Safety

Mitigate Venting Hazards by Steam Injection

Victor H. Edwards, Lee L. Hu, Ben D. Ababio, Steve E. Jones and Michael C. Livingston, Kvaerner Engineers and Constructors Andrea B. Cavalier and Norman Thompson, Sr. DuPont

Safe atmospheric venting can be achieved by using very tall stacks. A more practical approach can be using a shorter stack and injecting steam into the vented vapors to facilitate dispersion.
and when they are hazardous, then it is usually advisable to install containment and treatment systems. This is particularly true when the uids contain environmentally persistent compounds. However, there are processes that have never or only rarely experienced a pressure relief event, and the process uids are not environmentally persistent. In such cases, atmospheric venting can offer a safe and economical approach. Use of the environment to dispose of rare pressure-relief discharges of biodegradable compounds may be a prudent use of natural resources. Atmospheric venting may have a lesser environmental impact than the commitment of human and other natural resources to the creation of a large, costly and seldom-used treatment system. This approach is somewhat analogous to the choice of natural attenuation (when it is the best choice) for remediation of contaminated soil and groundwater (12). Whenever atmospheric venting of hazardous materials is considered, a simplied quantitative consequence analysis should be performed. This analysis should evaluate the potential effects, where applicable, of the following (2, 4, 7): vapor cloud explosion thermal radiation from continuous burning of the vented vapors impingement on nearby equipment by a jet ame a ash re toxic gas exposure. The components of the uids to be relieved should

he chemical engineering industries (CEI) use processes that release or transfer very large amounts of energy. Process upsets, such as external re exposures, can result in high rates of uncontrolled transfer of thermal energy into equipment, thereby vaporizing liquids that may result in emergency venting. Since equipment seldom has the holding capacity for these large volumes, equipment must either contain the vapor by compressing to high pressures or the vapor must be vented to prevent excessive pressures from building up within the process equipment (1, 2). A typical process plant relies upon dozens to hundreds of pressure relief systems to prevent excessive overpressures. Gases and liquids discharged from pressure-relief systems are usually rst separated in a gas/liquid separator (1, 2) because the liquid of a typical two-phase release could be more than half of the mass produced. Conversely, large volumes of vented gases almost always require that they be either treated or directly released to the atmosphere. These gases may be hazardous by virtue of toxicity and/or ammability (1, 38). Direct atmospheric venting of ammable gases poses a number of potential hazards, including thermal radiation from an ignited release, engulfment in a reball, and vapor cloud explosions (2, 4, 9, 10). Delayed ignition of a vapor cloud allows wind to transport the cloud hundreds of feet from the source before a ash re or a vapor cloud explosion occurs (11). When process uids must be released frequently,

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also be evaluated for non-persistence in the environment. Unfortunately, the quantitative consequence analysis is often not done. Therefore, we will present a detailed method for conducting this important step.

Steam Supply

Relief Outlet Piping Relief Valve

FC PS1

Consequence analysis Methods for conducting a simplied quantitative consequence analysis are outlined here and illustrated with a practical example. Because the concentrations of heavy and hazardous organics may be high in relieved uids, safe venting may require tall stacks, because the heavy gases are denser than air. By use of steam injection, the relieved gas stream can be made more buoyant and less concentrated, and the gases may be vented at a higher velocity, favoring better dispersion. And steam injection systems cost much less than endof-pipe treatment systems such as ares or scrubbers. However, one potential drawback of this method is that the steam consumption and the instantaneous steam demand may result in additional relief valves lifting. Another disadvantage may be the possibility of partial condensation at high ratios of steam-to-vented hazardous gas, particularly during humid weather. But, with the proper system design, these problems can be overcome. Fluids exiting a relief valve are subject to mechanical shear. The greater the pressure differential between the process uid and the atmosphere, the greater the shear. If the uid is a gas, then the shearing action translates into additional turbulence. For a liquid, the shearing action may be enough to atomize all or part of the uid, producing a mist or an aerosol. When a large amount of a volatile, ammable material is rapidly dispersed to the atmosphere, a vapor cloud forms and disperses (4). A lighter-than-air cloud may dissipate with little or no ground-level impact. If the cloud is heavier, it will fall to the ground before it can dissipate. Vapor clouds contacting an ignition source, such as static electricity, can produce a deagration, which generally results in a ash re. A ash re can also migrate back to the release point and ignite the vapor at the discharge of the relief valve tail-pipe, if the relieving conditions continue unmitigated. Two important mechanisms for ame acceleration are thermal expansion and turbulence. Process structures contribute to partial connement and turbulence. Thus, if many pieces of process equipment and other structures are present, it is likely that a ash re will make the transition to an unconned vapor-cloud explosion (UVCE) (4). If the cloud is toxic, plant personnel and civilians in the surrounding areas may be subjected to harmful concentrations of the material. Various exposure limits have been published for hazardous materials. These include the timeweighted averages (TWAs) for exposures up to 10-h in a workday during a 40-h work week, the short-term exposure limit (STEL) for a 15-min TWA exposure, and the thresh-

To High-Pressure Alarm
PS2

Protected Vessel

To High-Pressure Alarm Legend: PS1 = Pressure transmitter or pressure switch that senses pressure in presure-relief outlet piping. PS2 = Pressure transmitter or pressure switch that senses pressure in protected vessel. FC = Flow controller that turns on steam whenever either PS1 or PS2 detects high pressure.

s Figure 1. Pressure-relief system augmented by steam injection increases

dispersion.

old limit values (TLVs) for 8-h TWA concentrations. For exposures of brief duration, the STEL and the immediately dangerous to life and health (IDLH) concentrations for a 30-min exposure have often been used.

