Sulfuric Acid Properties Technical Information Usage Storage Handling TABLE OF CONTENTS Introduction 1 Product Stewardship 2 Sulfuric Acid Process 3 Physical Properties 4 Thermal Properties 5 Personal Safety and First Aid 9 Health Hazards 9 Safety Precautions 9 Personal Protective Equipment 10 Site Facilities 12 First Aid 12 Handling Precautions 13 Spills or Leaks 13 Hazardous Chemical Reactions 13 Corrosion Hazards 14 Fire and Explosion Hazards 14 Fire Fighting 14 Engineering Control of Hazards 15 Transportation Emergencies 15 Waste Disposal 16 Shipping Containers 16 Unloading and Transfer 17 Tank Cars 17 Frozen Cars 22 Tank Trucks 23 Frozen Trucks 25 Pump Transfer to Process 25 Measuring Storage 25 Equipment 26 Corrosion Hazards 26 Storage Tanks 26 Vents 28 Piping 29 Pumps 30 Valves 30 Gaskets and Packing 30 Spill or Leak Prevention and Control 31 Spills and Leaks 31 Cleaning Storage Tanks 31 Pipeline Repairs 34 Conversion Tables 35 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. Some of the industries that find sulfuric acid essential include: • Fertilizers • Inorganic chemical manufacturing (including chlorine drying) • Petroleum refining (principally alkylation) • Pharmaceuticals (sulfonations/sulfations) • Soaps and detergents (sulfonations/sulfations) Veolia is the global leader in optimized resource • Pigments and dyes management, providing water, waste and energy (sulfonations/sulfations) management solutions that contribute to the • Textiles sustainable development of communities and industries. Through our complementary business • Pulp and paper activities, Veolia helps to develop access to (chlorine dioxide generation and pulp pH control) resources, preserve available resources and to • Metals replenish them. We are committed to providing • Steel high-quality services to our customers and operate (pickling) within a Goal Zero safety culture - focused on continuous improvement toward an overarching • Car batteries/lead-cell batteries goal of zero injuries, zero incidents and zero impacts (battery acid) on the environment. Some synonyms for sulfuric acid include: In July 2016, Veolia North America finalized an • H2SO4 agreement with Chemours (formerly DuPont) to purchase the assets of its Sulfur Products division. • Oil of Vitriol (OV) The asset purchase agreement included 7 operating • Vitriolic acid locations; corporate and functional support teams; • Hydrogen sulfate and the Acid Technology Center, a dedicated team of engineers who exclusively support the sulfuric • Oleum (Fuming sulfuric acid, >100% H SO )* 2 4 acid business. Chemours, and previously DuPont, were widely recognized as global leaders in chemical *Oleum is a blend of sulfuric acid and sulfur trioxide. manufacturing. DuPont had been involved in the A sulfuric acid concentration greater than 100% refers to a sulfuric acid business since 1865, supplying John D. mixture of 100% sulfuric acid and sulfur trioxide (SO ). 3 Rockefeller’s first oil refinery (Standard Oil of Ohio) The concentration represents the amount of sulfuric acid that with barrels of sulfuric acid on horse-drawn wagons. would be present if all of the free SO were converted to H SO . 3 2 4 The business today, under Veolia’s ownership, For information about Oleum, refer to the Veolia North America continues to be the benchmark for sulfuric acid Sulfur Trioxide and Oleum “Properties, Uses, Storage plant operations and services. and Handling” 1 I Veolia North America “We will work with you to ensure you have the training necessary to safely handle and use Veolia’s sulfuric acid products. ” Veolia owns and operates seven sulfuric acid We know how to run a safe and environmentally- plants throughout the United States. Some of friendly plant. And we are willing to share our these plants are sulfur-burning plants that use knowledge on the safe handling, use and storage a contact process (refer to “Sulfuric Acid Process, of sulfuric acid with our customers. page 3). Other plants use Spent Acid Regeneration (SAR) processes, where unreacted sulfuric acid that was used in other processes is regenerated Product Stewardship for re-use. We can supply a range of sulfuric Veolia fully endorses American Chemical acid products, varying in strength and quality Council’s (ACC) Responsible Care® seven codes of requirements. Management Practice. We encourage customers Besides having a strong product base, we are to thoroughly review their safety management experts in distribution and logistics. We have a practices in the handling of sulfuric acid. In variety of means available to us for transporting support of product stewardship, Veolia is willing sulfuric acid, including barges, rail cars and to consultant