PPV Ses ay Ost [ ised ee uu INFORMATION MANUAa EY - Foreword vary dsotul? 190 of Uses for alt polution contre he Multitude of chemical “s, Individtals seeking information not covered in this. booklat aré urged to'contact * LaRoche directly. Copyight @ 1987 by LaFtache Industies Ine Ai rights reserved Guoteion or rermoduction ri wnela oF m part witioul writen parminalna is expressly prohibited.Contents Foreword Definition Production . Product Specifications Analytical Methods Transporiation Delivery Storage Materials Compatibiliy Emergency Response Environmentat Safety Regulations Chemical Properiies Physical Properties Conversions References, beet neee ee Appendix A - Charts, Graohs and Tables Specific Gravity Pressure Solubility Freezing Point Boiling Peint Appendix B - Product Specitications Appendix C - Analytical Methods Appendix D - Material Safety Data Sheet ... Appendix € - Federal DOT Reguations Appendix F - Deivery and Storage Information ‘Truck Delivery Methods Typical Storage Tank Billing Information ‘Appendix Contents. + 20-40 41-50 51-53 55-58 59-63 60 - 81-62 63 64Definition Aqua ammonia, aqueous ammonia and ammonium hydroxide are synonymous terms referring toa solution of ammonia in water. Tha chamical formula for ammonium hydroxide is NH,CH. Ammonia dis- solved In water Is present principally as the ion NH,*. Non-ionized molecular NH,OH, sometimes referred to as an associated form of ammonium hydroxide, Is atso present, Hydrated molecules of NHg may also exist as NHesH1,0 or NHa2H,0. Ammonia dissolved in water is commonly referred to simply as ‘ammonia’. Understand that this usage of the word does not refer to anhydrous ammonia! Preduction Aqua ammonia (ammonium hydroxide) is produced commercially by reacting anhydrous ammonia with water to font a solution which is approximately 30% ammoria by weight. Prior to reaction, the water is commonly purified by treatment with either: 1) A conventional sodium-form water-sottening ion exchange resin which replacas all cations pregant with sodium ions: 2) Both hydrogentorm eation resin and hydroxy#form anion rasin, resulting in total de-ionizetion of the water, or 3) Reverse osmosis punfication equipment, which also results in total de-ionizaton of the water. |i the water hardness is suitably low and/or suitabie filtration is avaitable to remove the precipitate formed during the reaction of arnmonia with water hardness, product can be manufectured without pre-treatment of the walec. For most water supplies, the precipitate is principally caicum carbonate. ‘The reaction of ammonia and water generates a substantial amount of heat, necessitating the use of heat exchangers to control ths temperature. The resulting aqua ammonia contains ammonium ions (NH,*), hydroxyl ions (OF), and non-ionized ammonium hydroxide molecules (NH,OH}. The chemical reactions are: Nity#HO a NH,OH NHgOH —» NH,* + OH Product Specifications The most common aqua ammonia (ammonium, hydroxide) concentration is 29.4% ammonia by weight. Certain LaFioche plants produce additional ‘ower concentration products. 29.4% ammonia preduct is also irequenty described as 25°B6 product. Dagress Baume is a system for dansity measurement, Since the density of aqua ammonia is inversely proportional ta con- centration, degrees Baumé can be used as an indi- cator of concentration, Degrees Baume is related to specific gravity by the formula: “Be = (140/sp.97}-130 “26* Baumé density at 60°F", “29.4% ammonia by weight” and 0.88974 specific gravily at 60°F" are all terms reierring to an identicat concentration of aqua ammonia. Specitic gravity and dagress Baumé of aqua ammonia both vary with temperature. See Appendix A, pages 15-28. For mare information on the degrees Bauré measurement system, refer ‘0 LaRoche’s Tach News, Volume 1, Number 9, (December 1990). Aqua ammonia is available at several different purl- ty levels. LaRoche utilizes the following Product Specification Grades: Grate Specification Reagent P39 Technical PO4 P3-10 P3141 5-12 NF. (formerly U.S.P.) PS-5 ‘Commercial P36 Neutralization PS-7 Foo PSB NOTE: Not all of these grades are avaliable at each LaRoche production point. For specific avail- ability information, contact LaRache Industries Ine. ‘The American Chemical Society {ACS) defines reagent grade; Federal Specification OA.451-F defines technical grade aqua ammonia; the National Formulary Monograph defines NF. grade: and the Food Chemical Codex defines FCC Grace whic is also referred to as food grace. Product Specifications for aqua arnmonia grades ara presented in Append B, pages 29-40.Analytical Methods Information on analytical procedures required for the analysis of aqua ammonia (ammonium hydrox ide} to determine compliance with the requirements of various specticatians are given in Appsndix