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Using the ideal gas specific heat ratio for Relief-valve Sizing
In API Recommended Practice 520, the basis for evaluating the ideal gas specific heat ratio has been modified from standard conditions (in the sixth edition) to relieving conditions (in the seventh edition). This provides the impetus for evaluating the use of the ideal gas specific heat ratio in the vapor-sizing equations as well as the validity of the ideal gas assumption to provide a good estimate of the mass flux through a nozzle (see the box, Changes to API-RP 520, on p. 58). Presented here are the results of an evaluation for a few pure components, which indicates that the ideal gas specific heat ratio at the inlet temperature provides a very good estimate of the isentropic expansion coefficient under ideal gas conditions, although the temperature choice does not appear to have a significant effect on the mass-flux calculations. On the other hand, the use of the actual inlet density (typically via the inlet compressibility factor) can lead to under-prediction of the required discharge area for a relief valve if used in conjunction with the ideal gas specific heat ratio under some conditions. Isentropic nozzle flow The inlet converging nozzle of a fully-opened pressure-relief valve is commonly assumed to be the limiting flow element and thus provides the model on which to determine the capacity of the relief device. To calculate the mass flux through the relief device, the inlet nozzle is assumed to be adiabatic and reversible, leading to the isentropic flow assumption. The general volumetric energy balance for isentropic nozzle flow of a homogeneous fluid forms the basis for this mass flux calculation [1, 2], which is subsequently modified to account for nonidealities in the actual relief device: (1) In this expression, the subscript max represents the maximization of this calculation to account for potential choking of a compressible fluid, where the flow through the nozzle no longer increases with decreasing downstream pressure. It is important to note that this energy balance is irrespective of the non-ideality or compressibility of the fluid. As a result, Equation 1 forms the basis of the two-phase flow calculations in the homogeneous equilibrium model (HEM), which is commonly employed in relief valve calculations for two-phase flow. In addition, in the limit of an incompressible fluid a common assumption for liquids this equation reduces to the commonly recognized liquid flow calculation with no potential energy effects [2]. P-V correlations for gases With the generic nozzle flux equation, one needs the density (or specific volume) of the fluid at various stagnation pressures from the inlet of the nozzle to the throat of the nozzle, where the cross-sectional area of the nozzle is minimized. Given these values, one can perform the numerical integration calculation and determine the maximum mass flux through the nozzle; however, numerical integration is computationally intensive and not readily implemented via hand calculations, and isentropic flashes may not be available. As a result, various functional correlations for the relationship between the specific volume and the pressure at constant entropy have been sought. The most commonly employed functional correlation for vapors and gases is the following, where the variable n is referred to as the isentropic expansion coefficient: (2) This correlation has found widespread use not only because of its general applicability but also because the relationship can be proven thermodynamically for an ideal gas with a constant ratio of the specific heat capacity at constant pressure to the specific heat capacity at constant volume henceforth referred to as the specific heat ratio. Taking the partial derivative of this expression with respect to temperature at constant entropy yields an expression for the isentropic expansion coefficient in terms of thermodynamic state variables (see box at the top of p. 58) [3]:

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(3) It is important to note that the only assumption required to derive this expression is that the isentropic expansion coefficient is constant over the range of pressures from the inlet to the throat. This has been found to be a very reasonable assumption in most cases. If the isentropic expansion coefficient is indeed relatively constant, then Equation 3 can be evaluated at any point along the isentropic path the inlet stagnation conditions being the most convenient. For an ideal gas, the partial derivative of pressure with respect to volume at constant temperature is easily found, and the isentropic expansion coefficient for an ideal gas can be expressed simply as the ideal