Ethylene Oxide Explosion

Kentucky, USA 1962 Ethylene oxide Explosion equal to 18 tonnes of TNT, 1 killed and 9 injured UVCE ... 

SAFETY PROFILE A poison by subcutaneous route. Questionable carcinogen with experimental tumorigenic data. Catalyzes the potentially explosive polymerization of ethylene oxide. Explosive reaction when heated with guanidinium perchlorate. Reaction with carbon monoxide may form an explosive product. Potentially violent reaction with hydrogen peroxide. 

By virtue of their unique combination of reactivity and basicity, the polyamines react with, or cataly2e the reaction of, many chemicals, sometimes rapidly and usually exothermically. Some reactions may produce derivatives that ate explosives (eg, ethylenedinitrarnine). The amines can cataly2e a mnaway reaction with other compounds (eg, maleic anhydride, ethylene oxide, acrolein, and acrylates), sometimes resulting in an explosion. 

Ethylene oxide is a colorless gas that condenses at low temperatures into a mobile Hquid. It is miscible in all proportions with water, alcohol, ether, and most organic solvents. Its vapors are flammable and explosive. The physical properties of ethylene oxide are summarized in Tables 1—7. 

Process Safety Considerations. Unit optimization studies combined with dynamic simulations of the process may identify operating conditions that are unsafe regarding fire safety, equipment damage potential, and operating sensitivity. Several instances of fires and deflagrations in ethylene oxide production units have been reported in the past (160). These incidents have occurred in both the reaction cycle and ethylene oxide refining areas. Therefore, ethylene oxide units should always be designed to prevent the formation of explosive gas mixtures. 

Explosibility and Fire Control. As in the case of many other reactive chemicals, the fire and explosion hazards of ethylene oxide are system-dependent. Each system should be evaluated for its particular hazards including start-up, shut-down, and failure modes. Storage of more than a threshold quantity of 5000 lb (- 2300 kg) of the material makes ethylene oxide subject to the provisions of OSHA 29 CER 1910 for "Highly Hazardous Chemicals." Table 15 summarizes relevant fire and explosion data for ethylene oxide, which are at standard temperature and pressure (STP) conditions except where otherwise noted. 

Liquid mists of ethylene oxide will decompose explosively in the same manner as the vapor. Burning rate increases with decreased droplet size. 

Liquid ethylene oxide under adiabatic conditions requires about 200°C before a self-heating rate of 0.02°C/min is observed (190,191). However, in the presence of contaminants such as acids and bases, or reactants possessing a labile hydrogen atom, the self-heating temperature can be much lower (190). In large containers, mnaway reaction can occur from ambient temperature, and destmctive explosions may occur (268,269). 

Ethylene oxide has been studied for use as a rocket fuel (276) and as a component in munitions (277). It has been reported to be used as a fuel in FAE (fuel air explosive) bombs (278). 

Explosion prevention can be practiced by mixing decomposable gases with inert diluents. For example, acetylene can oe made nonexplosive at a pressure of 100 atm (10.1 MPa) by including 14.5 percent water vapor and 8 percent butane (Bodurtha, 1980). One way to prevent the decomposition reaction of ethylene oxide vapor is to use methane gas to blanket the ethylene oxide hquid. 

Ethylene oxide <-18 CH, CH, 7 o 429 3.0-100 0.9 1.5 11 Colourless gas at room temperature Irritant to eyes and respiratory tract, and an experimental carcinogen Polymerizes uncontrollably with immense explosive force on contact with certain chemicals (e.g. ammonia)... 

One Dies in Union Carbide Ethylene Oxide Plant Explosion ... 

An explosion and fire (March 13, 1991) occurred at an ethylene oxide unit at Union Carbide Chemicals Plastics Co. s Seadrift plant in Port Lavaca, TX, 125 miles southwest of Houston. The blast killed one, injured 19, and idled the facility, that also produces ethylene, ethylene glycol, glycol ether ethanolamines, and polyethylene. Twenty-five residents were evacuated for several hours as a safety precaution. The plant lost all electrical power, for a few days, because its cogeneration unit was damaged. The Seadrift plant, with 1,600 workers, is capable of making 820 million lb per year of ethylene oxide which is one-third of Carbide s worldwide production of antifreeze, polyester fibers, and surfactants Seadrift produces two thirds of Carbide s worldwide production of polyethylene. 

Despite these precautions, an explosion occurred. One day, when ethylene oxide addition was started, the pressure in the reactor rose. This showed that the ethylene oxide was not reacting. The operator decided that perhaps the temperature point was reading low or perhaps a bit more heat was required to start the reaction, so he adjusted the trip setting and allowed the indicated temperature to rise to 200°C. Still the pressure did not fall. 

An explosive decomposition in an ethylene oxide (EO) distillation column, similar in its results to that described in Section 7.3.2, may have been set off by polymerization of EO in a dead-end spot in the column base where rust, a polymerization catalyst, had accumulated. Such deadends should be avoided. However, it is more likely that a flange leaked the leaking gas ignited and heated an area of the column above the temperature at which spontaneous decomposition occurs. The source of ignition of the leak may have been reaction with the insulation, as described... 

