FIG.
5-1 (Cont’d)
Nomenclature
r = ratio of downstream pressure to upstream pres-
sure, P2/P1
R = distance from flame center to point X, m
J Wf
Ro = universal gas constant = 8314
kg • mol K
Re = Reynolds number (dimensionless)
S = specific heat, kJ/(kg • °C)
t = temperature, °C
T = absolute temperature of the inlet vapor, K
Tn = normal operating gas temperature, K
T1 = gas temperature, K, at the upstream pressure
Tw = vessel wall temperature, K
Ud = maximum allowable vapor velocity for vertical
vessel, m/s
V = gas velocity, m/s
Vex = exit velocity, m/s
Vl = flow rate, liters/s at flowing tempera-
ture and pressure
Vw = wind velocity, m/s
Nomenclature for this section is covered in Fig. 5-1. Pres-
sure relief valve is a generic term applied to relief valves,
safety valves, or safety relief valves. Definition by type of relief
valve is covered in the relief device description. Relief valve
characteristics related to pressure vessel requirements are il-
lustrated in Fig. 5-2.
RELIEF DEVICE DESIGN
Pressure relief valves or other relieving devices are used to
protect piping and equipment against excessive over-pressure.
Proper selection, use, location, and maintenance of relief de-
vices are essential to protect personnel and equipment as well
as to comply with codes and laws.
Determination of the maximum relief required may be dif-
ficult. Loads for complex systems are determined by conserva-
tive assumptions and detailed analysis. By general
assumption, two unrelated emergency conditions caused by
unrelated equipment failures or operator error will not occur
simultaneously (no double jeopardy). The sequence of events
must be considered. The development of relief loads requires
the engineer to be familiar with overall process design, includ-
ing the type of pump drives used, cooling water source, spares
provided, plant layout, instrumentation, and emergency shut-
down philosophy.
This section suggests methods to calculate relief capacity for
most emergency conditions, including fire. A common refer-
ence for determining individual relieving rates is contained in
Section 3 of API RP 521.1 The design of the proper relieving
device must take into consideration all of the following upset
conditions for the individual equipment item if such upset can
occur. Each upset condition must be carefully evaluated to de-
termine the "worst case" condition which will dictate the re-
lieving device capacity.
5-2
W =
flow, kg/h
Whc =
hydrocarbon flow, kg/h
Wstm =
steam flow, kg/h
=
flare gas flow rate, kg/h
Wr =
vapor rate to be relieved by the relief valve, kg/h
xi =
weight fraction of component i in total stream
X =
distance from the base of the stack to another
point at the same elevation, m
Xc = see Fig. 5-21
Yc = see Fig. 5-21
Z = compressibility factor at flowing conditions
Greek
∆ = prefix, indicates finite increment
ε = fraction of heat radiated
ρL = density of liquid, kg/m3
ρv = density of vapor, kg/m3
θ = angle of flare flame from vertical, degrees
µ = viscosity at flowing temperature,
mPa • s
Blocked Discharge
The outlet of almost any vessel, pump, compressor, fired
heater, or other equipment item can be blocked by mechanical
failure or human error. In this case, the relief load is usually
the maximum flow which the pump, compressor, or other flow
source produces at relief conditions.
Fire Exposure
Fire is one of the least predictable events which may occur
in a gas processing facility, but is a condition that may create
the greatest relieving requirements. If fire can occur on a
plant-wide basis, this condition may dictate the sizing of the
entire relief system; however, since equipment may be dis-
persed geographically, the effect of fire exposure on the relief
system may be limited to a specific plot area. Vapor generation
will be higher in any area which contains a large number of
uninsulated vessels. Various empirical equations have been
developed to determine relief loads from vessels exposed to
fire. Formula selection varies with the system and fluid con-
sidered. Fire conditions may overpressure vapor-filled, liquid-
filled, or mixed-phase systems.
Tube Rupture
When a large difference exists between the design pressure
of the shell and tube sides of an exchanger (usually a ratio of
1.5 to 1 or greater), provisions are required for relieving the
low pressure side. Normally, for design, only one tube is con-
sidered to rupture. Relief volume for one tube rupture can be
calculated using appropriate sizing equations in this section.
When a cool media contacts a hot stream, the effects of flashing
should be considered. Also the possibility of a transient over-
pressure caused by the sudden release of vapor into an all-liq-
uid system should be considered.
Control Valve Failure
The failure positions of instruments and control valves must
be carefully evaluated. In practice, the control valve may not
fail in the desired position. A valve may stick in the wrong
Revised (5–99)
 FIG. 6-21
Partial Volume in Horizontal and Vertical Storage Tanks with Ellipsoidal or Hemispherical Heads

 H1 
Tota l volum e = volume in 2 heads + volu me in cylinder α = 2 x At an 




√  D 2 
2 x H1 x 2 −H1 

 
= 1/6 π K1 D + 1/4 π D L
3 2

K1 = 2 b/D Ze = H1/D Zc = H1/D wher e α is in radians

Part ial volu me= 1/6 π K1 D × [f(Ze)] + 1/4 π D L × [ f(Zc)]
3 2

 α − sin (α ) x cos (α ) 
f(Zc) = Hor izontal cylinde r coefficient(see Fig. 6−22) or f(Zc) =  
 π 
2
 H1   2H1 
f(Ze) = Ellipsoi dal coefficient (see Fig. 6−23) f(Ze) = −   x  −3 +
D 
or
D 
For ell ipt ical 2:1 hea ds, b = 1/4 D , K1 = 1⁄2

VERTICAL CYLINDRICAL TANKS

D D D

b b H2 b

L H3
L L

H3

H1 b H1 b H1 b

Total v olume = volum e in heads + volume in cylinder

3 2
= 1/6 π K1 D + 1/4 π D L
3 2
Par t ial voul me = 1/6 π K1 D × [f(Ze)] + 1/4 π D H3

K1 = 2 b/D

Ze = (H1 + H2)/K1 D
2
 H1 + H2    H1 + H2 
f(Ze) = Ellipsoidal coefficient (see Fig. 6−23) or f(Ze) = −   x −3 +  
 2b    b 

6-19 Revised (5-99)

 FIG. 8-1 (Cont’d)
Nomenclature

T = temperature, K Subscripts
∆T = temperature difference, °C a = atmospheric air at operating conditions
t = fin thickness, mm as = air at standard conditions
U = overall heat transfer coefficient, W/(m2 • K) B = barometric
UHT = useful heat transfer or heat duty, W b = bulk
V = velocity, m/s c = convective
w = weight of air, kg cs = cross section, projection
wt = wall thickness, mm f = fin; fouling; friction; Fanning
∆x = distance in direction of heat transfer, m or mm g = gas
Y = expansion factor, dimensionless gs = gas at standard conditions
Greek i = inside, internal
β = volumetric coefficient of thermal expansion, LM = log mean base e
1/(°C or K) m = middle surface
ε1, ε2, = emissivities of combustion gases and wall, o = outside, external, overall
respectively p = pipe
µ = viscosity of fluid, mPa • s r = radiant
ρ = density of fluid, kg/m3 s = stack
σ = Stefan-Boltzmann constant, w = wall
5.67 (10–8) W/(m2 • K4) 1 = burner operating conditions 2
π = 3.1416 2 = burner operating conditions 2

FIG. 8-2 ∆T
Q = 1000 • k • A • Eq 8-1
wt
Heater Applications and Characteristics
For heat transfer in cylindrical geometry where the heat
Direct Fired Firetube transfer is normal to the axis, as in heat flow through a cylin-
Applications drical vessel or pipe wall:
Hot oil heater Indirect fired water bath 2 • π • L • k • ∆T 2 • π • L • k • ∆T
Q= = Eq 8-2a
Regeneration gas heaters heaters (line heaters) ln (Do /Di) ln(do /di)
Amine and stabilizer reboilers Propane and heavier hydro-
carbon vaporizers For radial heat flow through a spherical vessel:
Hot oil and salt bath heaters
2 • π • k • ∆T π • k • ∆T
Glycol and amine reboilers Q= = Eq 8-2b
(1 / Di ) + (1 / Do ) (500 /di ) + (500 /do )
Low pressure steam generators
Characteristics Fig. 8-3 gives the thermal conductivities and densities of
More ancillary equipment Heat duty usually less than
commercial refractories and insulation. Similar data for met-
and controls 2930 kW als are given in Fig. 8-8 and Fig. 9-8.
Higher thermal efficiency Easily skid mounted Example 8-1 — Estimate the loss per linear meter through a
Requires less plot space Forced or natural draft 25 mm layer of block insulation covering a 200 mm NPS Sch 40
Forced or natural draft combustion steam header. Assume:
combustion Less likely to have hot spots Ti = 120°C
or tube rupture
To = 10°C
k = 0.0721 W/(m • °C)
HEAT TRANSFER
Solution Steps
Conduction
do = 269.9 mm
Fourier’s law of conduction gives the rate of heat transfer through
substances resulting from vibrations and interactions between ad- di = 219.1 mm
jacent molecules as opposed to overall motion or mixing of the mole-
cules. Conduction always applies to solids and rarely to fluids. L =1m

