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Development of a Steel Component Combustion Model for Fires Involving Pure Oxygen Systems

Delmar Trey Morrison III, Ph.D., P.E. Exponent, Inc. 4580 Weaver Parkway, Suite 100, Warrenville, Illinois 60555 tmorrison@exponent.com Ryan J. Hart, Ph.D., Sean J. Dee, and Brenton Cox, Ph.D. Exponent, Inc., Warrenville, Illinois

Prepared for Presentation at American Institute of Chemical Engineers 2013 Spring Meeting 9th Global Congress on Process Safety San Antonio, Texas April 28 May 1, 2013 UNPUBLISHED

AIChE shall not be responsible for statements or opinions contained in papers or printed in its publications

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Development of a Steel Component Combustion Model for Fires Involving Pure Oxygen Systems

Delmar Trey Morrison III, Ph.D., P.E. Exponent, Inc. 4580 Weaver Parkway, Suite 100, Warrenville, Illinois 60555 tmorrison@exponent.com Ryan J. Hart, Ph.D., Sean J. Dee, and Brenton Cox, Ph.D. Exponent, Inc., Warrenville, Illinois Keywords: oxygen, steel, pure oxygen systems, process design, loss of containment, flammability

Abstract
Pure oxygen systems pose significant fire and explosion risk to equipment, operations, and personnel if a loss of oxygen containment occurs. In industrial oxygen systems, combustion of metal can be initiated by a variety of ignition sources. The combustion of process vessel walls, components, or piping can result in loss of containment of pressurized oxygen. Automatic shutdown and isolation systems are designed to detect loss of containment, incipient loss of containment due to process parameters (e.g., pressure drop), or internal fire conditions. The effectiveness of these isolation systems is dependent upon the speed with which they activate after the initiating event. The prediction of failure modes and time scales can be an important tool in the design, operation, and maintenance of industrial high purity oxygen systems. Modeling of metal consumption in oxygen fueled fires requires consideration of multiple ignition mechanisms. Previously published experimentation has been motivated by the need to compare the relative burn resistance of metals and nonmetals under a variety of operating conditions, but has not produced a tool to inform the potential for loss of containment in oxygen systems based on the different ignition mechanism failure modes. This work aims to develop a series of theoretical models using experimental results and kinetic relationships, to predict loss of containment in piping for industrial systems for combinations of different failure modes. Using this type of analysis, process designers can make informed decisions on the design of high purity oxygen systems, the timescale required by emergency shutdown systems, and schedules for routine maintenance and inspection.

Introduction

Many industrial systems rely upon pressurized oxygen (O2) supplies as part of their design. Pressurized O2 may be found at small scale in health care applications, but our focus here is on large scale industrial systems that may rely upon O2 at high pressures and continuous supplies.

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Such O2 distribution systems can be found in space rocket engines, oxygen-enhanced combustion systems, and chemical oxidation process units, among others. Purity and concentration of oxygen are two important factors to consider when designing a safe oxygen handling system. Specifically, gaseous oxygen (enriched) systems are defined as containing at least 23.5% O2 by volume with the remaining volume being inert [1]. Oxygen systems can be further classified into one of three categories according to their purity [1]: Low purity oxygen contains less than 35% O2 by volume Standard purity oxygen - equal or greater than 99.5% O2 by volume Ultra high purity oxygen - greater than 99.999% O2 by volume

The safe handling and use of oxygen gas in industrial applications requires special considerations for fire and explosion safety. Industrial standards and the underlying research efforts by industrial oxygen users have promulgated standards including ASTM G94-05, ASTM G63-99, ASTM G88-05, CGA G-4.4, NFPA 50, and NFPA 53, which provide safety and design guidance for oxygen distribution systems.[1-6] The ignition of both metallic and nonmetallic components is a concern in enriched O2 atmospheres (i.e., greater than 23.5% O2). System components that would not normally burn in ambient air (i.e., 21% O2) may burn vigorously in an enriched O2 environment. This can lead to loss of containment of high purity oxygen and rapid escalation of fire and explosion incidents [7, 8]. The fire hazard in oxygen systems is significant because O2 is normally present at high concentration. High oxygen concentration combined with a potential fuel and ignition source can result in rapid loss of containment of pressurized oxygen, rapid fire growth, and rapid fire extension to other areas. 1.1 Modes of Ignition

