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PROCESS/PLANT OPTIMIZATION SPECIALREPORT

Fine-tune relief calculations


for supercritical fluids
Improved process simulation assists with relief load and valve sizing
P. NEZAMI, Jacobs Engineering, Houston, Texas;
and J. PRICE, Jacobs Consultancy, Houston, Texas

I
n the past 40 years, several different methods have been suggested Both the volumetric and mass relief rates will change during
for relief load and pressure relief valve (PRV) orifice sizing calcu- the course of a relief as the specific volume and enthalpy of the
lations for a supercritical fluid exposed to an external heat source. fluid change. To estimate the relief rates at different intervals, one
The following sources include some of these methods: can generate a property table in a process simulator to calculate
• API 521 suggests the use of a latent heat of 50 Btu/lb for the densities and specific enthalpies of the fluid at a constant
hydrocarbons near the critical point. In the absence of a better relief pressure over a given temperature range. The volumetric
method, this led to the use of 50 Btu/lb for even supercritical fluids. and mass relief rates for each interval can be calculated using Eq.
• “A Calculation of Relieving Requirements in the Critical 1 and Eq. 2, respectively.
Region”1 In this study, a series of calculations were conducted for ran-
• “Rigorously Size Relief Valves for Supercritical Fluids”2 domly selected n-paraffins, i-paraffins and aromatic compounds
• “Calculation of Relief Rate Due to Fluid Expansion and from C1 to C16 , using the Peng-Robinson equation of state
External Heat.”3 (EOS). The results indicate that the maximum mass relief rate
The most recent method, “Calculation of Relief Rate Due to occurs at lower temperature than the maximum volumetric relief.
Fluid Expansion and External Heat,” was presented at the API Both temperatures where the maximum relief rates occur are
2010 Summer Meeting. As the title suggests, the relief load is cal- greater than the critical temperature. Improving the calcula-
culated based on the expansion of the fluid due to absorbed heat. tion precision by reducing the temperature increments does not
This method can be used for any fluid, including vapor and liquid, affect the temperatures at which the mass and the volume relief
as long as no phase change occurs. To maintain a constant pressure rates peak. (Smaller temperature increments result in a smaller
at a fixed volume, the relief rate at any interval must be equal to the enthalpy change, Δh, which translates to a smaller time span.)
additional volume created by the change in specific volume from In fact, it is possible to mathematically prove that the two peaks
heat input to the fluid. However, some assumptions must be made occur at two different temperatures for real gas. This is where
and some basis must be set to make this method viable: this article differs from the one presented at the API meeting.3
• Other than the relieving stream, no fluid enters or leaves the
vessel during the course of relief 48 37
• There is no change of phase during the course of relief.
A simple equation can be set to calculate the relief rate at each 47
interval: 36
46
⎛1 1⎞
×⎜⎜ − ⎟⎟⎟
Q
Volume relief rate, 100 ft3/hr
Mass relief rate, 1,000 lb/hr

VR = (1)
h2 − h1 ⎝ ρ2 ρ1 ⎟⎠
⎜ 45 35

where: 44
VR = Volumetric relief rate 34
43
Q = Heat input
h1 = Initial specific enthalpy 42 33
h2 = Final specific enthalpy
1 = Initial density 41 Mass method 1
2 = Final density Mass method 2 32
40 Volume method 1
The mass relief rate can be determined using the average of the Volume method 2
initial and final densities for each interval. 39 31
⎛ ρ + ρ2 ⎞⎟ 505 510 515 520 525 530 535 540
M R = ⎜⎜⎜ 1 ⎟×V Temperature, °F
⎝ 2 ⎟⎠ R (2)
where: FIG. 1 Volumetric and mass relief rates (10 data points).
MR = Mass relief rate
HYDROCARBON PROCESSING JUNE 2012
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SPECIALREPORT PROCESS/PLANT OPTIMIZATION

