Document JY56aM0Vojp54EEEoO15NZb6

Table of Contents 1. INTRODUCTION ................................................................................................................ 1 1.1 SCOPE .......................................................................................................................... 1 1.2 CHLORINE INSTITUTE STEWARDSHIP PROGRAM............................................................... 2 1.3 ABBREVIATIONS AND DEFINITIONS .................................................................................. 2 1.4 CHEMICAL SYNONYMS ................................................................................................... 3 1.5 DISCLAIMER .................................................................................................................. 3 1.6 REPRODUCTION ............................................................................................................ 4 1.7 APPROVAL .................................................................................................................... 4 1.8 REVISIONS .................................................................................................................... 4 2. CHLORINE ......................................................................................................................... 5 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 CHLORINE REACTIVITY WITH MATERIALS CHART.............................................................. 5 CHLORINE REACTIVITY WITH OTHER CHEMICALS CHART .................................................. 5 ACCEPTABLE MATERIALS FOR CHLORINE SERVICE .........................................................15 TITANIUM .....................................................................................................................16 CARBON STEEL ............................................................................................................18 HYDROGEN ..................................................................................................................20 FIBER REINFORCED POLYMER (FRP).............................................................................21 GASKETS .....................................................................................................................22 OIL, GREASES, LUBRICANTS, AND OTHER HYDROCARBONS ............................................22 SELECTED SAFE PRACTICES FOR CHLORINE ..................................................................24 3. SODIUM AND POTASSIUM HYDROXIDES (50%) ...........................................................26 3.1 SODIUM AND POTASSIUM HYDROXIDE (50%) REACTIVITY WITH MATERIALS CHART.................26 3.2 SODIUM AND POTASSIUM HYDROXIDE (50%) REACTIVITY WITH OTHER CHEMICALS CHART ......26 3.3 ALUMINUM....................................................................................................................37 3.4 OTHER METALS ............................................................................................................38 3.5 HYDROCARBONS ..........................................................................................................38 3.6 FIBER REINFORCED POLYMER (FRP).............................................................................40 3.7 SELECTED SAFE PRACTICES FOR SODIUM AND POTASSIUM HYDROXIDE (50%)................41 4. REFERENCES ..................................................................................................................44 4.1 CHLORINE INSTITUTE REFERENCES ...............................................................................44 4.2 OTHER REFERENCES....................................................................................................44 4.3 ADDITIONAL OUTSIDE REFERENCES ..............................................................................45 APPENDIX A - MATERIAL INCLUSION REQUEST FORM ....................................................46 APPENDIX B - PAMPHLET 164 CHECKLIST.........................................................................47 i The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 1 1. INTRODUCTION 1.1 SCOPE This pamphlet is intended to provide information to producers, users, and handlers of chlorine and/or 50% sodium and potassium hydroxides concerning the compatibility of these two substances with a variety of materials and their reactivity with other chemicals. The information considers only those materials and chemicals typically found in facilities producing, using, or otherwise handling chlorine and/or sodium and potassium hydroxide and is not meant to be an exhaustive list. Users of this pamphlet might include persons responsible for operations and maintenance, hazards analyses, and/or emergency response of facilities producing, using or otherwise handling chlorine and/or sodium and potassium hydroxide. This pamphlet is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of compatible materials. While the information provided should be of help to emergency responders, this pamphlet is not intended to provide technical guidance to the first persons on the scene in an emergency response. This pamphlet does not address nitrogen trichloride. CI Pamphlet 152 (4.1) provides a full discussion of this topic. Additionally, this pamphlet lists some brand names of materials known to be compatible. Pursuant to its written policy, CI does not endorse any particular product or brand. This listing of materials was initially compiled from a survey of CI members in 2016 who had successfully used the listed substances. Additional materials will be added to the pamphlets after they meet the criterion described below and are reviewed by the assigned task group. To have a material added to this pamphlet, submit a notice to the Secretary of the Institute at CL2.com. The notice should include contact information from the material manufacturer and the member company that used the material. The Task Group that reviews the pamphlet will verify that new materials added to the pamphlet were used and found acceptable by a chlor-alkali producer or user member company. The following information will typically be requested from the material manufacturer and/or member company for verification that the material was used successfully by the member company (see Appendix A for a suggested format): Name of member company where material was in service. Material manufacturer and style/model. Service conditions (temperature and pressure ranges, etc.) and Class if applicable. Statement about material performance in the above service. Quantity and duration of material in service. Compatibility testing information. The Chlorine Institute, Inc. 2 PAMPHLET 164 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 chemicals1. 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 ABBREVIATIONS AND DEFINITIONS Detonation A particularly severe form of an explosion and the most destructive for the chemicals involved. There is a significant difference between the damage potential of a detonation compared to other types of explosions. The velocity of a detonation reaction always exceeds the velocity of sound. Dry Chlorine Gas Chlorine with a water content less than or equal to that which would exist if the gas were in equilibrium with dry liquid chlorine (i.e., by increasing the pressure at the same temperature). See CI Pamphlet 100 (4.1). Dry Chlorine Liquid Chlorine with a water content less than or equal to the solubility of water in chlorine Exothermic (A reaction that) generates heat Explosion (reaction) A sudden and violent release of energy, dissipated in a shock wave. psi Pounds per square inch Reaction The combination of chemical substances. It may be fast (violent) or slow. Heat may be generated or required. Wet Chlorine Gas Chlorine with a water content greater than that which would exist if the gas were in equilibrium with dry liquid chlorine (i.e., by increasing the pressure at the same temperature). See CI Pamphlet 100 (4.1). Wet Chlorine Liquid Chlorine with a water content greater than the solubility of water in chlorine 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. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 3 1.4 CHEMICAL SYNONYMS Caustic Common name for sodium hydroxide Caustic soda Another common name for sodium hydroxide Caustic potash Another common name for potassium hydroxide Chlorine Elemental or molecular chlorine CPVC Chlorinated PVC EDC Ethylene dichloride (1,2 -dichloroethane) EPDM Ethylene propylene diene monomer FRP Fiber reinforced plastic PCBs Polychlorinated biphenyls Potassium hydroxide As used in this pamphlet, it is meant to be 50 % solution. PTFE Polytetrafluoroethylene PVC Polyvinyl chloride PVDF Polyvinylidene Difluoride Sodium hydroxide As used in this pamphlet, it is meant to be 50 % solution. VCM Vinyl chloride monomer 1.5 DISCLAIMER The information in this document 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 changes in the applicable laws, regulations or technology may require a change in the recommendations herein. Following the outlined steps are not substitutes for and do not supersede federal, state, provincial, municipal or insurance requirements, or with national safety codes. The Chlorine Institute, Inc. 4 PAMPHLET 164 1.6 REPRODUCTION The contents of this pamphlet are not to be copied for publication, in whole or in part, without prior Institute permission. Copyright 2023 ALL RIGHTS RESERVED. This 2023 CI Pamphlet 164, Reactivity and Compatibility of Chlorine, Sodium Hydroxide, and Potassium Hydroxide with Various Materials, Edition 4, is a copyrighted work owned by the Chlorine Institute ("CI"). Without advance written permission from CI, no part of this publication may be reproduced, distributed or transmitted in any form or by any means, including, without limitation, electronic, optical or mechanical means (by way of example, and not limitation, photocopying or recording by or in an information storage retrieval system or shared network). For information on use rights and permissions, please contact: CL2.com. To order additional copies or download for additional users please go to the bookstore on the Chlorine Institute website https://bookstore.chlorineinstitute.org/. 