BLEVE

A Boiling Liquid Expanding vapour Explosion (BLEVE) is caused by the catastrophic failure of a pressure vessel containing a liquid which is well above its boiling point at atmospheric pressure. Although rare events, the consequences of a BLEVE can be catastrophic, leading to the prominent position of the phenomenon in the safety analysis of LPG transport and storage.

Experimental observations show five distinct stages in the development of fireballs:

Stage 1: The vessel fails, missiles are generated and ejected and an initial overpressure wave, Ps1, is produced by the expanding vapour phase. The overpressure pulse is followed by a rarefaction.

Stage 2: The bursting vessel ejects a cloud of liquid droplets which flash adiabatically as the
pressure in the cloud drops. The mass, and therefore ultimately volume, of vapour flashed from the liquid droplets vastly exceeds that of the vapour initially released in Stage 1. There is little mixing with the surrounding air. The cloud pressure, eventually drops to the surrounding atmosphere and the volume of the cloud then becomes equal to the volume of flashed vapour at saturation temperature and pressure. If the outward radial velocity of the cloud exceeds the local speed of sound in the rarefaction following Ps1, then a blast wave can form as a result of the vapour expansion from the flashing liquid. As it separates from the outer cloud boundary, this blast wave, Ps2, leaves the cloud in a highly turbulent state at ambient pressure. It has been observed from experiments that the blast wave is only associated with the initial high fill ratio. At lower levels of fill the blast wave is unlikely to occur.

Stage 3: At this stage the overpressure peaks Ps1 and Ps2 leave the cloud. The cloud continues to expand due to outward radial momentum but the radial expansion velocity slows as the turbulent mixing entrains more and more air. Rapid expansion continues until the random velocities in the turbulent eddies overwhelm the radial expansion velocity, further expansion being due to the turbulence alone.

Stage 4: Ignition occurs near the centre of the cloud and an hemispherical fireball develops. The
expansion is suddenly arrested as the last visible part of the vapour cloud is consumed by flame. At this point the fireball is at its brightest. Since the cloud contains air, it is assumed that during this stage the flashed vapour is consumed, there being insufficient time for radiation to substantially heat and flash the cold liquid droplets. The expansion causes an overpressure pulse in the surrounding atmosphere which travels outwards from the cloud. The pulse is followed by a
rarefaction caused by the sudden arrest in cloud expansion. The expansion velocity of the fireball is equal to the flame propagation velocity through the turbulent vapour cloud. The heat radiation
pulse from the fireball peaks at the end of this stage.

Stage 5: The hemispherical fireball rises to become a sphere sitting on the ground. Combustion
continues but the fireball does not expand, indicating that the air required for combustion is already pre-mixed into the cloud. The fuel for combustion is supplied by the liquid droplets. The fireball then rises at approximately constant velocity and volume, and assumes a typical mushroom shape. The visible flame area decreases as the fireball becomes patched with sooty combustion products. Once combustion is substantially complete, the smoky torrid of hot combustion products rises, expands and dissipates with a flow pattern similar to a thermal. The heat radiation pulse decreases systematically to zero during this phase.

GAS EXPLOSIONS

Flash Point and Flammable Limits
Flash points and flammable limits in percent by volume have been tabulated by the National Fire Protection Association (NFPA) (National Fire Protection Association, Fire Hazard Properties of Flammable Liquids, Gases, and Volatile Solids, NFPA 325, Quincy, Mass.). Pressure particularly affects flash point and the upper flammable limit (UFL); see later section entitled “Effect of Temperature, Pressure, and Oxygen.” Mists of high-flash-point liquids may be flammable; the lower flammable limit (LFL) of fine mists and accompanying vapor is about 48 g/m3 of air, basis 0°C and 1 atm (0.048 oz/ft3). For practical purposes, LFL is the same as lower explosive limit (LEL). (Ignitability limits depend upon the strength of the ignition source; the ignitability range for relatively weak ignition sources is less than the flammable range.) LFLs in percent by volume generally decrease as molecular weight increases.

