Acetylene detonation

Finally, acetylene detonates violently when it comes into contact with an ozone/oxygen mixture in which the quantity of ozone exceeds 50 mg/l. 

Catalytic forms of copper, mercury and silver acetylides, supported on alumina, carbon or silica and used for polymerisation of alkanes, are relatively stable [3], In contact with acetylene, silver and mercury salts will also give explosive acetylides, the mercury derivatives being complex [4], Many of the metal acetylides react violently with oxidants. Impact sensitivities of the dry copper derivatives of acetylene, buten-3-yne and l,3-hexadien-5-yne were determined as 2.4, 2.4 and 4.0 kg m, respectively. The copper derivative of a polyacetylene mixture generated by low-temperature polymerisation of acetylene detonated under 1.2 kg m impact. Sensitivities were much lower for the moist compounds [5], Explosive copper and silver derivatives give non-explosive complexes with trimethyl-, tributyl- or triphenyl-phosphine [6], Formation of silver acetylide on silver-containing solders needs higher acetylene and ammonia concentrations than for formation of copper acetylide. Acetylides are always formed on brass and copper or on silver-containing solders in an atmosphere of acetylene derived from calcium carbide (and which contains traces of phosphine). Silver acetylide is a more efficient explosion initiator than copper acetylide [7],... 

Thus gas detonations initiate condensed explosives (if at all) by some direct heat transfer process. In oxy-acetylene detonations, the equilibrium temperature (CJ temp) is quite high 4500°K... 

The writer (unpublished results) was able to initiate Lead Azide pellets of ca 2.5 g/cc density with oxy-acetylene detonations. However ca 1.2 g/cc PETN pellet could not be initiated under these conditions. Gordeev et al [Nauchn-Tekhn Probl Goreniya Vzryva (1965) p 12 CA 64 1894 (1966)] succeeded in initiating liquid mixtures of tetranitromethane (TNM) and benzene with stoichiometric methane-oxygen detonations. For 1.5 vol parts of TNM 1 vol p of benz the initial pressure, P0, of the detonating gas mixture had to be greater than 2 atm to initiate the liquid. Initiation delays decreased as P0 increased delays were 350, 10 0 psec for P0 of 2, 12 24 atm. For 4 1 by vol TNM/benz initiation of the liquid was observed for Po>0.7 atm. At Po 0.7 atm the initiation delay for this liquid mixture was 70 jusec... 

Nickel catalysts are utilized for the industrial synthesis of acrylic acid or esters either in a semicatalytic process with Ni(CO>4 or a catalytic process with NiBft (equation 44).73 The reaction is carried out in THF containing water or alcohol (to avoid acetylene detonation at 60 bar). 

Berthelot and Vielle have shown that, in order for acetylene to explode in contact with a platinum wire brought to incandescence, it was necessary to submit the gas to an initial pressure measured by 137 centimetres of mercury. But acetylene detonates by the explosion of a cartridge containing 0.1 gr. of mercury fulminate, as soon as the initial pressure is measured by 100 centimetres of mercury. 

Fig. 1. Pressure required for propagation of decomposition flame through commercially pure acetylene free of solvent and water vapor in long horizontal pipes. Gas initially at room temperature ignition by thermal nonshock sources. Curve shows approximate least pressure for propagation (0), detonation,...

The calculated detonation velocity in room temperature acetylene at 810 kPa is 2053 m/s (61). Measured values are about 1000-2070 m/s, independent of initial pressure but generally increasing with increasing diameter (46,60—64). In a time estimated to be about 6 s (65), an accidental fire-initiated decomposition flame in acetylene at ca 200 kPa in an extensive piping system traveled successively through 1830 m of 76—203-mm pipe, 8850 m of 203-mm pipe, and 760 m of 152-mm pipe. 

The predetonation distance (the distance the decomposition flame travels before it becomes a detonation) depends primarily on the pressure and pipe diameter when acetylene in a long pipe is ignited by a thermal, nonshock source. Figure 2 shows reported experimental data for quiescent, room temperature acetylene in closed, horizontal pipes substantially longer than the predetonation distance (44,46,52,56,58,64,66,67). The predetonation distance may be much less if the gas is in turbulent flow or if the ignition source is a high explosive charge. 