gas specific heat ratio: (4) Note that this same expression can be derived for an ideal gas undergoing a reversible, adiabatic expansion process using a different approach starting with the first law of thermodynamics [4]. For an ideal gas, these specific heat capacities are a function of temperature only. The ideal gas specific heat capacity at constant pressure is a common thermodynamic function measured (or estimated) and implemented in various thermodynamic engines and process simulators, making the ideal gas specific heat ratio an easily obtainable approximation of the isentropic expansion coefficient. Solution for an ideal gas Using Equations 2 and 4 as the functional correlations for the isentropic behavior of an ideal gas, the energy balance in Equation 1 can be analytically integrated. Simplification of this analytical expression arises when the flow through the nozzle is choked and the pressure at the throat can be determined based on the choking pressure ratio for an ideal gas [4,5]: (5) For choked flow conditions, the analytical integration yields the following: (6) The vapor-sizing equations presented in API Recommended Practice 520 are obtained from Equation 6 by substituting the mass flowrate divided by the effective discharge area for the mass flux; rewriting the inlet specific volume in terms of pressure, temperature, and compressibility; accounting for deviations from ideality using the various modifying coefficients (Kd, Kb, and Kc); and solving for the effective discharge area. Note that the compressibility factor is present in the API RP 520 equations only to provide an accurate calculation of the specific volume of the fluid at the inlet to the nozzle, and does not account for any non-ideal gas behavior with respect to the isentropic expansion of the fluid through the nozzle. In fact, others have indicated that the compressibility factor cannot be used to account for the isentropic expansion of a real gas compared to that of an ideal gas [6]. The ideal gas assumptions The accuracy of ideal gas assumptions was tested using various pure components having an IUPAC equationof-state and a readily-available, temperature-dependent ideal gas specific heat capacity at constant pressure relationship [7]. These components included n-butane, propane, methanol, ethylene, water, nitrogen, and argon. The mass-flux integration expressed in Equation 1 was carried out numerically using fluid properties generated from the IUPAC equation-of-state thermodynamic model for each fluid, and the flux obtained at choking conditions was used as a consistent basis for comparison. The fluids were tested over a range of conditions; specifically, inlet pressures from a reduced pressure of 0.1 to the maximum supported by the thermodynamic model (typically 20 to 100), and inlet temperatures from a reduced temperature of 1.0 to the maximum supported by the thermodynamic model (typically 3 to 10). It is important to note that, in some cases, the thermodynamic models predicted the formation of liquid as the pressure was decreased due to retrograde condensation (specifically, cases where the inlet conditions were close to the thermodynamic critical point). In these cases, the overall specific volume of the fluid was used in the

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integration (corresponding to the homogeneous equilibrium assumption for two-phase mixtures). This rigorously computed mass flux provides the basis of comparison for the various ideal gas assumptions. While the ideal gas specific heat ratio is expected to be relatively constant for conditions where the ideal gas assumption is applicable, there is still a question as to what temperature provides the best estimate for the ideal gas specific heat ratio if it is not constant over the range of interest. The mass flux predicted using the ideal gas specific heat ratio evaluated at various temperatures was thus examined to determine the appropriate temperature for use in the determination of the ideal gas specific heat ratio (again, it is important to note that the ideal gas specific heat ratio is only a function of temperature). The temperatures evaluated included the inlet temperature, the temperature at standard conditions (60 the throat temperature (found as a result of the F), rigorous numerical integration), and an average temperature between the inlet and throat conditions. In these cases, the mass flux predicted using the ideal gas specific heat ratio was calculated using Equation 6. The results from the comparison of various temperatures at which the ideal gas specific heat ratio could be evaluated indicate that there is not a significant difference in the mass flux based on the different temperatures; however, the ideal gas specific heat