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

37

48
47

36
46
35

45
44

34
43
33

42
41

Mass method 1
Mass method 2
Volume method 1
Volume method 2

40
39
505
FIG. 1

510

515

520
525
Temperature, F

Volume relief rate, 100 ft3/hr

where:
VR = Volumetric relief rate
Q = Heat input
h1 = Initial specific enthalpy
h2 = Final specific enthalpy
1 = Initial density
2 = Final density
The mass relief rate can be determined using the average of the
initial and final densities for each interval.
+ 2
M R = 1
V
(2)
2 R
where:
MR = Mass relief rate

Both the volumetric and mass relief rates will change during
the course of a relief as the specific volume and enthalpy of the
fluid change. To estimate the relief rates at different intervals, one
can generate a property table in a process simulator to calculate
the densities and specific enthalpies of the fluid at a constant
relief pressure over a given temperature range. The volumetric
and mass relief rates for each interval can be calculated using Eq.
1 and Eq. 2, respectively.
In this study, a series of calculations were conducted for randomly selected n-paraffins, i-paraffins and aromatic compounds
from C1 to C16 , using the Peng-Robinson equation of state
(EOS). The results indicate that the maximum mass relief rate
occurs at lower temperature than the maximum volumetric relief.
Both temperatures where the maximum relief rates occur are
greater than the critical temperature. Improving the calculation precision by reducing the temperature increments does not
affect the temperatures at which the mass and the volume relief
rates peak. (Smaller temperature increments result in a smaller
enthalpy change, h, which translates to a smaller time span.)
In fact, it is possible to mathematically prove that the two peaks
occur at two different temperatures for real gas. This is where
this article differs from the one presented at the API meeting.3

Mass relief rate, 1,000 lb/hr

n the past 40 years, several different methods have been suggested

for relief load and pressure relief valve (PRV) orifice sizing calculations for a supercritical fluid exposed to an external heat source.
The following sources include some of these methods:
API 521 suggests the use of a latent heat of 50 Btu/lb for
hydrocarbons near the critical point. In the absence of a better
method, this led to the use of 50 Btu/lb for even supercritical fluids.
A Calculation of Relieving Requirements in the Critical
Region1
Rigorously Size Relief Valves for Supercritical Fluids2
Calculation of Relief Rate Due to Fluid Expansion and
External Heat.3
The most recent method, Calculation of Relief Rate Due to
Fluid Expansion and External Heat, was presented at the API
2010 Summer Meeting. As the title suggests, the relief load is calculated based on the expansion of the fluid due to absorbed heat.
This method can be used for any fluid, including vapor and liquid,
as long as no phase change occurs. To maintain a constant pressure
at a fixed volume, the relief rate at any interval must be equal to the
additional volume created by the change in specific volume from
heat input to the fluid. However, some assumptions must be made
and some basis must be set to make this method viable:
Other than the relieving stream, no fluid enters or leaves the
vessel during the course of relief
There is no change of phase during the course of relief.
A simple equation can be set to calculate the relief rate at each
interval:
1
Q
1
VR =

(1)

h2 h1 2 1

32

530

535

31
540

Volumetric and mass relief rates (10 data points).

HYDROCARBON PROCESSING JUNE 2012

I 77

SPECIALREPORT

PROCESS/PLANT OPTIMIZATION

The subject was examined using two different approaches to

calculate maximum relief rates (volumetric and mass) for n-hexane
at 660-psia relief pressure with 5 million Btu/hr absorbed heat and
a one-hour duration.
In the first approach, the relief rates were calculated by setting
up property tables and using Eqs. 1 and 2 for three different temperature increments. The second approach was based on stepwise
simulation models with three different time spans. The initial and
final temperatures were made the same to apply the same bases for
all calculations. Results are plotted in Figs. 1, 2 and 3.
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
impact of reducing time span on the temperatures at which the
relief rates peak is insignificant. It is also obvious that the two
methods yield almost the exact same results for the volumetric
relief rates and very similar results for the mass relief rates. The
small difference in mass relief rate is due to the fact that, in the
first approach, at each interval the average of the initial and the
final densities are used to convert volumetric relief rate to mass
37

48
47

35

44
34
43
42

33

41

Mass method 1
Mass method 2
Volume method 1
Volume method 2

40
39
500
FIG. 2

505

510

515
520
525
Temperature, F

32

530

535

PRV orifice calculation. The API 520 equation for compress-

ible gas, which is derived from an ideal gas along an isentropic path,
is not a suitable method for supercritical fluids, since supercritical
fluids are far from ideal gas. Instead, an isentropic mass flux expression should be used for sizing relief valves in supercritical service:
P

2 vdP

(3)
P1
2

G =
2

vt

MAX
where:
G = Mass flux
v = Fluid-specific volume
P = Fluid pressure
vt = Specific volume at throat conditions
P1 = Fluid pressure at the inlet of the nozzle
120
100
Maximum value, %

45

Volume relief rate, 100 ft3/hr

Mass relief rate, 1,000 lb/hr

36
46

relief rate. In the second approach, only the final density is used
to convert volumetric relief rate to mass relief rate.
The main objective of this exercise (and the next step in the
relief valve calculation) is to size the PRV orifice area. The PRV
orifice area is a function of relief valve set pressure, relief load,
density and some other properties of the relieving fluid. In a
scenario where a vessel or container is exposed to external heat,
the fluid properties (and the relief load) vary during the course
of a relief. The goal is to find the maximum required orifice area,
as outlined below.