C, pages 41-50, itis important to understand that an aqua ammonia sample exposed to the air in a samoling container will rapidly lose ammonia vapor ana significantly decrease in concartration and increase in density. This anaiytical error can be minimized by cooling the sampling container fo 5-10°C {40-50°F) prior to collection of the sample, If the density/concentra~ tion analysis is not io be done immediately, coal the sample and container subsequent to collection and during storage. If the eemple ig to be reiained, the cortainer should be kept tightly closed except for sample withdrawal, Withdrawal of a sample and its densityiconcentration analysis should be accom plished as quickly as possitic, For the most accurate analysis, the sample should be analyzed immediately. Transportation Aqua ammonia (ammonium hydroxide) is transport ed by LaRtoche In cargo tanks constructed in accor dance with Department of Transpariation (DOT) Specification MC-307 or MC-407. The use of other cargo tanks, such a8 MO-312 or MC-412, is autho- ‘ized provided they are in compliance with the seguirements of 49 CFR 173.241 Transportation of aqua ammonia with a concentra- tion groator than 10% és regulated by the federal DOF, which classifies it as @ “CORROSIVE” and assigns it the Identification Number UN2672. Applicable DOT reguiations should be carefully iol lowed when transporting aqua ammonia. The prop- er shipping name for aqua ammonia is ‘Ammonia Solutions”. is a Hazard Claas 8, Packing Group Itt chemical. Re-packagers cf bulk aqua ammonia use many dit- ferent types of shipping containers including $5-gal- lon steel drums, carboys and plastic containers. Effective October 1. 1996, ail non-buik containers must meet the performance-oriented standards as teferenced in 49 CFR 172.101 and defined in 49 CER 173.208. See Appendix E, pages 35-58 for DOT regulatory references. For chemical transportation emergencies, contact CHEMTREC at (800) 424-9300. Any release of this material, during the course of loading, transporting, unloading or temporary stor- age, must be reported to the DOT as required by 49 GFR 171,16 and 171.16. Delivery Deliveries into aqua ammonia (ammonium ydrox- ide) storage tanks ara made by cargo tank trans- ports having a capacity of approximately 7,000 gat- lons. Transfer of the product is usually effected either by the use of a pump, a compressor or a source of compressed air or nitrogen. The pump may be mounted on the delivery cargo tank trans- pott or it may be a part of the receiving storage system, Refer to Appendix E, page 60. if compressed air or nitrogen ia used to effect deliv- ery, the piping system shall inchide a backtlow check valve fo provant ammonia vapor fram onter- ing the air or nitrogan fine, Additionally, a scrubber or other similar sysiem should be used to control tha release af vapers trorn the tank when this type of delivery 's employed Pressure tanks should not be filed to more than 95% of their volume. Storage Bulk storage of aqua ammonia (ammonium hydrox- ide) should utilize ASME Code pressure vessels constructed for a design pressure (Maximum Allowable Working Pressure} af at least 25psig. ‘Any alterations or repairs to such storage tenks must be accomplished in accordance with ASME, Code requirements. Tanks shall be equipped with relief vaiva(s) in accordance with the design pressure. Each tank should also be equipped with a vacuum breaker set at 2-4 ounces of vacuum. A conservative mathod for calculating te relief capacity for the tank utilizes the formula: CFMyq = 22, 118022, where Ais the outer surface area of the vessel in squars feet. (See Appendix B of the ANS! K51.1-1989 Standard for the Storage and Handting af Anhydrous Ammonia). The discharge from relief valves shall be directed uncbstructed to the air anc away from personnel Atypical bulk storage tank for aqua ammonia is shown in LaReche Technical Bulletin TB-8-8, which also describes the functions of the various tank openings and appurtenances. This auletin is repro- duced in Appendix E, pages 61-62 aAQUA AMMON' Aluminum, stainless steel and carbon steel ate acceptanle metals for use in fabricating aqua ammonia storage vesse's, Tank linings or coatings of plastic or otner materials shavid be used only if approved by the tank fabricator for use with aqua ammonia. Such linings or coatings are not com- monly used. Each tank or container should be clearly marked “AMMONIUM HYDROXIDE! Great care must be takon if bocomes necessary to introduce water into a storage tank containing ammonia vapors. Extremely rapid absorption of the ammonia vapors will occur with concurrent rapid reduction in pressure. The vaculurn-breaker (with whieh most tanks are equipped) does nct allow for a sufficiently rayid enough introduction of alr into, the vessel