The subject was examined using two different approaches to relief rate. In the second approach, only the final density is used
calculate maximum relief rates (volumetric and mass) for n-hexane to convert volumetric relief rate to mass relief rate.
at 660-psia relief pressure with 5 million Btu/hr absorbed heat and The main objective of this exercise (and the next step in the
a one-hour duration. relief valve calculation) is to size the PRV orifice area. The PRV
In the first approach, the relief rates were calculated by setting orifice area is a function of relief valve set pressure, relief load,
up property tables and using Eqs. 1 and 2 for three different tem- density and some other properties of the relieving fluid. In a
perature increments. The second approach was based on stepwise scenario where a vessel or container is exposed to external heat,
simulation models with three different time spans. The initial and the fluid properties (and the relief load) vary during the course
final temperatures were made the same to apply the same bases for of a relief. The goal is to find the maximum required orifice area,
all calculations. Results are plotted in Figs. 1, 2 and 3. as outlined below.
The time spans in these plots are six minutes for Fig. 1, three
minutes for Fig. 2, and two minutes for Fig. 3. It is clear that the PRV orifice calculation. The API 520 equation for compress-
impact of reducing time span on the temperatures at which the ible gas, which is derived from an ideal gas along an isentropic path,
relief rates peak is insignificant. It is also obvious that the two is not a suitable method for supercritical fluids, since supercritical
methods yield almost the exact same results for the volumetric fluids are far from ideal gas. Instead, an isentropic mass flux expres-
relief rates and very similar results for the mass relief rates. The sion should be used for sizing relief valves in supercritical service:
small difference in mass relief rate is due to the fact that, in the ⎡ P ⎤
⎢ −2 v×dP ⎥
first approach, at each interval the average of the initial and the ⎢ ∫ ⎥
final densities are used to convert volumetric relief rate to mass 2
⎢ ⎥ (3)
G = ⎢ P1

⎢ 2
vt ⎥
⎢ ⎥
48 37 ⎢ ⎥
⎢ ⎥
47 where: ⎣ ⎦ MAX
36 G = Mass flux
46
v = Fluid-specific volume
Volume relief rate, 100 ft3/hr
Mass relief rate, 1,000 lb/hr

45 35 P = Fluid pressure
vt = Specific volume at throat conditions
44 P1 = Fluid pressure at the inlet of the nozzle
34
43
120
42 33
100
41 Mass method 1
Maximum value, %

Mass method 2 32 80
40 Volume method 1
Volume method 2
60
39 31
500 505 510 515 520 525 530 535 540
40
Temperature, °F
Volume
FIG. 2 Volumetric and mass relief rates (20 data points). 20 Mass
Orifice area
0
1.05 1.15 1.25 1.35 1.45 1.55 1.65 1.75
Reduced temperature
48 37
FIG. 4 Methane relief at 1,346 psia.
47
36
46
Volume relief rate, 100 ft3/hr
Mass relief rate, 1,000 lb/hr

120
45 35
Volume
100 Mass
44 Orifice area
Maximum value, %

34 80
43

42 33 60

41 Mass method 1 40
Mass method 2 32
40 Volume method 1 20
Volume method 2
39 31 0
500 505 510 515 520 525 530 535 540 1.05 1.10 1.15 1.20 1.25 1.30 1.35 1.40
Temperature, °F Reduced temperature
FIG. 3 Volumetric and mass relief rates (30 data points). FIG. 5 Iso-octane relief at 745 psia.

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SPECIALREPORT PROCESS/PLANT OPTIMIZATION

Eq. 3 is the result of a volumetric energy balance for an isen- between the maximum relief rates (mass and volumetric) and the
tropic nozzle, and it is valid for any homogeneous fluid regard- maximum required orifice area for the relief valve for some of
less of the non-ideality or compressibility of the fluid. Deriva- the hydrocarbons used in this study.
tion details of the equation and the numerical examples for mass Fig. 8 shows the relationship between the maximum mass
flux calculation are presented in Appendix B of API 520. relief rate, the maximum volumetric relief rate, and the maxi-
Eq. 3 can be solved with a numerical integration technique. mum required orifice area for n-pentane at various relief pres-
With the use of a process simulator, a property table can be gener- sures. The maximum required orifice area appears at a tempera-
ated along the isentropic line to find specific volumes at various ture between the corresponding temperatures of the maximum
pressures, beginning at relief pressure and moving down to the volumetric and maximum mass relief rates for relief pressures
relief valve back pressure. Solving Eq. 3 for each downstream from PR = 1 to PR = 7. Similar patterns were observed for other
pressure will result in a series of mass fluxes, which will peak when pure hydrocarbons used in the study.
the flow is choked in the nozzle. The required orifice area for the
relief valve may be simply calculated by dividing the mass flux by Numerical example. The following example illustrates
the mass relief rate and the discharge coefficient: relief load and orifice-sizing calculations for a vessel containing
MR (4) n-hexane and absorbing 5 million Btu/hr of heat with a relieving
A= pressure of 660 psia (PR = 1.5).
G Kd Relief load calculation. A spreadsheet is used to calculate
where: the relief rates at various stages of a relief incident. Utilizing a
A = Required orifice area process simulator, a property table was created to calculate densi-
Kd = Relief valve discharge coefficient ties, along with specific enthalpies and entropies of the fluid at
It is surprising that the maximum required orifice area is not various temperatures.
in line with either the maximum mass relief rates or the maxi- Using Eqs. 1 and 2, the volumetric and mass relief rates are
mum volumetric relief rates. Figs. 4–7 illustrate the relationship calculated at different temperatures. The relief rates will peak if