31
540

80
60
40

0
1.05
37

48

Volume
Mass
Orice area

20

Volumetric and mass relief rates (20 data points).

FIG. 4

1.15

1.25

1.35
1.45
1.55
Reduced temperature

1.65

1.75

Methane relief at 1,346 psia.

47

44
34
43
33

42
Mass method 1
Mass method 2
Volume method 1
Volume method 2

41
40
39
500

FIG. 3

78

505

510

515
520
525
Temperature, F

32

Volume
Mass
Orice area

100
80
60
40
20

530

535

Volumetric and mass relief rates (30 data points).

I JUNE 2012 HydrocarbonProcessing.com

120

Maximum value, %

35

45

Volume relief rate, 100 ft3/hr

Mass relief rate, 1,000 lb/hr

36
46

31
540

0
1.05
FIG. 5

1.10

1.15

1.20
1.25
1.30
Reduced temperature

Iso-octane relief at 745 psia.

1.35

1.40

SPECIALREPORT

PROCESS/PLANT OPTIMIZATION

Eq. 3 is the result of a volumetric energy balance for an isentropic nozzle, and it is valid for any homogeneous fluid regardless of the non-ideality or compressibility of the fluid. Derivation details of the equation and the numerical examples for mass
flux calculation are presented in Appendix B of API 520.
Eq. 3 can be solved with a numerical integration technique.
With the use of a process simulator, a property table can be generated along the isentropic line to find specific volumes at various
pressures, beginning at relief pressure and moving down to the
relief valve back pressure. Solving Eq. 3 for each downstream
pressure will result in a series of mass fluxes, which will peak when
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
the mass relief rate and the discharge coefficient:
(4)
MR
A=
G Kd
where:
A = Required orifice area
Kd = Relief valve discharge coefficient
It is surprising that the maximum required orifice area is not
in line with either the maximum mass relief rates or the maximum volumetric relief rates. Figs. 47 illustrate the relationship

between the maximum relief rates (mass and volumetric) and the
maximum required orifice area for the relief valve for some of
the hydrocarbons used in this study.
Fig. 8 shows the relationship between the maximum mass
relief rate, the maximum volumetric relief rate, and the maximum required orifice area for n-pentane at various relief pressures. The maximum required orifice area appears at a temperature between the corresponding temperatures of the maximum
volumetric and maximum mass relief rates for relief pressures
from PR = 1 to PR = 7. Similar patterns were observed for other
pure hydrocarbons used in the study.
Numerical example. The following example illustrates

relief load and orifice-sizing calculations for a vessel containing

n-hexane and absorbing 5 million Btu/hr of heat with a relieving
pressure of 660 psia (PR = 1.5).
Relief load calculation. A spreadsheet is used to calculate
the relief rates at various stages of a relief incident. Utilizing a
process simulator, a property table was created to calculate densities, along with specific enthalpies and entropies of the fluid at
various temperatures.
Using Eqs. 1 and 2, the volumetric and mass relief rates are
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/ft

Enthalpy, Btu/lb

Entropy, Btu/lbmolF

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

100

100

80
60
40
Volume
Mass
Orice area

20
0
1.01
FIG. 6

80

Maximum value, %

120

Maximum value, %

120

1.03

1.05

1.07
1.09
1.11
Reduced temperature

Hexadecane relief at 412 psia.

I JUNE 2012 HydrocarbonProcessing.com

1.13

Vol. relief rate, ft/hr Mass relief rate, lb/hr

80
60
40
Volume
Mass
Orice area

20
1.15

0
1.05 1.075 1.1 1.125 1.15 1.175 1.2 1.225 1.25 1.275 1.3
Reduced temperature
FIG. 7

Benzene relief at 1,428 psia.

