel 200
tionable constituent. It is removed either before or during Transfer Piping. .....•.•.•...... Nickel 200 or alloy 400
the evaporation step by one of several proprietary
6
Brine Processing
Diaphraghm Cell
Caustic Plant
Caustic Treatment
Figure 5
Flow diagram of a diaphragm-cell caustic plant showing the brine processing circuit to the electrolytic cells, the chlorine
handling and caustic treatment. (Courtesy Occidental Chemical Corp., Ref. 11.)
The adverse effect of chlorates in a triple-effect evapo rate either before or during the evaporation process. The
rator has been reported (Reference 14). Life of the conventional treatment is extraction by ammonia, which
first-effect tubing (the hottest tubes and at the highest also reduces the dissolved salt content. Recently, a
caustic concentration, 47-50%) was found to vary from proprietary process has been commercialized which decom
3 to 12 years. The investigation showed that nickel pick poses chlorate with by-product hydrogen in the presence
up in the caustic was directly proportional to the chlorate of a catalyst. Alloys 200 (N02200) and 400 (N04400) have
concentration in the cell liquor, within the 120-200 ppm been used for the reactor, feed heater and feed/product
range encountered. Corrosion of nickel and reduction of interchanger in the hot caustic in this process.
chlorate occurs simultaneously across the first-effect heater.
Laboratory studies at J48 °C (300°F), the first-effect tem
perature, confinned plant experience. Corrosion rates for Salt Settlers
Alloy 200 (N02200) increase dramatically with caustic con The salt settlers (sometimes with filters) are tradition
taining I 00 ppm or more of chlorate. ally Alloy 200 (N02200). When cooling is required, the heat
Because of this adverse effect, many plants destroy chlo- transfer surfaces of the heat exchanger are also nickel.
7
70 PAMPHLET 94
Triple Effect Soda Evaporation System