Fundamental equations for steady heat conduction through From Eq 8-2a

some common solid shapes, ignoring border conditions, are:
2 • π • L • k(Ti − To ) 2 (3.1416)(1)(0.0721)(120−10)
Q = =
For unidimensional perpendicular heat flow through flat ln (do /di ) ln (269.9 / 219.1)
walls, as in heat flow through a square or very large cylindrical
tank wall: = 239 W per linear m

8-2 Revised (5–99)

 FIG. 9-13 FIG. 9-14
Heat Exchanger Detail Design Results Propane Condensing Curve

vapor. Under this “wet wall” condition, the effective tempera-

Leakage – use TEMA tolerances
tube hole = 576 • 19.05 • π • 0.4
shell crack = 762π • 4.445 • 0.60
Window flow area:
window area = 0.237 • (762)2
tubes in window = 208 • 0.785 • (19.05)2
Cross flow area:
Free area = 171.45 mm • 473.08
Leakage
Net cross flow area
BP = baffle pitch = 473.08 mm
FD = free diameter = 171.45 mm
Note: window area ≅ cross flow area
ture of the vapor is the saturation temperature, and the effec-
tive heat transfer mechanism is condensation. The
determination of the point in the desuperheating zone of a
condenser where “drywall” conditions cease and “wet wall”
conditions begin is a trial and error procedure. A method fre-
quently employed to give a safe approximation of the required
surface is to use the condensing coefficient and the CMTD
based on the vapor saturation temperature to calculate the
surface required for both the desuperheating zone and the con-
densing zone.
= 13 789 mm2
= 6 385 mm2 The following Example 9-2 will illustrate the use of the heat
20 174 mm2 release curve to calculate the surface required and the LMTD
for each zone in a condenser for a pure component application.
= 137 613 mm2 Example 9-2 — A propane refrigerant condenser is required
= 59 255 mm2 to condense the vapor stream using the heat release curve as
78 358 mm2 shown in Fig. 9-14. This stream enters the condenser super-
leak 20 174 mm2 heated and leaves the condenser as a subcooled liquid. Assume
98 532 mm2
that a single-tube pass, single-shell pass, counterflow ex-
changer is used so that LMTD correction factors do not apply.
Note that the propane is on the shell side. The overall heat
= 81 109 mm2 transfer coefficients for each zone are as follows:
= 20 174 mm2
= 101 283 mm2 Desuperheating: (82°C to 42°C)
Uv = 396.6 W/(m2 • °C)
hv = 630.4 W/(m2 • °C)

Condensing: (42°C to 42°C)

The condensing of a pure component occurs at a constant
temperature equal to the saturation temperature of the in- Uc = 794.4 W/(m2 • °C)
coming vapor stream. Frequently a vapor enters a condenser
superheated and must have the sensible heat removed from Subcooling: (42°C to 35°C )
the vapor before condensation can occur. If the condensing sur-
face temperature is greater than the incoming vapor satura- UL = 649.7 W/(m2 • °C)
tion temperature, the superheat in the vapor is transferred to
the cold surface by a sensible heat transfer mechanism (“dry-
wall” condition). If the condensing surface temperature is less Solution Steps
than the saturation temperature of the incoming vapor, a con-
densate film will be formed on the cold surface. The sensible 1. Calculate the surface temperature (outside wall) on the
heat is removed from the vapor at the condensate-vapor inter- vapor side at the refrigerant stream inlet using the fol-
face by vaporizing (flashing) condensate so that the heat of lowing equation:2
vaporization is equal to the sensible heat removed from the Two = Tv – [Uv (Tv – TC)/hv]

9-10 Revised (5–99)

 FIG. 15-32 (Cont’d.)
1997 Basic Specifications – Gas Turbine Engines

Continuous Output
at ISO Conditions Pressure Turbine Output
Heat Rate Ratio Mass Flow Inlet Exhaust Shaft
Manufacturer and Fuel bhp kW Btu/(hp·hr) kJ/(kW·hr) lb/s kg/s Temp, Temp, Speed,
Model Number °C °C r/min
GENERAL ELECTRIC MARINE &
INDUSTRIAL ENGINES & ENGINE
SERVICES
LM6000PA G 56,220 41,920 6290 8900 29.6 280 127 832 460 3600
LM6000PA L 56,300 41,980 6340 8970 29.6 280 127 845 469 3600
LM6000PC G 59,835 44,620 5974 8451 29.4 280 127 837 450 3600
LM5000PC G 47,000 35,050 6840 9680 25.5 275 124 686 432 3000
LM5000PC L 47,000 35,050 6880 9735 25.5 275 124 696 440 3000
LM5000PC G 47,000 35,050 6730 9520 24.8 267 121 694 434 3600
LM5000PC L 47,000 35,050 6775 9585 24.8 267 121 704 442 3600
LM2500+(PK) G 37,000 27,600 6542 9255 21.6 178 80.8 797 503 3600
(Introductory)
LM2500+(PK) G 39,000 29,085 6495 9188 22.2 183 82.9 812 510 3600
(Design)
LM2500+(PV) G 38,200 28,500 6376 9020 21.7 179 81.3 798 496 6100
(Introductory)
LM2500+(PV) G 40,200 29,980 6317 8936 22.3 183 83.0 812 502 6100
(Design)
LM2500PE G 31,200 23,270 6777 9588 18.8 152 69.0 832 523 3600
LM1600PA G 19,200 14,320 6892 9750 21.5 103 46.7 737 488 7000
LM500 G 5600 4176 8180 11,580 14.3 35.0 15.9 768 540 7000
LM500 L 5600 4176 8220 11,630 14.4 35.0 15.9 780 550 7000
GE POWER SYSTEMS
*Regenerative Cycle
M3142(J) G 15,140 11,290 9500 13,440 7.1 117 53 542 6500
M3142R(J)* G 14,520 10,830 7390 10,450 7.3 117 53 370 6500
M5261(RA) G 26,400 19,690 9380 13,270 7.5 205 92 531 4860
M5322R(B)* G 32,000 23,870 7070 10,000 8.2 253 114 352 4670
M5352(B) G 35,000 26,110 8830 12,490 8.6 273 123 491 4670
M5352R(C)* G 35,600 26,550 6990 9890 8.7 267 121 367 4670
M5382(C) G 38,000 28,340 8700 12,310 8.9 278 126 515 4670
M6511(B) G 50,690 37,810 7860 11,120 10.9 287 130 547 4860
M7111(EA) G 109,370 81,590 7790 11,020 11.8 614 278 546 3460
KAWASAKI HEAVY INDUSTRIES, LTD.
M1A-06 G 2005 1495 11,640 16,470 9.0 20.5 9.3 960 535 1500/1800
M1A-06 L 1965 1465 11,820 16,720 9.0 20.5 9.3 960 936 1500/1800
M1A-13D G 2079 1550 10,090 14,270 9.5 17.6 8.0 1002 529 1500/1800
M1T-13D G 4090 3055 10,240 14,490 9.5 17.6 8.0 1002 529 1500/1800
M1T-06 G 3768 2810 12,130 17,160 9.0 20.5 9.3 945 525 1500/1800
M1T-06 L 3681 2745 12,330 17,440 9.0 20.5 9.3 945 526 1500/1800
M7A-01 G 7992 5960 12.7 47.4 21.5 1500/1800
M7A-01 L 12.7 47.4 21.5 1500/1800
M7A-02 G 9601 7160 8200 11,600 15.5 57.9 26.3 530 1500/1800
KIRLOSKAR OIL ENGINES LTD.
*Gas Turbine Packages
MARS-14000 G 13,410 10,000 7989 11,305 16.0 85.9 39.0 499 1500-1800
MARS-12000 L/G 11,854 8840 8187 11,585 15.7 84.0 38.1 465 1500-1800
TYPE-H L/G 5417 4040 9095 12,870 9.8 40.8 18.5 496 1500-1800
T4700* L/G 4385 3270 9611 13,600 10.0 40.6 18.4 432 1500-1800
Centaur Taurus* L/G 6088 4540 8869 12,550 10.9 45.5 20.6 489 1500-1800
Saturn-1500* L/G 1515 1130 10,498 14,855 6.5 14.3 6.5 484
MTU
LM1600-PA G/L 19,200 14,320 6892 9750 21.5 103 46.7 737 488 7000
LM2500 PE G/L 31,200 23,270 6777 9588 18.8 152 68.9 818 523 3600
LM2500 PH G/L 38,350 27,630 6301 8581 20.2 167 75.8 807 500 3600
LM2500+(PK) G/L 39,000 29,085 6495 9188 21.6 183 83.0 797 510 3600
LM2500+(PV) G/L 40,200 29,980 6317 8936 22.3 183 83.0 796 502 6100
LM6000 PC G/L 60,150 44,850 5962 8435 29.4 280 127.0 838 450 3600

Fuel: L—Liquid (Distillate); G—Gaseous (Natural Gas)

Data reproduced by permission from Diesel & Gas Turbine Worldwide Catalog, courtesy of Diesel & Gas Turbine Publications.