PROCESS/PLANT OPTIMIZATION

Reduced pressure

the temperature range is wide enough to cover the temperatures

at which the peaks occur. Table 1 is a sample calculation for
n-hexane at PR = 1.5. As shown in Table 1, the maximum mass
relief rate occurs when the temperature in the vessel reaches
510.9F (TR = 1.062) and the maximum volumetric relief rate
is 528.9F (TR = 1.081).
Relief valve orifice calculation. In the process simulator,
a constant entropy table has been developed for each entropy
between the maximum mass and the maximum volumetric relief
rates in Table 1. The property tables include the specific volume
of the fluid at different pressures, from relief pressure to PRV
back pressure. Using a spreadsheet, the mass flux is calculated
by numerically integrating v P along the range of pressures,
from relief pressure to the PRV back pressure. The maximum
mass flux represents the choked conditions in the nozzle. Tables
24 show sample calculations for three different entropies.
Now the final table can be generated to calculate the maximum required orifice area throughout the relief event. Each row
of the table will include throat pressure, specific entropy, mass
relief rate, maximum mass flux, and the required orifice area,
which is calculated from the mass relief rate and the mass flux
using Eq. 4. The orifice area calculation is presented in Table

SPECIALREPORT

5. For a relief valve with a 0.95 discharge coefficient, the actual

required orifice area would be 0.564/0.95 = 0.594 in2.
Takeaway. As process simulator capability increases, the
ability of engineers to utilize this software allows for a significantly more precise calculation process. The possibility to
generate additional data points for this calculation by decreasing the step change in enthalpy will help increase the precision
of the calculation.
However, it is shown that, at extremely small step changes,
the temperatures at which the maximum mass rate and maximum volume rate are generated do not approach each other.
Sizing a relief device in this fashion will ensure that the orifice
is adequately sized without the application of an overly conservative factor. HP

TABLE 3. Mass flux calculation for s = 54.10

Btu/lbmolF
Pressure,
psia

Specific volume,
ft/lb

2vdP,
ft/s

Mass flux,
lb/sec.ft2

660.0

0.07954

610.4

0.08749

38,414

2,240.2

560.7

0.09839

81,162

2,895.6

511.1

0.11339

129,865

3,178.3

461.4

0.13367

186,683

3,232.3

411.8

0.16047

254,328

3,142.8

362.2

0.19550

336,193

2,965.9

312.5

0.24187

436,777

2,732.5

262.9

0.30539

562,633

2,456.2

213.3

0.39756

724,295

2,140.7

163.6

0.54390

940,810

1,783.3

114.0

0.81382

1,253,057

1,375.5

64.3

1.48679

1,782,147

897.9

14.7

6.46163

3,610,108

294.0

5
4
3
Max. mass
Max. volume
Max. orice

1
1.00 1.05 1.10 1.15 1.20 1.25 1.30 1.35 1.40 1.45 1.50
Reduced temperature
FIG. 8

N-pentane supercritical relief.

TABLE 4. Mass flux calculation for s = 54.96

Btu/lbmolF

TABLE 2. Mass flux calculation for s = 53.18

Btu/lbmolF
2vdP,
ft/s

Pressure,
psia

660.0

0.08665

34,720

2,367.1

610.4

0.09576

41,951

2,138.8

3,075.2

560.7

0.10785

88,777

2,762.8

0.12383

142,057

3,043.8

Specific volume,
ft/lb

660.0

0.07225

610.4

0.07872

560.7

0.08788

73,034

Specific volume,
ft/lb

2vdP,
ft/s

Mass flux,
lb/sec.ft2

Pressure,
psia

Mass flux,
lb/sec.ft2

511.1

0.10124

116,526

3,371.9

511.1

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

0.25379

469,756

2,700.6

312.5

0.22824

399,025

2,767.6

312.5

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

0.83444

1,313,031

1,373.2

114.0

0.79141

1,185,404

1,375.7

114.0

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

I 81

SPECIALREPORT

PROCESS/PLANT OPTIMIZATION

TABLE 5. Mass flux and PRV orifice area calculation

Throat pressure, psia

Entropy, Btu/lbmoleF

Vol. relief rate, lb/hr

Mass relief rate, lb/hr

Mass flux, lb/sin.

Orifice area, in.

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

Francis, J. O. and W. E. Shackelton, A Calculation of Relieving Requirements

in the Critical Region, API ProceedingsRefining Department, 50th MidYear Meeting, 1985.

Engineering in Houston, Texas. He holds a BS degree in chemical engineering from

Sharif University of Technology in Tehran, Iran, and has more than 30 years of experience in the design and engineering of chemical, petrochemical and refining projects.

Ouderkirk, R., Rigorously Size Relief Valves for Supercritical Fluids,

Chemical Engineering Progress, August 2002.

Freeman, S., and D. Huyen, Calculation of Relief Rate Due to Fluid

Expansion and External Heat, API Summer Meeting, 2010.

Jerry Price is a refining and petrochemicals consultant for Jacobs Consultancy

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
engineer for Jacobs Engineering Group. He holds a BS degree in chemical engineering
from Washington University in St. Louis, Missouri.

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