1.7 APPROVAL The Health, Environment, Safety and Security Issue Team approved the third edition of this pamphlet on January 31, 2023. 1.8 REVISIONS Suggestions for revisions should be directed to the Secretary of the Institute in writing at (.CL2.com. 1.8.1 Significant Revisions in this Edition This edition has been updated to include potassium hydroxide reactivity. A new section discusses reactivity with various resins in chlorine service (Section 2.6 and sodium and potassium hydroxide service (Section 3.6)). All lubricants, greases, and sealants were taken out of the tables and listed only in Section 2.3. Clarifying statements were made throughout the pamphlet. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 5 2. CHLORINE This section provides information on the reactivity of chlorine with materials more commonly found in facilities producing, using, or otherwise handling chlorine and on the reactivity of chlorine with chemicals that may typically be found in such facilities. Chlorine gas or liquid is not explosive or flammable, but it is a strong oxidant and will support combustion. Both chlorine liquid and gas react with many substances. Chlorine is only slightly soluble in water. The gas has a characteristic penetrating odor, a greenish yellow color and is about two and one-half times as heavy as air. Thus, if chlorine escapes from a container or system, it will tend to concentrate in the lower levels of buildings or outside areas. Although dry chlorine (gas or liquid) normally does not react with or corrode metals such as copper or carbon steel, it is strongly reactive (strongly corrosive) when moisture is present. Materials may be compatible with both wet and dry chlorine, compatible with neither (i.e., reactive with both), or compatible with wet but not dry chlorine, or vice versa. Dry chlorine is defined as chlorine with its water content dissolved in solution. If water exists beyond that which is dissolved in the chlorine (i.e., separate phase), the chlorine is considered wet. CI Pamphlet 100 (4.1) provides a more detailed discussion of this topic. 2.1 CHLORINE REACTIVITY WITH MATERIALS CHART See Table 2.1. 2.2 CHLORINE REACTIVITY WITH OTHER CHEMICALS CHART See Table 2.2. The Chlorine Institute, Inc. 6 PAMPHLET 164 Table 2.1 - Chlorine Reactivity with Materials 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. Liq.= Liquid Reactivity NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Material Acid brick Alloy 400 (UNS N04400) Aluminum Asbestos, compressed Brass Carbon steel, non-alloyed Cast iron Wet Chlorine Gas Liq. 1 1 1 Dry Chlorine Gas Liq. 1 1 1 1 1 1 1 Comments See Note 1 See CI Pamphlet 95 (4.1) For dry chlorine at less than 300F (149C) See Section 2.5; See Note 1 Materials known to be brittle Copper 1 CPVC (chlorinated PVC) 1 1 Ductile iron 1 EPDM (ethylene propylene diene monomer) Mechanical integrity concerns; See Note 1 For dry chlorine less than 300F (149C) See Note 1 and CI Pamphlet 95 (4.1); Not suitable for high pressure in liquid service Fiberglass See specific resins Note 1 - The specified material is a generic reference to a class of materials with different grades, manufacturers and/or registered trade names. While specific instances of this material have been verified by the literature and/or CI members in accordance with the rating given, it is possible other materials within the same generic class might not behave the same. Therefore, it is incumbent upon the end user to verify that the specific material being used is appropriate for the fluid service conditions. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 7 Table 2.1 - Chlorine Reactivity with Materials (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. Liq.= Liquid Reactivity NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Material Glass Graphite Grease (organic) Hypalon (chlorosulfonated polyethylene) Heat Transfer Oils Ni-Cr (Example Alloy 625, UNS N06625) Ni-Fe-Cr Group of Alloys (Example Alloy 825, UNS N08825) Lead Wet Chlorine Dry Chlorine Gas Liq. Gas Liq. 1 1 1 1 1 1 1 1 1 1 1 1 Comments Mechanical integrity concerns; See Note 1 Mechanical integrity concerns; resin must be chlorine resistant See Section 2.3 and 2.9 See Section 2.9 For dry chlorine less than 932F (500C); See Note 1 For dry chlorine less than 932F (500F); See Note 1 Metals (finely divided) e.g., steel wool; See Section 2.5 Note 1 - The specified material is a generic reference to a class of materials with different grades, manufacturers and/or registered trade names. While specific instances of this material have been verified by the literature and/or CI members in accordance with the rating given, it is possible other materials within the same generic class might not behave the same. Therefore, it is incumbent upon the end user to verify that the specific material being used is appropriate for the fluid service conditions. The Chlorine Institute, Inc. 8 PAMPHLET 164 Table 2.1 - Chlorine Reactivity with Materials (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. Liq.= Liquid Reactivity NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Material Mineral Oil Wet Chlorine Dry Chlorine Gas Liq. Gas Liq. Comments Molybdenum Ni-Cr-Mo Group of Alloys (Example Alloy C-276, UNS 1 1 N10276) Neoprene For dry chlorine less than 932F (500C); See Note 1 Nickel 200 (UNS N02200) 1 1 Oils (organic) See Section 2.9 Note 1 - The specified material is a generic reference to a class of materials with different grades, manufacturers and/or registered trade names. While specific instances of this material have been verified by the literature and/or CI members in accordance with the rating given, it is possible other materials within the same generic class might not behave the same. Therefore, it is incumbent upon the end user to verify that the specific material being used is appropriate for the fluid service conditions. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 9 Table 2.1 - Chlorine Reactivity with Materials (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. Liq.= Liquid Reactivity NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Material Polyethylene Wet Chlorine Dry Chlorine Gas Liq. Gas Liq. Comments Mechanical integrity concerns Polypropylene PTFE (polytetrafluoroethylene); Teflon is a form of PTFE PVC (polyvinyl chloride) (PVDF) Polyvinylidene Difluoride Resin, epoxy Mechanical integrity concerns 1 1 1 1 1 Can become impregnated with chlorine 1 (permeability issue); See Note 1 Mechanical integrity concerns; See Note 1 1 1 1 1 Mechanical integrity concerns See Note 1 Resin, Chlorendic polyester 1 1 1 1 See Note 1 Silicon, rubbers or lubricants Resin, Bisphenol A Epoxy vinyl ester Suitable only at low concentration Resin, Epoxy Novalac vinyl ester 1 1 Mechanical integrity concerns for liquid chlorine; See Note 1 Rubber, butyl Rubber, natural Note 1 - The specified material is a generic reference to a class of materials with different grades, manufacturers and/or registered trade names. While specific instances of this material have been verified by the literature and/or CI members in accordance with the rating given, it is possible other materials within the same generic class might not behave the same. Therefore, it is incumbent upon the end user to verify that the specific material being used is appropriate for the fluid service conditions. The Chlorine Institute, Inc. 10 PAMPHLET 164 Table 2.1 - Chlorine Reactivity with Materials (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. Liq.= Liquid Reactivity NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Material Stainless Steel, 17-4 PH Wet Chlorine Dry Chlorine Gas Liq. Gas Liq. Comments Stress cracking may occur Stainless Steel, 304 Stress cracking may occur Stainless Steel, 316 Stress cracking may occur Superferritic Stainless Steel, UNS S44627 Stress cracking may occur; See Note 1 Tantalum 1 1 1 1 Less than 300F (149C); See Note 1 Tin Titanium 1 1 See Section 2.4; See Note 1 Viton (Fluorocarbon elastomer) 1 1 1 1 See Note 1 Zinc Note 1 - The specified material is a generic reference to a class of materials with different grades, manufacturers and/or registered trade names. While specific instances of this material have been verified by the literature and/or CI members in accordance with the rating given, it is possible other materials within the same generic class might not behave the same. Therefore, it is incumbent upon the end user to verify that the specific material being used is appropriate for the fluid service conditions. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 11 Table 2.2 - Chlorine Reactivity with Other Chemicals 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Chemicals Acetaldehyde Acetic Acid Acetone Acetylene Alcohols Alkanolamines Ammonia Ammonium Acetate Ammonium Chloride Ammonium Hydroxide Benzene Calcium Carbonate Carbon Disulfide Carbon Tetrachloride Caustic Soda Chloroform Chloroethylene Copper Sulfate Dibutylphthalate Dichloroethane Dichloroethylene Diesel Fuel Reactivity 1 Comments Explosive and detonation potential under certain conditions See Ethanol and Methanol See CI Pamphlet 152 (4.1) Can explode when catalyzed by iron See Section 2.9 The Chlorine Institute, Inc. 12 PAMPHLET 164 Table 2.2 - Chlorine Reactivity with Other Chemicals (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Chemicals Diethyl Ether EDC (Ethylene Dichloride) Ethanol Ethylene Ethane Ethylene Glycol Ferric Chloride Gasoline Glycerin Halocarbon refrigerants Hexachlorobenzene Hexachlorobutadiene Hexachloroethane Hydrocarbons Hydrochloric Acid Hydrogen Hydrogen Peroxide Hydrogen Sulfide Hydroxylamine Lithium Bromide Magnesium Chloride Magnesium Sulfate The Chlorine Institute, Inc. Reactivity 1 1 1 1 1 1 Comments Explosive and detonation potential under certain conditions Explosive and detonation potential under certain conditions See Section 2.9 See Section 2.9 Explosive and detonation potential under certain conditions REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 13 Table 2.2 - Chlorine Reactivity with Other Chemicals (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Chemicals Methane Methanol Methyl Chloroform Naphtha Nitric Acid Nitroparaffins PCBs (Polychlorinated Biphenyls) Potassium Hydroxide Propylene Silicone Oil Sodium Bisulfite Sodium Carbonate Sodium Chlorate Sodium Chloride Sodium Chlorite Sodium Hydroxide Sodium Hypochlorite Sodium Sulfide Sodium Sulfite Sodium Thiosulfate Sulfur Dioxide Sulfur Reactivity 1 Comments Explosive and detonation potential under certain conditions See Section 2.9 See Section 2.9 See Section 2.9 The Chlorine Institute, Inc. 14 PAMPHLET 164 Table 2.2 - Chlorine Reactivity with Other Chemicals (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Chemicals Sulfuric Acid Trichloroethylene VCM (Vinyl Chloride Monomer) Vinyl Acetate Vinylidene Chloride Water Zinc Oxide Reactivity Comments For wet chlorine. With dry chlorine there is little or no reaction. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 15 2.3 ACCEPTABLE MATERIALS FOR CHLORINE SERVICE A survey was conducted in 2016 to determine what materials were in use among the Chlorine Institute membership. There were over 60 respondents, comprised of chlorine producer, chlorine packager, and chlorine user facilities. The results below are not endorsements or approval of the materials/products, but rather materials that CI's individual members have found to be suitable in the service indicated. The materials listed below are not intended to be an exhaustive list. Users may find other materials acceptable in chlorine service and are encouraged to review manufacturer compatibility information and/or conduct compatibility testing. Lubricants Castrol Braycote (1728, 1729) Fluorolube o GR-362 (-40 to 300F) (-40 to 148C), o GR-554, and o GR-470 (0 to 300F) (-17 to 148C) Fluoramics, Inc. LOX-8 Halocarbon (HC25-5S [InfinX MRO 2505], HC-56, 4.2, 6.3) Krytox (GPL-106, GPL-205, GPL 227) Loctite 567TM PST* Loctite Grade AA (089)TM *Not recommended for direct contact with chlorine. Sealants on Threaded Connections Climax Lubricant FL-5 CYL-SEAL Compressed Gas Pipe Thread Sealant Fluoramics Inc. LOX-8 High Side Chemical Leak Lock Joint Sealing Compound (Gold and Blue) Halocarbon MT-3I Krytox (GPL 220, GPL 226, TS4) The Chlorine Institute, Inc. 16 PAMPHLET 164 Teflon tape is not listed but has been used. If used on threaded connections, small pieces of Teflon tape may dislodge and clog piping and internal surfaces of the valve(s) and other fittings downstream. In general, the use of Teflon tape on threaded connections is not recommended. Sealant Material for Leak Clamps Colt 290 (CS290) Teflon (e.g., Deacon SP-375, Colt 590) Krytox (TS4) Cleaning Agents NOTE: Must remove all cleaning agents before introducing chlorine. Solvents (e.g., acetone, methanol, methylene chloride, perchloroethylene, butyl carbitol, 5% citric acid, etc.) NOTE: Many solvents can have adverse health or environmental effects therefore a thorough evaluation of potential hazards should be performed before use. Some of these solvents will react with chlorine, but their effective cleaning and highly volatile properties make them suitable for chlor-alkali process, as long as the solvent is allowed to evaporate and/or is removed prior to introducing chlorine. Electronic Component Cleaners (e.g CRC Lectra Clean, ChemoursTM VertrelTM MCA, Electra SAF-Plus, Solvon IP, etc.) Detergent (e.g. Bon-Ami, Dawn, etc.) Preservatives/Anti-Rust Materials Shell VPI 260 Flourolube 2.4 TITANIUM 2.4.1 Hazard Description: Titanium is frequently used in wet chlorine systems, contributing to the possibility of mistakenly installing this material into a dry application. This potential problem is compounded by the appearance of titanium, which is similar to that of tantalum and stainless steels. Titanium should only be used in chlorine applications where sufficient water is present to passivate the titanium surface so that a chlorine/titanium reaction does not occur. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 17 In the absence of sufficient water, titanium reacts rapidly with chlorine, causing the titanium to burn. This reaction can generate sufficient heat for other materials, such as steel, to ignite. It is most important that each application for titanium be evaluated to ensure that sufficient water (see Section 2.4.2) to prevent a chlorine/titanium reaction is always present. Another potential hazard associated with the use of titanium in chlorine service is the potential for crevice corrosion, which is a localized type of chemical attack. These crevices may be the result of how a component was designed, a structural feature such as a flange/gasket combination, or the buildup of deposits on the titanium surface. Titanium chlorides formed in this localized area or crevice are unstable and tend to hydrolyze, forming HCl. As a result, the pH of the solution in the crevice can drop to as low as 1, which will accelerate the overall corrosion rate even further. However, there are several options that can be employed in order to prevent crevice corrosion from occurring. For example, alloying the titanium with palladium, ruthenium or ensuring the presence of a small amount of a multivalent ion in the crevice (Ni, Cu, Mo) to counter the oxygen depletion will prevent initiation of this type of corrosion. 2.4.2 Safe Limits of Operation: Titanium is protected in wet chlorine applications with a titanium oxide layer formed at the water/titanium interface. Chlorine has a specific minimum water concentration that must be maintained to provide a stable titanium oxide layer in the chlorine atmosphere. Chlorine that is wet simply because it does not meet the definition of dry chlorine (see Definitions, Section 1.3) may not contain sufficient amount of water to allow for the use of titanium with chlorine. The paper, How to Use Steel and Titanium Safely, (4.2.4) provides an excellent discussion of this topic. A temperature of about 56F (13C) is considered the lowest temperature at which the water saturation of chlorine can prevent a chlorine/titanium fire. Water content below about 0.35 wt% at atmospheric pressure is considered unsafe, for temperatures below 158F (70C). At temperatures between 56F (13C) and 158F (70C), the minimum water content to prevent a fire increases only slightly as the temperature rises. At higher temperatures (158F (70C) and up), the amount of water needed to maintain a safe condition increases exponentially as the temperature increases. See CI Pamphlet 165 (4.1). At atmospheric pressure, a temperature of about 56F (13C) is considered the lowest temperature at which the water saturated chlorine can prevent a chlorine/titanium fire. However, the minimum temperature increases with increasing chlorine pressure. 2.4.3 Examples of Incidents: Incident 1: A butterfly valve with a titanium disk and a titanium stem was used to control the flow (differential pressure was approximately 5.9 psi (40.6 kPa)) of cold wash water saturated with chlorine. After some months of operation, a fire occurred in the valve burning away the valve disk and part of the stem. The investigators concluded that the causes were a combination of (1) too low a temperature; (2) drying resulting from the pressure throttling; and (3) continuous movement of the stem, causing the titanium stem to ignite. The Chlorine Institute, Inc. 18 PAMPHLET 164 By increasing the wash water temperature to above 60F (16C) and, in addition, spraying water continuously over the valve, a safe condition was achieved. Lessons Learned: Titanium will react violently with dry chlorine. There is a minimum amount of water that is required to protect the titanium from reacting with the chlorine and igniting. Incident 2: A chlorine vaporizer system was shut down for annual repair and inspection. The work was completed and upon startup, a gasket "blow out" occurred. The gasket in this flange had been changed during the shutdown. What remained of the failed gasket was examined and it appeared to be appropriate for the service: spiral wound, flexible graphite, the outer ring clearly indicated the metal parts were constructed of nickel. It was puzzling that while gasket filler residue was clearly present on the floor, there was no evidence of any metal gasket winding material. In the subsequent investigation, a trace analysis of the graphite filler revealed small amounts of titanium were present. Examination of other gaskets in the plant found two gaskets which were stamped consistent with nickel construction but were actually made of titanium. Lessons Learned: The gasket markings CLEARLY indicated it was identical to the one it was replacing. But, when the replacement gasket was installed, a change had occurred, where the spiral wound gasket contained titanium when it should have been nickel. This change seriously compromised safe operation of the facility. Materials of construction markings can be inaccurate. If proper material of construction is critical for safe operations, testing may be needed to verify appropriate materials were used. 2.5 CARBON STEEL 2.5.1 Hazard Description: A chlorine/steel fire is one of the most serious plant disruptions. Chlorine/steel fires will occur spontaneously when the iron or steel temperature is at or above 483F (250C). Depending on other factors (e.g., impurities, surface area), this reaction can occur at much lower temperatures. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 19 To prevent chlorine/steel fires from occurring, the Chlorine Institute recommends that the maximum temperature that chlorine/steel systems encounter be less than 300F (149C). This limit should be monitored and alarmed. Special attention should be given to systems subject to localized high temperatures (e.g., individual discharge valves on reciprocating chlorine compressors). Since chlorine is a very strong oxidant, chlorine fires are very difficult to extinguish. One method for fighting a chlorine/steel fire when the fire is inside equipment is: Stop the chlorine feed. Purge the equipment with an inert gas such as nitrogen to remove the chlorine. Prior to a breach in the pipe or equipment use water to reduce the outside surface temperature of the steel to prevent structural collapse. Some types of carbon steel can also become brittle at low temperatures (<20F; < -6.7C). An engineering study of stresses and pressures or low temperature carbon steel may be needed under these conditions. See ASME B31.3 (4.3.1). 2.5.2 Safe Limits of Operation Normally steel can be used in dry chlorine at temperatures below 300F (149C). However, incidents of ignition of steel have been reported at temperatures as low as 212F (100C) when impurities (e.g., rust, carbon) were present. Dry steel wool will ignite with chlorine at about 122F (50C) (4.2.2, 4.2.5). The reason for the substantial range of temperatures is the important roles that surface area and ferric chloride films play in affecting chlorine/steel reactions. CI Pamphlet 6 (4.1) provides detailed recommendations for steel components in chlorine service. 2.5.3 Examples of Incidents: Incident 1: A tower packed with steel pall rings ruptured 9 hours after the tower was shut down and an air purge was put on the tower to evaporate the liquid chlorine. The temperature downstream from the tower rose slowly to 74F (23C) over 2.5 hours and then increased to 200F (93C) over about 15 minutes. The temperature held at 200F (93C) for 6 hours and then rose rapidly for 12 minutes before the explosion. The steel pall rings were found to be heavily corroded when they were removed from the tower. Lessons Learned: Investigators concluded that a substantial amount of chlorine hydrate was present in the tower packing. The air melted the chlorine hydrate accelerating the corrosion of the carbon steel pall rings resulting in the ignition of the pall rings. Chlorine corrosion of steel can be vigorous enough to achieve the combustion temperature of the carbon steel. Incident 2: Welders had just completed welding a short section of two-inch (5.1 cm) carbon steel pipe attached to a long insulated carbon steel chlorine line. The weld that joined the new section of piping was about six inches (15.2 cm) from the adjacent thermal insulation that covered the long chlorine line. The Chlorine Institute, Inc. 20 PAMPHLET 164 After completion, an operator/loader pressurized the line with dry air and determined it was leak-free. He then opened the valve connecting the new two-inch line to 160 psig (1103 kPa) chlorine gas. Within seconds the pipe caught fire and the escaping gases roared like a jet with a brownish-orange plume of ferric chloride. The operator extinguished the fire by closing the valve which stopped the chlorine feed. The subsequent accident investigation determined that the fire started, not at the weld, but under the adjacent insulated pipe which trapped the heat and had not sufficiently cooled. Lessons Learned: Chlorine/carbon steel fires can occur any time process temperatures exceed safe limits. Practices such as welding on chlorine lines need to be approached with chlorine fires in mind. Carbon steel must be cool before returning the equipment to chlorine service. Incident 3: An astonished operations crew witnessed a body of a carbon steel filter used to filter chlorine spontaneously ignite and burn after maintenance personnel installed a replacement filter cartridge. The cartridge was selected from the warehouse inventory that had been originally specified for other chemical services. The cartridges consisted of fiberglass filter media on a tin-coated steel core. Investigators theorized that the tin reacted with the chlorine generating sufficient heat to ignite the carbon steel filter. Lessons Learned: Only equipment approved for chlorine service should be used in chlorine service. Chlorine reactions can generate high enough temperatures to start carbon steel burning. 2.6 HYDROGEN 2.6.1 Hazard Description: Hydrogen is a coproduct of the chlorine manufacturing process and can react explosively with either chlorine or air. The explosive force of chlorine and hydrogen is not as great as that of air (oxygen) and hydrogen. However, chlorine/hydrogen explosions can generate pressures up to fifty times the initial pressure. Chlorine, hydrogen, and air coexist in some processes (e.g., chlorine production processing and liquefaction areas). Care should be taken to prevent these materials from coexisting within the explosive range. Chlorine/hydrogen and air/hydrogen reactions are dependent on concentration, temperature, and pressure. As the hydrogen concentration increases relative to chlorine or air, the ignition temperature required to produce an explosion will decrease. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 21 2.6.2 Safe Limits of Operation: The concentration/ignition relationship between chlorine, hydrogen, and air is shown by the table entitled "Effect of Initial Temperature on Ignition Limits" in CI Pamphlet 121 (4.1). Information provided in the table is based on hydrogen content, percent by volume. See CI Pamphlet 121 for a fuller discussion of this topic. The concentration/ignition relationship between Hydrogen, Oxygen and Nitrogen is shown in CI Pamphlet 173 (4.1). 2.6.3 Example of Incidents: Incident 1: In the diaphragm cell chlorine manufacturing process, chlorine and hydrogen are separated by an asbestos fiber diaphragm. The diaphragm integrity is sensitive to pressure fluctuations. An explosion resulted in the separation of the end of a 60 inch (152.4 cm) pipeline and propelled it against a building 50 feet (15.2 m) away. The pipeline moved two feet (0.6 m) and was knocked off of its support beams. The subsequent investigation concluded that a hole in a diaphragm occurred. The hole allowed chlorine and hydrogen to mix which created an explosive condition. An ignition source, possibly electrical arcing within the cell, created an explosion. Lessons Learned: This incident demonstrates the destructive force that a chlorine/hydrogen explosion can generate. 2.7 FIBER REINFORCED POLYMER (FRP) Fiber Reinforced Polymers (FRP) have been used for wet and dry chlorine gas for many years. This was first used in a chlorine plant in 1952 when an FRP chlorine header was fabricated using a chlorendic polyester resin. This is currently being used by many of the chlor alkali manufacturing companies. 2.7.1 Hazard Description: FRP is commonly used in chlorine plants. The correct resin and the correct thickness of the corrosion barrier needs to be used to obtain a long service life. The chlorine gas will react with the resin on the surface of the FRP and form what is referred to as chlorine butter. This is chemical degradation of the resin. If a chlorendic polyester (also referred to as chlorendic anhydride) or novolac epoxy vinyl ester resin is used, the formation of the chlorine butter is slow and will provide some protection to the resin below the chlorine butter. It has been found that these resins can give up to 20 years of service life if the corrosion barrier thickness of the FRP is 0.51 inch (13 mm). 2.7.2 Safe Limits of operation: FRP can be used safely in wet or dry chlorine gas. The maximum operating temperature will depend on what resin is being used and if it is wet or dry chlorine gas. Above this temperature the attack on the resin will be accelerated and the life of the equipment will be reduced. The recommended corrosion barrier for this service would be 2 layers of Cglass veil backed by chopped strand boron free glass to a minimum corrosion barrier thickness of 0.51 inch (13 mm). The Chlorine Institute, Inc. 22 PAMPHLET 164 Chorendic polyester resins can be used in dry chlorine gas up to 302F (150C) and in wet chlorine gas to 221F (105C). Epoxy novolac vinyl ester resins can also be used in wet and dry chlorine gas to a maximum temperature of 212F (100C). The construction of the corrosion barrier of the FRP equipment is critical for a long service life. The corrosion barrier of FRP equipment consists of a veil layer that contains 90% resin and 10% fiber backed by a chopped strand glass layer that consists of 70% resin and 30% fiber. The number of layers and type of veil used is determined by the service conditions. For hot chlorine gas it is recommended to use 2 layers of C-glass veil backed by chopped strand boron free glass to a minimum corrosion barrier thickness of 0.51 inch (13 mm). It should be noted that the chlorine butter that is formed should not be removed or disturbed since this will help give a longer life of the FRP equipment. 2.8 GASKETS CI Pamphlet 95 (4.1) provides guidance for gasket material selection and gasket installation for wet and dry chlorine service. The Chlorine Institute does not approve, rate, certify or endorse any gasket. The information on gaskets and gasket materials reflects information obtained from member companies in their use and/or evaluation of the gasket or gasket material. 