15-17 Revised (5–99)

 FIG. 15-32 (Cont’d.)
1997 Basic Specifications – Gas Turbine Engines

Continuous Output
at ISO Conditions Pressure Turbine Output
Heat Rate Ratio Mass Flow Inlet Exhaust Shaft
Manufacturer and Fuel bhp kW Btu/(hp•h)r kJ/(kW•hr) lb/s kg/s Temp, Temp, Speed,
Model Number °C °C r/min
NUOVO PIGNONE
PGT2 2820 2100 9680 13,700 12.5 23.4 10.8 525 22,500
PGT5 7300 5440 9520 13,470 6.6 56.8 25.8 533 10,290
PGT10 14,300 10,660 7810 11,050 14 92.8 42.1 484 7900
MS3002 15,140 11,290 9500 13,440 7.1 117 53.1 542 6500
MS3002R 14,520 10,830 7390 10,450 7.3 117 53.1 370 6500
PGT16 18,600 13,870 6980 9870 21.5 100.3 45.5 493 7900
PGT25 31,200 23,270 6760 9570 18 149.7 67.9 524 6500
PGT25- 38,200 28,490 6380 9030 20.7 176.8 80.2 496 6100
LM2500 31,200 23,270 6760 9570 18 149.7 67.9 524 3600
MS5002 38,000 28,340 8700 12,310 8.9 278 126.1 516 4670
MS5002R 35,600 26,550 6980 9890 8.7 267 121.1 367 4670
MS6001 55,170 41,140 7680 10,870 11.9 308 139.7 539 5094
LM6000 56,130 41,860 6370 9010 27.8 277 125.8 447 3600
MS7001 118,250 88,180 7570 10,710 12.6 647 293.5 534 3600
PRATT & WHITNEY CANADA, INC.
ST6L-721 L/G 624 465 11,378 16,100 7 6.61 3.00 509 33,000
ST6L-795 L/G 878 655 10,671 15,100 7.5 7.12 3.23 598 33,000
ST6L-813 L/G 1093 815 10,177 14,400 8.5 8.77 3.98 574 30,000
ST6T-76 L 1442 1075 11,943 16,900 7.7 12.98 5.89 575 6600
ST18 L/G 2661 1984 9046 12,800 15.0 17.55 7.96 532 20,000
ROLLS-ROYCE INDUSTRIAL AND
MARINE GAS TURBINES LIMITED
AVON G/L 20,360 15,182 8663 12,258 8.8 170 77.1 442 5500
RB211 G/L 39,500 29,455 6695 9473 20.8 208 94.3 490 4800
TRENT G/L 70,470 52,550 5993 8480 35.0 350 158.8 428 3000/3600
SOLAR TURBINES
"MD" bhp and kW rating at
output shaft
Saturn 20 G 1590 1185 10,370 14,670 6.6 14.3 6.5 520 22,300
Centaur 40/40S G 4700 3505 9125 12,910 10.1 41.9 19.0 446 15,500
Centaur 50/50S G 5820 4335 8640 12,225 10.3 40.8 18.5 513 16,500
Centaur 50L/50LS G 5940 4430 8460 11,970 10.1 40.6 18.5 508 14,300
Taurus 60/60S G 6960 5190 7960 11,260 11.4 47.2 21.4 482 14,300
Taurus 70S G 9660 7205 7490 10,595 15.0 56.2 25.5 479 12,000
Mars 90/90S G 13,000 9695 7690 10,885 16.2 86.4 39.2 464 9500
Mars 100/100S G 15,000 11,185 7490 10,595 17.5 91.8 41.6 486 9500
TEXTRON LYCOMING
TF15 L 1500 1119 9080 12,848 14.0 11.45 5.36 499 3000
TF40 L/G 4000 2983 9002 12,739 8.4 28.0 12.8 610 15,400
THOMASSEN INTERNATIONAL BV
M3142(J) G 15,140 9500 7.1 53 965 542 LP 6500
HP 7107
M3142R(J) G 14,520 7390 7.3 53 370 LP 6500
HP 7107
M5261(RA) G 26,400 9380 7.5 93 938 531 4860
M5382(C) G 38,000 8700 8.9 126 963 516 LP 6500
HP 7107
M5352R(C) G 35,600 6990 8.7 121 367 LP 4670
M6501(B) G 50,010 7930 10.9 131 550 4860

TURBOMECA LAND AND MARINE GAS

TURBINES
Makila TI L/G 1648 1230 9133 12918 9.9 12.1 5.5 525 1500-6000

TURBO POWER & MARINE

L/G 33,545- 25,015- 6540- 9255- 19.7- 185- 85.2- 455- 3000-
68,780 51,290 6675 9445 20.3 376 170.4 459 5000

Fuel: L— Liquid (Distillate); G—Gaseous (Natural Gas)

Data reproduced by permission from Diesel & Gas Turbine Worldwide Catalog, courtesy of Diesel & Gas Turbine Publications.

15-18 Revised (5–99)

 FIG. 15-35
Engine Ratings and Operating Parameters

Revised (5–99)
15-23
 FIG. 15-35 (Cont'd.)
Engine Ratings and Operating Parameters

Revised (5–99)
15-24
(often referred to as simply the Darcy) equation. This equation Friction Factor and Effect of Pipe Roughness
can be rationally derived by dimensional analysis, with the
When the fluid flow is laminar (Re<2000), the friction factor
exception of the friction factor, fm, which must be determined has a direct relationship to the Reynolds number, such that:
experimentally. Expressed in meters of fluid this equation is:
fm = 64 /Re or ff = 16 /Re Eq 17-8
fm L V2
hL = Eq 17-6 Pipe roughness has no effect on the friction factor in laminar
2gD flow.
Converting to kPa, the equation becomes: Substitution of the formula for Reynolds number, Eq 17-4,
into Eq 17-8, yields the following:
0.5 ρfm LV2 64 µ
∆Pf = Eq 17-7 fm = Eq 17-9
d DVρ
The Moody friction factor3, fm, is used in the equations above. This expression can then be substituted for the friction fac-
Some equations are shown in terms of the Fanning friction factor, tor in Eq 17-7, resulting in the following formula for pressure
ff, which is one fourth of fm (fm = 4.0 ff). A graph of both Fanning loss in kPa:
and Moody friction factors as a function of Reynolds number ap- 32 000 µLV
∆Pf = Eq 17-10
pears in Fig. 17-2. d2
The Darcy-Weisbach equation is valid for both laminar and tur- Eq 17-10 is commonly known as Poiseuille’s law for laminar
bulent flow of any liquid, and may also be used for gases with flow.
certain restrictions. When using this equation, changes in eleva- When the flow is turbulent, the friction factor depends on
tion, velocity, or density must be accounted for by applying Ber- the Reynolds number and the relative roughness of the pipe,
noulli’s theorem. The Darcy-Weisbach equation must be applied ε/D, which is the roughness of the pipe, ε, over the pipe diame-
to line segments sufficiently short such that fluid density is essen- ter, D. Fig. 17-2 incorporates the relative roughness of the pipe
tially constant over that segment. The overall pressure drop is the into the determination of the friction factor. Fig. 17-3 indicates
relative roughness and friction factors for various piping ma-
sum of the ∆ Pf values calculated for the individual segments. For
terials. These figures are based on the iterative solution of the
gas applications the segmental length may be relatively short, as following equation developed by Colebrook.4
compared to liquid applications, since many gas applications in-
1  ε 2.51 
volve compressible gases where gas densities vary with pressure. = −2 log 10  +  Eq 17-11
fm
√  3.7 d Re √
fm 
FIG. 17-2
Friction Factors5

17-3 Revised (5–99)

 1⁄ 2
 (P1 − P2) d5 
FIG. 17-5 Q = 0.821   Eq 17-29
  91.44 
Deviation Factors8  γ L 1 + + 0.00118 d 
  d 