Initial ignition of a component or particle within an oxygen system may lead to a kindling chain mechanism of fire growth where the energy released from an initial, smaller, easily ignitable fuel source causes ignition and combustion of a more ignition-resistant material [3, Section 5.2.14]. The kindling chain may quickly lead to fire growth within a system and overcome (i.e., ignition and continued combustion) the burn resistance of the components in a piping system leading to loss of O2 containment. Ignition and burn resistance of materials are related to the material composition, thickness, configuration, and environment (e.g., temperature, pressure, and velocity). Several potential ignition mechanisms for metal alloys have been identified in the literature [1]: Particle impact Mechanical friction1

While frictional heating may occur from gaseous flow against a pipe wall or through a small opening, flow frictional heating causing ignition of metals is generally only supported by unverifiable anecdotes in high pressure oxygen systems (e.g., greater than 500 psi) [ASTM G88-05, 5.2.12 5.2.12.1]. Hence, frictional heating is more appropriately discussed from a standpoint of surface friction induced by internal moving components in valves, pumps, or other devices with moving parts.

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Adiabatic compression Promoted ignition Electrical arcing (e.g., static electric discharge, lightning strike, electrical system fault)

The collision of high velocity particles with stationary surfaces can generate localized heating of the particles due to the conversion of kinetic energy to heat at the impact point. If the heat generated is sufficient, ignition and combustion of the particle may occur which could then ignite the impacted material or other nearby fuels (e.g., polymeric gaskets). Both impinging (impact face-on in the direction of flow), and non-impinging (impact obliquely or parallel to the direction of flow) impact with internal piping system surfaces may result in ignition of either the particle or the surface material [3, Section 5.2.6]. Particles may be introduced from the attrition of surface scale deposits from corrosion in piping, mechanical wear of system internals, or other sources of particle contamination. The nature of the particle along with the velocity and other system conditions will affect the likelihood of ignition of the particle. For example, silica particles are non-ignitable, but rust particles are ignitable. Mechanical frictional heating may result from metal-to-metal rubbing, which can be experienced in moving valve internals. This rubbing mechanism can wear protective coatings from surfaces as well as generate small particles [3, Section 5.2.8.1]. Adiabatic compression of oxygen can occur when a valve is opened to a dead end space in a pipe with O2 at a lower pressure. The resulting mechanical compression of the gas in the dead space as it is pressurized to the pipeline pressure can result in heating sufficient to ignite non-metallic valve seats or gaskets [3, Section 5.2.7]. These could, in turn, ignite metallic components leading to a system fire. Several design steps can be taken to limit the potential for ignition, or to stop the kindling chain before the system is breached. The use of filters can reduce the presence of particles, but it is infeasible to remove all particles for an oxygen system [3, Section 5.2.6.1]. The likelihood of ignition from both frictional heating and particle impact can be limited by selecting combustionresistant materials of construction [3, Sections 7.6.3 and 7.8.3]. The likelihood of ignition by adiabatic compression can be limited by system design and throttling controls, for example to limit the rate of valve opening/closure or ignition resistance of materials in the adiabatic compression zone. 1.2 Steel Alloys in Oxygen Service

Metal alloys for use in O2 service are classified as either combustion-resistant or exempt, based upon the alloy, configuration, temperature, pressure, and gas flow velocity. A combustion resistant material at the given conditions may undergo ignition, but the combustion process will quench with limited propagation away from the point of ignition. An exempt material has no thickness or pressure limitation for use in O2 systems, based upon the standards. Although the alloys listed are referred to as exempt from velocity limitations, this does not mean that the metals are immune to oxygen-enhanced combustion. Sufficient evidence exists in the literature and from practical experience to indicate that damage can occur to these materials from repeated non-propagating combustion events. Ignition and self-sustained combustion of materials can be evaluated based upon the energy balance.