ratio evaluated at the inlet temperature produces the best-estimate in most cases. The results for n-butane, shown in Figure 2, are typical. In addition, the effect of using the actual inlet specific volume in conjunction with the ideal gas specific heat ratio was also evaluated. Since the ideal gas assumption implicitly requires a compressibility factor of 1, the effect of using the actual specific volume of the fluid at relieving conditions could potentially lead to errors in the application of the vapor sizing equations. The mass flux calculated using the actual inlet specific volume and the mass flux using the inlet specific volume predicted by the ideal gas law based on the inlet pressure and temperature, were compared to the rigorously computed mass flux. In both cases, the ideal gas specific heat ratio was evaluated at the inlet temperature for a consistent basis. The results from the comparison of the specific volumes indicate that the use of the actual inlet specific volume in the mass flux calculation, in conjunction with the ideal gas specific heat ratio, tends to over-predict the capacity of the relief valve (thus under-predicting the required discharge area a non-conservative result with respect to relief valve sizing), especially at conditions approaching the thermodynamic critical point. On the other hand, the use of the specific volume calculated using the ideal gas law tends to under-predict the capacity of the relief valve (thus over-predicting the required discharge area) for conditions less than a reduced pressure of approximately 1020. These results are consistent with previous work published by Leung and Epstein [6]. Again, the results for n-butane, shown in Figure 3, are typical. Conclusions When the gas is known to behave ideally (that is, for reduced pressures much less than unity or reduced temperatures much greater than unity), the ideal gas specific heat ratio can be used as an estimate of the isentropic expansion coefficient. The ideal gas specific heat ratio should be determined at the relief temperature to provide the best estimate; however, the choice of temperature does not appear to have a significant effect on the mass flux calculation. For those thermodynamic engines or process simulators that provide the ratio of the specific heats for the real gas, the isentropic expansion coefficient can be calculated using Equation 4. In the case where the use of the ideal gas specific heat ratio is still desired, it should be determined using the specific heat capacity at constant pressure evaluated at the relief temperature and zero pressure absolute (or negligible pressure). The ideal gas specific heat ratio can then be calculated using Equation 4. An example makes things clear A feed vessel in a poly-butylene unit contains isobutylene (molecular weight = 56.108 kg/kmol) and is being evaluated for the external fire overpressure scenario. The vessel has a maximum allowable working pressure (MAWP) of 22 barg (319 psig); therefore, the maximum allowable accumulation pressure is 26.62 barg (corresponding to 21% accumulation). Based on the estimated heat flux to the vessel from the fire, and assuming complete vapor-liquid disengagement within the vessel, the required relief rate is determined to be 68,000 kg/h (150,000 lb/h) of saturated isobutylene vapor at a relief pressure of 26.62 barg (2,763 kPaa) and a relief temperature of 395.5 K. A process simulator was used to find the remaining fluid properties at relieving conditions, including a real gas

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specific heat ratio of 1.887, a vapor density of 81.98 kg/m3 (5.118 lb/ft3), and a compressibility factor of 0.575. The ideal gas correlation for isobutylene was obtained from Perrys Chemical Engineering Handbook [1]. At the relief temperature, the ideal gas specific heat ratio was found to be 1.082. At standard conditions corresponding to a temperature of 288.7 K, the ideal gas specific heat ratio was found to be 1.107. A pressure-relief valve is being designed to provide overpressure protection, and must be sized to adequately handle the required relief rate during the external fire overpressure scenario. For the preliminary design, the back pressure on the relief valve is assumed to be within acceptable limits; therefore, the flow will be choked and the back pressure correction factor, Kb, is equal to 1. In addition, a rupture disk device will not be used on the inlet; therefore, the combination capacity factor, Kc, is equal to 1. In all cases, Equation 3.2 in API RP 520 (7th Edition) is used to determine the required discharge area for the relief valve: (7) (8) Case I. Actual isentropic expansion coefficient: Using the actual isentropic expansion coefficient for the fluid at relieving