Plant Piping Gas Flow

For estimating pressure drop in short runs of gas piping,
such as within plant or battery limits, a simplified formula for
compressible fluids is accurate for fully turbulent flow, assum-
ing the pressure drop through the line is not a significant frac-
tion of the total pressure (i.e. no more than 10%).
The following method is a simplification of the Darcy for-
mula, which eliminates calculation of fm, the Moody friction
factor. This simplification was checked over a wide range of
flows and densities for pressure drops of 6 to 35 kPa/100 m.
Density was varied over a range of 100 to 1; flows varied over
a range of 75 to 1. Pressure variation was from atmospheric to
7000 kPa (abs). The error from using the simplified approach
as compared to the actual friction factor calculated in the Darcy
formula was from zero to 5%, with the simplified approach giv-
ing consistently lower calculated pressure drop for a given flow.
The Darcy formula can be written in the simple form:

W2  62 530 (10 ) f 
2
∆P100 =   Eq 17-30
ρ  d5 
62.530 (1014) f
Simplifying, C1 = W2 (10−9), and C2 = , then
d5
C1 C2
∆P100 = Eq 17-31
ρ
(∆P100) ρ
C1 = = discharge factor from chart, Fig. 17-8
C2
(∆P100) ρ
C2 = = size factor Fig. 17-9
C1
Note: Refer to Section 23 for more accurate compressibility factors.

Reference should be made to “Steady Flow in Gas Pipe-
lines”6, published by American Gas Association, for a complete
analysis of steady flow in gas pipelines.
Low Pressure Gas Flow
Gas gathering often involves operating pressures below
690 kPa. Some systems flow under vacuum conditions. For
these low pressure conditions, equations have been developed
that give a better fit than the Weymouth or Panhandle equa-
tions. Two such formulas are:
C2 incorporates the friction factor, assuming clean steel. Us-
ing this simplified approach, new lines can be sized by setting
the desired ∆P100 and solving for C2 with a given flow. For a
given flow and pipe size, ∆P100 can be solved directly.
Example 17-1 — Calculate the pressure drop in a 10-in.,
Schedule 40 pipe (250 mm) for a flow of 68 400 kg/h of meth-
ane. Temperature is 15°C and pressure is 5200 kPa. The com-
pressibility factor is 0.905 (from Fig. 23-3).

The Oliphant Formula9 for gas flow between vacuum and Solution Steps
690 kPa:
16.042 (5200)
ρ = = 38.48 kg/m3
 d3   99.3   Tb  8.3145 (273 + 15) (0.905)
Q = 0.051 d2.5 +    
 30   Ps   288.9  C1 from Fig. 17-8 is 4.7
1⁄ 2 C2 from Fig. 17-9 is 78.7
 0.6   288.9   P21 − P22  C1C2 4.7 (78.7)
     Eq 17-28 ∆P100 = =
 γ   T   Lm  ρ 38.48
The Spitzglass Formula for gas flow below 7 kPa (ga) at 15°C: = 9.61 kPa/100 m using Eq 17−31

17-7 Revised (5–99)

 FIG. 17-7
Comparison of Gas Equation Transmission Factors for Nominal 500 mm Pipe

Example 17-2 — Calculate the required line size (of Sched- addition, several graphical aids are available for pressure drop
ule 40 pipe) to give ∆P100 = 25 kPa or less when flowing 34 000 calculation. Elevation pressure drops must be calculated sepa-
kg/h of methane at 2800 kPa and 38°C. The compressibility rately using Eq 17-32. These elevation pressure gains or losses
factor is 0.96 (from Fig. 23-8). are added algebraically to the frictional pressure drops.
Solution Steps ∆Pe = (0.00981) ρL Ze Eq 17-32
16.062 (2800) Water — A graph showing pressure drop for water per 100 m
ρ = = 18.12 kg/m3 as a function of flow rate in m3/h and pipe size is shown in Fig.
8.3145 (273 + 38) (0.96)
17-10. These data are based on the Hazen and Williams empirical
C1 from Fig. 17-8 is 1.16 formula10 using a “C” constant of 100 which is commonly used for
(∆P100) ρ 25 (18.12) design purposes in welded and seamless steel pipe.
C2 = = = 390.5
C1 1.16 Hazen and Williams formula for flow of water:
From Fig. 17-9 the smallest size of Schedule 40 pipe with C2 0.54
 P1 − P2 
less than 390 is 8-in. pipe. For 8 in. Sch 40 pipe, C2 is 257. The q = 3.765(10)−6 d2.63 C   Eq 17-33
actual pressure drop can then be calculated as:  L 
1.16 (257) Where:
∆P100 = = 16.45 kPa/100 m
18.12 C = 140 for new steel pipe
using Eq 17-31 for the above flow conditions.
C = 130 for new cast iron pipe
Liquid Flow
C = 100 is often used for design purposes to account for
For the calculation of pressure drop in liquid lines, the
pipe fouling, etc.
Darcy-Weisbach method, Eq 17-6, can be used. The calculation
is simplified for liquid flows since the density can reasonably Hydrocarbon — A graph showing pressure drop for hydro-
be assumed to be a constant. As a result, the Darcy-Weisbach carbons per 100 meters as a function of flow rate in m3/h and
calculation can be applied to a long run of pipe, rather than pipe size is shown in Fig. 17-11. This graph assumes a relative
segmentally as dictated by the variable density in gas flow. In density of 1.0 (water). To correct for different liquid densities,

17-10 Revised (5–99)

 To be effective, the inhibitor must be present at the very water phase and hydrocarbon phase compositions. Fig. 20-52
point where the wet gas is cooled to its hydrate temperature. presents experimental data32,33,34 showing solubility of metha-
For example, in refrigeration plants glycol inhibitors are typi- nol in a paraffinic hydrocarbon liquid as a function of tempera-
cally sprayed on the tube-sheet faces of the gas exchangers so ture and methanol concentration. Methanol solubility in
that it can flow with the gas through the tubes. As water con- naphthenic hydrocarbons is slightly less than paraffinic, but
denses, the inhibitor is present to mix with the water and pre- solubility in aromatic hydrocarbons may be four to six times
vent hydrates. Injection must be in a manner to allow good higher than in paraffinic.
distribution to every tube or plate pass in chillers and heat
Solubility of EG in the liquid hydrocarbon phase is ex-
exchangers operating below the gas hydrate temperature.
tremely small.29 A solubility of 40 g/m3 of NGL is often used
The inhibitor and condensed water mixture is separated for design purposes. However, entrainment and other losses
from the gas stream along with a separate liquid hydrocarbon may result in total losses significantly higher than this.
stream. At this point, the water dewpoint of the gas stream is Example 20-10—2.83 (106) Sm3/day of natural gas leaves an
essentially equal to the separation temperature. Glycol-water offshore platform at 38°C and 8300 kPa (abs). The gas comes
solutions and liquid hydrocarbons can emulsify when agitated onshore at 4°C and 6200 kPa (abs). The hydrate temperature
or when expanded from a high pressure to a lower pressure, of the gas is 18°C. Associated condensate production is 56
e.g., JT expansion valve. Careful separator design will allow m3/Standard m3 (106). The condensate has a density of
nearly complete recovery of the diluted glycol for regeneration 778 kg/m3 and a molecular mass of 140. Calculate the amount
and reinjection. Fig. 20-43 shows a flow diagram for a typical of methanol and 80 mass% EG inhibitor required to prevent
EG injection system in a refrigeration plant. hydrate formation in the pipeline.
The regenerator in a glycol injection system should be operated
Solution Steps:
to produce a regenerated glycol solution that will have a freezing
point below the minimum temperature encountered in the sys- Methanol
tem. This is typically 75-80 mass%. Fig. 20-44 shows the freezing
point of various concentrations of glycol water solutions. 1. Calculate the amount of water condensed per day
from Fig. 20-3, Win = 850 mg/Sm3
The minimum inhibitor concentration in the free water
phase may be approximated by Hammerschmidt’s equation.25 152 mg/Sm3_
Win = ___________
KH X I ∆W = 698 mg/Sm3
d = Eq 20-4
MI (1 − X I) Water condensed = (2.83 x 106)(698) =
where KH(glycol) = 2222 and KH(methanol) = 1297. 1975 (10 6) mg/day = 1975 kg/day
Eq 20-4 should not be used beyond 20-25 wt% for methanol and 2. Calculate required methanol inhibitor concentration
60-70 wt% for the glycols. For methanol concentrations up to about from Eq 20-4 and 20-5.
50%, the Nielsen-Bucklin equation26 provides better accuracy: d = 14°C M = 32
d = −72 ln(xH2O) Eq 20-5 Solving for XI,
Note that “xH2O” in Eq 20-5 is a mole fraction, not a mass frac- XI = 0.255, Eq 20-4
tion. Fig. 20-45 provides the conversion from mass percent XI = 0.275, Eq 20-5 (use this value in subse-
methanol to mole fraction water. quent calculations)
Maddox et.al.27 presents a method of estimating the re- 3. Calculate mass rate of inhibitor in water phase (assume
quired inhibitor concentration for both methanol and EG. The
100% methanol is injected)
method is iterative but converges easily after a few iterations.
X R • m H2O (0.275) (1975)
Figs. 20-46 thru 20-50 provide a comparison of various in- mI = = = 749 kg/day
hibitor correlations with experimental data.28,29,30 Experimen- XL − XR (1 − 0.275)
tal data at very high inhibitor concentrations is limited. 4.Estimate vaporization losses from Fig. 20-51.
Once the required inhibitor concentration has been calcu- @ 4°C and 6200 kPa (abs),
lated, the mass of inhibitor required in the water phase may kg/m3
be calculated from Eq 20-6 lo sses = 16.8 (10-6)
wt% MeOH
XR • m H2O
mI = Eq 20-6 daily losses = (1.68 x 10-6)(2.83 x 106)(27.5) =
XL − XR 1310 kg/day
The amount of inhibitor to be injected not only must be suf- 5. Estimate losses to hydrocarbon liquid phase from Fig.
ficient to prevent freezing of the inhibitor water phase, but 20-52.
also must be sufficient to provide for the equilibrium vapor
phase content of the inhibitor and the solubility of the inhibi- @ 4°C and 27.5 wt% MeOH, xMeOH ≈ 0.2 mol%
tor in any liquid hydrocarbon. The vapor pressure of methanol lb • mols of condensate per day –
is high enough that significant quantities will vaporize.
Methanol vaporization losses may be estimated from Fig. 20-  2.83 x 106 Sm3   56m3   778kg  1 kg • mol 
51.31 Fig. 20-51 is extrapolated above 4800 kPa (abs) and may   6 3  3   
 day   10 Sm   m   140 kg 
underestimate vapor phase methanol losses at higher pres-
sures. Glycol vaporization losses are generally very small and = 881 kg • mol/day
are typically ignored in calculations.
kg • mol methanol = (881)(0.002) = 1.76 kg • mols/day
Inhibitor losses to the hydrocarbon liquid phase are more
difficult to predict. Solubility is a strong function of both the kg methanol = (1.76) (32) = 56 kg/day

