Case Study: Gaylord Chemical: Explosion due to Corrosion by Process Chemicals

BACKGROUND INFORMATION: Corrosion is the largest single cause of plant and equipment breakdown in process industries. For most applications it is possible to select materials of construction that are completely resistant to attack by the process fluids, but the cost of such an approach is often prohibitive. In practice it is usual to select materials that corrode slowly at a known rate and to make an allowance for this in specifying the material thickness. Corrosion in metallic components occurs when pure metals and their alloys form stable compounds with the process fluid by chemical reaction or electrochemical processes resulting in surface wastage.

Figure 1. Superheated steam blew a 2-foot-wide hole in the pipe

Figure 2: Initial measurements showed that the steam had corroded the pipe from .4 inches to .06 inches, less than one-third the minimum safety standard. Appreciable corrosion can be permitted for tanks and piping if anticipated and allowed for in design thickness, but essentially no corrosion can be permitted in fine mesh wire screens, orifice plates and other items in which small changes in dimensions are critical. Rates of corrosion can be heavily affected by temperature changes. While a material of construction may be suitable at one temperature it may not be appropriate for use at a higher temperature with the same process fluid. The corrosion of metallic materials is essentially a process that manifests itself as swelling, cracking or softening of the material of construction that may lead to damage of structures as was revealed by the explosion at the Bogalusa facility.

Gaylord Chemical is a wholly owned subsidiary of Gaylord Container Corporation, and while Gaylord Container's plant is situated geographically adjacent to Gaylord Chemical's facility in Bogalusa, Louisiana (USA), the two corporations operate on separate manufacturing and sales activities. Gaylord Container operates a paper mill and manufactures paper products. Gaylord Chemical manufactures several specialty chemicals. Nevertheless, some of Gaylord Chemical's production activities are conducted using waste byproducts of Gaylord Container's paper mill operations, the byproducts of which are piped to Gaylord Chemical from the adjacent Gaylord Container Plant. The two businesses are also physically connected by utility and telephone wires.

THE DISASTER At 3:55 p.m. on October 23, 1995, at the Gaylord Chemical Corporation plant in Bogalusa, Louisiana, yellow-brown vapors began leaking from the dome of the railroad tank car UTLX 82329 that contained a mixture of nitrogen tetroxide, which is a liquefied poisonous gas and oxidizer. The vapors initially formed a plume between 10 and 15 feet in diameter. Plant personnel notified emergency response agencies and used two plant fire hoses to spray water into the plume to suppress the vapors. About 4:30 p.m. Bogalusa fire personnel arrived at the plant and set up fire hoses to help-suppress the vapors. The head on the B-end of the tank car failed about 4:45 p.m., resulting in one end of the tank car jacket being torn away and thrown about 350 feet. The tank car was then propelled 35 feet down the track and derailed at a track bumping block. A large reddishbrown vapor cloud was released from the tank car. Vapors continued to be released from the opening in the tank car for another 36 hours until the chemical reaction that had occurred within the tank was brought under control through neutralization and dilution. Some 3,000 people were evacuated from the area as a result of the vapor cloud. Of 4,710 people who were treated at local hospitals, 81 people were admitted.

Sequence of events Pursuant to its ongoing manufacture of a particular chemical, Gaylord Chemical had ordered a railcar of nitrogen tetroxide from Vicksburg Chemical Corporation; that railcar arrived at Gaylord's plant on October 10, 1995. Employees of Gaylord Chemical, though, soon discovered that the railcar's contents were contaminated with water" and "knew [that] the contaminated nitrogen tetroxide had to be removed from the railcar. Plans were then made for the transfer of the contaminated nitrogen tetroxide to stainless steel tank trucks, which could [safely] hold nitric acid. At the direction of Vicksburg's hazardous materials team, Gaylord Chemical employees flooded the railcar

with water. During the next ten days, however, the gauge on the railcar continued to indicate that the pressure [of the gas still] in the car was rising until at approximately 4:45 p.m. on October 23, 1995, the railcar's south end cap blew off," releasing the gaseous contents of the railcar, primarily in a massive brown and orange cloud" that slowly settled on land in Louisiana and nearby Mississippi.

PLANNING THE INVESTIGATION (Cause of the accident) According to a 1998 report by the US National Transportation Safety Board (NTSB), the probable cause of the accident was the lack of adequate procedures on the part of the Gaylord Chemical Corporation and the Vicksburg Chemical Company to prevent or detect the contamination of nitrogen tetroxide with water, resulting in the formation of an extremely corrosive product and the subsequent failure of the tank car. AFTERMATH: Gaylord Chemical Corporation has discontinued the use of tank cars to transport nitrogen tetroxide and now uses smaller tanks that hold only 3 percent of the volume capacity of the tank car involved in the accident. Cargo purity assurance procedures, including the testing of cargo before and after loading, have been implemented to prevent the transport of contaminated cargo. The plant has additionally installed equipment to warn residents of any accidental release and, in coordination with the city of Bogalusa, has developed emergency procedures and conducted training. The tank car destroyed in this accident was the last carbon steel tank car in use that had been approved by the US Department of Transportation for transporting nitrogen tetroxide.