Rainout Aerosols containing large-diameter particles released in atmospheric conditions favorable for condensation may produce rainout. Aerosol rainout can result in a liquid pool adjacent to the release point or at some distance downwind, depending upon the meteorological conditions. The liquid pool can absorb heat from the environment and vaporize, contributing to the initial vapor cloud or can continue producing a lower-concentration cloud after the relief valve release has been mitigated. If the material is ammable, the liquid pool can be ignited and form a pool re. Modern consequence analysis tools, such as the PHAST (Process Hazards Analysis Software Tool) program (from DNV Risk Management Software, Oslo, Norway), can quantitatively model rainout phenomena. Toxic exposure criteria The American Industrial Hygiene Associations (AIHA) Emergency Response Planning Guidelines (ERPG) lists exposure concentrations for 77 hazardous materials (13). The AIHA categorizes expsoure into the following levels:
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s Figures 24 (left to right;a is top gure; b is bottom). Wind speed = 1.5 m/s; F stability atmosphere; Compound A = 160,000 lb/h; Steam injection =
16,000 lb/h (lower gures only); Figure 2: Weather 1 Sunny day; Figure 3: Weather 2 Winter day; Figure 3: Weather 3 Design winter day. KEY s 5ppm, s 75ppm, s 500, ppm s 1E3 ppm

ERPG-3 The maximum airborne concentration points for offsite consequence analysis. The RMP rule also below which it is believed nearly all individuals could be stipulates use of a 1.5 m/s wind speed and Class F atmoexposed for up to 1-h without experiencing or developing spheric stability for the worst case scenario. life-threatening health effects. Modeling methodology ERPG-2 The maximum airborne concentration below which it is believed nearly all individuals could be exposed The PHAST program can be set up to use multiple for up to 1-h without experiencing or developing irreversible different wind-speed/stability-class combinations for or other serious adverse health effects or symptoms that each model run. The program also contains ERPG, could impair an individuals ability to take protective action. IDLH and STEL concentrations for the toxic materials ERPG-1 The maximum airborne concentration below which it is believed Table 1. Steps in the design of a safe atmospheric-dispersion system. nearly all individuals could be exposed 1: Evaluate the potential hazards of the current or proposed (for a new facility) Step for up to 1-h without experiencing, otheratmospheric-venting system. than mild, transient adverse health effects 2: If the existing system presents unacceptable atmospheric venting hazards, or without perceiving a clearly dened Step determine the feasibility of achieving safe venting by modifications to the vent objectionable odor. system. When the EPA nalized its Risk Man3: If reasonable changes in vent elevation and outlet size alone are insufficient, Step agement Program (RMP) rule, ERPG-2 evaluate steam injection as a means to achieve safe atmospheric venting. values were identied as the toxic end-