conditions, 0.746, based on the guidance presented in Appendix B of API RP 520, the discharge area for the relief valve is or the area must be, at a minimum, 2,375 mm2. This calculation produces the best estimate of the required discharge area that would be calculated using the numerical integration. Given the required discharge area, a relief valve with an N area designation (2,800 mm2) would be chosen. Case II. Real gas specific heat ratio at relieving conditions: Without knowledge of the background information regarding the isentropic expansion coefficient for vapor sizing, one may read API RP 520 (7th Edition) and apply Section 3.6.2.1.1 incorrectly using the information obtained from the process simulator, specifically using the real gas specific heat ratio at relieving conditions. This could result in a significantly undersized relief valve as the required area is found to be therefore, a relief valve with an L area designation (1,841 mm2) would be chosen. Case III. Ideal gas specific heat ratio at relief temperature, actual compressibility factor: If one understood that the ideal gas specific heat ratio was intended for use in Section 3.6.2.1.1 and thus evaluated the ideal gas specific heat ratio at the relief temperature for use in the vapor sizing equations, one would find a required area of therefore, a relief valve with an M area designation (2,323 mm2) would be chosen. Case IV. Ideal gas specific heat ratio at standard temperature, actual compressibility factor: If one instead used the ideal gas specific heat ratio at standard conditions, one would find a required area of therefore, a relief valve with an M area designation (2,323 mm2) would be chosen. Case V. Ideal gas specific heat ratio at relief temperature, ideal gas compressibility (Z=1): If one applies the ideal gas assumption in a conservative method using the ideal gas specific heat ratio at the inlet temperature as an estimate of the isentropic expansion coefficient, and forcing the compressibility factor of the fluid to be 1, one would find a required area of therefore, a relief valve with an N area designation (2,800 mm2) would be chosen. Case VI. Ideal gas specific heat ratio at standard temperature, ideal gas compressibility (Z=1): Finally, if one uses the ideal gas specific heat ratio at standard conditions and force the compressibility factor of the fluid to be 1, one would find a required area of therefore, a relief valve with an N area designation (2,800 mm2) would be chosen. Summary

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The results of the various approaches are shown in the table above. While the use of the isentropic expansion coefficient and fluid properties at the inlet conditions is expected to produce the best estimate of the required discharge area, the use of the consistent ideal gas assumptions (ideal gas specific heat ratio and a compressibility factor equal to 1) is likely to produce a conservative result. In no case should the real gas specific heat ratio be used as an estimate of the isentropic expansion coefficient, as this can lead to significant under-prediction of the required discharge area for the relief valve. Edited by Gerald Ondrey Does A Process Simulator or Thermodynamic Engine Return Heat Capacity Ratios for real- or ideal-Gas Conditions? Typically, the ideal gas specific heat ratio falls in the range of 1 to 1.67, while the real gas specific heat ratio can easily exceed values of 1.67 under certain conditions. A relatively simple test case using air can be performed to determine if your process simulator or thermodynamic engine returns the specific heat ratio for the ideal gas or the real gas. Perrys Engineering Handbook [7] Table 2200 gives real gas specific heat ratios for air at various conditions, and the value at 200K and 100 bars is given as 2.093. The ideal gas specific heat ratio should be approximately 1.3 at these conditions. Alternatively, other fluids can be used as test cases; for example, the real gas specific heat ratio for ethylene at 300K and 80 bars is approximately 4, while the ideal gas specific heat ratio should be approximately 1.2. Changes to API-RP 520 and their Implications The American Petroleum Institute Recommended Practice (RP) 520, entitled Sizing, Selection, and Installation of Pressure-Relieving Devices in Refineries, details the various equations used in sizing pressure-relief devices and is commonly used throughout many industries. Within this document, the vapor sizing equations for relief valves are specified, and the ideal gas assumption is employed in this specification. Between the sixth edition (March 1993) and seventh edition (January 2000) of RP 520, the basis for the evaluation of the ideal gas specific heat ratio was changed from standard