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Any constitutive equation for mass consumption must be solved in parallel with the conservation of energy equation by solving simultaneously for the reaction temperature and rate of propagation. The energy balance is summarized as: Qb-Qs-Qr-Qc-Qh=0 [Eq. 5] where Qb is the heat generated by oxidation in the molten mass, Qs is the heat transferred to the solid metal across the metal/melt interface, Qr is the radiative heat loss, Qc is the convective heat loss, and Qh represents the heat that is used to warm the molten metal from melting temperature to the burning temperature. Qb is the product of the heat of combustion of the metal times the combustion rate, but the other terms are geometry dependent. Metals are more difficult to ignite than non-metals due to their higher ignition temperature, higher thermal conductivity, and ability to generate ignition-resistant oxide coatings [2, Section 5.4.2]. If sufficient energy can be added to initiate combustion (i.e., ignition), then a given material may start to burn. However, if the oxygen concentration, density, and velocity are not within certain bounds, the combustion event will extinguish. In practical terms, repeated particle impact may be able to eventually cause a hole in a non-exempt material part. Examples of metallic alloys used in O2 distribution systems are provided in Table 1 [1, Appendix C and D]. The table lists some common stainless steel alloys and nickel alloys. Carbon steel alloys are unsuitable for use in oxygen systems at concentrations greater than 35% by volume due to their reduced resistance to combustion [1, Section 4.2.3.2]. The exemption status of a given metal is determined based upon a distance of burning greater than 30 mm in the standardized tests. For a material in a thickness less than that tested, the standards indicate that it should be treated as flammable at pressure and velocity above the exemption curves as displayed below. Table 1. Example O2 oxygen system alloy exemption pressures and minimum thicknesses.
Nominal Composition 67Ni, 32Cu, 1Fe 66.5Ni, 30Cu, 3(Al, Ti) 56Ni, 12Cr, 13.5Mo, 4Fe, 3W, 2.5Co 74Ni, 15.5Cr, 7Fe, 2.5Ti, 1Al 19Cr, 11Ni, 3Mo, 1.5Si, 1.5Mn, Bal. Fe 17Cr, 12Ni, 2Mn, 3Mo, 1Si, Bal. Fe 3C, 2Si, 0.8Mn, Bal. Fe Min. Thickness None Specified None Specified None Specified None Specified 3.18 mm (0.125 in) 6.35 mm (0.250 in) 3.18 mm (0.125 in) 6.35 mm (0.250 in) 3.18 mm (0.125 in) Exemption Pressure 21 MPa (3000 psig) 21 MPa (3000 psig) 5.3 MPa (750 psig) 6.9 MPa (1000 psig) 1.4 MPa (200 psig) 2.0 MPa (290 psig) 1.4 MPa (200 psig) 2.0 MPa (290 psig) 0.27 MPa (25 psig)

Material Monel 400 Monel K-500 Hastelloy C-276 Inconel X-750 Stainless Steel, cast, CF-8M2 Stainless Steel, wrought, 316 Gray Cast Iron

Cast analog of 316L/316 stainless steels.

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For non-exempt materials (i.e., combustion-resistant), velocity limitations for impingement and non-impingement oxygen flow are shown in Figure 1 and Figure 2, respectively reproduced from pgs. 12-13 in reference [1]. For each graph, systems containing oxygen-contact stainless steel alloy components should be designed to keep the pressure and velocity below and to the left of the curve to limit particle kinetic energy [3, Section 7.6.2]. The velocity limit as a function of pressure is lower for the impingement curve than the non-impingement curve because a theoretical particle impact face-on to a surface will generate more energy than an oblique impact.

CGA G-4.4; Figure 1, p12

Figure 1.

Impingement velocity curve.

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CGA G-4.4; Figure 2, p13

Figure 2.

Non-impingement velocity curve.

Stainless steels are widely used materials of construction in industrial oxygen systems, despite their well-established flammability. At high oxygen pressure and flow velocity, stainless steel components are susceptible to ignition due to various mechanisms, including particle impact and frictional heating. Even when isolated via emergency shutdown (ESD) systems, releases of pressurized O2 have occurred and resulted in significant damage to process systems. Additional information relevant to past incidents and for the design and maintenance of oxygen systems can be found in the cited references.