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Table 2. Steps in the analysis of the consequences of atmospheric venting from a new pressure-relief system. input into the program. (PHAST has the data for 59 common chemicals.) Step 1: Define credible relief scenarios for a pressure-relief system. The user can manually enter physical Step 2: Size the relief valve orifice or the rupture disk diameter adequately to relieve the controlling relief scenario. and chemical properties for additional Step 3: Design the inlet piping to the relief device and the outlet piping from the materials. relief device to the atmosphere, including a vapor-liquid separation device if the To demonstrate the use of steam in relief system may be required to discharge liquids or two-phase mixtures. mitigating potential ground-level Step 4: Assure that the proposed new system will vent at the minimum safe elevation for personnel protection from the direct effects of the relief system ERPG-2 impacts from relie-valve disdischarge. (Typical criteria are that the vent outlet is at least 10 ft above the charges to the atmosphere, an example nearest walkway or platform where personnel might be found.) Also, be certain of a hazardous material release is prethat noise insulation is provided where necessary. sented. The results are shown for releas- Step 5: Conduct process simulations of atmospheric dispersion for the major credible relief or blowdown scenarios with the existing atmospheric-venting system. es with and without steam injection, Evaluate the following potential process hazards: (1) thermal radiation from a using input data from the process simusteady burning of the vented gases; (2) hazards from a fireball caused by ignition lation-package Aspen Plus. This softof a vapor cloud; (3) explosion overpressure from deflagration of a vapor cloud ware predicts the relief conditions for formed by atmospheric release; and (4) atmospheric dispersion of toxic gas. the mixture of fluid and injected steam, since PHAST is not programmed to combine two fluid streams prior to release to the atmosphere. Table 3. Steps toward achieving the safest atmospheric venting from a new The major steps for designing a safe ator existing pressure-relief system. mospheric-dispersion system are listed in Step 1:Examine the root cause of the worst credible relief-venting case to see if Table 1. Table 2 outlines the key steps in pressure-relief venting can be prevented by controlling the source of energy that for evaluating the consequences of atmois powering the pressure-relief event. Propose instrumentation and controls to spheric venting from a new pressure-relief prevent relief venting whenever that approach is practical. For cases that cannot system (2, 4). There are many existing rebe effectively prevented or mitigated by instrumentation and controls, proceed lief systems that vent hazardous uids for with the steps below. Step 2: Using the appropriate consequence-modeling software, predict the which not all of these steps have been folconsequences of atmospheric venting if the vent-stack outlet-diameter is decreased. lowed. The adequacy of these systems can (Note: decreasing the tip diameter of the vent stack is usually more effective in be evaluated by a similar procedure. Likeimproving dispersion than increasing stack elevation.) wise, the safety of atmospheric venting by Step 3: The allowable pressure drop in the pressure-relief outlet piping determines existing or proposed pressure let-down the minimum allowable tip diameter of the vent stack. Step 4: For a pressure-relief-valve discharge, the allowable outlet pressure drop systems can be evaluated by an analogous is 10% of the set pressure (expressed as gage pressure) for conventional relief method. valves. For balanced bellows pressure relief valves, the allowable outlet pressure Table 3 summarizes the steps in evaludrop is typically about 40% of the set pressure. (Determine the exact backpressure ating the feasibility of achieving safe atallowable for a given relief-valve model by consulting with the manufacturer and mospheric venting of relief discharges by referring to the manufacturers catalog.) modifying a new or existing vent system. Step 5: For relief discharge through a burst rupture disk, the smallest allowable relief outlet diameter is determined by confirming that the relief piping, including the burst These steps should be followed when an rupture disk, will permit the required maximum-credible relieving flow through the existing or proposed new system has been relief system without exceeding the maximum allowable overpressure in the found to create unacceptable hazards durprotected equipment. ing pressure-relief venting. Step 6: To optimize atmospheric venting at a given stack elevation, consider using The best approach is to prevent presoutlet relief piping that is one line size larger than necessary up to the outlet tip of the relief system. This maximizes the allowable pressure loss across the outlet, sure-relief venting. This may be feasible thereby minimizing the outlet-tip diameter and maximizing the outlet velocity and for many relief scenarios. For example, plume rise. when relief venting from a distillation col Step 7: The discharge-piping tip should be gradually tapered from the upstream pipe umn is caused by loss of condensing, indiameter down to the tip diameter to promote smooth flow and maximize plume rise. strumentation and controls can be provided Step 8: If decreasing the vent-tip diameter does not result in adequate dispersion, to shut off steam to the reboiler. Dependthen repeat the dispersion calculations for higher stack-tip elevations. Step 9: If practical changes in vent elevation and vent outlet size alone are ing upon the process dynamics of the coninsufficient, evaluate steam injection as a means for safe atmospheric venting. trolled system, pressure-relief venting will be either prevented completely or limited to a brief release. However, many relief scenarios cannot be eliminated by instrumentation and conboundaries. In those cases, Table 3 recommends a procetrol systems; examples include runaway reactions, external dure for developing a safe atmospheric venting system. re exposure and some cases of failure of internal-pressure Because higher vent-tip velocities give much higher

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in the relief discharge piping, following the guidelines in Table 3. This assumes that the initial stack-tip elevation is al Step 1: If changes in vent elevation and outlet size alone are insufficient, evaluate ready high enough to avoid any adverse steam injection as a means to safe atmospheric venting. effects on personnel near the relief system Step 2: Calculate the minimum steam injection rate that will decrease the density of when it discharges. the vented mixture of injected steam plus the relieved hazardous gas to a value less than the density of ambient air. Call this steam rate Sr. If using a small vent-tip diameter with Step 3: Compute the temperature, pressure and composition of the vented mixture of a conventional relief valve does not give injected steam plus relieved gas for several steam rates varying from no steam to 1.5 Sr. Correct use of a process simulator makes these calculations simple and accurate. adequate dispersion, then choose a balanced-bellows relief valve (or consider Step 4: Conduct a quantitative consequence analysis for each of the vented mixtures from the previous step. Begin at the lowest steam rate. Stop when a steam rate is buying a bellows conversion kit for an exfound that effectively mitigates the release. isting conventional relief valve). This will Step 5: Recalculate the total pressure losses in the relief outlet piping. The total gas permit a further increase in the relief-tip flowrate upstream of the steam piping entry point = (relief rate of hazardous gas), discharge-velocity by use of a smaller tip, while total gas flowrate downstream of the steam piping entry point = (relief rate of hazardous gas) + (steam injection rate). which, in turn, is allowed by the higher re Step 6: If the total pressure losses in the relief outlet piping are unacceptably high, lief-piping outlet-pressure-loss. If this modify tip diameter (and also the outlet-piping diameter, if necessary) to achieve maximum tip velocity still has not providacceptably low pressure losses. Increase the steam-injection rate, if necessary, to ed adequate atmospheric dispersion, then achieve an acceptable risk reduction, and if required by a larger tip diameter of relief outlet piping. consider increasing the stack-tip elevation. However, if a narrowed relief-tip diameter and an elevated stack adequately Table 5. Characteristics of Compound A and of the purification column. mitigate the worst-credible relief case, then consequence analysis calculations should Molecular weight of Compound A = 86 also be conducted for lower venting rates Lower flammable limit = 2.6% Upper flammable limit = 13.4% associated with other credible relief cases. ERPG-1 = 5 ppm; ERPG-2 = 75 ppm; ERPG-3 = 500 ppm (by volume) This is because the lower relief-tip veloci(Based on 60 min exposure time) ties may give less-effective dispersion for Set pressure of purification column relief-valve = 20 psig lower venting rates. Vent-tip elevation = 115 ft, pointed vertically Relief valve tail-pipe length = 30 equivalent ft If changes in vent outlet-piping tipVent-tip dia. = 12 in. size and in tip elevation alone do not mitiMaximum allowable pressure-drop in relief discharge piping = 8 psig gate pressure relief discharges adequately, (40% of set pressure for balanced-bellows relief valve) then steam injection should be considered Release duration = 10 min* Optional release duration = 60 min (Table 4). Design concepts for a steam injection system are outlined in the next secNotes: tion of this article. Steam injection pro* Release duration includes time for operators to acknowledge cause(s) of release and mitigate the cause(s), per EPAs Risk Management Program Offsite Consequence Analysis Guidance vides the following benets: document (for releases of 10 min or less). dilutes vented organics Relief valve discharged modeled as User Defined Source. User Defined Source was based on usually decreases the average molecASPEN PLUS simulation of mixture of Compound A plus steam for steam injection cases. ular weight and density of the vented stream Table 6. Credible overpressure scenarios for the purification column. often increases the temperature of the vented stream, thereby decreasing its denScenario Relieving Components of Relief pressure in sity further Flowrate, lb/h Relieved Fluid column A1, psig may decrease the risk of condensation Loss-of-condensing 160,000 Compound A 22 of vented vapors External fire exposure 12,000 Compound A 24 increases the tip velocity in the outlet of the relief piping, thereby increasing Reboiler tube rupture 13,200 Compound A plus steam 22 plume rise. Although no credit is taken for this efSteam cleaning by 8,500 Steam 22 water boilup: loss-offect, a properly designed steam-injection condensing system, using high-velocity injection directed upward near the outlet of the relief plume rises for vented gases, the quickest way to nd the piping, may help to act as an ejector to give an even highbest venting conditions is to rst determine the smallest er vent velocity, a better plume rise and an increased vent-tip diameter that will give acceptable pressure losses atmospheric dispersion.
Table 4. Steps in the design of a steam injection system to mitigate hazardous pressure-relief discharges.