An ethylene oxide plant tripped, and a light on the panel told the operator that the oxygen valve had closed. Because the plant was going to be restarted immediately, he did not close the hand-operated isolation valve as well. Before the plant could be restarted, an explosion occurred. The oxygen valve had not closed, and oxygen continued to enter the plant (Figure 14-5). 

A more serious incident occurred at a plant in which ethylene oxide and aqueous ammonia were reacted to produce ethanolamine. Some ammonia got back into the ethylene oxide storage tank, past several check valves in series and a positive pump. It got past the pump through the relief valve, which discharged into the pump suction line. The ammonia reacted with 30 m of ethylene oxide in the storage tank. There w as a violent rupture of the tank, followed by an explosion of the vapor cloud, which caused damage and destruction over a wide area [4],... 

Storage tanks containing ethylene oxide are usually inerted with nitrogen. One plant used nitrogen made by cracking ammonia. The nitrogen contained traces of ammonia, which catalyzed an explosive decomposition of the ethylene oxide. Similar decompositions have been set off by traces of other bases, chlorides, and rust. 

A manufacturer of ethylene oxide received some old returned cylinders in which the ethylene oxide had partly polymerized, sealing the valves. They were taken to an explosives testing site and blov/n up [20]. 

Thibault, P., Britton, L. G., and Zhang, F. 2000. Deflagration and Detonation of Ethylene Oxide Vapors m Pipelines. Process Safety Progress, 19(3), 125-139. an Dolah, R. W. and Burgess, D. S. 1974. Explosion Problems in the Chemical Industry. 

Specific Volume of Gases Formed on Explosion. 723ml/g (NG 712ml) (Ref 46) Stabilization. Chromatographically pure Mannitol Hexanitrate was mixed with varying percentages of 22 stabilizers and the mixts tested for stability in the 100° heat test best results were obtained with a mixt of 96% MHN, 2% Amm oxalate, and 2% dicyandiamide (4.07% wt loss after 48 hours, 5.74% after 96 hours) (Ref 56). The use of ethylene oxide as a stabilizer is reported in Ref 27 Thermal Decomposition. Slow heating causes decompn at 150° with evolution of red fumes (Ref 20, p 249)... 

The composition of the gas mixture, which is introduced into the tube bundle reactor (tubes of 6-12 m length and 20-50 mm diameter, filled with the Ag catalyst) consists of 15-50 vol % ethylene, 5-9% oxygen, as much as 60% methane as dilution gas, and 10-15% carbon dioxide. The reaction therefore proceeds above the upper explosion limit. The ethylene conversion runs up to 10% per cycle through the reactor. The ethylene oxide selectivity amounts to 75-83 % maximum. The formed ethylene oxide is recovered by scrubbing with water and the newly formed carbon dioxide is separated from the cycle gas, e.g., by hot potash washing process. 

Ethylene oxide gas is highly explosive in mixtures of >3.6% vN in air, in order to reduce this explosion hazard it is usually supplied for sterilization purposes as a 10% mix with carbon dioxide, or as an 8.6% mixture with HFC 124 (2 chloro-1,1,1,2 tetrafluoroethane) which has replaced fluorinated hydroearbons (freons). Alternatively, pure ethylene oxide gas can be used at below atmospheric pressure in sterihzer chambers from which all air has been removed. 

It has been shown, particularly for the latter reaction and for the ethylene oxide process, that micro reactors allow safe processing of otherwise hazardous oxidations [4, 26, 40, 42, 43, 84]. This is first due to the fact that the inner volume of micro reactors is small so that explosions also happen only on a micro scale . The... 

When analysing the previous table, it shows the ambiguity of NFPA reactivity codes vis-a-vis instability. It is not so much an instability code but rather, like its name indicates, a code related to dangerous chemical reactions. Degrees 3 and 4 are the only ones that are more or less usable for defining an instability level, with the exception of ethylene oxide. So, even ethylene oxide s main hazard is not its explosive decomposition but its very violent polymerization caused by catalytic impurities (see chapter 6). 

Explosion of three tons of an ethylene oxide/glycerol mixture when heated to 200°C instead of 115-125 C. 

Twenty tons of ethylene oxide were contaminated by ammonia accidentally. The tank broke open releasing a fume cloud , which gives rise to a devastating explosion. Again, it is rather difficult to interpret this accident. Indeed, it could be a violent polymerisation, which was the result of the catalytic effect of ammonia or a very exothermic reaction ... 

Similarly, another accident occurred when metallic silver came into contact with aziridine. According to the authors of the report, the accident was interpreted by the formation of an aziridine silver derivative. Comparing this behaviour with the one of ethylene oxide when silver is present, a danger which is of the same nature is demonstrated. The interpretation that had been given at the time was based on the presence of acetylene in ethylene oxide, whose silver derivatives are very sensitive explosives. It may be that acetylene traces were present in aziridine although none of the authors mentioned such as possibility as far as we know. 

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