conditions (60F and 1 atm) to inlet relieving condition s (relief temperature and relief pressure); however, justification for this change was not detailed in the recommended practice. The derivation of an expression for the isentropic expansion coefficient in terms of thermodynamic state variables indicates that the ideal gas specific heat ratio should be evaluated at conditions along the isentropic expansion path (the most convenient conditions being the inlet conditions at relief), and this conclusion is supported by comparisons performed as part of this analysis (although the comparisons indicate that the differences between various temperatures are not significant at all). Note that both bases can be problematic when using commercial process simulators to evaluate the specific heat ratio. At standard conditions, the fluid being relieved may very well be a liquid or two-phase mixture, and many process simulators will return the specific heat ratio for the fluid at these conditions (if it returns one at all). In addition, many process simulators will return the real gas specific heat ratio at the conditions specified, which potentially results in a specific heat ratio at the relief pressure and relief temperature that can be significantly different than the ideal gas specific heat ratio, even if the fluid behavior itself may be adequately modeled as an ideal gas. These real gas specific heat ratios can be significantly greater than the ideal gas specific heat ratios, and may result in a potential overprediction of the capacity of the relief valve (thus, an under-prediction of the required discharge area for the relief valve). In the case where the process simulator employed to generate fluid properties reports a real gas specific heat ratio, the fluid should be evaluated at the relief temperature and zero (or negligible) absolute pressure to generate the best estimate of the ideal gas specific heat ratio. Alternatively, the isentropic expansion coefficient can be calculated directly using the real gas specific heat ratio and the fluid properties at the inlet conditions using Equation 3 yielding an even better estimate of the isentropic expansion behavior of the fluid than the ideal gas specific heat ratio. References

1. Design Institute for Emergency Relief Systems, DIERS Project Manual, editor H.G. Fisher, AIChE, New York, N.Y., 1992.

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2. Darby, R., F.E. Self, and V.H. Edwards, Properly Size Pressure Relief Valves for Two-Phase Flow, Chem. Eng., Vol. 109, No. 6, pp. 68-74, 2002, . 3. Giles, B.L., Analytical Determination of Isentropic Coefficients of Expansion for Ethane, Propane, nButane, and n-Pentane, Attachment to Giles-3-55 in the API RP 520 Task Force Proceedings, American Petroleum Institute, Washington D.C., 1955. 4. Smith, J.M. and H.C. Van Ness, Introduction to Chemical Engineering Thermodynamics, 4th edition, McGraw-Hill, New York, N.Y., p. 66, 1987. 5. American Petroleum Institute, Sizing, Selection, and Installation of Pressure-Relieving Devices in Refineries, API RP 520, 7th Edition, Part I, Washington D.C., January 2000. 6. Leung and Epstein, A Generalized Critical Flow Model for Nonideal Gases, AIChE Journal, Vol. 34, No. 9, pp. 1568-1572, 1988. 7. Perrys Chemical Engineering Handbook, editors R.H. Perry and J.O. Maloney, 7th edition, McGraw-Hill, New York, N.Y., 1997.
Author

Aubry Shackelford is a project manager at Berwanger, Inc. (4615 SW Freeway, Suite 900, Houston, Tex. 77027. Phone: 713-570-2961; Fax: 713-570-2999; E-mail: shackelford@berwanger.com), where his responsibilities includes relief system evaluation project execution and technical consultation. As lead technical liaison for Berwangers pressure relief system analysis group, he gives training courses, represents the company at forums such as the DIERS (Design Institute for Emergency Relief Systems) group meetings and API (American Petroleum Institute) meetings, and develops relief system evaluation guidelines. He has a wide range of experience in many diverse industries. This experience encompasses technical consultation, team management, software development for engineering applications, overpressure protection analysis in the petroleum and petrochemical industries, production engineering in the coatings industry, in-depth research and development of cell culture production technology in the biotechnology industry, and hands-on applications of working pilot plant operations in the chemical industry. Shackelford received a B.S. in chemical engineering (summa cum laude) from Northeastern University (Boston), and is a member of AIChE. At the time of writing, he was about to take the Professional Engineering exam.

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