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s Figures 57 (left to right;a is top gure; b is bottom). Wind speed = 1.0 m/s; D stability atmosphere; Compound A = 160,00 lb/h; Steam injection =
16,000 lb/h (lower gures only. Figure 5: Weather 1 Sunny day; Figure 6: Weather 2 Winter day; Figure 7: Weather 3 Design winter day. KEY s 5ppm, s 75ppm, s 500, ppm s 1E3 ppm

Figure 1 is a schematic of a typical steam injection system. Steam is supplied to the relief-outlet piping through a control valve. The valve is opened by the ow controllerFC, whenever a high pressure is sensed either in the relief outlet piping by pressure switch (or pressure transmitter) PS1, or in the protected vessel by pressure switch (or pressure transmitter) PS2. The vent tip of the relief-outlet piping is pointed vertically upward and is tapered to give the maximum exit velocity. The steam is injected vertically along the centerline of the relief-outlet piping. The use of redundant pressure sensors, in conjunction with a control strategy that turns on the steam when either sensor deModel Case tects a high pressure, increases the reliability of the injection system. More imporCF-1 tantly, using independent pressure sensors CF-2 at two different locations improves funcF-1 tionality. Pressure sensor PS1 in the reliefF-2 outlet piping ensures that steam will be in-

jected into the system discharge whenever the relief device is venting to the atmosphere. In that way, steam will be injected when venting is occurring during abnormal conditions. For example, if the spring in the relief valve breaks during pressure relief, or if the blowdown setting on the relief valve is incorrect, the relief valve may not reclose at the intended pressure. PS1 ensures that steam injection will continue as long as relief venting is occurring, despite a column pressure below the setting where PS2 would indicate to FC to stop steam injection.
Table 7. Model scenarios. Compound A, lb/h 160,000 160,000 12,000 12,000 Steam, lb/h Figures 0 16,000 0 16,000 Corresponding Figures 2a10a, 21a22a 2b10b, 21b22b 11a19a 11b19b

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s Figures 810 (left to right;a is top gure; b is bottom). Wind speed = 5.0 m/s; D stability atmosphere; Compound A = 160,00 lb/h; Steam injection = 16,000 lb/h (lower gures only. Figure 8: Weather 1 Sunny day; Figure 9: Weather 2 Winter day; Figure 10: Weather 3 Design winter day. KEY s 5ppm, s 75ppm, s 500, ppm s 1E3 ppm Pressure sensor PS2, which detects the column pressure, will start steam injection just before the relief valve opens. This alerts personnel that pressure relief is about to begin, so that they can leave the area. It also establishes an upward ow of air near the vent tip before venting begins. This updraft should improve dispersion of the hazardous vapors during the initial period of venting.
Table 8. Weather conditions. Weather Designation Parameters Ambient Temperature, F Relative Humidity, % Surface Temperature, F Wind Speed and Stability 1 Sunny Day 77 76 82 Velocity, m/s 1.5 1.0 5.0 2 Winter Day 35 76 40 Stability Class F D D

Practical application of steam injection Consider a distillation column of moderate size that is used to purify Compound A. Table 5 summarizes the characteristics of the pressure-relief venting system and Compound A. Table 6 lists the various credible pressure-relief events that could lead to atmospheric releases. Because the mixture within the column only contains small amounts of impurities, the vented mixture is modeled as pure Compound A. Consequence modeling was done using Version 6.0 of PHAST. The program provides quantita3 tive estimates of a variety of potential adDesign Winter Day verse consequences of the release of a 35 ammable and toxic chemical or mixture. 100 40 Consequences of the rst two relief events listed in Table 6 (loss of condensing and external re exposure) were modeled because they would lead to the highest concentrations of Compound A. For