20-19 Revised (5-99)

 FIG. 20-42
Physical Properties of Selected Glycols and Methanol

Ethylene Diethylene Triethylene Tetraethylene

Glycol Glycol Glycol Glycol Methanol
Formula C2H6O2 C4H10O3 C6H14O4 C6H18O5 CH3OH
Molecular Mass 62.1 106.1 150.2 194.2 32.04
Boiling Point* at
760 mm Hg, °F 387.1 472.6 545.9 597.2 148.1
Boiling Point* at 760
mm Hg, °C 197.3 244.8 285.5 314 64.5
Vapor Pressure at
77°F (25°C) mm Hg 0.12 <0.01 <0.01 <0.01 120
Density
(g/cc) at 77°F (25°C) 1.110 1.113 1.119 1.120 0.790
(g/cc) at 140°F (60°C) 1.085 1.088 1.092 1.092
kg/m3
at 77°F (25°C) 1110 1113 1119 1120 790
Freezing Point, °C –13 –8 –7 –5.5 –97.8
Pour Point, °C — –54 –58 –41
Viscosity in centipoise
at 77°F (25°C) 16.5 28.2 37.3 44.6 0.52
at 140°F (60°C) 4.68 6.99 8.77 10.2
Surface Tension at
77°F (25°C), dynes/cm 47 44 45 45 22.5
Refractive Index
at 77°F (25°C) 1.430 1.446 1.454 1.457 0.328
Specific Heat
at 77 °F (25°C) kJ/(kg•K) 2.43 2.30 2.22 2.18 2.52
Flash Point, °C (PMCC) 116 124 177 204 12
Fire Point, °C (C.O.C.) 118 143 166 191

Note: These properties are laboratory results on pure compounds or typical of the products, but should not be confused with, or
regarded as, specifications.
* Glycols decompose at temperatures below their atmospheric boiling point. Approximate decomposition temperatures are:

Ethylene Glycol 165°C Triethylene Glycol 207°C

Diethylene Glycol 164°C Tetraethylene Glycol 238°C

Total methanol injection rate = 749 + 1310 + 56 GAS DEHYDRATION

= 2115 kg/day
Methanol left in the gas phase can be recovered by conden-
sation with the remaining water in downstream chilling proc-
esses. Likewise, the methanol in the condensate phase can be
recovered by downstream water washing.
80 wt% EG
Glycol Dehydration Systems
In those situations where inhibition is not feasible or practical,
dehydration must be used. Both liquid and solid desiccants may
be used, but economics frequently favor liquid desiccant dehy-
dration when it will meet the required dehydration specification.

1. Calculate required inhibitor concentration from Eq 20-4. Liquid desiccant dehydration equipment is simple to operate
and maintain. It can easily be automated for unattended opera-
d = 14°C M = 62 tion; for example, glycol dehydration at a remote production well.
Solving for XI, XI = 0.28 Liquid desiccants can be used for sour gases, but additional pre-
2. Calculate mass rate of inhibitor in water phase. cautions in the design are needed due to the solubility of the acid
gases in the desiccant solution. At very high acid gas content and
(0.28)(1975) relatively higher pressures the glycols can also be “soluble” in the
mI = = 1063 kg/day
(0.8 − 0.28) gas.

Vaporization and liquid hydrocarbon losses are negligible.
Inhibitor losses represent a significant operating cost and can
cause problems in downstream process units. Efficient inhibi-
tor separation should be provided.
Glycols are typically used for applications where dew point de-
pressions of the order of 30° to 70°C are required. Diethylene
glycol (DEG), triethylene glycol (TEG), and tetraethylene glycol
(TREG) are used as liquid desiccants, but TEG is the most com-
mon for natural gas dehydration.

20-23 Revised (5-99)

 FIG. 20-51
Ratio of Methanol Vapor Composition to Methanol Liquid Composition

Fig. 20-54 is based on equilibrium data published by Parrish,
et. al.35 Several equilibrium correlations36,37,38,39,40 have been
presented since 1950. Previous editions of the GPSA data book
presented an equilibrium correlation based on the work of Wor-
ley.38 In general, the correlations of Worley,38 Rosman39 and Par-
rish35 agree reasonably well and are adequate for most TEG
system designs. All are limited by the ability to measure accu-
rately the equilibrium concentration of water in the vapor phase
above TEG solutions. The Parrish correlation has been included
in this edition because equilibrium water concentrations in the
vapor phase were determined at infinite dilution (essentially
100% TEG). The other correlations use extrapolations of data at
lower concentrations to estimate equilibrium in the infinite dilu-
tion region.
Please note that the equilibrium water dewpoints on the ordi-
nate of Fig. 20-54 are based on the assumption the condensed
water phase is a metastable liquid. At low dewpoints the true
condensed phase will be a hydrate. The equilibrium dewpoint
temperature above a hydrate is higher than that above a metas-
table liquid. Therefore, Fig. 20-54 predicts dewpoints which are
colder than those which can actually be achieved. The difference
is a function of temperature, pressure and gas composition but
can be as much as 8-11°C (see Fig. 20-13). When dehydrating to
very low dewpoints, such as those required upstream of a refrig-
eration process, the TEG concentration must be sufficient to dry
the gas to the hydrate dewpoint.
Once the lean TEG concentration has been established, the
TEG circulation rate and number of trays (height of packing)
must be determined. Most economical designs employ circulation
rates of about 15-40L TEG/kg H2O absorbed. The relationship
between circulation rate and number of equilibrium stages em-
ploys the absorption calculation techniques set out in Chapter
19. This has been done for TEG systems with the results pre-
sented in Figs. 20-55 through 20-59.
Conversion from equilibrium stages to actual trays can be
made assuming an overall tray efficiency of 25-30%. For pack-
ing, Height of Packing Equivalent to a Theoretical Plate
(HETP) varies with TEG circulation rate, gas rate, and gas
density but a value of about 1.5 m is usually adequate for
planning purposes. When the gas density exceeds about 100
kg/m3 (generally at very high pressures), the above conver-

20-28 Revised (5-99)