Limiting Oxidant Concentration (LOC)
It is often prudent to base explosion prevention on inerting. The LOC is the concentration of oxidant—normally oxygen—below which a fuel-oxidant explosion cannot occur. (The LOC is also called MOC, the minimum oxygen for combustion.) With adequate depletion of oxygen, an explosion cannot occur whatever the concentration of fuel. Nevertheless, in these circumstances a fuel–air–inert gas mixture may become flammable if
sufficient air is added. Many LOCs are given in NFPA 69. In general, organic flammable gases or vapors will not propagate flame in mixtures of the organic, added nitrogen, and air below about 10.5 percent by volume O2 at 1 atm and near normal room temperature. Hydrogen (LOC = 5 percent) and some other inorganic gases have lower LOCs. For LOCs of 5 percent and greater, the O2 concentration should not exceed 60 percent of the LOC, but with continuous monitoring the O2 may be kept 2 percent below the LOC (NFPA 69, 1992). Neutronics, Inc., of Exton, Pennsylvania, supplies an inerting control system that has had wide application in many industries.Explosion prevention by inerting has several advantages over explosion protection techniques, such as explosion venting. For example, with successful inerting, fires or business interruptions cannot occur. Nevertheless, beware of the potential of asphyxiation with inerting; proper vessel entry procedures must be implemented and occasionally it may be prudent to monitor for oxygen in workplaces.

Explosion Pressure An explosion
Is the action of “going off ” with a loud noise under the influence of suddenly developed internal energy. Thus, an explosion is a result, not a cause. Deflagrations and detonations cause chemical explosions. A deflagration is a reaction that propagates to the unreacted material at a speed less than the speed of sound in the unreacted material. A detonation is a reaction that propagates to the unreacted material at a speed greater than the speed of sound in the unreacted material; it is accompanied by a shock wave and inordinately high pressure.

Explosion Protection
Where prevention of flammable mixtures may not be feasible, protection facilities must be installed; sometimes, too, backup explosion protection facilities are used in conjunction with inerting systems. Containment, suppression, or venting are used for protection against internal deflagrations in fuel-air mixtures.Although these methods may protect against deformation or rupture of a vessel, damage to internal appurtenances may still occur. Containment and suppression prevent the discharge of environmentally unacceptable materials to the atmosphere.

Pumps and Gaskets

Fugitive emissions often occur as a result of leakage of process materials through leak paths in rotating seals and susceptible gasketed joints such as are found in pipe flanges. When properly maintained, fugitive emissions from most conventional joints and sealing systems used in industry can be kept to a minimum. For volatile organic compounds (VOCs) this is usually significantly less than 500 ppm as measured at the leak path by a portable VOC analyzer specified in USEPA reference method 21 (40 CFR 60, Appendix A, Method 21). However, for some sealing systems such as packing glands on pump shafts in some services, the necessary maintenance frequency and potential risks of noncompliance have caused some companies to eliminate them from services where fugitive emissions are a concern and use tighter sealing systems such as mechanical seals instead. In services where entrained solids or fouling are not present to a significant extent and additional cost is justified, magnetic drive and canned-motor pumps, which have become more reliable and available in a wide variety of configurations and materials, are being used to virtually eliminate fugitive emissions from pumps. In services where fugitive emissions are a concern, valves such as quarter turn, diaphragm seal, or bellows seal valves, which are less susceptible to leakage, are sometimes being used in place of gate or globe valves with packed stem seals.

However, under many service conditions, high-cost equipment options are not necessary to comply with the provisions of fugitive emission regulations. Properly maintained packing glands or single mechanical seals on valves and pumps can often meet all emissions requirements. An informed choice should be made when specifying new valves and pumps, considering factors such as the type of service, accessibility for maintenance, cost, and the degree of emission reductions which may be achieved. The most common maintenance problem with centrifugal pumps is with the seals. Mechanical seal problems account for most of the pump repairs in a chemical plant, with bearing failures a distant second. The absence of an external motor (on canned pumps) and a seal is appealing to those experienced with mechanical seal pumps. Sealless pumps are very popular and are widely used in the chemical industry. Sealless pumps are manufactured in two basic types: cannedmotor and magnetic-drive.