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s Figures 1113 (left to right;a is top gure; b is bottom). Wind speed = 1.5 m/s; F stability atmosphere; Compound A = 12,00 lb/h; Steam injection =
16,000 lb/h (lower gures only. Figure 11: Weather 1 Sunny day; Figure 12: Weather 2 Winter day; Figure 12: Weather 3 Design winter day. KEY s 5ppm, s 75ppm, s 500, ppm s 1E3 ppm

comparison, consequence modeling was also done for each of those two cases mitigated with steam injection at a constant rate of 16,000 lb/h. Table 7 summarizes the specic model scenarios. Because the Aspen Plus simulation predicted that small amounts of condensate could be formed during steam-mitigated pressure relief and during humid weather, PHAST simulations were carried out using the nonequilibrium rainout option. Three types of weather conditions were modeled for several wind velocities and stability classes. The conditions are summarized in Table 8. Results are summarized in Figures 2 through 4 and Figures 11 through 13 for the F-type atmospheric stability and a wind speed of 1.5 m/s. (Note; for Figures 221, a refers to the upper part of the gure, and b to the lower part.) These conditions are the same as those required to be modeled for preparing risk management plans under the EPAs RMP. The F-stability atmosphere is considered a moderately stable condition, with minimum turbulence and the air

stratied near the ground. It is commonly found during calm nighttime conditions with little or no cloud cover. This type of stability rarely occurs near small islands or offshore installations. The F stability conditions modeled here are relatively unfavorable for atmospheric dispersion and are often treated as worst-case credible atmospheric conditions. In the example results shown in Figures 2a through 4a, a 10-min release due to loss of condensing at the high relief rate of 160,000 lb/h would result in 60-min averaged concentrations of Compound A, exceeding the ERPG-2 level of 75 ppm for a substantial region downwind for all three weather designations. However, injection of 16,000 lb/h of steam greatly reduces ground-level exposure concentrations to well below the ERPG-2 level (Figures 2b through 4b). Figures 11a through 13a show that for the reduced rate of venting of Compound A (12,000 lb/h) that would occur with the re exposure case, ERPG-2 levels are reached at grade for only a very small region, even without steam injection. Steam injection for these three cases lifts

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s Figures 1416 (left to right;a is top gure; b is bottom). Wind speed = 1.0 m/s; D stability atmosphere; Compound A = 12,000 lb/h; Steam injection =
16,000 lb/h (lower gures only. Figure 14: Weather 1 Sunny day; Figure 15: Weather 2 Winter day; Figure 16: Weather 3 Design winter day. KEY s 5ppm, s 75ppm, s 500, ppm s 1E3 ppm

the ERPG-2 zone to above the vent stack tip of 115 ft in all three weather designations (Figures 11b through 13b). Other choices (for example, D-type atmospheric stability and a wind speed of 1.0 m/s) are possible and would give somewhat different results. D stability is considered neutral, with no thermal or vertical mixing currents produced by solar heating during windy daytime conditions. This stability can also be typical of nighttime conditions with overcast or low-level cloudiness. Figure 5 shows that, although steam injection of 16,000 lb/h helps to disperse Compound A in the loss-of-condensing relief scenario, levels would still exceed ERPG-2 for a substantial zone downstream during a relief event during the sunny summer day conditions and low wind speed of Weather Designation 1. In contrast, Figures 6 and 7 show that steam injection would be effective in dispersing Compound A during the loss-of-condensing scenario under the winter day conditions of either Weather Designation 2 or 3. Figures 14 through 16 illustrate how the greater density of cool winter

air helps to elevate the dispersing plume. Wind speed also has a strong effect on dispersion. Figures 8, 9 and 10 show that, for the loss-of-condensing relief scenario, wind alone effectively disperses a 160,000 lb/h release sufficiently to prevent an ERPG-2 level from ever reaching ground. Figures 17, 18 and 19 demonstrate that, with steam injection for the relief scenario of external fire exposure, even the ERPG-1 level of 5 ppm of Compound A is not exceeded at grade level. Although the results presented above for a steam injection rate of 16,000 lb/h effectively mitigate the worst credible release of Compound A under F stability, steam injection does not adequately mitigate a release during D stability under Weather Designation 1. Therefore, higher steam rates were investigated. Figure 20 shows that increasing the steam injection rate to 24,000 lb/h lifts the ERPG-2 boundary to at least 50 ft above grade at all downwind locations. Figure 21 shows that

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s Figures 1719 (left to right;a is top gure; b is bottom). Wind speed = 5.0 m/s; D stability atmosphere; Compound A = 12,000 lb/h; Steam injection =
16,000 lb/h (lower gures only). Figure 17: Weather 1 Sunny day; Figure 18: Weather 2 Winter day; Figure 19: Weather 3 Design winter day. KEY s 5ppm, s 75ppm, s 500, ppm s 1E3 ppm

a further increase to 28,000 lb/h keeps the ERPG-2 level well above the stack tip at all downwind locations. Thus, the higher rate of 24,000 lb/h is selected, even though 16,000 lb/h is adequate to meet EPAs criterion of F stability.