Steel Combustion Models3

System designers have several resources to use in the prevention or mitigation of potential ignition sources in oxygen systems, but ignition incidents may still occur. In order to prevent potentially catastrophic releases of pressurized oxygen, it may be helpful to quantify the speed at which an ESD system must detect and respond to an impending loss-of-containment. Because steel components may be susceptible to ignition and combustion, an initially small hole can quickly grow to a large size. The resulting release of oxygen in the area of the leak may therefore accelerate with time and lead to a rapidly escalating fire or explosion event involving nearby equipment or structures. In this section, models of increasing sophistication are presented to describe steel consumption due to combustion. First, propagation rates directly measured from experiments are compiled. Second, a semi-empirical model for oxidation rate constructed from propagation rate data and Arrhenius-type kinetics is considered. Then a model derived from transport equations and process geometry is discussed.

For sake of brevity, the term steel will be applied to all grades of stainless steel.

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Combustion of steel involves the oxidation of iron (Fe) in the steel along with other elemental components. The carbon in carbon steel alloys may be partially oxidized to carbon monoxide (CO) or fully oxidized to carbon dioxide (CO2). However, the oxidation of Fe is the primary reaction involved in the burning of steel. Based upon the literature, the oxidation reaction occurs between molten Fe and gaseous oxygen. Molten Fe is oxidized to molten iron oxide (FeO), which then falls or is blown away from the combusting metal surface [9]. The balanced combustion reaction is given in Eq. 1. Fe(molten) + O2 (gas) FeO(liquid) Ho298 = -63.8 kcal/mole [Eq. 1]

Thermal conductivity and heat transfer are very important in metal combustion due to the high melting temperature. If the heat input is insufficient to melt the metal given the boundary conditions, then propagating combustion will not occur. While a sophisticated model describing these processes may seem to be optimal, the available process and material data required to employ such a model may necessitate that a less sophisticated model be employed for a desired level of confidence. The availability of experimental data required to compute model parameters and the difficulty to employ the model are also discussed. 2.1 Propagation Rate Approach

The simplest means of estimating the consumption rate of steel components in a pure oxygen environment is the direct application of propagation rate (cm/s) measured in a comparable scenario. As discussed by Benz, et al., measurements of propagation rate in metal rods dates back to the late 1950s, and a breadth of experimental data is available [11]. In particular, Benz et al. cites German studies by L. Kirschfeld that summarized the results from a variety of experiments in which he measured average propagation rates of solid metal rods. Unfortunately, the original data from this article was not available to us. Here, we summarize Benzs results for 316 and 304 stainless steel rods with diameters of 1/8 inch (0.32 cm) and lengths of 5 inches (12.7 cm) (see Figure 3 (a)). Propagation rate, (cm s-1) was measured as a length-wise rate of consumption (see Figure 3 (b)). Propagation rate data for other metals from this and other sources can also be found in ASTM G94-05 [2].

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Figure 3. Rod combustion. 2.1.1 Iron Rods, 1/8 Inch (320 mm) Diameter

Steinberg et al. burned pure iron rods of 320 mm diameter in 100% oxygen at 1000 psig (6.9 MPa) [13]. The rods were oriented vertically and ignited at the bottom to allow upward propagation of the burning front. The authors recorded a melting rate of 1.14 0.025 cm s-1. 2.1.2 316 Stainless Steel, 1/8 Inch Diameter

Benz reported data at five different pressures between 1,000 psig and 10,000 psig for 316 stainless steel, as summarized in Table 2. While experiments were performed at 500 psig, the fire extinguished after consuming less than 40% of the rod, so no propagation rate was reported.

Table 2.
Pressure (psig) 500 1,000 3,000 4,000 7,000 10,000 Pressure (MPa) 3.45 6.89 20.67 27.57 48.24 68.91

Data for 316 Stainless Steel [10]

Propagation rate (cm s-1) < 40% consumed 1.12 1.22 1.24 1.44 1.58 Propagation rate (in s-1) < 40% consumed 0.441 0.480 0.488 0.567 0.622

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2.1.3

304 Stainless Steel, 1/8 Inch Diameter

Benz reported data at 3,000 psig and 5,000 psig for 304 stainless steel, as summarized in Table 3. Again, experiments were performed at 500 psig, but the fire extinguished after consuming less than 40% of the rod, and so no propagation rate was reported. Table 3.
Pressure (psig) 500 3,000 5,000 3.45 20.67 34.46

Data for 304 Stainless Steel [10].