 Decisions in selecting a gas treating process can many times Concentration, mole/liter
pH
be simplified by gas composition and operating conditions. High H+ OH –
partial pressures (345 kPa) of acid gases enhance the probability 1 1.0 • 10–1 1.0 • 10–13
of using a physical solvent. The presence of significant quantities
Acid Side 2 1.0 • 10–2 1.0 • 10–12
of heavy hydrocarbons in the feed discourages using physical sol-
(Excess H+) 3 1.0 • 10–3 1.0 • 10–11
vents. Low partial pressures of acid gases and low outlet specifi-
cations generally require the use of amines for adequate treating. 4 1.0 • 10–4 1.0 • 10–10
Process selection is not easy and a number of variables must be 5 1.0 • 10–5 1.0 • 10–9
weighed prior to making a process selection. Fig. 21-2 gives a 6 1.0 • 10–6 1.0 • 10–8
summary for a number of processes. Neutral Solution 7 1.0 • 10–7 1.0 • 10–7
Controlling pH is very important in most of the processes 8 1.0 • 10–8 1.0 • 10–6
discussed in this section. The following is offered to assist in 9 1.0 • 10–9 1.0 • 10–5
understanding electrolyte solutions and pH. 10 1.0 • 10–10 1.0 • 10–4
11 1.0 • 10–11 1.0 • 10–3
An electrolyte is a substance or material that will provide
Basic Side 12 1.0 • 10–12 1.0 • 10–2
ionic conductivity when dissolved in water. Both bases and
acids, if they ionize in water, can be electrolytes. In water, 13 1.0 • 10–13 1.0 • 10–1
acids ionize or split, into H+ and the cation. The H+ combines Examination of the table leads one to the conclusion that
with a water molecule to form H3O+ which is usually written “weak” electrolytes (those to which the concept of pH can be
as H+ and is referred to as a hydrogen ion, or proton. Water- usefully applied) range over strong acid (base) concentrations
soluble bases, on the other hand, ionize in water to produce up to 0.1 gram mole / liter.
hydroxyl or OH– ions and an anion. Pure water ionizes such
that the concentration of H+ (and OH–) in the solution is 10–7 Example 21-1 — 20 m3 of amine solution with a pH of 12 is to
gram ions / liter. be neutralized by the addition of hydrochloric acid (HCl). How
many kg of pure HCl will be required?
The method used for measuring hydrogen and hydroxyl ion
Solution steps:
concentrations uses pH (from the French pouvoir hydrogene),
where the pH of a solution is the logarithm (base 10) of the 20 m3 • 1000(liter/m3) = 2.0 • 104 liters
reciprocal of the hydrogen ion concentration (gram mole / li-
ter). For pure water, then, the pH would be: For each liter of solution the change in OH– (H+) required is

pH = log (1/ [H+]) = 7 (10−2) − (10−7) = 1.0 • 10−2 gram moles

When a water molecule dissociates, one proton and one hy-
droxyl ion are formed. The concentration of OH– in pure water,
then, is also 10–7 mole / liter.
A strong acid (or strong base) is one which ionizes completely
in water solution. Typical are HCl or NaOH. At an acid con-
centration of 0.1 mole / liter, the pH of a strong acid will be 1.
The following table will be helpful in understanding the rela-
tive concentrations of H+ and OH – in solutions of different pH.
FIG. 21-2
Process Capabilities for Gas Treating
The total requirement of HCl is
(2.0 • 104) liter • (1.0 • 10–2) (g mole/liter) = 200 g mole
or
(200 g mole)(36.5 g/g mole)
= 7.3 kg HCl
1000 (gram/kg)
Note that at a pH of 7, all of a weak acid (base) would prob-
ably not be neutralized. The pH required to have all of a weak
acid (base) neutralized will vary with the acid but will usually
be less (greater) than 7. In the example all of the HCl is neu-
tralized because it is completely ionized in the water solution.

Normally Capable of Removes Selective H 2S Solution Degraded

Meeting 0.25 grain* H2S Mercaptans and COS Removal (By)
Primary Amine Yes Partial No Yes (COS, CO2, CS2)
Secondary Amine Yes Partial No Some (COS, CO2, CS2)
Tertiary Amine Yes Partial Yes+ No
Hybrid/Mixed*** Yes Yes Yes+ Some (CO2, CS2)
Physical Solvent Maybe** Yes Yes+ No
Solid Bed Yes Yes Yes+ No
Liquid Redox Yes No Yes CO2 at high conc.
Sacrificial Yes Partial Yes No
* 0.25 grains H2S/100 scf ≈ 5.7 mg/m3 (4 ppmv) ** Can make 0.25 grain under some conditions
+ Some selectivity exhibited *** e.g., Sulfinol®

21-5 Revised (5-99)

 FIG. 23-31 FIG. 23-32
Thermal Conductivity of Natural and Hydrocarbon Gases Thermal Conductivity Ratio for Gases
at One Atmosphere [101.325 kPa (abs)]

Data Sources

1. "Thermal Conductivity of Light Hydrocarbon

/ (m • ˚C)

and Methane-Propane Mixtures at Low Pressures,"

Smith, Durbin and Koboyashi: J. Chem Eng. Data,
Vol 5, No. 3, July 1960.
2. "Self-Consistent Correlation of Thermodynamic
and Transport Properties," K.E. Starling, et al,
W

GRI/AGA Project No. BR-111-1: OU-ORA Project

No. 2036 156-716. Report: GR/AGA/BR-111-1/77-36.

Experimental data on mixtures indicate

this plot can be used to estimate the
thermal conductivity (± 10%) of mixtures
using the mixture molecular mass.

determined by the “cube root rule.”56 This rule is applicable SURFACE TENSION
to mixtures of simple gases; it does not apply to mixtures con-
taining CO2 because the thermal conductivity goes through a
maximum. The interior molecules of a liquid exert upon the surface
molecules an inward force of attraction which tends to mini-
Σ (yi ki √ )
3
MW i mize the surface area of the liquid. The work required to en-
km = 3 Eq 23-30 large the surface area by one square centimeter is called the
Σ yi √
MW i surface free energy. The perpendicular force in the liquid sur-
face, called surface tension, exerts a force parallel to the plane
The cube root rule was tested56 against 17 systems with an of the surface. Surface tension, an important property where
average deviation of 2.7%. wetting, foaming, emulsification, and droplet formation are
encountered, is used in the design of fractionators, absorbers,
The thermal conductivity of a liquid mixture is best deter- two-phase pipelines, and in reservoir calculations.
mined by the method of Li,55 based on volume fractions.
Example 23-12 — Find the thermal conductivity of the gase- Pure Components
ous mixture shown in Fig. 23-37 at 100°C and one atmosphere.
The surface tension of pure hydrocarbons as a function of
0.10780 temperature may be obtained from Fig. 23-38.
km = = 0.0382W/(m • °C)
2.822
Mixtures
Surface tension for binaries of known composition at or near
atmospheric pressure may be calculated78 using:
TRANSPORT PROPERTY REFERENCES
σ1 • σ2
σm = Eq 23-31
There are no simple correlations for the transport properties σ1 • x2 + σ2 • x1
of viscosity and thermal conductivity, as evident from the pre-
ceding paragraphs. For pure components, the best approach The presence of inert gases, such as N2 and CO2, in the liquid
is a complicated equation with many constants that must be phase tends to lower the surface tension of the liquid. Where the
fitted to experimental data, or extensive tables. Vargaftik62 concentration of inert gases in the liquid exceeds 1.0 mole%, es-
and Touloukian65 each have extensive collections of experi- timated values of surface tension may be 5 to 20% higher than
mental data. actual values for the mixture.