Mitigation of ammability hazard The PHAST program provides quantitative prediction of vapor cloud dispersions, jet ames, pool res, BLEVEs and explosions. However, the program does not adequately calculate ammability limits when one of the major components is water. This does not affect the dispersion analysis predictions, but does require that the analyst override the ammability limits in the materials section before the model is run. The ammability limits in air of pure Compound A were used for the analysis. Only experimentation can determine the true ammability limits for Compound A when mixed with air and steam.

Loss-of-condensing results The ammability hazards for the current example are limited. A review of the various output reports indicates that the upper ammability limit (UFL) concentrations only extend a short distance from the discharge point (typically less than 1 ft), whether steam is injected or not. Apparently, the velocity and momentum jet-effects provide sufficient air entrainment to rapidly diffuse the mixture below the UFL concentration. And, the mass of steam is only 10% that of Compound A, so the impact of steam on the UFL is negligible. The downwind distances for the lower flammability limit (LFL) concentrations range from 510 ft from the discharge point. The one-half LFL concentrations a conservative value typically used to partially offset the possible effects of imperfect mixing that may give local concentrations higher than those predicted by the dispersion modeling algorithms range from 1426 ft. Again, no significant impacts were predicted when steam was injected in the relief-valve discharge pipe.
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Similarly, the LFL concentrations extended from 1326 ft from the release point. And, the one-half LFL concentrations extend out between 2653 ft. A jet ame might form. If it did, the length is predicted to range from 5097 ft for no steam injection. Such a ame could produce maximum thermal radiation intensities at grade of 4556 Btu/hft2, measured at 250 ft from the base of the stack. For the case of steam injection at 16,000 lb/h, thermal radiation intensities of only 811 Btu/hft2 are predicted. These intensities are not hazardous. No vapor cloud explosion results were predicted.

Key learnings from the example Note that the example uses a combined strategy for mitigating the various pressure-relief events. The worst-credible relief scenario is loss-of-condensing. It leads to a release rate of 160,000 lb/h of Compound A. This scenario dictates the size of the pressure-relief system. Use of a smaller vent tip, in combination with an elevated stack, is impractical. The required stack height would be approximately 200 ft above grade, more than 85 ft above the top of the distillation column. Injection of a large owrate of steam (24,000 lb/h) is required to achieve mitigation of this s Figures 20 and 21 (left to right;a is top gure; b is bottom). Wind speed = 1.0 m/s; D stability atscenario by steam injection. The injecmosphere; Compound A = 160,000 lb/h; Weather 1 sunny day. Steam injection = 24,000 lb/h (Figure tion system costs less than one-fourth of 20b) = 28,000 lb/h (Figure 21b) (lower gures only). the cost of an elevated stack. Such a KEY s 5ppm, s 75ppm, s 500, ppm s 1E3 ppm stack was also deemed impractical beIf the one-half LFL concentration-envelope were to cause the required guy wires would limit access to columns come in contact with an ignition source, a deagration and other equipment in the plant, especially during shutcould occur and propagate back to the release point, and downs. The elevated stack would also be an eyesore and a subsequently produce a jet ame. Under this scenario, the navigation hazard for aircraft. An end-of-pipe treatment jet ame could extend from 120185 ft from the source. system to scrub or are the relief effluent would have an Maximum thermal radiation intensities at grade are preinitial cost an-order-of-magnitude greater than an automatdicted to range from 320600 Btu/hft2 for the no-steam-inic steam injection system. jection cases, measured at 250 ft from the base of the stack. Interlocking-shut the steam supply to the reboiler for For the case of 16,000 lb/h steam injection, thermal radiathe column when high base-column pressure is detected tion intensities are predicted to range from 210390 will stop the pressure relief event either before it begins or Btu/hft2. These intensities are not hazardous. No vapor soon after it starts. Even if this interlock were not functioncloud explosion results were predicted. ing, operating personnel should be able to identify the cause of a column overpressure and manually shut off the Fire-case results steam to the reboiler within 10 min. The UFL concentrations were predicted to extend beThe base-column-pressure-interlock on reboiler steam tween 12 ft from the release point. Injection of steam does will also mitigate two other relief scenarios: (1) tube rupnot appear to signicantly alter the distances from the reture in the reboiler; and (2) loss of condensing during water lease point to the UFL concentration, even though the mass boilup during column cleaning. However, interlocking the of steam is 130% of the mass of Compound A. reboiler steam will not prevent pressure relieving during an