Propagation rate (cm/s) < 40% consumed 1.19 1.30 Propagation rate (in/s) < 40% consumed 0.469 0.512

Pressure (MPa)

A more recent study by Slockers, et al. investigated the burn behavior of 304 stainless steel rods at 1000 F, of 1/8 in. diameter and 4.4 in. length, at 85 psig (0.7 MPa) [12]. The authors reported a burn length of around 0.28 in. (0.7 cm), consistent with the finding that at lower pressures, the combustion of steel is not likely to be self-propagating. Given the similarity in the data, the most simplistic model would be to use the linear burning rate (e.g., 1 cm/s) to calculate the rate of hole size growth. If one assumes that the hole grows in a flat sheet as an approximation of a pipe or component wall, then the rate of hole size growth is shown in Equation 2, where Rhole is the rate of hole size increase in units of length2/time during the time interval t from initiation of the hole. This approach can be used for an average propagation rate or a value from the literature representing the conditions of concern. This equation can be applied with more complex models for the linear rate of combustion as described below. Rhole = 2 t 2.2 Semi-empirical Kinetic Approach [Eq. 2]

A semi-empirical equation was employed by Slockers and Robles-Culbreth to capture the dependence of propagation rate () on oxygen pressure (Pox) and an Arrhenius-type dependence on substrate temperature (Ts) and activation energy (Ea). [11] The general form for this correlation is shown in Equation 3, = C Poxl Tsn exp(-Ea/RTs) [Eq. 3]

where C is an unknown proportionality constant, l and n are exponential quantities established experimentally, and R is the universal gas constant. Values for C, n and Ea were not reported, but a value of l was reported for mild steel and 316 stainless steel. Benz et al., also cited Kirschfelds observation that was inversely proportional to the diameter of the rod. Thus, for a cylindrical geometry, comparison to measured values of and Pox can be achieved by the Equation 4:

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= 0 (d0/d)(Pox/Pox,0)l [Eq. 4] For mild (carbon) steel, a value l=0.4 +/- 0.5 was reported for Pox between 44 and 1450 psig [11].For Type 316 stainless steel, a value of l = 0.075 was reported for Pox between 1000 and 4000 psig and l=0.26 for Pox greater than 4000 psig. For example, Eq. 3 is employed using the measured values of 0=1.12 cm/s at Pox,0=1000 psig for Pox less than 4000 psig, and 0=1.24 cm/s at Pox,0=4000 for Pox 4000 psig and greater. The projection compares favorably to subsequently measured values, as shown in Figure 4(note: this is not surprising, as these values were used to find l).

Figure 4. Propagation rate versus oxygen pressure using Eq. 4. 2.3 Conservation of Mass and Energy Approach

A model derived from more fundamental mass and energy balances was presented by Sato, et al., for the specific scenario of a burning metal rod, in which it was assumed that the oxidation reaction occurs in a mass of molten metal which forms from the solid [12]. In this model, the mass balance is calculated from the rate at which oxygen is absorbed into the molten metal, which results in an equation functionally similar to Eq. 3. Specifically, = jm/o S C Poxlexp(-Ea/RTb)*1/(Asm) [Eq. 5] where, in addition to previously defined quantities, jm/o is the weight ratio of the metal oxide and oxygen, S is the surface area of the molten mass, Tb is the molten mass temperature, m is the density of the metal, C is a proportionality constant, and l is the exponent discussed in Section 2.2. Additionally, As is the cross-sectional area of the rod, and is the product of Ac and hc, a parameter corresponding to the configuration of the solid/liquid interface and the heat transfer coefficient across that interface, respectively. Note that in their study, Sato, et al. assign a value of 1, which assumes a flat interface and neglects the effects of convection.

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While models of this type allow for greater adaptability, the mass balance requires two more parameters than Eq. 3 (S, Ac and hc, in exchange for eliminating the temperature exponential n). Additionally, the energy balance requires several more circumstance-specific parameters in the form of heat transfer coefficients and the emissivity of the molten mass. It is unlikely that this type of model would provide substantial improvement to the accuracy of propagation rates in most industrial applications.