TABLE 1. Volumetric and mass relief rates at different temperatures


Temperature, °F Reduced temperature Density, lb/ft³ Enthalpy, Btu/lb Entropy, Btu/lbmol–°F Vol. relief rate, ft³/hr Mass relief rate, lb/hr
504.2 1.054 14.93 –679.84 52.46 3,037 45,903
506.4 1.057 14.55 –677.12 52.70 3,143 46,331
508.7 1.059 14.19 –674.41 52.94 3,242 46,596
510.9 1.062 13.84 –671.73 53.18 3,331 46,693
513.2 1.064 13.50 –669.07 53.42 3,410 46,621
515.4 1.067 13.18 –666.44 53.65 3,478 46,390
517.7 1.069 12.87 –663.86 53.88 3,534 46,014
519.9 1.072 12.57 –661.31 54.10 3,578 45,511
522.2 1.074 12.29 –658.81 54.32 3,612 44,901
524.4 1.076 12.03 –656.34 54.54 3,635 44,205
526.7 1.079 11.78 –653.92 54.75 3,650 43,443
528.9 1.081 11.54 –651.55 54.96 3,657 42,633
531.2 1.084 11.32 –649.21 55.16 3,657 41,791
533.4 1.086 11.11 –646.90 55.36 3,651 40,929
535.7 1.089 10.91 –644.64 55.56 3,640 40,060

120 120

100 100
Maximum value, %

Maximum value, %

80 80

60 60

40 40
Volume Volume
20 Mass 20 Mass
Orifice area Orifice area
0 0
1.01 1.03 1.05 1.07 1.09 1.11 1.13 1.15 1.05 1.075 1.1 1.125 1.15 1.175 1.2 1.225 1.25 1.275 1.3
Reduced temperature Reduced temperature
FIG. 6 Hexadecane relief at 412 psia. FIG. 7 Benzene relief at 1,428 psia.

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PROCESS/PLANT OPTIMIZATION SPECIALREPORT

the temperature range is wide enough to cover the temperatures 5. For a relief valve with a 0.95 discharge coefficient, the actual
at which the peaks occur. Table 1 is a sample calculation for required orifice area would be 0.564/0.95 = 0.594 in2.
n-hexane at PR = 1.5. As shown in Table 1, the maximum mass
relief rate occurs when the temperature in the vessel reaches Takeaway. As process simulator capability increases, the
510.9°F (TR = 1.062) and the maximum volumetric relief rate ability of engineers to utilize this software allows for a sig-
is 528.9°F (TR = 1.081). nificantly more precise calculation process. The possibility to
Relief valve orifice calculation. In the process simulator, generate additional data points for this calculation by decreas-
a constant entropy table has been developed for each entropy ing the step change in enthalpy will help increase the precision
between the maximum mass and the maximum volumetric relief of the calculation.
rates in Table 1. The property tables include the specific volume However, it is shown that, at extremely small step changes,
of the fluid at different pressures, from relief pressure to PRV the temperatures at which the maximum mass rate and maxi-
back pressure. Using a spreadsheet, the mass flux is calculated mum volume rate are generated do not approach each other.
by numerically integrating “v ΔP ” along the range of pressures, Sizing a relief device in this fashion will ensure that the orifice
from relief pressure to the PRV back pressure. The maximum is adequately sized without the application of an overly con-
mass flux represents the choked conditions in the nozzle. Tables servative factor. HP
2–4 show sample calculations for three different entropies.
Now the final table can be generated to calculate the maxi- TABLE 3. Mass flux calculation for s = 54.10
mum required orifice area throughout the relief event. Each row Btu/lbmol–°F
of the table will include throat pressure, specific entropy, mass
relief rate, maximum mass flux, and the required orifice area, Pressure, Specific volume, ∫–2vdP, Mass flux,
which is calculated from the mass relief rate and the mass flux psia ft³/lb ft²/s² lb/sec.–ft2
using Eq. 4. The orifice area calculation is presented in Table 660.0 0.07954 – –
610.4 0.08749 38,414 2,240.2
8 560.7 0.09839 81,162 2,895.6
7 511.1 0.11339 129,865 3,178.3