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Table 9. Environmental emissions from a flare used to treat pressure relief effluents. Basis: Conventional elevated flare external re exposure to the column. Tip dia. = 12 in. Nonetheless, in the re scenario, a compar3 continuous pilots; each consuming at 45 std ft3/h natural gas atively low steam injection rate of 16,000 Plant and flare in operation for 330 d/yr lb/h is more than adequate to decrease Purge gas is natural gas at flowrate = 0.25 ft/s (Equivalent to 700 std ft3/h of natural gas) grade-level concentrations of Compound A Natural gas cost = $3 per thousand std ft3 from near the hazardous 500 ppm ERPG-3 Flare and pilot combustion efficiency = 99.78% level to well below the acceptable 75 ppm Excess air in flare offgas = 50% ERPG-2 level. This is because the relief Carbon monoxide concentration in flare offgas = 3.2 ppm Total nitrogen oxides concentration in flare offgas = 8.2 ppm rate for the re scenario is only 12,000 lb/h Frequency of pressure relief event = once in 30 yr of Compound A. Although the plume rise Relief rate = 160,000 lb/h of Compound A due to velocity is much less than in the Relief duration = 10 min loss-of-condensing scenario, the high proSteam-mitigated atmospheric venting of emergency relief: portion of steam in the vented vapors One release of 27,000 lb of Compound A once in 30 yr greatly decreases the mean molecular (i. e., 10 min at 160,000 lb/h) weight and the density of the plume. Use of a combined strategy of both an Flared atmospheric release of emergency relief: One release of (1 0.9978) x 27,000 = interlock on the base-column pressure to 60 lb of Compound A once in 30 yr the reboiler steam, and an interlock on the Natural gas consumption = 200 million ft3 (during 30 yr operation) relief-outlet-piping pressure to steam injecCost of natural gas = $600,000 tion has another advantage. When an interCarbon dioxide emissions to atmosphere = 23 million lb (during 30 yr) Unburned hydrocarbon emissions = 19,000 lb (during 30 yr) mediate steam ow is injected automaticalCarbon monoxide emissions = 700 lb (during 30 yr) ly in response to an elevated pressure in Nitrogen oxide emissions = 1,800 lb (during 30 yr) the relief-outlet piping, it will mitigate those momentary relief discharges that Environmental implications might occur with scenarios other than the re case. This is important because the response time of the control system Any substantial releases to the environment are undesirto a pressure surge caused by loss of condensing or a tube able, and operating staff strive to keep plants running rupture may not be quick enough to prevent a brief relief smoothly and under control. Emergency-relief events are discharge of, at most, several minutes duration. If desired, just that emergencies. Pressure-relief systems are dedynamic process modeling could be used to quantitatively signed to prevent emergency situations from escalating to evaluate the combined response of the column relief and more hazardous conditions and even greater releases of promitigation systems. cess uids. One plant, which has a relief system similar to

Literature Cited
1. Center for Chemical Process Safety (CCPS), Guidelines for Pressure Relief and Effluent Handling Systems, CCPS, AIChE, New York (1998). 2. Edwards, V. H., et al., Guidelines for Pressure Relief System Modernization, in Proc. International Symposium on Runaway Reactions and Pressure Relief Design, G. A. Melhem and H. G. Fisher, eds., pp. 648667, AIChE, New York (1995). 3. Bravo, F., et al., Wisely Use Emergency Scrubbers with Vent Systems, Chem. Eng. Progress, 93 (8), pp. 6268 (Aug. 1997). 4. Center for Chemical Process Safety (CCPS), Guidelines for Chemical Process Quantitative Risk Analysis, CCPS, AIChE, New York (1989). 5. Ta-Cheng Ho, T.-C., et al., Case Studies of Incidents in Runaway Reactions and Emergency Relief, Proc. Safety Progress, 17 (4), pp. 25262 (Winter 1998). 6. LeVine, R., Guidelines for Safe Storage and Handling of High Toxic Hazard Materials, Center for Chemical Process Safety (CCPS), AIChE, New York (1988). 7. Prugh, R. W., and R. W. Johnson, Guidelines for Vapor Release Mitigation, Center for Chemical Process Safety (CCPS), AIChE, New York (1988).

8. Samdani, G. S., ed., Safety and Risk Management Tools and Techniques in the CPI, McGraw-Hill, New York (1996). 9. Bodurtha, F. T., Industrial Explosion Prevention and Protection, McGraw-Hill, New York (1980). 10.Nolan, D. P., Handbook of Fire and Explosion Protection Engineering Principles for Oil, Gas, Chemical, and Related Facilities, Noyes, Westwood, NJ (1996). 11.Lees, F. P., Loss Prevention in the Process Industries, three vols., 2nd ed., Butterworth-Heinemann, Oxford, U.K. (1996). 12.Swett, G. H., and D. Rapaport, Natural Attenuation: Is the Fit Right?, Chem. Eng. Progress, 94 (6), pp. 3743 (June 1998). 13. AIHA Emergency Response Planning Committee, Emergency Response Planning Guidelines, Stock Number 359-EA-99, American Industrial Hygiene Assn., Alexandria, VA (1999).

Acknowledgments
We thank Michael Henry for conducting the Aspen Plus simulations of vented mixed gases. Thanks also to Mike Butler and Dwane Stone for reviewing the manuscript. We gratefully acknowledge the support of this work by DuPont and by Kvaerner.

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the example illustrated here, has operated safely for more than 30 yr without a relief event in its purication column. Still, the potential environmental impact of a release should be compared with the environmental consequences of an end-of-pipe treatment system. A few approximate calculations are presented in Table 9 for a are system to destroy any pressure-relief effluents. Table 9 shows that a conventional elevated are would greatly reduce the emissions of Compound A if a relief event occurred. However, if past experience of 30 yr is indicative of future performance, then a are would impose substantial costs, both economic and environmental. One of the tasks of todays engineers is to work with the regulatory and environmental communities to nd the best choice among various options for emergency venting.

ronment as hazardous substances, and provided that releases to the environment are rare. If atmospheric venting is selected as the disposal method of choice, then a quantitative consequence analysis should be conducted to assure safety in atmospheric venting. If atmospheric venting could occur frequently, or if vented uids persist in the environment and cause harmful effects, then treatment and containment systems should be considered to prevent release. If an existing or proposed vent system presents unacceptable hazards, rst consider decreasing the outlet nozzle size and raising the stack height to improve safety. Typically,, these measures will not suffice, but steam injection into the outlet section of relief piping will often make relief CEP venting to the atmosphere safer.