Conclusions

Three approaches for calculating the flame propagation rate in steel components were presented. These approaches were presented in order of complication. The first method employed direct experimental evidence at varying pressures as a look-up table. The second method was based upon a semi-empirical equation but resulted in an empirical fit, by which propagation rates could be predicted from experimental values. The third method, based upon the conservation of mass and energy, was outlined.

References

1. CGA G-4.4, Oxygen Pipeline and Piping Systems, Compressed Gas Association, 2012. 2. ASTM G94-05, Standard Guide for Evaluating Metals for Oxygen Service, ASTM International, October 2005. 3. ASTM G88-05, Standard Guide for Designing Systems for Oxygen Service, ASTM International, November 2005. 4. ASTM G63-99, Standard Guide for Evaluating Nonmetallic Materials for Oxygen Service, ASTM International, May 2007. 5. NFPA 50, Standard for Bulk Oxygen Systems at Consumer Sites, National Fire Protection Association, 2001. 6. NFPA 53, Recommended Practice on Materials, Equipment and Systems Used in OxygenEnriched Atmospheres, National Fire Protection Association, 2011. 7. Kletz, T. A., Fires and Explosions of Hydrocarbon Oxidation Plants, Plant/Operations Progress, Volume 7, NO. 4, 1988, pp. 226-230. 8. Christianson, R., and Stoltzfus, J. M., Selecting Materials for Use in Oxygen-Enriched Atmospheres, ASME Winter Annual Meeting, 1993. 9. Lanyi, M. D., Discussion on Steel Burning in Oxygen (from a Steelmaking Metallurgist's Perspective), Flammability and Sensitivity of Materials in Oxygen-Enriched Atmospheres: Ninth Volume, ASTM STP 1395, T. A. Steinberg, H. D. Beeson and B. E. Newton, Eds., American Society for Testing and Materials, West Conshohocken, PA, 2000. 10. Benz, F. J., Shaw, R. C., and Homa, J. M., Burn Propagation Rates of Metals and Alloys in Gaseous Oxygen, Flammability and Sensitivity of Materials in Oxygen-Enriched Atmospheres: Second Volume. ASTM STP 910. M. A. Bennings, ED., American Society of Testing and Materials, Philadelphia, 1986, pp. 135-152.

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11. Slockers, M. J., and Robles-Culbreth, R, Ignition of Metals at High Temperatures in Oxygen, Journal of ASTM International, Volume 3, NO. 9, 2006. 12. Sato, J. and Hirano, T., "Fire Spread Limits Along Metal Pieces in Oxygen," Flammability and Sensitivity of Materials in Oxygen-Enriched Atmospheres: Third Volume, ASTM STP 986, D. W. SchroU, Ed., American Society for Testing and Materials, Philadelphia, 1988, pp. 158-171. 13. Steinberg, T. A., Mulholland, G. P., Wilson, D. B., and Benz, F. J., "The Combustion of Iron in High-Pressure Oxygen," Combustion and Flame, Vol. 89, 1992, pp. 221-228.

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Other Useful References

ASTM G63 99 (Reapproved 2007), Standard Guide for Evaluating Nonmetallic Materials for Oxygen Service ASTM G72 Test Method for Autogenous Ignition Temperature of Liquids and Solids in a High-Pressure Oxygen-Enriched Environment ASTM G86 Test Method for Determining Ignition Sensitivity of Materials to Mechanical Impact in Ambient Liquid Oxygen and Pressurized Liquid and Gaseous Oxygen Environments G88 Guide for Designing Systems for Oxygen Service G93 Practice for Cleaning Methods and Cleanliness Levels for Material and Equipment Used in Oxygen-Enriched Environments G124 Test Method for Determining the Combustion Behavior of Metallic Materials in Oxygen-Enriched Atmospheres G126 Terminology Relating to the Compatibility and Sensitivity of Materials in Oxygen Enriched Atmospheres G128 Guide for Control of Hazards and Risks in Oxygen Enriched Systems Rosales, K., Shoffstall, M., and Stoltzfus, J., Oxygen Compatibility Assessment on Components and Systems, Journal of ASTM International, Volume 3, NO. 7, 2006.

D. E. F. G. H. I.