2.9 OIL, GREASES, LUBRICANTS, AND OTHER HYDROCARBONS 2.9.1 Hazard Description Chlorine is a very strong oxidizing material and can react violently with a number of organic materials. Caution should be exercised before organic materials are used in chlorine service. A study should be completed before using new materials in chlorine systems. New valves and piping should be degreased before placing in service the first time. CI Pamphlet 6 (4.1) provides further information. Organic materials present hazards because they react with chlorine. The reactions between chlorine and some hydrocarbons are potentially very violent and explosive. Under certain conditions, detonations can occur. The reactivity is dependent on the concentrations of the chlorine and the hydrocarbon. The reaction between chlorine and oil/grease or some other hydrocarbons is highly exothermic. The heat liberated can be sufficient to initiate a chlorine/iron fire. Reactions of oils with chlorine can cause the oils to lose their lubricating properties. Other organic materials can cause fires or form other chemicals and polymers that can accumulate in chlorine systems. 2.9.2 Safe Limits of Operation: Safe limits of operation between chlorine and specific hydrocarbons vary for each hydrocarbon. Procedures should be in place to specify compatibility and safe limits of operation. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 23 Facilities should also have procedures to inspect the cleanliness of equipment and piping prior to placing it in chlorine service. Use of white and black light and wiping with white rags are methods that may be used to detect the presence of oils and other organics. See "Standards of Cleanliness" in CI Pamphlet 6 (Piping Systems for Dry Chlorine) for more information. Another method is to put a solvent through the affected process equipment or piping and analyze the effluent for the presence of hydrocarbons. 2.9.3 Examples of Incidents: Incident 1: An employee unknowingly applied a generic hydrocarbon grease, instead of fluorolube, to hold a gasket on a chlorine exchanger. The grease was in an unlabeled one gallon (3.8 liters) bucket that looked identical to the fluorolube bucket. Fortunately, the incident resulted only in a near miss as an experienced employee observed the slight color difference between the grease and fluorolube and corrected the situation before contact between the incompatible lubricant and chlorine occurred. Lessons Learned: All chlorine approved materials should be marked for chlorine service and only those materials so marked should be used with chlorine. Incident 2: While attempting to free up a two-inch (5 cm) plug valve in chlorine service, a chemical plant operator located a lubricant gun that was marked for chlorine service. The operator checked the cartridge and it was properly labeled as the specified chlorine compatible grease. The operator connected the grease gun to the valve fitting and injected a small amount of grease. Before the operator could disconnect the grease gun, the grease and chlorine reacted and destroyed the valve. The subsequent incident investigation determined that, prior to the incident, someone had contaminated the gun with grease that is incompatible with chlorine. Lessons Learned: Procedures and training should be in place to prevent contamination of chlorine approved material. Incident 3: A one-quarter inch (0.64 cm) stainless steel ball valve in liquid chlorine service ruptured violently. Silicone oil leaked into the chlorine feed line due to corrosion of the stainless steel diaphragm in a flow transmitter causing the subsequent violent reaction with liquid chlorine. Lessons Learned: Equipment specifications should be written to exclude materials that will react with chlorine (such as silicone oil) from being used in applications where direct contact with chlorine is possible. Incident 4: An article published in 1925 describes an accident at a natural gasoline plant in which gasoline backed into a cylinder of liquid chlorine and detonated. In a subsequent demonstration test, 14 pounds (6.4 kg) of gasoline was introduced into an inverted cylinder containing 100 pounds (45.4 kg) of liquid chlorine. The pressure rose slowly for about 40 minutes then a detonation fragmented the cylinder and tore down a 14 inch (35.6 cm) diameter oak tree standing 20 (6.1 m) feet away. The Chlorine Institute, Inc. 24 PAMPHLET 164 Lessons Learned: Liquid chlorine reacts violently with most hydrocarbons. Incident 5: A filter in liquid chlorine service violently exploded and propelled steel shrapnel as far away as 50 feet (15.2 m). Liquid chlorine was being fed from a one ton (907 kg) container through a polypropylene cartridge type filter. Prior to the explosion, new polypropylene filter elements recommended by the vendor for chlorine service had been installed. The filter exploded releasing a white cloud of fumes (probably hydrogen chloride) followed by a large amount of chlorine gas. The reaction between chlorine and polypropylene was probably initiated by zinc chloride. Analysis of the filter core indicated a high concentration of zinc oxide present as a filler in the polypropylene. Lesson Learned: Traces of metal elements could contribute to catalyzing explosive reactions. Care should be taken to ensure material used in chlorine service does not contain incompatible materials. 2.10 SELECTED SAFE PRACTICES FOR CHLORINE List 2.1 is a brief summary highlighting some of the key concerns one should consider when addressing reactivity and compatibility issues associated with chlorine. List 2.1 is not meant to be a comprehensive listing of such concerns but is meant to highlight selected issues. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 25 List 2.1 - Selected Safe Practices for Chlorine 1. Do Not Allow Nitrogen Trichloride to Accumulate. a. Nitrogen trichloride is very unstable. Maintain low concentrations. b. Minimize the flashing of liquid chlorine containing nitrogen trichloride. Remove chlorine as a liquid or mix with inert solvent before flashing. 2. Do Not Allow Systems Containing Hydrogen to Reach Explosive Limits. a. Chlorine/hydrogen mixtures can be explosive. b. Hydrogen concentrations above 4-6% in chlorine systems are explosive. c. The dilution effect must be considered when measuring H2 in membrane electrolytic cells. All of the H2 must be considered as being generated in a single cell. 3. Do Not Allow Moisture/Water to Enter Dry Chlorine Systems. a. Water can cause corrosion, which can lead to pluggage and can result in fires. b. Dew points should be maintained below -40F (-40C) before putting in chlorine service. c. Air addition systems in chlorine service should be maintained below -40F (-40C). 4. Do Not Allow Chlorine to Come into Contact with Organic Oils and Greases. a. Chlorine reacts violently with most organic oils and greases. b. All equipment and packing must be free of organic oils and greases before entering chlorine service. c. Oil-free air compressors must be used. 5. Avoid High Temperatures in Chlorine Systems. a. Carbon steel will burn in the presence of chlorine at 483F (250C). b. The maximum recommended temperature for carbon steel equipment is 300F (149C). 6. Select Correct Materials of Construction. a. Titanium will burn in dry chlorine service. b. Carbon steel is not suitable in wet chlorine service c. Utilize a system to ensure positive material identification. The Chlorine Institute, Inc. 26 PAMPHLET 164 3. SODIUM AND POTASSIUM HYDROXIDES (50%) This section provides information on the reactivity of sodium and potassium hydroxides, referred to within this pamphlet simply as "the hydroxides" to refer to both NaOH and KOH, with materials more commonly found in facilities producing, using, or otherwise handling the hydroxides and on the reactivity the hydroxides with chemicals that may typically be found in such facilities. Edition 4 of this pamphlet added potassium hydroxide (KOH) in addition to previous guidance for sodium hydroxide (NaOH). KOH metallurgy requirements and corrosion are very similar to NaOH. There are a few temperature difference limitations and while in general what works for one works for the other, users should fully understand the distinctions and amend their processes and procedures as necessary. Detailed corrosion and material selection information is available from the Nickel Institute (4.2.1 and 4.2.3). Sodium and potassium hydroxides are not combustible, have no flash point, no autoignition temperature, and no explosion limits. Generally the hydroxides are regarded as stable, but the chemical reactivity of the hydroxides with many inorganic and organic substances makes it an important raw material in a wide variety of industrial applications. Solutions of the hydroxides are strongly alkaline and have a high pH. Improper mixing of water with the hydroxides can be hazardous and should be approached with the basic understanding that heat will be generated. Always mix strong sodium or potassium hydroxide with the coolest water available and stir the solution. The user must be mindful that strong solutions of sodium or potassium hydroxide release large amounts of heat when diluted. The high heat of dilution can result in violent boiling and generate steam explosively causing this corrosive solution to spray and spatter. When mixing sodium or potassium hydroxide solutions or sodium or potassium hydroxide with water, it is better to slowly add the stronger sodium or potassium hydroxide to the weaker (or water). Continuous stirring is strongly advised to help dissipate the heat generated. If there are no provisions for stirring, a layer of concentrated solution may form, accumulate and later suddenly mix with a layer of less concentrated solution resulting in some combination of spray, splatter or boiling. The hydroxides will react violently with acidic materials such as sulfuric acid and hydrochloric acid. Sodium or potassium hydroxide will react vigorously with some metals such as aluminum, tin, and zinc and with organic compounds. The hydroxides destroy material such as hair, leather, and wool, and less aggressively attack matter such as wood, cotton, and linen. 