Magnetic-drive pumps have thicker “cans,” which hold in the process fluid, and the clearances between the internal rotor and can are greater compared to canned-motor pumps. This permits more bearing wear before the rotor starts wearing through the can. Many magnetic-drive pump designs now have incorporated a safety clearance, which uses a rub ring or a wear ring to support the rotating member in the event of excessive bearing wear or failure. This design feature prevents the rotating member (outer magnet holder or internal rotating shaft assembly) from accidentally rupturing the can, as well as providing a temporary bearing surface until the problem bearings can be replaced. Because most magnetic-drive pumps use permanent magnets for both the internal and external rotors, there is less heat to the pumped fluid than with canned-motor pumps. Some canned-motor pumps have fully pressure-rated outer shells, which enclose the canned motor; others don’t. With magnetic-drive pumps, containment of leakage through the can to the outer shell can be a problem. Even though the shell may be thick and capable of holding high pressures, there is often an elastomeric lip seal on the outer magnetic rotor shaft with little pressure containment capability. Canned-motor pumps typically have a clearance between the rotor and the containment shell or can, which separates the fluid from the stator, of only 0.008 to 0.010 in (0.20 to 0.25 mm). The can has to be thin to allow magnetic flux to flow to the rotor. It is typically 0.010 to 0.015 in (0.25 to 0.38 mm) thick and made of Hastelloy.

The rotor can wear through the can very rapidly if the rotor bearing wears enough to cause the rotor to move slightly and begin to rub against the can. The can may rupture, causing uncontrollable loss of the fluid being pumped. It should not be assumed that just because there is no seal, sealless pumps are always safer than pumps with seals, even with the advanced technology now available in sealless pumps. Use sealless pumps with considerable caution when handling hazardous or flammable liquids. Sealless pumps rely on the process fluid to lubricate the bearings. If the wear rate of the bearings in the fluid being handled is not known, the bearings can wear unexpectedly, causing rupture of the can. Running a sealless pump dry can cause complete failure. If there is cavitation in the pump, hydraulic balancing in the pump no longer functions and excessive wear can occur, leading to failure of the can. The most common problem with sealless pumps is bearing failure, which occurs either by flashing the fluid in the magnet area because of a drop in flow below minimum flow or by flashing in the impeller eye as it leaves the magnet area. It is estimated that nine out of ten conventional canned-motor pump failures are the result of dry running. Canned pumps are available which, their manufacturer claims, can be operated dry for as long as 48 h. It is especially important to avoid deadheading a sealless pump. Deadheaded sealless pumps can cause overheating. The bearings may be damaged and the pump may be overpressured. The pump and piping systems should be designed to avoid dead spots when pumping monomers. Monomers in dead spots may polymerize and plug the pump. There are minimum flow requirements for sealless pumps. It is recommended that a recirculation system be used to provide internal pump flow whenever the pump operates. Inlet line filters are recommended, but care must be taken not to cause excessive pressure drop on the suction side. Typical inlet filters use sieve openings of 0.0059 in (0.149 mm).

