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A Detailed Reaction Study of Phosphorus Trichloride and Water

This paper reports on a comprehensive literature search and small scale experimental work on the reaction characteristics of phosphorous trichloride and water. More than 30 tests were conducted, including both closed and open test cells. The water to phosphorus trichloride molar ratio was varied form 1 to 25. When in contact, water and phosphorus trichloride will form two liquid layers with a reaction starting at the interface. The impact of variables on reaction rates (including the interface surface area, layer depth, and stirring were investigated experimentally. A reaction rate model that fits all the measured data is presented. Case studies illustrating the use of this data for emergency relief systems and vent containment design are presented in reference [1]. Read more

A Kinetic Model for the Polymerization and Decomposition of Acrylonitrile

Acrylonitrile (AN) was first discovered in 1893 and copolymerized with butadiene during WW II to form oil resistant rubber for the military. When acrylonitrile polymerizes, the CH2=CH breaks releasing 17.3 kcal/gmol, making the reaction difficult to control. Read more

A Systematic Approach to Chemical Reactivity Evaluation

Reactive chemicals are materials capable of giving rise to an uncontrolled chemical reaction (a.k.a., a runaway reaction). Reactions with a significant release of heat, gas and/or toxic materials have the potential to cause harm to people, property or the environment. Despite OSHA’s Process Safety Management Standard (PSM) and EPA’s Risk Management Plan (RMP) regulations, accidents with reactive chemicals continue to happen. In their 2002 report, the U.S. Chemical Safety and Hazard Investigation Board (CSB) identified failure of management systems for reactive chemistry as a key root cause of reactive chemical accidents. Managing reactive chemistry involves a systematic approach. The approach presented here incorporates both screening and experimental steps. As seen in Table 1, it begins with computational assessment, followed by experimental screening and finally, experimental testing. Read more

Addressing Combustible Dust Hazards

Many industries — from chemicals, plastics, and pharmaceuticals to food processing and mineral recovery — face combustible dust hazards in their facilities. Incidents such as the explosions and fires at the Imperial Sugar refinery in Port Wentworth, GA in February 2008 demonstrate the need to effectively manage these risks. Follow this approach to understand and mitigate your combustible dusts. Read more

Butadiene Thermal DimerizationTrimerization, Free-Radical Polymerization, and Polymer Decomposition Reactions

1,3-butadiene monomer undergoes thermally initiated, reversible dimerization/trimerization reactions with essentially the same kinetics in both the gaseous and liquid phases. Kinetics for formation of the dimer and the trimer are available from the open literature. The rate of reaction becomes significant (0.02°C/min = 29°C/day) at temperatures above 70-80°C. Inhibitors (t-butylcatechol, et al.) are used to prevent/minimize free-radical polymerization reactions in the liquid phase and to maintain product quality at ambient or subambient temperatures. These inhibitors do not prevent dimerization/trimerization reactions. Unless adequate emergency relief is provided, emergency relief is provided, the adiabatic temperature rise from the dimerization/trimerization reactions can lead to both a free-radical polymerization, initiated by adventitious peroxides, and a thermal decomposition of the resultant polymer to produce residues, volatiles, and not condensable gases. Temperatures of 600°C and pressures of over 2,000 psig are possible. Heat rates of 10,000°C/min pressure rise rates of 10,000 psig/min are also possible in unvented/undervented vessels. Emergency relief devices protecting vessels containing high concentrations of 1,3-butadiene should be reviewed to identify potentially reactive cases. This review is recommended to ensure that current that current emergency relief system designs are adequate and that equipment is being operated with an adequate margin safety. Read more

Chemical Reactivity Data in PSM and RAGAGEP

A chemical reactivity hazard is a situation with the potential for an uncontrolled chemical reaction: Temperature increase, pressure increase, gas evolution. Chemical reactivity incidents can be initiated by various process upsets: Unintentional interaction, self-reactivity, accumulation of reactants, loss of cooling, catalyst mischarge, fire. The first step is understanding where a chemical reactivity hazard might exist. Read more

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