3.1 SODIUM AND POTASSIUM HYDROXIDE (50%) REACTIVITY WITH MATERIALS CHART See Table 3.1. 3.2 SODIUM AND POTASSIUM HYDROXIDE (50%) REACTIVITY WITH OTHER CHEMICALS CHART See Table 3.2. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 27 Table 3.1 - Sodium and Potassium Hydroxide (50%) Reactivity with Materials 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Acid brick Material Reactivity Comments See Note 1 Alloy 400 (UNS N04400) 1 Aluminum See Section 3.3 Asbestos, compressed 1 Brass Carbon steel, non-alloyed Cast iron See Section 3.4 See Section 3.4; See Note 1 Copper See Section 3.4 CPVC (chlorinated PVC) Ductile iron 1 Meleecvhaatendictaelminpteegrarittuyrceo; nSceeernNsowteit1h See CI Pamphlet 94 (4.1) EmPoDnoMm(eert)hylene propylene diene 1 See Note 1 Fiberglass See specific resins Glass SusceptibleSteoeeNtcohtineg1; Note 1 The specified material is a generic reference to a class of materials with different grades, manufacturers and/or registered trade names. While specific instances of this material have been verified by the literature and/or CI members in accordance with the rating given, it is possible other materials within the same generic class might not behave the same. Therefore, it is incumbent upon the end user to verify that the specific material being used is appropriate for the fluid service conditions. The Chlorine Institute, Inc. 28 PAMPHLET 164 Table 3.1 - Sodium and Potassium Hydroxide (50%) Reactivity with Materials (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Graphite Material Grease (organic) Hypalon (chlorosulfonated polyethylene) Ni-Cr-Mo Group of Alloys (Example Alloy C-276, UNS N10276) Ni-Cr (Example Alloy 625, UNS N06625) Ni-Fe-Cr Group of Alloys (Example Alloy 825, UNS N08825) Krytox Reactivity 1 1 Comments See Note 1 1 See Note 1 1 Mechanical integrity concerns wteitmhpeeleravtautreed. 1 See Note 1 1 See Note 1 See Note 1 (PVDF) Polyvinylidene Difluoride Lead Metals (powders) Mineral Oil 1 Applies to distilled petroleum products Molybdenum Neoprene Note 1 The specified material is a generic reference to a class of materials with different grades, manufacturers and/or registered trade names. While specific instances of this material have been verified by the literature and/or CI members in accordance with the rating given, it is possible other materials within the same generic class might not behave the same. Therefore, it is incumbent upon the end user to verify that the specific material being used is appropriate for the fluid service conditions. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 29 Table 3.1 - Sodium and Potassium Hydroxide (50%) Reactivity with Materials (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Material Nickel 200 (UNS N02200) Reactivity 1 Comments Oils (organic) Polyethylene Polypropylene PTFE (polytetrafluoroethylene) PVC (polyvinyl chloride) Resin, epoxy Resin, amine-cured epoxy Resin, polyester Resin, silicon Resin, Bisphenol A vinylester Resin, Chlorendic polyester 1 See Note 1 1 Mechanical integrity concerns wtiethmepleervaatuterde 1 Mechanical integrity concerns wtiethmepleervaatuterde 1 See Note 1 1 Mechanical integrittyecmopnecreartnusrew; iStheeeleNvoatteed1 See Note 1; Care should be taken to ensure hardener is suitable for service. 1 enSsuereeNhoatrede1n; eCraisressuhitoaubllde bfoer tsaekrevnicteo. See Note 1 See Note 1 1 3M9%atesrtiyarleinnteegcorintytemnat ionrtagirneeadtewr;itShemeinNimotuem1 3 Resin, Epoxy Novalac vinyl ester 3 Rubber, butyl 1 See Note 1 Rubber, natural 1 See Note 1 Note 1 The specified material is a generic reference to a class of materials with different grades, manufacturers and/or registered trade names. While specific instances of this material have been verified by the literature and/or CI members in accordance with the rating given, it is possible other materials within the same generic class might not behave the same. Therefore, it is incumbent upon the end user to verify that the specific material being used is appropriate for the fluid service conditions. The Chlorine Institute, Inc. 30 PAMPHLET 164 Table 3.1 - Sodium and Potassium Hydroxide (50%) Reactivity with Materials (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Silicone Oil Material Reactivity 1 Comments Stainless Steel, 17-4 PH 1 Stainless Steel, 304 Stainless Steel, 316 Superferritic Stainless Steel, UNS S44627 Tantalum 1 elevaMteedchteamnipcearlaintutereg;riStyeecoSneccetrinosn w3.i4th. 1 elevaMteedchteamnipcearlaintutereg;riStyeecoSneccetrinosn w3.i4th. 1 See Note 1 Tantalum is susceptible to damage by hot sodium hydroxide Tin Titanium Viton (Fluorocarbon elastomer) Mechanical integrity concerns with 1 elevated temperature, refer to Section 3.4.2; See Note 1 See Note 1 Zinc Suitable for use in galvanized coating external to process Note 1 The specified material is a generic reference to a class of materials with different grades, manufacturers and/or registered trade names. While specific instances of this material have been verified by the literature and/or CI members in accordance with the rating given, it is possible other materials within the same generic class might not behave the same. Therefore, it is incumbent upon the end user to verify that the specific material being used is appropriate for the fluid service conditions. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 31 Table 3.2 - Sodium and Potassium Hydroxide (50%) Reactivity with Other Chemicals 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Chemical Acetaldehyde Acetic Acid Acetone Acetylene Acrolein Acrylonitrile Alcohols Aldehydes Alkanolamines Ammonia Ammonium Acetate Ammonium Chloride Ammonium Hydroxide Reactivity Comments See Section 3.5 See Section 3.5 See Ethanol and Methanol See Section 3.5 1 1 1 Releases ammonia when in contact with sodium hydroxide 1 The Chlorine Institute, Inc. 32 PAMPHLET 164 Table 3.2 - Sodium and Potassium Hydroxide (50%) Reactivity with Other Chemicals (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Benzene Chemical Calcium Carbonate Carbon Disulfide Carbon Tetrachloride Chlorine Chloroform Chloroethylene Chlorophenol Chlorothene Copper Sulfate Dichloroethane Dichloroethylene Reactivity 1 1 1 1 Comments See Section 3.5 See Section 3.5 The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 33 Table 3.2 - Sodium and Potassium Hydroxide (50%) Reactivity with Other Chemicals (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Diesel Fuel Chemical Diethyl Ether EDC (Ethylene Dichloride) Ethane Ethanol Ethylene Ethylene Dichloride Ethylene Glycol Ferric Chloride Fluorolube Gasoline Glycerin Hexachlorobenzene Hexachlorobutadiene Reactivity 1 1 1 1 Comments Large heat of dilution The Chlorine Institute, Inc. 34 PAMPHLET 164 Table 3.2 - Sodium and Potassium Hydroxide (50%) Reactivity with Other Chemicals (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Chemical Hexachloroethane Hydrocarbons Hydrochloric Acid Hydrogen Peroxide Hydrogen Sulfide Hydroxylamine Lithium Bromide Magnesium Chloride Magnesium Sulfate Methane Methanol Naphtha Nitric Acid Nitromethane Reactivity 1 1 1 Comments See Section 3.5 Large heat of dilution See Section 3.5 The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 35 Table 3.2 - Sodium and Potassium Hydroxide (50%) Reactivity with Other Chemicals (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Chemical Nitroparaffins Nitrophenol PCBs (Polychlorinated Biphenyls) Phosphorous Pentoxide Potassium Hydroxide Propylene Propylene Oxide Sodium Bisulfite Sodium Carbonate Sodium Chlorate Sodium Chloride Sodium Chlorite Sodium Hypochlorite Sodium Sulfide Reactivity 1 1 1 1 1 1 Comments See Section 3.5 See Section 3.5 See Section 3.5 The Chlorine Institute, Inc. 36 PAMPHLET 164 Table 3.2 - Sodium and Potassium Hydroxide (50%) Reactivity with Other Chemicals (Continued) 1 Little or no reaction. Potentially reactive under conditions. Rapid reaction. NOTE: This table is not intended to provide detailed technical information needed by process engineers, nor is it intended to provide economic evaluations of different materials. Chemical Sodium Sulfite Sodium Thiosulfate Sulfur Dioxide Sulfuric Acid Trichloroethane Trichloroethanol Trichloroethylene VCM (Vinyl Chloride Monomer) Vinyl Acetate Vinylidene Chloride Water Zinc Oxide Reactivity 1 1 1 Comments See Section 3.5 See Section 3.5 See Section 3.5 See Section 3. Large heat of dilution. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 37 3.3 ALUMINUM 3.3.1 Hazard Description The hydroxides and aluminum readily react and cause catastrophic failure of the metal. The reaction of the hydroxides and aluminum produces hydrogen gas as a byproduct. Accumulation of hydrogen can cause a combustible atmosphere. 3.3.2 Safe Limits of Operation Aluminum should not be used in applications involving sodium or potassium hydroxide. 