Sulfur Trioxide and Oleum Properties Technical Information Usage Storage Handling TABLE OF CONTENTS Introduction 4 Shipping Containers 24 Product Stewardship 5 Portable Tank 24 Regulatory Compliance 5 Tank Truck 24 Acid Production Process 6 Rail Car 25 Chemical and Physical Properties 6 Barge 25 Sulfur Trioxide (SO3) 7 Unloading and Transfer 26 Oleum (Fuming Sulfuric Acid) 7 Portable Tank 26-28 Special Product Training 12 SO3 Tank Truck 29-31 Fuming Acids Safety Symposiums 12 Oleum Tank Truck 32 Fuming Acids Spill Mitigation Workshop 12 SO3 Tank Car 32-36 Personal Safety and First Aid 13 Oleum Rail Car 36-38 Health Hazards 13 Equipment 39 Safety Precautions 13 Materials of Construction 39 Personnel Protective Equipment 14-16 Storage Tanks 39-40 Site Facilities 17 Building 40 Handling Precautions 18 Vents 41 Spill Mitigation 18 Fume Scrubber/Demister 41 Hazardous Chemical Reactions 19 Recirculation Line 41 Corrosion Hazards 20 Piping 42 Fire and Explosion Hazards 20 Valves 42 Fire Fighting 20 Pumps 42 Engineering Control of Hazards 20-22 Gaskets 42 Transportation Emergencies 22-23 Instrumentation 43 Waste Disposal 23 Unloading Hoses 43 Remote Leak Detection 44 Cleaning Storage Tanks 44 Sulfur Trioxide and Oleum I 3 INTRODUCTION Sulfuric acid is one of the oldest known industrial chemicals. It is a very strong inorganic acid with qualities that make it very useful for a number of industries. More sulfuric acid is produced and consumed than any other chemical in the world. Sulfur trioxide and oleum are the strongest inorganic acid produced from sulfur. Some of the industries that find sulfur trioxide and oleum essential include: • Surfactants • Soaps/detergents In July 2016, Veolia North America finalized an agreement with Chemours (formerly DuPont) to • Shampoo bases purchase the assets of its Sulfur Products division. • Personal care products The asset purchase agreement included 7 operating locations; corporate and functional support teams; • Bromide-based flame-retardants and the Acid Technology Center, a dedicated team of engineers who exclusively support the sulfuric “In July 2016, Veolia North America finalized • Engineering polymers acid business. Chemours, and previously DuPont, were widely recognized as global leaders in chemical an agreement with Chemours (formerly DuPont) to • Inorganic chemicals (FSA) manufacturing. DuPont had been involved in the purchase the assets of its Sulfur Products division.” • Oil well drilling muds sulfuric acid business since 1865, supplying John D. Rockefeller’s first oil refinery (Standard Oil of Ohio) • Optical brighteners with barrels of sulfuric acid on horse-drawn wagons. The business today, under Veolia’s ownership, Product Stewardship Regulatory Compliance • Chemical intermediates continues to be the benchmark for sulfuric acid Veolia fully endorses American Chemistry Sulfur trioxide (SO ) and oleums are included in plant operations and services. 3 • Dyes and pigments Council’s (ACC) Responsible Care® seven codes of the SARA Extremely Hazardous Substance, CERCLA Veolia owns and operates seven sulfuric acid plants Management Practice. We encourage customers Hazardous Material, and SARA Toxic Chemical lists. • Nitrocellulose & high explosives production throughout the United States. Some of these plants to thoroughly review their safety management SO3/oleums are also specifically listed in Appendix • Ion exchange resins are sulfur-burning plants that use a contact process practices in the handling of sulfuric acid. In A of the Process Safety Management Regulation (refer to “Acid Production”, page 6). Other plants use support of product stewardship, Veolia is willing (29 CFR 1910.119) and are listed as a regulated Veolia is the global leader in optimized resource Spent Acid Regeneration (SAR) processes, where to consultant with our customers in the design of toxic substance in 40 CFR 68.130 in EPA’s Risk management, providing water, waste and energy unreacted sulfuric acid that was used in other unloading and handling facilities, as well as make Management Plan regulation (40 CFR Part 68) as management solutions that contribute to the processes is regenerated for re-use. We can supply recommendations for first aid, medical treatment, directed by the Accidental Release Provisions of sustainable development of communities and a range of sulfuric acid products, varying in strength personal protective equipment (PPE), emergency the Clean Air Act. The storage, handling and use industries. Through our complementary business and quality requirements. response, spill mitigation, and materials of of SO3/oleums may require compliance with the activities, Veolia helps to develop access to construction selection. We will work with you to above regulations, and there may be additional resources, preserve available resources and to Besides having a strong product base, we are experts ensure you have the training necessary to safely federal, state and local regulations. Be sure to replenish