to prevent inward collapse of pressure vessels of retatively low design pressures. Metals All tank openings exogpt those for relief devicas and float gauges shalt he aquippad with shutoff valves, Shut-off valves shall not d¢ installed between the relief devices and the tank. ‘Small containers of aqus such as drums and car- boys should be stored ina cool place and out of direct suntignt. The maintananos of aqua ammonia storage sys- tems usually consists of 1) protection of any axter- nal stccl surfaces from possible corrosion by inspection, re-priming and finish coat painting as necessary and 2) checking for leaks. The facation of leaks tends to be obvious; however, sources can be pinpointed by using LaRoche ammonia test paper (phenolphthalein paper). Note that notches in the side edges af the hexagonal packing nuts found on many ammonia valves indicate the use of teft- hand threads. Turn counter-clockwlse ta tightsn. Elastusners: Carbon steel tanks used for the storege of aqua ammonia are not subject to intemal corrosion after passivation. However, residual rust formed curing any hydrostatic preseure test conducted at the time of fabrication and rust rom attached steel pipe and ‘tings may be present. Aluminum and stainless stee! tanks ere not subject 'o intemal corrosion. Palnting of exterior surfaces of such tanks is optional Maintenance pracedures requiring tha removal of any valve or fitting directly attached to the tank should be performed only after all aqua ammonia has been removed from the tank and ammoria vapor fumes purged frorn ft Materials Compatibility A le Catbon Steel Stainiess Steet Aluminum Cast Iron Tin Lead Hastelloy B,C, D Nt Avceptabte Copper Copper Alloys (such as brass and bronze) Zinc (gelvanized aurtaces) Cadmium Silver (¢.g., silver brazed two-part “all steel’ valves) Nickel Manel Acceptable Neoprene Ethylene Propylene Butyl Buna Teflon Haveg 41, 60 Hastaflor Fluorthene Not Recommended Natural Rubber Nitrile. Polyurethane Hypalon Silicone VitonEmergency Response Personnel responcing to the accidentat release of hazardous material must be treined in accordance with the HAZWOPER reguiation (29 CFR 1910.120}, The folowing are suggested steps to be followed in the event of an accidental release of aqua ammenia {ammonium hydroxide}: 1. Report the release immediately to the National Response Center (1,000 Ibs. or more In any 24-hour period). Report io state and local authorities as required. 2, Alert ali on-site personnel and shut dewn all aqua ammoria operations, Account for all on-site personnel, 4, Administer first aid to injured personnel 5, Evaluate the amergency and assess the possible nead for an evacuation, 6. Contact off-site emergency responders as neacssaty. 7, Coordinate with off-site responders. 8. Direct site activities. §. Identity the source of the aqua ammonia tak. 10. isolate and control tha source of leak. 11. Record site events (ongoing). 12, Monitor the leak (ongoing). The application of a water fog to absorb ammonia vapors immediataly dawnwind of a spill is an efiec- tive mitigation taal. Determine the potential tlow pattem of the ammonia-water solution beforehand lt necessary. create preper pathways for retaining the dilute ammonia-water solution, Environmental Properly designed containment systems may be used for confining aque ammonia (ammonium hydroxide) in the event of a large spill. Spills should not be washed into ground water. Release Into sewers is not permitted without appropriate approvals and dilution. For information, contact your lecal, state and federal reculatory agencies. Secure regulatory and/or sanitary district approval rior to disposal into a sewer, For hazardous waste Tegulations, contact the federal RCRA Hotline at (600) 424-caa6. ‘Aqua ammonia in concentrations as tow as S ppm can be harmful to aquatic lie. Aqua ammonia is a ‘egulated material and repcrting of any release may be required Safety A Material Safety Data Sheet for LaRoche aqua ammenia is reproduced in Appendix D, pages 61-53, Primary Hazards ‘Aqua ammonia (ammonium hydroxide| is an aka- line material and raacts corrosively with human tis- sue in varying degrees depending on concentration and the time duration of the exposure. Ammonia vapars from aqua ammonia can be suffocating and iertating to mucous membranes and lung tissue. Skin contact can cause severe irritation and burns. Eye contact with aqua ammonia may be severely irrtating; ammonia vapor contact with oyes may bo mildly irritating. Ingestion can causa vomiting, nau- sea and corrosive bums to the esophagus and stomach. Ammonia iS not fsted as a carcinogen hy IARC, NPT or OSHA. The easily recognized ador of aqua ammonia pro- vides adequate waming of its presence, Aqua ammonia is not flammable. However, ammo- nia vapors present in aqua