Runaway reactions causes

The most famous case of a runaway reaction caused by contamination is Bhopal (see Section 21.1). In this case the reaction occurred in a storage vessel. It did not burst but was distorted, and the discharge of vapor was larger than the scrubbing and flare systems could have handled, even if they had been in operation. 

Castleford, England (Ref. 13) 5 (3 in buildings) Heat-sensitive and unstable nitrotoluene residue was overheated during the preparation for maintenance. A runaway reaction caused a jet flame that destroyed a wooden control room. 

On the first full-scale run of a modified process for the nickel catalysed isomerisation of the oxime to the corresponding amide, on 1200 kg scale in toluene solution under reflux in place of the previous water, the reaction overheated (to >180°C), pressurised, and then escaped confinement. Investigation showed the explosion to be purely a runaway reaction caused by a slower start than previously. It was recommended that the oxime be charged in portions, and the solvent changed to the higher-boiling xylene. 

A plant manufactured a dye by mixing and reacting two chemicals, ortho-nitrochloro-benzene (o-NCB) and 2-ethylhexylamine (2-EHA). A runaway reaction caused an explosion and flash fires that injured nine workers. The runaway reaction was the result of the following factors (1) The reaction was started at a temperature higher than normal, (2) the steam used to initiate the reaction was left on for too long, and (3) the use of cooling water to control the reaction rate was not initiated soon enough. 

What if area wide electrical power fails. (UPS instrumentation power remains) Runaway reaction through loss of agitation. Indicated by agitator motor off, low coolant flow, high reactor pressure, and high reactor temperature. Runaway reaction causes reactor overpressure and loss of containment. Add shortstop and burp reactor to stop runaway. Depressurize reactor - SIS (Pressure safety valve sized for this event). Use LOPA to determine required SIL ... 

Runaway Reactions Runaway temperature and pressure in process vessels can occur as a resiilt of many fac tors, including loss of cooling, feed or quench failure, excessive feed rates or temperatures, contaminants, catalyst problems, and agitation failure. Of major concern is the high rate of energy release and/or formation of gaseous produc ts, whiai may cause a rapid pressure rise in the equipment. In order to properly assess these effec ts, the reaction kinetics must either be known or obtained experimentally. 

When the steam was shut off and, 15 minutes later, the agitator was switched off, heat transferred from the hot wall above the liquid level to the top part of the liquid, which became hot enough for a runaway reaction to start. This resulted in a release of TCDD (dioxin), which killed a number of nearby animals, caused dermatitis (chloracne) in about 250 people, damaged vegetation near the site, and required the evacuation of about 600 people (Kletz 1994). 

Loss of agitation causing stratification of immiscible layers. Insufficient mixing of reactants results in unwanted accumulation of unreacted reactants. Possibility of runaway reaction upon resumption of agitation. 

Low temperatures can cause a phase separation in stabilized solutions in which case one phase can become deficient in stabilizer and subject to runaway reactions. Acrylic acid can crystallize out of stabilized solution, and subsequent thawing of these essentially pure acrylic acid crystals can initiate runaway reactions, often with severe consequences. Thawing of crystallized (frozen) materials needs to be accomplished using established procedures in thaw boxes or similar devices. If established procedures are not available, a safety review needs to be conducted and a procedure developed prior to thawing the material. 

The sudden mixing of large amounts of reactants under heating, instead of cooling, caused a runaway reaction. Once the pressure reached 16 bar pressure safety devices were actuated, the temperature at that point had reached 160°C,... 

Adequate heat removal facilities are generally important when controlling the progress of exothermic chemical reactions. Common causes of thermal runaway in reactors or storage tanks are shown in Figure 7.4. A runaway reaction is most likely to occur if all the reactants are initially mixed together with any catalyst in a batch reactor where heat is supplied to start the reaction. 

Thermal runaway reactions are the results of chemical reactions in batch or semi-batch reactors. A thermal runaway commences when the heat generated by a chemical reaction exceeds the heat that can be removed to the surroundings as shown in Figure 12-5. The surplus heat increases the temperature of the reaction mass, which causes the reaction rate to increase, and subsequently accelerates the rate of heat production. Thermal runaway occurs as follows as the temperature rises, the rate of heat loss to the surroundings increases approximately linearly with temperature. However, the rate of reaction, and thus the... 

The released energy might result from the wanted reaction or from the reaction mass if the materials involved are thermodynamically unstable. The accumulation of the starting materials or intermediate products is an initial stage of a runaway reaction. Figure 12-6 illustrates the common causes of reactant accumulation. The energy release with the reactant accumulation can cause the batch temperature to rise to a critical level thereby triggering the secondary (unwanted) reactions. Thermal runaway starts slowly and then accelerates until finally it may lead to an explosion. 

Passive A reaction capable of generating 150 psig pressure in case of a runaway, done in a 250 psig reactor. The reactor can contain the runaway reaction. However, if 150 psig pressure is generated, the reactor could fail due to a defect, corrosion, physical damage or other cause. 