ALLOYS FOR PROCESSES USING
Evaporator Condenser
CAUSTIC SODA
There are a number of commercial processing areas in
which corrosion-resistant materials are required to with
stand caustic conditions.
Petroleum Refining
Mercaptans and other organic sulfur compounds may
be removed from refinery streams with either caustic soda
or caustic potash (KOH). Since economy requires regener
ation of the caustic, with temperatures and concentrations
which exceed the capability of steel, Alloy 400 (N04400)
is frequently used for stripping-tower internals, tubular
heaters and reboilers. These handle caustic solutions up
Figure 6 to 45% concentration to about 150 °C (300 °F).
Flow diagram of a triple effect caustic soda evaporation When aminodiisopropanol is used for similar sulfur
system. removal operations, it is recovered by caustic treatment.
In such recovery units, steel would be corroded by sulfur
rich oils and austenitic stainless steel, e.g., Type 316L
(S3 l 603) is employed, the temperatures and concentration
However, nickel tubes recently failed in this application of caustic not requiring high-nickel alloys.
when seawater was used as coolant, and replacement in
Alloy 400 (N04400), welded with Alloy 625 (N06625) was Bauxite Refining
recommended. The salt-settling tank and slurry-holding
tank, prior to recycling of the crystallized salt, are fre In the Bayer Process for separation of alumina from iron
quently made of Alloy 400 (N04400). oxide in the ore, caustic soda is employed to solubilize the
aluminum oxide and remove the insoluble iron component.
Storage Tanks and Heaters The alumina is then crystallized out of the cooling caustic
solution.
Stress-relieved carbon steel tanks are employed, with While carbon steel is suitable for heating the caustic solu
specialty internal organic coatings to minimize iron pick tion to moderately high temperatures (there are certain
up. For high purity grades, Alloy 200 (N02200)-clad steel inhibiting constituents in the process solution), Alloy 400
tanks have also been employed. To maintain the caustic (N04400) tubing is used in the higher-temperature heaters.
above its freezing point; internal heating coils (or U-tube Either solid Alloy 200 (N02200) or nickel-lined steel piping
bundles) are employed. Tubes and tubesheets are either transfers the solution from the heaters to the reactors.
Alloy 200 (N02200) or Alloy 400 (N04400), to have equiva
lent thermal expansion of both components.
Soap Manufacture
73% and Anhydrous Caustic Soaps are made by saponifying fatty acids with caustic
soda. To minimize iron contamination and extend the
Evaporators useful life of the process equipment, Alloys 200 (N02200)
and 400 (N04400) have been commonly used for saponifi
Alloy 200 (N02200) is the conventional material for cation vessels, replacing the original steel and iron
caustic evaporation to 73%, having a low corrosion rate equipment.
and causing minimal metal ion contamination. For higher
concentrations up to the anhydrous product, high
temperature heat transfer fluids or molten salts are Sodium Hydrosulflde (NaSH)
employed at temperatures to 315°C (600 °F), or higher, and
Alloy 20 l (N0220I) is required, as previously noted, to void The reaction of hydrogen sulfide with 50% caustic
graphitic embrittlement. produces sodium hydrosulfid� at about 45-50% concen
If sulfur compounds are known or anticipated, Alloy 600 tration. The temperatures involved are at least 107 °C
(N06600) is required. Because it is susceptible to stress (225° F). While some producers have obtained reasonable
corrosion-cracking, thermal stress relief is required. Where reactor life with the 18-8 austenitic stainless steels, Alloy
this alloy has been employed with this precaution, service 20Cb3 (N08020) has proven superior in cases where the
performance has been equivalent to Alloy 201 (N02201). 18-8 has suffered general thinning. Field corrosion tests
suggest that Alloy 600 (N06600) should be the preferred
Tanks and Heaters alloy for this application.
The same stipulations described for 50% caustic apply,
except that resistant internal organic linings or nickel clad Caustic Fusion Reactions
ding are required to maintain product purity and obtain Reactions involving an organic compound and molten
an economical service life. caustic soda are referred to as caustic fusions. Because tern-
8
Diaphragm-Cell Caustic Soda Plant
Brine
Saturator
Salt
\
\
Chlorine Hydrogen
MONEL 25%
Alloy Salt Electrolytic
Brine Pump MONEL Diaphragm
MONELAlloy400 400
Alloy400 Cell
NICKEL200
12%Caustic
16%Salt
Water
Vapor
73%or
1 00%Caustic
NICKEL200
NICKEL201
Multiple Multiple
Caustic Ellect Recycle Effect
Storage Evaporators Salt Evap()rators
NICKEL200
Figure 7
Schematic flow sheet of diaphragm-cell caustic soda plant, showing typical alloy selections. (Courtesy INCO Alloys International)
peratures are usually above 315 °C (600° F), Alloy 201 3. A. A. Berk and W. F. Waldeck, Chemical Engineering, Vol 57 (6),
(N0220I) is the preferred material of construction, provided p 235, 1950.
no sulfur compounds are present. 4. "Corrosion Resistance of Nickel and Nickel-Containing Alloys in
When sulfur compounds are present (e.g., in the caustic Caustic Soda and Other Alkalies," Corrosion Engineering Bulletin
CEB-2, 1973, International Nickel Company, New York, NY.
fusion of benzene metasulfonic acid to produce resorcinol), 5. F. L. LaQue and H. R. Copson, "Corrosion Resistance of Metals
stress-relieved Alloy 600 (N06600) is preferred. Alloy 201 and Alloys," Reinhold Publishing Corporation, New York, NY,
(N02201) would be attacked in an intergranular mode by 1963.
the nickel sulfide eutectic which would form at the reac 6. C. W. Funk and G. B. Banon, "Caustic StressCorrosion Cracking,"
tion temperature. CORROSI0Nn7, Paper No. 54, National Association of Corro
sion Engineers, Houston, TX, I 977.
7. E. C. Hoxie, "Some Considerations in the Selection of Stainless Steel
Miscellany for Pres- sure Vessels and Piping," International Nickel Co., New
York, NY, 1975.
When molten sodium is used as a carrier (e.g., in certain 8. R. P. Tracy and B. R. Chuba, "Corrosion Resistance, Application,
hydrogenation reactions), traces of water in the reactants and Economics of Electroless Nickel Coatings inNaOH Production,"
may form anhydrous caustic dissolved in the sodium. NACE Corrosion 87, Paper No 462.
Austenitic stainless steels and even high-performance 9. C. M. SchillmoUer, "Amine Stress Cracking: Causes and Cures,"
nickel-rich alloys can crack very quickly at elevated tem Hydrocarbon Processing, June 1986, pp 37-39.
peratures. Alloy 200 (N02200) or Alloy 600 (N06600) JO. P. J. Gegner, Corrosion, Vol 12, p 261, June 1956.
stress-relieved clad steel vessels are mandatory. I I. B. M. Barke!, "Accelerated Corrosion of Nickel Tubes in Caustic
Evaporation Service," CORROS10Nn9, Paper No 13, National
Association of Corrosion Engineers, Houston, TX, 1979.
12. J. K. Nelson, "Materials of Consuuction for Alkalies and Hypo
REFERENCES chlorites," Process Industries Corrosion, NACE 1986, pp 297-3 JO.
13. J. R. Crum and W. G. Lipscomb, "Correlation Between Labora·
I. P. J. Gegner, "Corrosion Resistance of Materials in Alkalies and tory Tests and Field Experience for Nickel 200 and 26-I Stainless
Hypochlorites," Process Industries Corrosion Short Course, Paper Steel in Caustic Service," CORROSION/83, Paper No 23, National
No. 27, National Association of Corrosion Engineers, Houston, TX, Association of Corrosion Engineers, Houston, TX, I 983.
1974. 14. M. Yasuda, F. Takeya, F. Hine, "Corrosion Behavior of Nickel in
2. H. W. Schmidt, P. J. Gegner, G. Heinemann, C. F. Pogacar, and Concentrated NaOH Solutions Under Heat Transfer Conditions,"
E. H. Wyche, Corrosion, Vol 7, p 295, 1951. Corrosion, Vol 39 (10), October, 1983.
9
72 PAMPHLET 94
APPENDIX G
PAMPHLET 94 CHECKLIST
This checklist is designed to emphasize major topics for someone who has already read and
understood the pamphlet. Taking recommendations from this list without understanding related
topics can lead to inappropriate conclusions.
Place a check mark () in the appropriate box below:
Yes No N/A
   1. Is the reactivity and compatibility information from Section
2.3 incorporated in procedures and programs? {2.3}
   2. Does the facility have a spill prevention program in place?