Conclusions Atmospheric venting can be a safe and economical way of dispersing vapors relieved from processes during emergencies, provided the uids do not accumulate in the enviVICTOR H. EDWARDS is process director for Kvaerner Engineers and Constructors (7909 Parkwood Circle Dr., Houston, TX 77036; Phone: (713) 270-2817; Fax: (713) 270-3650; E-mail: vic.edwards@kvaerner.com). He leads process engineering, environmental engineering and process safety management for the engineering projects done for DuPont sites on the U.S. Gulf Coast as an alliance engineering contractor. One of his primary activities during the past 18 years has been working on more than one hundred DuPont projects. He also contributed to the development of a commercial process for hazardous waste destruction using high-temperature gas-phase chemical reduction, and is co-inventor of a viable process for the demilitarization of chemical weapons. Edwards chaired the first Process Plant Safety Symposium. He has received three awards for engineering excellence and two awards for safety, health and environmental excellence from DuPont. In 1998, he was named Kvaerner Employee of the Year. He received his BA from Rice Univ. and his PhD in chemical engineering from the Univ. of California at Berkeley. A registered professional engineer in Texas, he is an AIChE Fellow and a member of American Association for the Advancement of Science, American Chemical Society, National Society of Professional Engineers, Phi Lambda Upsilon, and Sigma Tau. LEE L. HU is a senior process engineer with Kvaerner Engineers and Constructors in Houston. He has over 30 years of diversified chemical engineering experience in process design, plant safety engineering and plant operation, and has worked with operating companies, engineering firms and the U.S. Army Ordnance Works of the Dept. of Defense. During the past ten years, he has been working on DuPont projects and is a recent recipient of the DuPont Shield of Irenee award for engineering excellence. Currently, he is assigned to the Process Group of the Facilities Engineering Team at the DuPont plant in Orange, TX (Phone: (409) 886-6657; Fax: (409) 886-6774; E-mail: lee.l.hu@usa.dupont.com). He received his BS from Chung Yuan Univ. in Taiwan and MS in chemical engineering from Univ. of Missouri-Rolla. He is a registered professional engineer in Texas and a member of AIChE. BEN D. ABABIO is a senior process engineer with Kvaerner Process, Inc. (Phone: (713) 414-2212; Fax: (713) 270-3650; E-mail: ben.ababio@kvaerner.com). His expertise includes process modeling and process safety engineering. He received an award from DuPont in safety, health and environmental engineering excellence. He has a BSc in chemical engineering from Kwame Nkrumah Univ. of Science and Technology, Kumasi, Ghana, and a PhD in chemical and process engineering from Univ. of Canterbury, Christchurch, New Zealand. Ababio is a member of AIChE and secretary to the Ghana Institution of Engineers (GhIE), North American Chapter. STEVE E. JONES is a manager of engineering projects at the DuPont plant in La Porte, TX, (Phone: (281) 470 3028; Fax: (281) 470-3935; Fax: steve.e.jones@usa.dupont.com). He is a recent recipient of the DuPont Shield of Irenee award for engineering excellence. He has more than 25 years of construction and engineering experience. He has worked internationally and has completed major industrial projects in the Middle East and South America. Jones is a registered professional engineer with a degree in civil and environmental engineering from the Univ. of Rhode Island. MICHAEL C. LIVINGSTON is manager of process safety and fire protection for Kvaerner Engineers and Constructors (Phone: (713) 270-2999; Fax: (713) 270-3195; E-mail: michael.livingston@kvaerner.com). He conducts or directs process-hazards-identification reviews, consequence analyses, fire-risk-assessment surveys, and design of fire detection and suppression systems for onshore and offshore oil-and-gas production and processing installations, and chemical and petrochemical facilities. He received his BS in chemical engineering and his MS in environmental engineering (civil sanitary) from the Univ. of Arkansas at Fayetteville. Livingston is a registered professional engineer in Oklahoma, Texas and Alaska, and is a member of AIChE and the American Society of Safety Engineers. ANDREA B. CAVALIER is a division engineer for the Packaging and Industrial Polymers Business within DuPont (Strang Road, LaPorte, TX 77572; Phone: (281) 470-3614; Fax: (281) 470-3529; E-mail: Andrea.B.Cavalier-1@usa.dupont.com). She performs project process support, assists operations, troubleshoots process problems, and has led numerous hazards reviews for the operating area. She has received an engineering excellence award and an award for safety, health and environmental excellence from DuPont. Cavalier received her BS in chemical engineering from Carnegie-Mellon Univ. in 1984. A registered professional engineer in West Virginia, she is a member of the Society of Women Engineers and has worked as a process engineer for Witco Chemical prior to joining DuPont in 1990. NORMAN THOMPSON, SR. is project manager for The Lubrizol Corp. (41 Tidal Road, Deer Park, TX 77536; Phone: (281) 479-2851; Fax: (281) 884-5243; E-mail: ntho@lubrizol.com). He has extensive experience in project management and process development. Thompson received BS degrees in math and mechanical engineering and a masters in mechanical engineering from Lamar Univ. (Thompson worked on this article when he was a project manager for DuPonts La Porte plant.)

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