For many plants handling monomers and other hazardous materials, sealless pumps are the first choice. They can practically eliminate the pump problems that can occur due to seal leaks, which can include product loss, flammability, waste disposal, and exposure of personnel to hazardous vapors. A number of liquids require special attention when applying canned-motor and magnetic-drive pumps. For example, a low-boiling liquid may flash and vapor-bind the pump. Solids in the liquid can also be bad for a sealless pump. Low-viscosity (in the range of 1 to 5 cP [1 ´ 10-3 to 5 ´ 10-3 Ns/m2]) fluids are normally poor lubricators and one should be concerned about selecting the right bearings. For viscosities less than 1 cP, it is even more important to choose the right bearing material. The Dow Chemical Company recommends canned-motor pumps or magnetic-drive pumps for phosgene service. Phosgene is an example of an extremely hazardous material. These pumps should have a secondary containment such that failure of the can does not create a phosgene release. The secondary containment should meet pipe specifications for pressure or relieve to the scrubber system in the plant. These pumps must have automated block valves on the suction and discharge. Operation of these valves should be managed such that the thermal expansion does not damage the pump. A mistreated sealless pump can rupture with potentially serious results. The can can fail if valves on both sides of the pump are closed and the fluid in the pump expands either due to heating up from a cold condition or if the pump is started up. If the pump is run dry, the bearings can be ruined. The pump can heat up and be damaged if there is insufficient flow to take away heat from the windings. Sealless pumps, especially canned-motor pumps, produce a significant amount of heat, since nearly all the electrical energy lost in the system is absorbed by the fluid being pumped. If this heat cannot be properly dissipated, the fluid will heat up with possibly severe consequences. Considerable care must be used when installing a sealless pump to be sure that misoperations cannot occur.

The instrumentation recommended for sealless pumps may seem somewhat excessive. However, sealless pumps are expensive and they can be made to last for a long time, compared to conventional centrifugal pumps where seals may need to be changed frequently. Most failures of sealless pumps are caused by running them dry and damaging the bearings. Close monitoring of temperature is necessary in sealless pumps. Three temperature sensors (resistance temperature devices, or RTDs) are recommended: (1) in the internal fluid circulation loop, (2) in the magnet, or shroud, area, and (3) in the pump case area. It is very important that sealless pumps be flooded with liquid before starting, to avoid damage to bearings from imbalance or overheating. Entrained gases in the suction can cause immediate imbalance problems and lead to internal bearing damage. Some type of liquid sensor is recommended. Sealless pumps must not be operated deadheaded (pump liquid full with inlet and/or outlet valves closed). Properly installed and maintained, sealless pumps, both canned and magnetic-drive, offer an economical and safe way to minimize hazards and leaks of hazardous liquids.

Combustion: Gas Characteristics and Sensitivity

Combustion thermodynamic calculations allow determination of peak deflagration and detonation pressures, plus stable detonation velocity. The peak pressure calculation may be used to determine combustion product venting requirements, although a conservative volume increase of 9:1 may be used for essentially closed systems. Other relevant gas characteristics are entirely experimental. The sensitivity to detonation depends on the detonatable range and fundamental burning velocity, although no specific correlations or measures of sensitivity exist based on fundamental properties. It is often considered that detonation sensitivity and the degree of difficulty in arresting flames increase with lower National Electrical Code (NEC) Groupings. Hence, Group A gases (acetylene) will be most sensitive and Group D gases (such as saturated hydrocarbons) will be least sensitive. This empirical method of characterizing gases is typically used in selecting deflagration arresters, where successful testing using one gas in an NEC electrical group is assumed to apply for other gases in that group. It is cautioned that, where the maximum experimental safe gaps (MESGs) of two gases within a single NEC group are significantly different, the assumption of equivalent sensitivity is dubious.

Regulations applying to detonation arresters in vapor control systems under the authority of the U.S. Coast Guard (USCG) provide that MESGs be solely used to characterize gases, under the assumption that mixtures with smaller MESGs are more difficult to stop. See “Deflagration and Detonation Flame Arresters,” (1993) for a discussion of MESG plus tabulated values.

Corrosion

Consideration should be given to possible corrosion of both the element material and the arrester housing, since corrosion may weaken the structure, increase the pressure drop, and decrease the effectiveness of the element. While the housing might be designed to have a corrosion allowance, corrosion of the element must be avoided by proper material specification. Common materials of construction include aluminum, carbon steel, ductile iron, and 316 stainless steel housings and aluminum or 316 stainless steel elements.

While special materials such as Hastelloy might be used for situations such as high HCl concentrations it may be more cost effective to use a hydraulic arrester in such applications.