{2.5}
   3. Were the materials of construction outlined in Section 4

taken into consideration when specifying caustic storage
tank? {4.6.3}
   4. Has material selection considered the potential for

external chloride corrosion?
{4.6.4,
4.6.6}
   5. Has material selection considered the compatibility of

glass with caustic? {4.6.7, 5.6}
   6. Have metal surfaces exposed to caustic been cleaned

before welding? {4.9.4}
   7. Is piping layout and design appropriate for the intended

caustic service? {5.2}
   8. Are materials of construction for piping and valves

appropriate for temperature and caustic concentrations? {5.3}
   9. Are gaskets used on caustic equipment compatible with

caustic? {5.3}
   10. Are instrumentation components consistent with Institute

recommendations? {5.6}
   11. Has heat tracing and line clearing methods been designed
to prevent stress corrosion cracking? {5.5}
   12. Has a preventive maintenance program been established

for caustic storage area? {5.7}
REMINDER: Users of this checklist should document exceptions

to the recommendations contained in this pamphlet.
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Telephone: (703) 894-4140 « Fax: (703) 894-4130
Email: pubs@CL2.com « Website: www.chlorineinstitute.org
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©The Chlorine Institute all rights reserved.

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1.2 CHLORINE INSTITUTE STEWARDSHIP PROGRAM

1.3 DEFINITIONS AND ACRONYMS

In this pamphlet, the following meanings apply unless otherwise noted:

Alloy 20 (also known as Carpenter 20) one of the so-called “super”

ANSI American National Standards Institute

API American Petroleum Institute

ASME American Society of Mechanical Engineers

ASTM ASTM International, formerly known as “The American Society

CANUTEC Canadian Transport Emergency Centre

caustic generic term for either caustic soda or caustic potash

caustic a term that describes the stress corrosion cracking

caustic potash solutions of varying concentration of potassium hydroxide

caustic soda solutions of varying concentration of sodium hydroxide (NaOH)

CERCLA Comprehensive Environmental Response, Compensation and

CFR Code of Federal Regulations (U.S.)

CHEMTREC Chemical Transportation Emergency Center

CPVC chlorinated polyvinyl chloride

DOT Department of Transportation (U.S)

ECTFE copolymer of ethylene and chlorotrifluoroethylene

EPDM ethylene propylene diene monomer or ethylene propylene diene

FEP fluorinated ethylene propylene

FRP fiberglass reinforced plastic

Hastelloy® a registered trademark of Haynes International, Inc.

HAZCOM Hazard Communication (refer to 29 CFR 1910.1200)

Inconel® a registered trademark of Special Metals Corporation

Institute The Chlorine Institute

Monel® a registered trademark of Special Metals Corporation

OSHA Occupational Safety and Health Administration, under the U.S.

OS&Y outside screw and yoke

psig pounds per square inch gauge

PVC polyvinyl chloride

release any loss of caustic to soil or water systems from the

SDS safety data sheet

SCC stress corrosion cracking

spill any loss of caustic from primary containment vessel, pipe or

transfer site any facility where product is loaded and/or unloaded

WHMIS Workplace Hazardous Material Information System (Canada)

1.4 SAFETY PROGRAMS

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

1.7.1 Significant Revisions in Current Edition

Added the use of acetic solution for maintenance to Section 4.9.4.

2.2 CAUSTIC IN TRANSPORTATION

2.3 REACTIVITY AND COMPATIBILITY DATA

2.4 PERSONAL PROTECTION INFORMATION

Detailed requirements for personal protective equipment should be established on a site-

2.5 SPILL PREVENTION PROGRAM

2.6 RELATED INSTITUTE PUBLICATIONS

For related information regarding physical properties, handling, protective equipment,

2.7 REGULATORY AND INSURANCE REQUIREMENTS

The location, capacity, design, maintenance and operation of caustic storage

3.1 EMERGENCY PLANNING

The DOT and TC have specific training requirements applicable to handling of

3.2 CHEMTREC AND CANUTEC

3.3 REPORTING OF RELEASE

Sodium hydroxide and potassium hydroxide are identified as hazardous substances in

• National Response Center (1-800-424-8802)

• Local Emergency Planning Committee

• Name of company involved