Exothermic reaction vessels

New systems or processes may also need to be qualified from an operational safety perspective. This is particularly relevant in the case of chemical synthesis involving exothermic reactions. Critical safety aspects are usually identified using hazard operability or HAZOP assessments and studies. For example, a HAZOP analysis of an exothermic reaction vessel would involve consideration of the consequence of failure of the motors for mixers or circulation pumps for cooling water. Thus, the qualification of such a system would involve checks and assessment to ensure that the system/process can be operated safely and that pressure relief valves or other emergency measures are adequate and functional. 

Class 1 safety instrumentation loops include alarms and trips on storage tanks containing flammable or toxic liquids, devices to control high temperature and high pressure on exothermic-reaction vessels, and control mechanisms for low-flow, high-temperature fluids on fired heaters. Other Class 1 instruments include alarms that warn of flame failure on fired heaters, and vapor detectors for emergency valve isolation and sprinkler-system activation. All of these alarms, shutdown valves, and other critical instruments are regularly proof-tested to a well-defined schedule. 

Also, the presence of strong bases, even in trace amounts, can promote the formation of isocyanurates or carbodiimides. In the event of gross contamination, the exothermic reaction can sharply increase the temperature of the material. Normally, the trimerization reaction occurs first and furnishes heat for the carbodiimide reaction. The carbodiimide reaction Hberates carbon dioxide and forms a hard soHd. The Hberation of carbon dioxide in a sealed vessel could result in overpressurization and mpture. 

Various processes have been disclosed wherein moist soHd sodium pyrosulfite [7681-57-4] is stirred in a steam-heated vessel with sodium carbonate. The exothermic reaction at 80—110°C results in the drying of the product. A lower grade of sodium sulfite is produced commercially in the United States as a by-product of the sulfonation—caustic cleavage route to resorcinol (333). 

Sulfurchlorination of unsaturated compounds or mercaptans is normally carried out at atmospheric pressure in a glass-lined reaction vessel because of the potential to Hberate HCl during the reaction. The sulfurchlorination vessel is equipped with a cooling jacket or coils (very exothermic reaction), a nitrogen or dry air sparging system, an overhead condenser, and a caustic or bleach scmbber. If one of the reactants (olefin or mercaptan) is alow boiling material, ie, isobutylene, a glass-lined pressure vessel is recommended. 

The reaction vessel (nitrator) is constructed of cast iron, mild carbon steel, stainless steel, or glass-lined steel depending on the reaction environment. It is designed to maintain the required operating temperature with heat-removal capabiUty to cope with this strongly exothermic and potentially ha2ardous reaction. Secondary problems are the containment of nitric oxide fumes and disposal or reuse of the dilute spent acid. Examples of important intermediates resulting from nitration are summarized in Table 3. 

NO -laden fumes are preheated by effluent from the catalyst vessel in the feed/effluent heat exchanger and then heated by a gas- or oil-fired heater to over 600° F. A controlled quantity of ammonia is injected into the gas stream before it is passed through a metal oxide, zeolite, or promoted zeolite catalyst bed. The NO is reduced to nitrogen and water in the presence or ammonia in accordance with the following exothermic reactions ... 

Vessel Filled with Reactive Gas Mixtures Most cases of damage arise not from the vessel failing at its normal operating pressure but because of an unexpected exothermic reaction occurring within the vessel. This usually is a decomposition, polymerization, deflagration, runaway reaction, or oxidation reaction. In assessing the damage... 

Polymerization Exothermic reaction which, unless carefully controlled, can run-away and create a thermal explosion or vessel overpressurization Refer to Table 7.20 for common monomers Certain processes require polymerization of feedstock at high pressure, with associated hazards Many vinyl monomers (e.g. vinyl chloride, acrylonitrile) pose a chronic toxicity hazard Refer to Table 7.19 for basic precautions... 

Imagine a closed reaction vessel in which an exothermic reaction proceeds at room temperature at a finite rate. Although the temperature in the reaction vessel is initially the same as room temperature, it rises gradually until the rate of heat generation due to the exothermic chemical reaction is equal to the rate of heat escape from the reaction vessel surface. However, if a thermal balance is not established for such a chemical reaction, the reaction rate is accelerated by self-heating as the temperature rises, leading to thermal runaway. The temperature change in a reaction vessel is represented by Eq. (1),... 

Figure 8. Clock or haystack-type reaction associated with thermal runaway derived from self-heating due to exothermic reactions in a closed vessel. Parameters ...

A. Available Design Methods for Vent Sizing. Several methods are available to size the vent with a wide range of sophistication. The FIA chart, Fig. 1 prepared by the Factory Insurance Association in the mid 1960 s is a simple chart summarizing a wealth of experience. Reactions are classed by the degree of exothermic reaction. With vessel size and a judgment of reaction type a vent size range can be selected. 

Exothermic reaction which, unless carefully controlled, can run-away and create a thermal explosion or vessel overpressurization... 

As a vessel of a given shape increases in size, both the surface area and the volume increase, but they do not increase at the same rate. For a sphere the surface area is a function of the diameter squared and the volume is a function of the diameter cubed. This is also true for a cylinder whose height is a multiple of its diameter. The polymerization of styrene is an exothermic reaction. The amount of energy released at any time is dependent on the volume of the reactor, and the rate of removal of that heat is dependent on the surface area. Unless the heat is removed, the temperature will rise and the reaction rate will increase. The result will be an uncontrolled reaction that not only may ruin the batch but could also damage the reactor and might cause a tire or explosion to occur. 

---