23-35 Revised (5-99)

 The adjusted mole fractions are calculated using the follow-
ing equation:
  Pow 
i = yi 1 − 
yw  = yi (1 − yw) Eq 23-37
  P 
For water saturated gas, water is added to the component
list and the xw
i values are used in the gross heating value and
the gas compressibility calculations. If the dry gross heating
value is known, the water saturated gross heating value can
be calculated by:
  1.7051   1.7051 • 29.94 
Hv(sat’d) = 1 −   Hv (dry) +   1984.
  P   P 
Eq 23-38
When the gas is wet but not water saturated and the com-
ponent analysis is on a dry basis, it is necessary to determine
the water content and to adjust the mole fractions to reflect
the presence of water. When the water mole fraction, yw, is
known, the adjusted mole fractions can be obtained from Eq
23-37.
The yiw values are used in the gross heating value and gas
compressibility calculations after adding water to the compo-
nent list. If the dry gross heating value is known, the effect of
the water content can be calculated using:
Hv (wet) = (1 − yw) Hv (dry) + 50.3 yw Eq 23-39
Calculations — Additional details on these calculational
methods and examples are given in GPA Standard 2172, "Calcu-
lation of Gross Heating Value, Relative Density and Compressi-
bility Factor for Natural Gas Mixtures from Compositional
Analysis." A listing of the Basic source code for a computer
program to perform the calculations is given in 2172.
REFERENCES
1. Standing, M. B. and Katz, D. L., "Density of Natural Gases,"
Trans. AIME 142 (1942).
2. Pitzer, K. S., et al., J. Am. Chem. Soc. 77, 3433 (1955).
3. Wichert, E. and Aziz, K., Hyd. Proc. 51, 199 (May, 1972).
4. Hall, K. R. and Yarborough, L., Oil Gas J. 71, No. 25, 82 (June 18,
1973).
5. Hall, K. R. and Yarborough, L., Oil Gas J. 72, No. 7, 86 (Feb. 18,
1974).
6. Robinson, R. L., Jr. and Jacoby, R. H., Hyd. Proc. 44, 141 (April,
1965).
7. Benedict, M., Webb, G. B., and Rubin, L. C., Chem. Eng. Prog.
47, No. 8, 419 (1951).
8. Starling, K. E. and Han, M. S., Hyd. Proc. 50, 129 (March, 1971).
9. Hopke, S. W. and Lin, C. J., 76th Nat’l AIChE Meeting, Tulsa,
Oklahoma, March, 1974.
10. George, B. A., Proc. 61st Ann. Conv. GPA, Dallas, Texas, p. 171
(March 15-17, 1982).
11. Brown, G. G., Katz, D. L., Oberfell, G. G., and Alden, R. C., "Natu-
ral Gasoline and the Volatile Hydrocarbons," Natural Gas Assoc.
of America, Tulsa, Oklahoma, 1948.
12. API Research Project 44, "Selected Values of Properties of Hydro-
carbons and Related Compounds," Thermodynamic Research
Center, Texas A&M University.
13. Starling, K. E., "Fluid Thermodynamic Properties for Light Pe-
troleum Systems," Gulf Publ. Co., Houston, 1973.
23-39
14. Physical Property Data Service, Institution of Chemical Engi-
neers, 165-171 Railway Terrace, Rugby, Warwickshire, U.K.
15. TRAPP by J. F. Ely and H. J. M. Hanley, U.S. National Bu-
reau of Standards, National Engineering Laboratory, Ther-
mophysical Properties Division, Boulder, Colorado 80303
(1983).
16. Petercon, J. N., Chem, C. C., and Evans, L. B., Chem. Eng. 85,
79 (July 31, 1978).
17. Garrett, J. R., Chem. Eng. 90, 149 (March 7, 1983).
18. "AIChE Applications Software Survey for Personal Computers
1984," American Institute of Chemical Engineers, New York, NY,
19. Deam, J. R., Kellizy, I. K. and Maddox, R. N., "Calculating Den-
sity of Saturated Hydrocarbon Mixtures," Proc. 48th Ann. Conv.
NGPA, Dallas, Texas, pp. 48-51 (March 1969).
20. Kay, W. B., J. Chem. Eng. Data, 15, 46 (1970).
21. Kay, W. B., Ind. Eng. Chem., 32, 353 (1940).
22. Gugnoni, R. J., Eldridge, J. W., Okay, V. C. and Lee, T. J., AIChE
J. 20, 367 (1974).
23. Reamer, H. H., Sage, B. H., and Lacey, W. N., Ind. Eng. Chem.,
43, 2515 (1951).
24. Sage, B. H. and Lacey, W. N., API Research Project 37 (1955).
25. Kay, W. B. and Price, D. B., Ind. Eng. Chem., 45, 615 (1953).
26. Kay, W. B. and Rambosek, G. M., Ind. Eng. Chem., 45, 221 (1953).
27. Bierlein, J. A. and Kay, W. B., Ind. Eng. Chem., 45, 618 (1953).
28. Arai, Y., Kaminishi, G. and Saito, S., J. Chem. Eng. of Japan, 4,
No. 2, 113 (1971).
29. Chappelear, P. S., "Low Temperature Data from Rice University
for Vapor-Liquid and P-V-T Behavior," GPSA TP-4 (April 1974).
30. Hiza, M. J. and Haynes, W. M., J. Chem. Thermodynamics, 9,
873 (1977).
31. Hiza, M. J. and Haynes, W. M., J. Chem. Thermodynamics, 12,
1 (1980).
32. Haynes, W. M. and Hiza, M. J., J. Chem. Thermodynamics, 12,
179 (1980).
33. Huang, E. T. S., Swift, G. W. and Kurata, F., AIChE J., 13, 846
(1967).
34. Gonzalez, M. H. and Lee, A. L., J. Chem. Eng. Data, 13, 172
(1968).
35. Turek, E. A., Metcalfe, R. S., Yarborough, L., and Robinson, R. L.,
DPE 9231 Presented at 55th Annual Fall Meeting of Soc. Pet.
Engrs., Dallas, Sept. 21-24, 1980.
36. Technical Data Book – Petroleum Refining American Petroleum
Inst., Washington, D.C. Procedures a: 4D4.1 (1980; b: 4D3.1
(1980); c: 4D3.2 (1980); d: 2B2.1.
37. Lee, B. I. and Kesler, M., AIChE J. 21, 510 (1975).
38. Edmister, W. C., Pet. Refiner, 37 (4), 173 (1958).
39. Smith and Watson, Courtesy of Brown and Root Inc.
40. Edmister, W. C., "Applied Thermodynamics," The Gulf Publish-
ing Co., Houston, 1961.
41. Dean, D. E. and Stiel, L. I., AIChE J., 11, 526 (1965).
42. Prausnitz, J. M. and Gunn, R. D., AIChE J., 4, 430 (1958).
43. Granet, I., and Kass, P., Pet. Ref. 31 (10), 113 (1952).
44. Kester, J., and Leidenfrost, W., "Thermodynamic and Transport
Properties of Gases, Liquids and Solids," p. 321, McGraw Hill
Book Co., Inc., New York, NY, 1959.
45. Thermodynamic Properties Research Center Data Book 2 Table
2048 (December 1962), Purdue University, Lafayette, Indiana.
Revised (5-99)
 ENTHALPY BEHAVIOR
The change of enthalpy with temperature and pressure is
complex. Predicting the enthalpy for a pure component or mix-
ture is a multi-step procedure that requires information that
can only be obtained by experimental measurement. For pure
components, use of a P-H diagram like those shown in Figs.
24-22 to 24-35 is recommended.
The enthalpy behavior of mixes can be predicted through
thermodynamic correlations. Use of a good contemporary
equation of state is recommended for mixture enthalpy pre-
dictions. Fig. 24-2 shows graphically the change in enthalpy
of three gas streams and two liquid streams as pressure is
changed at constant temperature. Values for the plot were
calculated by the Soave10 version of the Redlich-Kwong equa-
tion of state11. The curves in Fig. 24-2 are for no phase change
and show typical behavior of gas phase enthalpy decreasing
and liquid phase enthalpy increasing with increasing pres-
sure.
Enthalpies for mixtures of real gases and liquids can be pre-
dicted by hand calculation methods. The ones recommended
for use are based on an extension of the principle of corre-
sponding states and are shown graphically in Fig. 24-6 and
24-7.
Ideal Gas State Enthalpies
Enthalpies for pure component gases are readily correlated
as a power series of temperature for a wide range of compo-
nents including all of those that occur in natural gas streams.
Typical values for natural gas components are plotted in Figs.
24-3 and 24-4 for temperatures from -130 to 500°C. Enthal-
pies for gas mixtures can be obtained as the mole fraction av-
erage if molar enthalpies are used, or the weight fraction
average if mass enthalpies are used.
Many natural gas streams contain undefined, or pseudo,
components. Ideal gas enthalpies for pseudo components are
shown in Fig. 24-5. To use Fig. 24-5 the relative density, mo-
lecular mass and temperature must be known. Fig. 24-5 is for
paraffinic mixtures and should not be used for pseudo compo-
nents derived from aromatic crude oils.
The enthalpy datum chosen is zero enthalpy at zero pres-
sure and zero absolute temperature, the same datum as used
in API Project 44.1 The choice of datum is arbitrary and a mat-
ter of convenience. Enthalpy differences, the values of inter-
est, are not affected by the datum chosen. However, the same
enthalpy datum should be used for all components in any one
calculation.
CHANGE OF ENTHALPY WITH PRESSURE
For purposes of correlation and calculation, the ideal and
real gas behaviors are treated separately. The mixture ideal
gas enthalpy at a specified temperature is calculated; the en-
thalpy change of the real gas mixture is calculated from a cor-
relation prepared from experimental enthalpy measurements
on a variety of mixtures. This relation can be expressed as:
HPT − H00 = (H0T − H00) − (H0T − HPT) Eq 24-1
where:
(H0T − H00) the ideal gas state enthalpy above the da-
tum, H0, at the desired temperature (sub-
script T), kJ/kmole.
24-2
(H0T − HPT) the change of enthalpy with pressure, given
by the enthalphy difference between the
ideal gas state enthalpy and the enthalpy at
the desired pressure, both quantities at the
specified temperature, kJ/kmole.
0
Since H0 is zero at the chosen datum, zero absolute
temperature, Equation 24-1 can be written:
HPT = H0T − (H0T − HPT) Eq 24-2
Which can be simplified to:
H = H0 − (H0 − H) Eq 24-3
Values for the change of enthalpy with pressure for a real
gas or liquid are obtained from a correlation based on the prin-
ciple of corresponding states.2 The original correlation was ex-
tended to low reduced temperatures3 to cover low temperature
gas processing applications. The correlation shown in Figs.
24-6 and 24-7 consists of two parts. One part gives the change
of enthalpy with pressure for a simple fluid (fluid with zero
acentric factor). The second part is a correction for deviation
of a real fluid from the ideal fluid change of enthalpy with
pressure. The value of (H0 – H) in Eq. 24-3 is calculated by:
(0) (′)
 