The basic requirements of a reactor are 1) fissionable material in a geometry that inhibits the escape of neutrons, 2) a high likelihood that neutron capture causes fission, 3) control of the neutron production to prevent a runaway reaction, and 4) removal of the heat generated in operation and after shutdown. The inability to completely turnoff the heat evolution when the chain reaction stops is a safety problem that distinguishes a nuclear reactor from a fossil-fuel burning power plant. 

Liquid nitrogen should always be analyzed before it is off-loaded. The same applies in other cases where delivery of the wrong material could have serious unwanted results, such as a fire or runaway reaction, as in the two incidents that follow. If analysis causes too much delay, the new load should be put in a holding tank. 

The immediate cause of the disaster was the contamination of an MIC storage tank by several tons of water and chloroform. A runaway reaction occurred, and the temperature and pressure rose. The relief valve lifted, and MIC vapor was discharged to atmosphere. The protective equipment, which should have prevented or minimized the release, was out of order or not in full working order the refrigeration system that should have cooled the storage tank was shut down, the scrubbing system that should have absorbed the vapor was not immediately available, and the flare system that should have burned any vapor that got past the scrubbing system was out of use. 

The use of an unnecessarily hot heating medium led to the runaway reaction at Seveso, Italy, in 1976, which caused a fallout of dioxin over the sun ounding countryside, making it unfit for habitation. Although no one was killed, it became one of the best-known chemical accidents, exceeded only by Bhopal, and had far-reaching effects on the laws of many countries. 

A worker was told to control the temperature of a reactor at 60°C, so he adjusted the setpoint of the temperature controller at 60. The scale actually indicated 0-100% of a temperature range of 0-200°C, so the set point was really 120°C. This caused a runaway reaction which overpressured the vessel. Liquid was discharged and injured the worker. 

The most recent major expln in a US TNT plant occurred in May 1974 at the Radford Army Ammunition Plant. The accident completely destroyed one of the three continuous nitration lines at the plant. According to the AMC News, Sept 1974, the investigation board reported that an operator inadvertently introduced a 5 to 6-foot rubber hose to clean out unwanted material that had collected in a transfer line leading to the nitrator, when the hose was pulled from his hands into the nitrator. This resulted in a rapid temp rise and subsequent explosion. The hose was commonly used in this manner . The material causing the blockage in the transfer line was believed to be an oxidation product of TNT, 2,2 -dicarboxy-3,3, 5,5,-tetra-nitroazoxybenzene, also referred to as White Compound. The introduction of the rubber hose caused a rapid, exothermic oxidation reaction between the hose material and the mixed acid present. The heat generated by this reaction caused a local acceleration of the normal nitration/oxidation reactions which occur in the nitrator until a critical temp was reached, at which point rapid oxidation of DNT/TNT proceeded as a runaway reaction, igniting the material present in the vessel. 

The need for venting, or the cause of an emergency which results in a runaway reaction, can occur in several ways ... 

Oevere toxicological responses have been associated with certain chloro- dibenzodioxins. One of these responses is chloracne, a folliculosis first associated with skin contamination by chlorohydrocarbons in 1899 (3). Serious outbreaks of chloracne-like lesions associated with runaway reactions in the production of 2,4,5-trichlorophenol occurred in Germany in the early 1950 s (5). 2,4,5-Trichlorophenol itself does not cause acne (S), but the contaminants which may be formed in the uncontrolled production of 2,4,5-trichlorophenol are extremely potent acnegens (5). 2,3,7,8-Tetrachlorodibenzo-p-dioxin and tri- and tetra-... 

Changing process or mechanical conditions to reduce the potential for runaway reactions, accelerated corrosion or erosion, or other possible causes of undesirable events... 

Cascade control, along with ratio control, is used to control the temperature. The cold-water line is to have an air-to-close control valve. In case of failure in the air supply, the valve would open fully and a runaway reaction would be prevented. The hot-water line will have an air-to-open valve for similar reasons. After the two streams are mixed, the temperature will be measured. If it is above the desired temperature, the amount of air supplied to the valves will be reduced. This will increase the cold-water flow rate, and decrease the hot-water throughput. The result will be a reduction in the inlet water temperature. The desired temperature will be determined from a measurement of the reactor temperature. A deviation from the desired temperature will cause the set point of the second controller to be changed. This will result in a change of the inlet water temperature. 

However, one must remember that the accumulation of phenylhydroxy-lamines presents a serious danger because these compounds disproportionate with the liberation of much heat and may cause a runaway reaction, that is, an explosion (Fig. 2.33). This becomes especially dangerous if the reaction temperature gets close to 250°C, the autodecomposition temperature of phenylhy-droxylamine. Some of these accidents have been reported.277... 

Such nuclear reactions are controllable by keeping the sample size small. Most of the neutrons escape from the sample instead of causing further reactions. The smallest mass of sample that can cause a sustained nuclear reaction, called a chain reaction, is called the critical mass. Another way to control the nuclear reaction is to insert control rods into the nuclear fuel. The rods absorb some of the neutrons and prevent a runaway reaction. 

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