6 461.4 0.13367 186,683 3,232.3


Reduced pressure

411.8 0.16047 254,328 3,142.8


5
362.2 0.19550 336,193 2,965.9
4
312.5 0.24187 436,777 2,732.5
3
Max. mass 262.9 0.30539 562,633 2,456.2
2 Max. volume 213.3 0.39756 724,295 2,140.7
Max. orifice
1 163.6 0.54390 940,810 1,783.3
1.00 1.05 1.10 1.15 1.20 1.25 1.30 1.35 1.40 1.45 1.50
Reduced temperature 114.0 0.81382 1,253,057 1,375.5
64.3 1.48679 1,782,147 897.9
FIG. 8 N-pentane supercritical relief.
14.7 6.46163 3,610,108 294.0

TABLE 2. Mass flux calculation for s = 53.18 TABLE 4. Mass flux calculation for s = 54.96
Btu/lbmol–°F Btu/lbmol–°F
Pressure, Specific volume, ∫–2vdP, Mass flux, Pressure, Specific volume, ∫–2vdP, Mass flux,
psia ft³/lb ft²/s² lb/sec.–ft2 psia ft³/lb ft²/s² lb/sec.–ft2
660.0 0.07225 – – 660.0 0.08665 – –
610.4 0.07872 34,720 2,367.1 610.4 0.09576 41,951 2,138.8
560.7 0.08788 73,034 3,075.2 560.7 0.10785 88,777 2,762.8
511.1 0.10124 116,526 3,371.9 511.1 0.12383 142,057 3,043.8
461.4 0.12049 167,519 3,396.8 461.4 0.14473 203,819 3,119.3
411.8 0.14697 229,028 3,256.3 411.8 0.17184 276,623 3,060.8
362.2 0.18199 304,681 3,033.0 362.2 0.20708 363,766 2,912.5
312.5 0.22824 399,025 2,767.6 312.5 0.25379 469,756 2,700.6
262.9 0.29126 518,499 2,472.2 262.9 0.31796 601,247 2,438.7
213.3 0.38228 673,399 2,146.6 213.3 0.41135 768,974 2,131.8
163.6 0.52631 882,356 1,784.8 163.6 0.55995 992,352 1,779.0
114.0 0.79141 1,185,404 1,375.7 114.0 0.83444 1,313,031 1,373.2
64.3 1.45149 1,701,223 898.6 64.3 1.51947 1,854,378 896.2
14.7 6.32557 3,489,778 295.3 14.7 6.58830 3,718,987 292.7

HYDROCARBON PROCESSING JUNE 2012


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SPECIALREPORT PROCESS/PLANT OPTIMIZATION

TABLE 5. Mass flux and PRV orifice area calculation


Throat pressure, psia Entropy, Btu/lbmole–°F Vol. relief rate, lb/hr Mass relief rate, lb/hr Mass flux, lb/s–in.² Orifice area, in.²
488.8 52.46 3,037 45,903 3,606 0.509
488.8 52.70 3,143 46,331 3,531 0.525
488.8 52.94 3,242 46,596 3,464 0.538
475.6 53.18 3,331 46,693 3,405 0.549
475.6 53.42 3,410 46,621 3,354 0.556
475.6 53.65 3,478 46,390 3,308 0.561
475.6 53.88 3,534 46,014 3,267 0.563
475.6 54.10 3,578 45,511 3,230 0.564
462.5 54.32 3,612 44,901 3,196 0.562
462.5 54.54 3,635 44,205 3,167 0.558
462.5 54.75 3,650 43,443 3,140 0.553
462.5 54.96 3,657 42,633 3,115 0.547
462.5 55.16 3,657 41,791 3,092 0.541
462.5 55.36 3,651 40,929 3,070 0.533
462.5 55.56 3,640 40,060 3,050 0.525

LITERATURE CITED Piruz Latifi Nezami is a process engineering section manager with Jacobs
1 Francis, J. O. and W. E. Shackelton, “A Calculation of Relieving Requirements Engineering in Houston, Texas. He holds a BS degree in chemical engineering from
in the Critical Region,” API Proceedings—Refining Department, 50th Mid- Sharif University of Technology in Tehran, Iran, and has more than 30 years of experi-
Year Meeting, 1985. ence in the design and engineering of chemical, petrochemical and refining projects.

2 Ouderkirk, R., “Rigorously Size Relief Valves for Supercritical Fluids,” Jerry Price is a refining and petrochemicals consultant for Jacobs Consultancy
Chemical Engineering Progress, August 2002. Inc. in Houston, Texas. Jacobs Consultancy provides expert consulting services to the
global oil, refining and chemical industries. Mr. Price previously worked as a process
3 Freeman, S., and D. Huyen, “Calculation of Relief Rate Due to Fluid engineer for Jacobs Engineering Group. He holds a BS degree in chemical engineering
Expansion and External Heat,” API Summer Meeting, 2010. from Washington University in St. Louis, Missouri.

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