The pressure developed by decomposition of acetylene in a closed container depends not only on the initial pressure (or more precisely, density), but also on whether the flame propagates as a deflagration or a detonation, and on the length of the container. For acetylene at room temperature and pressure, the calculated explosion pressure ratio, / initial > deflagration and ca 20 for detonation (at the Chapman-Jouguet plane). At 800 kPa (7.93... 

Several studies of spherical and cylindrical detonation in acetylene—oxygen and acetylene—air mixtures have been reported (82,83). The combustion and oxidation of acetylene are reviewed extensively in Reference 84. A study of the characteristics and destmctive effects of detonations in mixtures of acetylene (and other hydrocarbons) with air and oxygen-enriched air in earthen tuimels and large steel pipe is reported in Reference 81. 

Liquid and Solid Acetylene. Both the Hquid and the soHd have the properties of a high explosive when initiated by detonators or by detonation of adjoining gaseous acetylene (85). At temperatures near the freezing point neither form is easily made to explode by heat, impact, or friction, but initiation becomes easier as the temperature of the Hquid is raised. Violent explosions result from exposure to mild thermal sources at temperatures approaching room temperature. 

Acetylene has a low solubiHty in Hquid oxygen. Excessive concentrations can lead to separation of soHd acetylene and produce accumulations that, once initiated, can decompose violently, detonating other oxidizable materials. Acetylene is monitored routinely when individual hydrocarbons are determined by gas chromatography, but one of the wet classical methods may be more convenient. These use the unique reaction of acetylene with Ilosvay s reagent (monovalent copper solution). The resulting brick-red copper acetyHde may be estimated colorimetricaHy or volumetricaHy with good sensitivity (30). 

Decomposition Flame Arresters Above certain minimum pipe diameters, temperatures, and pressures, some gases may propagate decomposition flames in the absence of oxidant. Special in-line arresters have been developed (Fig. 26-27). Both deflagration and detonation flames of acetylene have been arrested by hydrauhc valve arresters, packed beds (which can be additionally water-wetted), and arrays of parallel sintered metal elements. Information on hydraulic and packed-bed arresters can be found in the Compressed Gas Association Pamphlet G1.3, Acetylene Transmission for Chemical Synthesis. Special arresters have also been used for ethylene in 1000- to 1500-psi transmission lines and for ethylene oxide in process units. Since ethylene is not known to detonate in the absence of oxidant, these arresters were designed for in-line deflagration application. 

Fabiano et al. (1999) describe an explosion in the loading section of an Italian acetylene production plant in which the installed flame arresters did not stop a detonation. The arresters were deflagration type and the arrester elements were vessels packed with silica gel and aluminum plates (Fabiano 1999). It was concluded that the flame arresters used were not suitable for dealing safely with the excess pressures resulting from an acetylene decomposition, and may not have been in the proper location to stop the detonation. 

A number of gases may decompose (self-react) and propagate flames in the absence of any oxidant provided that they are above minimum conditions of pressure, temperature, and pipe diameter. Common examples are acetylene, ethylene oxide, and ethylene. Some, like acetylene, can decompose in a detonative manner, while ethylene cannot detonate in the absence of an oxidant, whatever the run-up length (CCPS 1993). Thus, detonation arresters must be used for acetylene, but deflagration arresters may be used for ethylene, even for in-line applications. 

Sutherland and Wegert (1972) describe the successful use of the Linde hydraulic valve arrester in stopping an acetylene decomposition detonation. As previously noted, these flame arresters are no longer being made by Linde (now Praxair Inc,), but are still available from ESAB Welding Sc Cutting Products of Florence, SC. 

One experiment (Moen et al. 1985) revealed that jet ignition of a lean acetylene-air mixture (5.2% v/v) in a 4-m-long, 2-m-diameter bag can produce the transition to detonation. 

A deflagration-detonation transition was first observed in 1985 in a large-scale experiment with an acetylene-air mixture (Moen et al. 1985). More recent investigations (McKay et al. 1988 and Moen et al. 1989) showing that initiation of detonation in a fuel-air mixture by a burning, turbulent, gas jet is possible, provided the jet is large enough. Early indications are that the diameter of the jet must exceed five times the critical tube diameter, that is approximately 65 times the cell size. 

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