3.3.3 Examples of Incidents Incident 1: An experiment was conducted to demonstrate the reaction of sodium hydroxide solution with aluminum. A test tube containing coarse aluminum powder was placed in a glass beaker. The beaker was used to provide secondary containment of the material within the test tube. A small amount of 40% sodium hydroxide solution was poured over the aluminum powder in the test tube. Within minutes, the material in the test tube began to foam and overflow into the beaker. Lessons Learned: The foaming was caused by the hydrogen produced from the reaction of the two substances. The experiment shows the violent effects of mixing the two materials and why exposure of the two materials to each other should be avoided. Incident 2: During a major sodium hydroxide plant expansion, industrial refrigeration units were purchased and installed that were equipped with safety relief valves made of aluminum bodies. The safety relief valves protected the refrigerant side. The engineers assigned to the project were inexperienced and failed to consider the materials aspects. Several years later the aluminum safety relief valves were removed for testing and found to be corroded shut. Incidental contact with sodium hydroxide over a period of time was believed to be the cause. Lessons Learned Sometimes equipment which is obtained as a packaged unit allows "out-of-spec" components to enter a chemical plant. The correct materials of construction are important for both the chemical containing components and those components that may be exposed to an occasional chemical drip or mist. Air compressor systems, refrigeration units and packaged boiler systems are prime examples of units which, if improperly specified, may allow out-of-spec elements into a chemical plant. The Chlorine Institute, Inc. 38 PAMPHLET 164 3.4 OTHER METALS 3.4.1 Hazard Description In addition to aluminum, the hydroxides react vigorously with some other construction metals such as magnesium, tin, and zinc. The reaction with these metals is violent and creates hydrogen. In certain equipment configurations, this hydrogen can accumulate above the reaction to form a flammable or explosive pocket. The hydroxides should not be used with these metals. Other metals that are not satisfactory for long term sodium hydroxide service because of a high corrosion rate include brass, bronze, copper, lead, tantalum, and alloys of these metals. 3.4.2 Safe Limits of Operation Carbon steel can be safely used with sodium hydroxide below about 120F (49C). Corrosion rates increase rapidly with increasing temperatures. Sodium hydroxide can be stored as a 50% solution in bare steel tanks but is usually not recommended above 120F (49C), due to potential stress corrosion cracking. Austenitic stainless steel is not recommended above 200F (93C). In addition, the presence of chlorides in the caustic solution increases stress corrosion cracking potential. CI Pamphlet 94 (4.1) provides more information on this topic. Nickel and nickel alloys have outstanding resistance to sodium hydroxide solutions over a wide range of concentrations and temperatures. Many stainless steels (e.g., 304, 316) and Alloy 400 are also commonly used in sodium hydroxide services. KOH will exhibit corrosion properties similar to NaOH with the following exceptions. According to AMPP/NACE Corrosion Data (4.3.6), KOH is a little more aggressive to 304, 316 and Titanium than NaOH. Stainless steels can be used, but corrosion rate will be slightly higher. 3.5 HYDROCARBONS 3.5.1 Hazard Description The hydroxides will react vigorously with many organic chemicals and caution is required. The hydroxides in prolonged contact with trichloroethylene or tetrachloroethanes can produce toxic, explosive products. Many organic compounds such as propylene oxide, acetaldehyde, and acrylonitrile can react violently on contact with sodium hydroxide. Reactions with nitromethane and nitrophenols produce shock-sensitive explosive salts. 3.5.2 Safe Limits of Operation Before using sodium or potassium hydroxide with any hydrocarbons, the user should become knowledgeable about the possible reactions between the substances. The user should ensure that any possible reactions between the substances are appropriately controlled, and possible consequences of such reactions are fully considered in the design of the system. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 39 3.5.3 Examples of Incidents Incident 1: A large quantity of chlorophenol left in contact with concentrated sodium hydroxide solution for 3 days decomposed, producing heat and liberating fumes which ignited explosively. Incident 2: Rags soaked in sodium hydroxide and in aldehyde overheated and ignited when they came into contact in a waste bin. Incident 3: Accidental contact of 50% sodium hydroxide solution with residual trichloroethanol in a pump caused an explosion. Incident 4: A chloroform-methanol mixture was put into a drum contaminated with sodium hydroxide. The substances reacted vigorously, and the drum exploded. The presence of methanol (or other solubilizer) increases the rate of reaction between chloroform and sodium hydroxide. Lessons Learned (for all four examples): Sodium hydroxide reacts vigorously with many hydrocarbons. Incident 5: A tank of an organic solvent product was found to be high in acidity and was out of specification due to color. The solvent contained an inhibiting stabilizer (nitromethane). It was the practice to neutralize slight acidity in such solvents in a pressure vessel (called a neutralizer) that was filled with solid sodium hydroxide flakes or beads. Such treatment was a common method to upgrade off-spec inventories of solvent intermediates and products. However, this particular product was solvent treated with about two percent of nitromethane stabilizer and was not like other intermediates or products previously processed. Subsequently, an explosion occurred creating a hole about 7 feet (2.1 m) in diameter and 3 feet (0.9 m) deep in the soil. The explosive forces were generated within a 15 inch (38.1 cm) diameter vessel and 6 feet (1.8 m) high. The explosive force severed the flange bolts on the vessel and propelled a two feet (0.6 m) diameter section of the vessel's thick steel plate over 450 feet (137.2 m) away. The accident investigators concluded that when the nitromethane contacted the caustic soda, a highly unstable sodium fulminate was probably created resulting in the explosion. Lessons Learned: This accident serves as a good example of the need to study any modifications involving reactive chemicals. Sometimes reactions between chemicals are taken for granted. Incident 6: Caustic spilled from a manual butterfly valve from the caustic recirculation tank. While the operator was trying to seat the valve, the stem came off and the handle came out spraying caustic out of containment, releasing 27,000 lbs of material. This particular valve had been in service for 4 years prior to failure. The Chlorine Institute, Inc. 40 PAMPHLET 164 Lessons Learned: There was a mix-up in the labeling of valves after the valve was received; it was ordered with 20 other unrelated valves. The Positive Material Identification (PMI) process was revamped as a result. Incident 7: " CPVC Ball Valves were installed in a new plant as anolyte (chlorinated brine) and caustic overflow/sample valves. Within one week, all of the caustic valves had broken at the upstream tightening ring. There was no problem with the anolyte valves. On disassembly, the internal o-rings made of Viton were found to have swollen and caused internal pressure which broke the tightening rings. New valves were installed with EPDM o-rings. Lessons Learned: Most commodity PVC/CPVC ball valves are supplied with Viton o-rings as default. EPDM is readily available but must be specified. 3.6 FIBER REINFORCED POLYMER (FRP) 3.6.1 Hazard Description: FRP is commonly used in facilities that use sodium and potassium hydroxide. The correct resin needs to be used and the correct thickness of the corrosion barrier to obtain a long service life. Sodium hydroxide and potassium hydroxide can be stored in FRP equipment if the correct resin and correct corrosion barrier are used. Sodium hydroxide can attack glass fibers so the veil in the corrosion barrier of the FRP must be a synthetic polyester veil or a carbon veil. It is recommended that 2 layers of veil be used to protect the glass fibers behind the veil layers. The minimum recommended corrosion barrier thickness for this service would be 0.12 in. (3 mm). The use of carbon veil is recommended for temperatures above 122F (50C) to have the longest service life. 3.6.2 Safe Limits of Operation: The maximum operating temperature will depend on the concentration of the sodium hydroxide or potassium hydroxide. A concentration of 50% sodium hydroxide can be handled with a bisphenol A epoxy vinyl ester resin with a minimum styrene concentration of 39% to a maximum temperature of 176F (80C). The sodium hydroxide becomes more aggressive at lower concentrations. The maximum temperature for sodium hydroxide concentrations of 10 to 30% would only be 149F (65C). If higher temperatures are required, then a dual laminate with a thermoplastic liner and a bisphenol A epoxy vinyl ester resin in the structure of the tank is recommended. The common thermoplastic liners used in chlorine plants for sodium hydroxide is polypropylene or polyvinyl chloride to a maximum temperature of 212F (100C). The tanks storing 50% sodium hydroxide will have to have a source of heating to keep the temperature above 59F (15C) to prevent the sodium hydroxide from precipitating out of solution. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 41 3.6.3 Examples of Incidents and FRP in Caustic Service Incident 1: A 50% sodium hydroxide storage tank at a wastewater treatment facility in Ohio showed chemical attack on the inside of the tank after several years. During the inspection of the tank, it was found that there was a burnt area where the heating coil was placed in the wall of the tank. The conclusion was that the heating coil malfunctioned and caused it to overheat and burn the resin in contact with the heating coil which in turn caused the sodium hydroxide to increase in temperature and attack the resin on the surface of the corrosion barrier. It is recommended that any heating device placed in the wall of the tank be monitored to make sure that it does not overheat and damage the tank. Incident 2: A tank that was designed for 50% sodium hydroxide at ambient temperature was used to dilute 50% sodium hydroxide down to 20% at least once a week. This dilution process is very exothermic. The resin on the inside of the tank was attacked in about 3 years. It was determined that the resin used for this tank was acceptable for 50% sodium hydroxide at ambient temperature but not for 20% sodium hydroxide at 149F (65C). The resin used for this tank was a bisphenol A epoxy vinyl ester resin with only 34% styrene. If the correct resin was used for this tank, it would not have had any issues. Example of FRP in Caustic Service: A 50% sodium hydroxide storage tank in Houston, TX was made using a bisphenol A epoxy vinyl ester resin with 44% styrene. The tank is also insulated. This tank has been in service for 29 years with no maintenance required and is still being used. 3.7 SELECTED SAFE PRACTICES FOR SODIUM AND POTASSIUM HYDROXIDE (50%) Lists 3.1 and 3.2 are a brief summary highlighting some of the key concerns one should consider when addressing reactivity and compatibility issues associated with 50 % sodium or potassium hydroxide. Lists 3.1 and 3.2 are not meant to be a comprehensive listing of such concerns, but are meant to highlight selected issues. The Chlorine Institute, Inc. 42 PAMPHLET 164 List 3.1 Selected Safe Practices for Sodium Hydroxide (50%) 1. Sodium Hydroxide Reacts Violently/Explosively with Acids. 2. Always Add Sodium Hydroxide to Water. a. Diluting sodium hydroxide with water is highly exothermic and proper precautions must be taken to minimize the effects. b. Cooling systems should be considered when sodium hydroxide and water are mixed. 3. Sodium Hydroxide Reacts with Aluminum, Tin, Copper, and Zinc. a. Use of these materials should be avoided. b. Reaction between sodium hydroxide and any of these materials will produce hydrogen gas which is highly flammable. 4. Sodium Hydroxide Corrodes Carbon Steel at Temperatures in Excess of 120F (49C). a. Sodium hydroxide causes excessive corrosion of carbon steel at temperatures above 120F (49C). b. Do not store sodium hydroxide in carbon steel vessels above 120F (49C). 5. Sodium Hydroxide Reacts with Many Organic Chemicals. 6. Welding on Piping/Equipment Can Cause Embrittlement, Stress Cracking, and the Evolution of Flammable Hydrogen Gas. a. Clean piping and equipment before welding. b. Metal surfaces must be cleaned/acidized prior to welding, cutting, or performing other forms of heat treatment. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 43 List 3.2 Selected Safe Practices for Potassium Hydroxide (50%) 1. Potassium Hydroxide Reacts Violently/Explosively with Acids. 2. Always Add Potassium Hydroxide to Water. c. Diluting potassium hydroxide with water is highly exothermic and proper precautions must be taken to minimize the effects. d. Cooling systems should be considered when potassium hydroxide and water are mixed. 3. Potassium Hydroxide Reacts with Aluminum, Tin, Copper, Zinc. c. Use of these materials should be avoided. d. Reaction between potassium hydroxide and any of these materials will produce hydrogen gas which is highly flammable. 4. Potassium Hydroxide Corrodes Carbon Steel at Temperatures in Excess of 120F (49C). c. Potassium hydroxide causes excessive corrosion of carbon steel at temperatures above 120F (49C). d. Do not store potassium hydroxide in carbon steel vessels above 120F (49C). 5. Potassium Hydroxide Reacts with Many Organic Chemicals. 6. Welding on Piping/Equipment Can Cause Embrittlement, Stress Cracking, and the Evolution of Flammable Hydrogen Gas. c. Clean piping and equipment before welding. d. Metal surfaces must be cleaned/acidized prior to welding, cutting, or performing other forms of heat treatment. The Chlorine Institute, Inc. 44 PAMPHLET 164 4. REFERENCES The following sections provide detailed bibliographic information on the Chlorine Institute publications and other documents. 4.1 CHLORINE INSTITUTE REFERENCES The following publications are specifically referenced in CI Pamphlet 164. The latest editions of CI publications may be obtained at http://www.chlorineinstitute.org. Pamphlet & Video # 6 94 95 100 121 152 165 173 Title Piping Systems for Dry Chlorine, ed. 17; Pamphlet 6; The Chlorine Institute: Arlington, VA, 2020. Sodium Hydroxide Solution and Potassium Hydroxide Solution (Caustic): Storage Equipment and Piping Systems, ed. 5; Pamphlet 94; The Chlorine Institute: Arlington, VA, 2018. Gaskets for Chlorine Service, ed. 6, Pamphlet 95; The Chlorine Institute: Arlington, VA, 2021. Behavior and Measurement of Moisture in Chlorine, ed. 5; Pamphlet 100; The Chlorine Institute: Arlington, VA, 2018. Explosive Properties of Gaseous Mixtures Containing Hydrogen and Chlorine: Operational Guidance and Research References ed. 5; Pamphlet 121; The Chlorine Institute: Arlington, VA, 2022. Safe Handling of Chlorine Containing Nitrogen Trichloride, ed. 4; Pamphlet 152; The Chlorine Institute: Arlington, VA, 2018. Instrumentation for Chlorine Service, ed. 5; Pamphlet 165; The Chlorine Institute: Arlington, VA, 2023. Hydrogen Handling in Chlor-Alkali Facilities ed. 1; Pamphlet 173; The Chlorine Institute: Arlington, VA, 2021. 4.2 OTHER REFERENCES The following documents are specifically referenced in CI Pamphlet 164. 4.2.1 Alloy Selection for Service in Caustic Soda, ed. 2, A Guide to the use of NickelContaining Alloys, The Nickel Institute, 2019. 4.2.2 Alloy Selection for Service in Chlorine, Hydrogen Chloride and Hydrochloric Acid, ed. 2., A Guide to the Use of Nickel-Containing Alloys, The Nickel Institute, 2018. The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 45 4.2.3 Corrosion Resistance of Nickel and Nickel-Containing Alloys in Caustic Soda and Other Alkalies, Volume 281, A Practical Guide to the Use of Nickel-Containing Alloys, The Nickel Institute, 2020. 4.2.4 TSEM 93/192 - How to Use Steel and Titanium Safely, Eurochlor, 1993. 4.2.5 Bretherick's Handbook of Reactive Chemical Hazards, Volumes 1-2, ed. 7, Urben, Peter G., 2007. 4.3 ADDITIONAL OUTSIDE REFERENCES 4.3.1 ASME B31.3, Process Piping, ASME: New York, NY, 2019. 4.3.2 Bretherick's Handbook of Reactive Chemical Hazards: An Indexed Guide to Published Data, ed. 7; Leslie Bretherick, P. J. Urben, and Martin J. Pitt E., 2006, Butterworth Heineman. 4.3.3 Chemical Process Safety, Learning from Case Histories; Roy E. Sanders, 2005, Butterworth Heineman. 4.3.4 Euro Chlor Document GEST 79/82, Materials of Construction for Use in Contact with Chlorine, 2013. 4.3.5 NFPA Bulletin 491, Guide to Hazardous Chemical Reactions, 1997 edition, National Fire Protection Association, Quincy, MA. 4.3.6 The Corrosion of Duplex Stainless Steels: A Practical Guide for Engineers, Francis, R., NACE, 2018. E-book. The Chlorine Institute, Inc. 46 PAMPHLET 164 APPENDIX A - MATERIAL INCLUSION REQUEST FORM Typical information to be submitted to the Secretary of the Institute for inclusion in Chlorine Institute Pamphlet 164. For each material model, submit a separate form.: Member Company*: ________________________________________ Member Company Contact*: _______________________________________________ Submittal Date: ____________ *This member company must be bulk user and/or producer of chlorine. Material Information Material Manufacturer: ____________________________________________________ Material Manufacturer Contact: _____________________________________________ Material Model Number: ___________________________________________________ Material and style (as descriptive as possible): __________________________________ Describe how material was used, include type of process equipment and service conditions: __________________________________________________________ Duration of Service (provide dates - minimum of 6 months): ______________________ Operating Conditions Temperature Range**: Min ________ Max ___________ Pressure Range*: Min ________ Max ___________ **Only complete if Wet or Dry Chlorine Service Describe the performance of the material: _____________________________________ Describe or attach compatibility testing performed: ______________________________ The Chlorine Institute, Inc. REACTIVITY AND COMPATIBILITY OF CHLORINE, SODIUM HYDROXIDE, AND POTASSIUM HYDROXIDE WITH VARIOUS MATERIALS 47 APPENDIX B - PAMPHLET 164 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 is discouraged since it can lead to inappropriate conclusions. Place a check mark () in the appropriate box below: Yes No N/A 1. For materials with different grades, has the user confirmed that the grade selected is appropriate for the selected service conditions? {2.1, 3.1} 2. For equipment where sodium or potassium hydroxide dilution will occur, has the user selected a material to withstand the heat of dilution? {3} 3. Is there a positive material identification system in place? {2.9} 4. For materials not listed in this pamphlet, has the user reviewed the manufacturer's compatibility information and/or conducted reactivity studies? 5. Are the service conditions for each application well understood (wet or dry, gas or liquid) and the appropriate materials selected? {2} 6. Have equipment, piping, valves, etc. for chlorine service been appropriately cleaned to remove organics or fine metals? {2} REMINDER: Users of this checklist should document exceptions to the recommendations contained in this pamphlet. The Chlorine Institute, Inc. THE CHLORINE INSTITUTE 1300 Wilson Boulevard Suite 525 Arlington, VA 22209 Telephone: Email: M@CL2.com Website: www.chlorineinstitute.org Technical inquiries: @CL2.com The Chlorine Institute all rights reserved.