them. We are committed to providing in distribution and logistics. We have a variety of handle and use Veolia’s sulfuric acid products. check the specific regulations that affect high-quality services to our customers and operate means available to us for transporting sulfuric acid, Veolia personnel may visit sites before making your location. within a Goal Zero safety culture—focused on including barges, rail cars, portable tanks and tank the first shipment. continuous improvement toward an overarching trucks. We partner with highly skilled transportation goal of zero injuries, zero incidents and zero providers to ensure the product gets to you on impacts on the environment. time and safely, and we provide them with annual training on the handling and management of sulfuric acid products. 4 I Veolia North America Sulfur Trioxide and Oleum I 5 SO Gas Stream Sulfur 2 Waste To Stack Heat Boiler Waste SO3 Gas Heat Stream Boiler Air Cooler Sulfur Furnace Cooler Water Water The Converter Economizer 93% Acid Stream Drying Tower Absorbing Tower 98% Acid Stream FIGURE 1: Acid Plant FIGURE 2: SAR Process crystals – the metastable beta form referred to Sulfur Trioxide (SO3) above, and the stable alpha form, which melts at Sulfur trioxide (SO ) is normally a clear, colorless, 62.3 C (144.1 F). Solid forms of SO rarely have well- Acid Production Process Chemical and Physical Properties 3 3 oily liquid that may contain a slight haze and be defined melting points because it may contain Figure 1 above is a typical flow diagram of the Sulfur trioxide and oleum have a strong, irritating, off-white to light brown in appearance when a mixture of the three forms. The theoretical shipped. As normally handled, SO has a vapor contact process for a sulfur-burning plant for acrid odor and are very hygroscopic. They react 3 possibility of a sudden increase in vapor pressure sulfuric acid. As you can see, sulfur and air are violently with water, so uncontrolled contact with pressure of up to 10 pounds per square inch (psi). accompanying the melting of the higher polymers SO fumes react with the moisture in the air brought in and burned to make sulfur dioxide any aqueous system should be avoided. They are 3 in such mixtures exists, but SO3 stabilization and (SO ). The SO goes through a series of gas cooling oxidizing agents and may cause ignition by contact to produce dense, white clouds of sulfuric acid the use of proper techniques in handling reduces 2 2 mist. Table 1 shows the physical and chemical and heat recovery operations, and then is run with combustible materials. this possibility. SO3 maintained in the liquid state properties of Sulfur Trioxide. Figures 3, 4A, and 5 through a catalytic converter to make sulfur will only consist of the gamma form. SO3 should be give the viscosity, vapor pressure, and specific stored at an elevated temperature of 35-41 C (95- trioxide (SO3). The sulfur trioxide is absorbed in sulfuric acid. Water is added to control the sulfuric gravity of Sulfur Trioxide, respectively, at 105 F) to minimize the formation of the undesirable acid to the desired strength. Chemically, sulfur different temperatures. polymeric forms (alpha and beta) and still be safely trioxide (SO ) reacts with water (H O) to make below the boiling point of 44.8 C (112 F). 3 2 Sulfur trioxide can exist in three forms: gamma, sulfuric acid (H SO ). 2 4 beta and alpha, each having different properties, Veolia also produces sulfuric acid using the Spent as shown in Table 2. Gamma is the desirable form and exists when SO is maintained absolutely pure Acid Regeneration process, as shown in Figure 2. 3 Oleum (Fuming Sulfuric Acid) In this process, spent sulfuric acid is combusted and anhydrous. Beta and alpha are the undesirable Oleum is the term used to describe fuming sulfuric in air to produce sulfur dioxide (SO ). The SO is forms, because they have higher melting points. 2 2 acids. Oleum is produced in various strengths cooled and cleaned through a series of scrubbers, Moisture is what promotes the formation of and consists of SO dissolved in 100% Sulfuric Acid reheated, and sent to a catalytic converter these undesirable forms. Moisture promotes 3 (H SO ). Thus, 20% oleum contains 20% SO and with more air to make sulfur trioxide (SO ). The polymerization, allowing the monomer and gamma 2 4 3 3 80% H SO by weight. More information on oleum remainder of an SAR plant process is essentially forms to polymerize to the straight chain beta form. 2 4 product specifications is given in Table 3. Oleum is the same as a sulfur-burning sulfuric acid plant. In time, cross-linking of the straight chains results in normally clear to turbid and off-white in appearance. For more information on Spent Acid, refer to the formation of the alpha form. Depending on strength, the vapor pressure is such Veolia’s Spent Sulfuric Acid “Properties, Uses, Veolia offers two grades of SO ; stabilized and that SO fumes evolve and combine with moisture Storage and Handling” bulletin.