 (H − H)   (H0− H) 
0

(H − H) =
0
RTc   +ω   Eq 24-4
 RT c  
  RTc  
where:
[(H0 −H) / RTc ] (o) the change of enthalpy of a simple
fluid with pressure from Fig. 24-6.
[(H0 −H) / RTc] ( ′) deviation from the change for a sim-
ple fluid from Fig. 24-7
Figs. 24-6 and 24-7 can be used for gas and liquid mixtures.
If the mixture is a gas, use the lower chart in each figure. For
liquids read the value from the isotherms at the top of the
chart. The units of (H0 – H) will depend on the units of the
universal gas constant, R, and Tc. For (H0 – H) in kJ/mole, R
= 8.3145 kJ/kmole • K) and Tc is in K.
The reduced temperature and pressure are defined as Tr =
T/Tc and Pr = P/Pc, where absolute temperature and pressure
must be used. Values for pure component critical temperature,
pressure and acentric factor are in Section 23 Physical Prop-
erties. Section 23 also contains graphs relating ASTM distil-
lation temperature, molecular weight, specific gravity
(relative density), critical temperature, and critical pressure
for undefined fractions. The fraction acentric factor can be es-
timated from Fig. 23-28.
To use Figs. 24-6 and 24-7, the mixture composition must be
known. The mole fraction average (pseudo) critical tempera-
ture and pressure are calculated using Kay’s Rule4 as illus-
trated in Fig. 23-3 (TCm = ΣyiTCi and PCm = ΣyiPCi). The mole
fraction average mixture enthalpy is calculated from:
H0m = ΣyiH0i Eq 24-5
The values of H0i are obtained by multiplying the enthalpy
value from Figs. 24-3 and 24-4 by the molecular weight of the
individual component.
The mole fraction average acentric factor is calculated:
ωm = Σyiωi Eq 24-6
The information necessary to evaluate enthalpies for the
mixture from Figs. 24-3 to 24-7 is now known. Use of the
method will be clearer after study of the following illustrative
calculation.
Revised (5-99)
 EXAMPLE CALCULATION
USING ENTHALPY CORRELATION
A gas with the composition shown in Fig. 24-8 is at 50°C and
7000 kPa(abs). Using Figs. 24-3 and 24-4 calculate the en-
thalpy of the gas. Following the example in Fig. 23-6, the mole
fraction average critical temperature is calculated as 205.9K,
and the pseudo critical pressure as 4613.3 kPa(abs). Following
the same procedure, the mixture acentric factor is 0.02476 and
the molar ideal gas state enthalpy 11419.8 kJ/kmole. With a
reduced temperature of 1.569 and a reduced pressure of 1.517,
the reading from Fig. 24-6 is 0.70 and from Fig. 24-7 is 0.020,
which give a mixture enthalpy at 50°C and 7000 kPa(abs) of
10220.6 kJ/kmole.
Total enthalpy charts — The total enthalpy charts shown
in Figs. 24-9 to 24-17 offer a rapid means of calculating en-
thalpy changes on essentially the same basis as previously
described. They may be used instead of carrying out the de-
tailed component-wise calculations for mixture enthalpies.
The charts cover the range of compositions, pressures and
temperature encountered in most natural gas systems.
The total enthalpy charts were developed from results cal-
culated for synthesized binary mixtures of the pure component
normal paraffin hydrocarbons next lighter and heavier than
the mixture molecular weights indicated. The calculations
were carried by a computer program which interpolated be-
tween adjacent values in the tabulated values of enthalpy de-
parture reported by Curl and Pitzer.2
Ideal gas enthalpy values for each pure normal paraffin
component were calculated and used to calculate the ideal gas
mixture enthalpy. The ideal gas state enthalpy equation used
for methane, ethane and propane was a curve fit of the data
shown in Fig. 24-3. For butane and heavier components a
fourth order polynomial with coefficients taken from the API
Data Book, Table A1.29 was used. The fifth coefficient reported
in the API table was dropped to convert to the 0 K, 0 kPa
enthalpy datum.
Ideal gas enthalpies were corrected for pressure changes by
interpolating the tabular data used to compile Figs. 24-6 and
24-7. Pressure calculations were made from reduced pressures
of 0.2 to 13800 kPa. Temperatures ranged from –160°C to Tr
= 0.35 minimum to 320°C maximum.
Caution: Some mixtures encountered in the calcula-
tions fell inside the phase envelopes of Figs. 24-6 and
24-7. Rather than extrapolate into the phase envelopes
of Figs. 24-6 and 24-7 for enthalpy pressure corrections,
the total enthalpies were first generated, plotted, and
then extrapolated.
Vapor enthalpies at 1000 kPa were extended to lower tem-
peratures by assuming the relative enthalpy change with tem-
perature to be the same as for the ideal gas.
ENTROPY CORRELATION
Entropy is most used as a guide for interpreting the behavior
of gases and liquids in compression and expansion processes.
The entropy of a multicomponent mixture may be calculated
by combing ideal gas state entropies from API 441 with the
Curl and Pitzer2 tables of values for the change of entropy with
pressure. Entropy equations for undefined mixtures (pseudo
components) are not available but, for most uses where the
pseudo components are present in small concentration, they
can satisfactorily be approximated by the nearest molecular
weight paraffin hydrocarbon.
24-3
EXAMPLE CALCULATION USING
ENTROPY CORRELATION
The same gas as in the enthalpy example (shown in Fig.
24-18) is at 50°C and 7000 kPa(abs). The pseudo criticals,
acentric factor, reduced temperature, and reduced pressure
have the same values as in the enthalpy example. The mixture
ideal gas state entropy is 218.6 kJ/(kmole• K). The value read
from Fig. 24-20 is 0.338 and that from Fig. 24-21 is 0.065.
These combine to give (remember P in lnP must be in atmos-
pheres) a real gas entropy of 184.5 kJ/(kmole• K).
REFERENCES
1. API Research Project 44, D “ ata on Hydrocarbons and Related
Compounds,” A& M Press, College Station, Texas.
2. Curl, R. F., Jr. and Pitzer, K. S., Ind. Eng. Chem., 50, 1958, p. 265.
3. Chao, K. C. and Greenkorn, R. A., GPA Research Report RR-3,
Gas Processors Association, Tulsa, Oklahoma, April 1971.
4. Kay, W. B., Ind. Eng. Chem., 28, 1936, p. 1014.
5. Jacoby, R. H. and Yarborough, L., Technical Report to GPA, 1966.
6. ASME Steam Tables, 3rd Ed., Amer. Soc. of Mech. Eng., New
York, N.Y., 1967.
7. Keenan, J. H., Keyes, F. G., Hill, P. G. and Moore, J. G., “Steam
Tables,”John Wiley & Sons, Inc., New York, N.Y., 1969.
8. Ely, J. F., Private Communication, 1985.
9. T
“ echnical Data Book — Petroleum Refining,”3rd Ed., American
Petroleum Institute, Washington, D.C., 1977.
10. Soave, G., “Equilibrium Costants from a Modified Redlich-Kwong
Equation of State,” Chem.Eng. Sci., Vol 27, No. 6, pp. 1197-1203, 1972.
11. Maddox, R.N. and Moshfeghian, M., Private Communication, 1996.
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Revised (5-99)