CONCLUSION: It is known that corrosion cannot be prevented, only minimized but accidents like the chemical explosion in Gaylord chemical plant would not have resulted to major damages if it was handled correctly. The incident in the in the Gaylord Chemical facility would not have resulted to a tragedy if the situation was handled properly and accurately. From the conducted investigations the chemical leak was made worst by improper chemical handling of the Vicksburg Chemical Company and Gaylord Chemical employees. Their failure to detect the contamination of nitrous oxide with water and the inadequate procedures of emergency transfer of contaminated cargo contributed to the severity of the accident. RECOMMENDATION: It is therefore highly recommended that all personnel working with hazardous chemicals should be professionally trained and knowledgeable in proper chemical handling. Maintenance of materials should also be done frequently to avoid major accidents as revealed by the accident in Gaylord Chemical plant. Corrosion is the largest single cause of plant and equipment breakdown in process industries. For most applications it is possible to select materials of construction that are completely resistant to attack by the process fluids, but the cost of such an approach is often prohibitive. In practice it is usual to select materials that corrode slowly at a known rate and to make an allowance for this in specifying the material thickness. These factors should also be considered when dealing with highly corrosive chemicals: Materials Selection & Design There is no material resistant to all corrosive situations but materials selection is critical to preventing many types of failures. When selecting a material, the required characteristics need to be defined in advance. If no material has every characteristic

that a specific project requires, a corrosion control system will be needed or the service conditions must be adjusted to meet the characteristics of the candidate material. Nitrogen tetroxide is compatible with a wide spectrum of materials of construction. However, considerable care must be exercised in selecting suitable materials due to the reactivity of the propellant and the need to prevent leaks and spills. In addition, the compatibility of several materials of construction with nitrogen tetroxide depends upon the amount of water contamination present in the propellant. Nitrogen tetroxide reacts with water to form nitric acid which is more corrosive to most materials of construction than nitrogen tetroxide itself. Therefore, all nitrogen tetroxide systems and components must be absolutely dry. Compatible Materials: The following materials and lubricants have been found to be compatible with nitrogen tetroxide: Aluminum Alloy No. 1100 Aluminum Alloy No. 5052 Aluminum Alloy No. 6061 Aluminum Alloy No. 6066 Aluminum Alloy No. 356 Aluminum Alloy No. B356 Aluminum Alloy Tens 50 Stainless Steel AISI 300 Series Stainless Steel AISI 400 Series Stainless Steel AM-350 Stainless Steel AM-355 Stainless Steel 17-4 P11 Stainless Steel 17-7 PH Iron-Base Superalloy A-286 Iron-Base Superalloy 16-25-6 Inconel-X Chromium Plating Teflon Teflon filled with asbestos or glass Teflon-fiberglass (LNP) Viton A Viton B NA2-205-2 (Alochlor-1254 Monsanto) Graphite (dry) Molycote Z (binderless)

Materials for Limited Service The following materials have been found to be satisfactory for limited service in nitrogen tetroxide: Mild Steels Fluoro-Silicone Rubber (LS-53 Series) Polyethylene Keroseal Saran Note: Since these materials are attacked by nitrogen tetroxide under some expected conditions or time duration, their use is not recommended. Incompatible Materials: The following materials and lubricants have been found to be incompatible with nitrogen tetroxide and must not be used: Aluminum Alloy No. 2024 Johns-Mansville Packing No. 60 K-Monel Johns Mansville Packing No. 76 Brass Kel-F Elastomer Bronze Mylar Silver Buna-N Copper Hypal on Titanium Dow Corning Lubricant No. 55 Zinc (MIL-G-4343) Cadmium Oxylube Nickel ?rL-L-6086 Micarta DC 11 MIL-L-25336 Factors that influence materials selection are corrosion resistance in the environment, availability of design and test data, mechanical properties, cost, availability,

maintainability, compatibility with other system components, life expectancy, reliability, and appearance. Appropriate system design also is highly important for effective corrosion control. Design includes the consideration of many factors, such as materials selection, process and construction parameters, geometry for drainage, avoidance or electrical separation of dissimilar metals, avoiding or sealing of crevices, corrosion allowance, operating lifetime, and maintenance and inspection requirements. Protective Coatings Putting a barrier between a corrosive environment and the material to be protected is a fundamental method of corrosion control. There are many organic and metallic coating systems to choose from, and they are available in various combinations. Coating system selection is similar to materials selection in that many factors need to be considered, including types of exposure, operating conditions, substrate, ambient conditions during application, environmental regulations, cost, application during operation or shutdown, time constraints, new construction or maintenance, shop or field application, and design/fabrication considerations. Common coating application methods include brush or roller, spray, and dipping. In addition to proper coating selection and application methods, substrate preparation is critical to the success of the coating. The majority of coating failures are caused either completely or partially by faulty surface preparation, such as leaving contaminants on the surface or having an inadequate anchor (sand blast) pattern. Maintenance Requirements Process equipment handling hazardous materials should be inspected at regular frequencies, both internally and externally. Localized corrosion can be unpredictable and fabrication defects such as poor welds can be present. Linings can deform or be damaged. Typically the glass lining on a jacketed reactor can suffer thermal shock or a static discharge may occur through the lining. The frequency of inspection can be amended once an inspection history has been built up and the condition of a piece of equipment can be reasonably predicted. The operator should demonstrate that it has

inspection and maintenance programs in place for hazardous process equipment including lagged systems. Where equipment is lined electrical continuity tests for lining defects should be carried out where appropriate. Cathodic and anodic protection systems should be regularly checked to ensure continued protection. Control of Operating Conditions Where control of corrosion is dependent on the concentration of contaminants or moisture the operator should demonstrate that procedures and the necessary controls are in place to maintain a safe operating condition. Similarly where inhibitors are added or systems such as cathodic protection are used the operator should demonstrate that these systems are inspected and adequately maintained to ensure continued protection of the process.

Gaylord Chemical
Explosion due to Corrosion by Process Chemicals

Chemical Process Equipment Design CHE 515

Submitted to: Engr. Caldona, MSChe Submitted by: Balinte, Reynaldo Serrano, Sidney Rufino, Kennedy

January 7, 2012