with our customers in the design of tank trucks. We partner with highly skilled unloading and handling facilities, as well as make transportation providers to ensure the product recommendations for first aid, medical treatment, gets to you on time and safely, and we provide personal protective equipment (PPE), emergency them with annual training on the handling and response, spill mitigation, and materials of management of sulfuric acid products. construction selection. We will work with you to Veolia has joined the American Chemical Council ensure you have the training necessary to safely (ACC) and is committed to Product Stewardship handle and use Veolia’s sulfuric acid products. and Responsible Care®. Our plant operators and Veolia personnel may visit sites before making the personnel are among the best in the world. first shipment. Sulfuric Acid I 2 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: Contact Process Sulfuric Acid Process Veolia also produces sulfuric acid using the Spent Acid Regeneration process, as shown below in Figure 1 above is a typical flow diagram of the Figure 2. In this process, spent sulfuric acid is contact process for a sulfur-burning plant for combusted in air to produce sulfur dioxide (SO2). sulfuric acid. As you can see, sulfur and air are The SO2 is cooled and cleaned through a series brought in and burned to make sulfur dioxide of scrubbers, reheated, and sent to a catalytic (SO2). The SO2 goes through a series of gas cooling converter with more air to make sulfur trioxide and heat recovery operations, and then is run (SO3). The remainder of an SAR plant process is through a catalytic converter to make sulfur essentially the same as a sulfur-burning sulfuric trioxide (SO3). The sulfur trioxide is absorbed in acid plant. For more information on Spent Acid, sulfuric acid. Water is added to control the sulfuric refer to Veolia’s Spent Sulfuric Acid “Properties, acid to the desired strength. Chemically, sulfur Uses, Storage and Handling” bulletin. trioxide (SO3) reacts with water (H2O) to make sulfuric acid (H2SO4). FIGURE 2: SAR Process 3 I Veolia North America TABLE 1: Typical Physical Properties of Sulfuric acid and Oleum Sp. Gr., Density at Approximate Approximate Viscosity Sp. Heat, Equiv. 15.6°C 15.6°C (60°F), Freezing Point Boiling Point at 20°C (68°F), cal/g·°C Strength H2SO4 (60°F) lb/gal °C / °F °C / °F cP (mPa·s) (Btu/lb·°F) 60° Bé 77.67 1.706 14.2 –10 13 19 380 17 0.45 66° Bé 93.19 1.835 15.3 –34 –29 279 535 22 0.38 96% 96 1.843 15.4 –14 6 308 586 23 0.36 98% 98 1.844 15.4 –2 29 327 621 25 0.35 99% 99 1.842 15.4 4 40 310 590 26 0.34 100% 100 1.839 15.3 11 51 274 526 28 0.34 10% oleum 102.25 1.880 15.7 0 32 173 344 31 0.32 20% oleum 104.50 1.915 16.0 –5 23 142 288 39 0.32 25% oleum 105.62 1.934 16.1 9 48 131 268 42 0.32 30% oleum 106.75 1.952 16.3 19 66 121 250 48 0.32 65% oleum 114.63 1.992 16.6 2 36 58 137 55 0.41 Conversion tables for concentrations are given on page 20. Physical Properties HIGH PURITY GRADES Water White: Physical properties same as 66º Bé Technical grade, except clarity is “water white”. Sulfuric acid (H2SO4, Molecular Weight 98.08) is a heavy, oily, strong, liquid mineral acid with a pH less than 1 and an acrid odor. It is completely Electrolyte 1,835: Physical properties same as soluble in water, and clear and colorless in pure 66° Bé Technical grade. Specification available form. Technical grades may be turbid and off- on request. white in appearance. Grades below 100% have a RELATED PRODUCTS very low vapor pressure of about 0.3 mm Hg at Sulfur Trioxide: Refer to the Veolia Safety Data room temperature. Pure sulfuric acid does not Sheet on Sulfur Trioxide and the Properties, Uses, have good warning properties, as it looks just Storage and Handling Bulletin on Sulfur Trioxide like water and has no fumes. As a vapor, sulfuric and Oleum. acid is more than three times as dense as air. Physical properties of technical grades of sulfuric acid are found in Table 1. Other grades of sulfuric acid and related products are also available from Veolia. Sulfuric Acid I 4 Thermal Properties Concentrated sulfuric acid is a strongly acidic material that reacts rapidly with water, evolving of H2SO4 Solutions considerable heat. When mixing or diluting Figures 3, 4, 5, and 6 give physical properties of sulfuric acid solutions, it is important to remember sulfuric acid solutions, such as freezing points, the following: boiling points and viscosities. If one mixes portions of acid at any two concentrations and temperatures, the temperature of any mixture will • Always add acid to water to prevent or lie on the straight line joining the points on Figure reduce boiling and spattering.