ammoria storage and handling equipment cen ignite in the piesence of a flame or spark at about 1200°F. The flammability range of ammonia vapor is approximataly 16-25% ‘of ammonia in air by volume. The NFPA hazard designation for anhydrous ammonia is 3-1-0 (Health = 3; Flammability = 1; Reactivity = 1) Before welding or cutting, aqua ammonia tanks and/or piping must be completely purged of all ammonia. Purge unti! no odor can be detected and continue the purging during the welding or cutting maintenance procedure. Itis suggested thet a CAUTION TO WELDERS label be placed on aqua ammonia storage and handling equipment. Other Hazards Aqua ammonia (ammonium hydroxide) may react with halogens such as bromine and chioring, with silver or with hypochlorites to form explosive and/or toxic compounds. Ammonia vapor begins to dissociate into nitrogen and highly flammable hydrogen at about B40°F if a Suitable catalyst is present. Iran pipe is one such catalyst. Aqua ammonia will react with many organic and inerganic acids to form ealts. These reactions are usually exothermic, ie. heat is generated. _——veal Human Physiological Effects Aqua ammonia (ammonium hydroxide) is not & cumulative metabolic polson. Ammonia is actually an important compound in life processes. Human blood contains about 1 ppm ammonia; humans produce about 4 grams of ammonia per day. Depending on concentration and time, the effects of exposure to ammonia vapor vary from none or ‘only mild Irritation, to obstruction of breathing from laryngeal anc bronchial spasm, to edema and severe damage of the miicasa membranes of the rasplratory tract with possible fatal results Contact of the skin or mucosa with aqua ammonia an result in a caustic bur, Exposure levels of ammonia vapor which are toler- ated by some persons may produce adverse reac. tions in others. People with chronic respiratory dis- ease or undue sensitivity 1o ammonia should not be exposed to It. The table below indicates human physiotogical response to the inhalation of various ‘concentrations of ammonia vapor in air, Paysiotogical Effects Of Ammonia Vapor Eifect EEMAmmona trai by Volume Least perceptble odor S ppm Readily detectable odor 20-50 ppm No discomfort or impairment of health for prolonged exposura 60-100 ppm General discomfort and eye-tearing; No lasting effect on shor exposure 150-200 ppm ‘Severs irrtation of eyes, ears, nose and throat; No tasting effect on short exposure 400-700 ppm ‘Coughing, bronchial spasirs 1,700 ppm Dangerous, less than 1/2-hour exposure may be fatal 2,000-3,000 opm Serious edema, strangulation, asphyxia, rapidly fatal Immediately tatal 5,000-10,000 ppm >10,000 ppm (From Anhydrous Ammonia G-2-1995, Eighth Edition, 1895, Compressed Ges Association, Inc.) The odor threshold of ammonia is from about § Rm to 50 ppm. This low threshold level typically provides more than ample warning of its presence, Exposure Limits For Vapor Ammonia OSHA regulations have established s Permissible Exposure Limit (PEL) of 80 pom of ammonia in air by volume as a time-weighted average (TAY, the definition for which is the average exposure in any S-hour work shift of a 40-hour work week. ‘The American Conference of Government and Industrial Hygienists (ACGIH) established an expo- sure limit of 25 ppm ammonia in air by volume as a time-weighted average (TWA). ACGIH also estab lished a 15-minute short term exposure limit (TEL) of 85 ppm. An STEL is a 15-minite timawaighted average which cannot be exceeded at any time curing a work day. NIOSH has set 309 pam of emmonia as ts immediately cangerous to life and health (IDLH) value Ammonia vapor is substantially lighter than ai, This property makes ventilation an important tool in pre- venting accumulations which may exceed these limits. Persunal Protective Equipment Persons working with aqua ammonia under routine circumstaness of operation and maintenance should wear chersical splash-proct goggles anc! rubber gauntlet gloves with rolled-up cuffs. A full face shicid may be worn over goggles for additional protection, but not as a substitute for the goggles. DO NOT wear contact lerses, Additional personal protective equipment includes: + Long-slaeve shirt and full-length pants * Hard hat with full face shield + Waterproof boots macie with special grip soles * Ralncoat Emergency Protective and Safety Ey Every location storing or handling aqua ammonia should have readily-available and freely-accessible ‘emergency protective and safety equipment as requitad by federal, state and local government regulations, The location of this equipment should be well Identified by appropriate signs, Depending on the size and nature of the aqua ammonia use, emergency protective and safety equipment may include one or more af the following! bri: a a ra ire ene Sica en