Professional Documents
Culture Documents
PRO/II 9.3
Reference Manual
May 2014
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Contents
Components and Thermodynamics 1
4
van Laar Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-137
Regular Solution Theory . . . . . . . . . . . . . . . . . . . . . . . . . . .2-138
Flory-Huggins Theory. . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-139
Wilson Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-140
NRTL Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-142
UNIQUAC Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-143
UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-146
Modifications to UNIFAC. . . . . . . . . . . . . . . . . . . . . . . . . .2-149
Fill Options . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-153
Henry's Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-156
Heat of Mixing Calculations . . . . . . . . . . . . . . . . . . . . . . . .2-158
Special Packages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-160
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-160
Alcohol Package (ALCOHOL). . . . . . . . . . . . . . . . . . . . . .2-160
Glycol Package (GLYCOL) . . . . . . . . . . . . . . . . . . . . . . . .2-165
Sour Package (SOUR). . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-167
GPA Sour Water Package (GPSWATER) . . . . . . . . . . . . . .2-170
Amine Package (AMINE). . . . . . . . . . . . . . . . . . . . . . . . . .2-173
Electrolyte Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-176
Electrolyte Mathematical Model. . . . . . . . . . . . . . . . . . . . .2-176
Electrolyte Thermodynamic Equations. . . . . . . . . . . . . . . .2-182
Thermodynamic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-200
Solid-Liquid Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-200
Transport Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-203
Index
Unit Operations 242
6
Column Hydraulics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-348
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-348
Tray Rating and Sizing . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-349
Random Packed Columns . . . . . . . . . . . . . . . . . . . . . . . . . .4-353
Structured Packed Columns . . . . . . . . . . . . . . . . . . . . . . . .4-358
Shortcut Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-364
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-365
Fenske Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-365
Underwood Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-366
Kirkbride Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-370
Gilliland Correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-370
Distillation Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-371
Simple Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-373
Complex Columns. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-374
Refinery Heavy Ends Columns. . . . . . . . . . . . . . . . . . . . . .4-376
Troubleshooting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-380
Liquid-Liquid Extractor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-384
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-384
Basic Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-384
Column Tray Efficiency Calculations . . . . . . . . . . . . . . . . . . . .4-387
Murphree Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-388
Vaporization Efficiency. . . . . . . . . . . . . . . . . . . . . . . . . . . .4-388
Equilibrium Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-389
Chapter 6: Reactors
Reactor Heat Balances. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-453
Heat of Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-455
Conversion Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-455
Shift Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-457
Methanation Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . 6-457
Equilibrium Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-457
Shift Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-460
Methanation Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . 6-461
Calculation Procedure for Equilibrium. . . . . . . . . . . . . . . . 6-462
Gibbs Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-462
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-462
Mathematics of Free Energy Minimization . . . . . . . . . . . . 6-463
Continuous Stirred Tank Reactor (CSTR). . . . . . . . . . . . . . . . . 6-469
Plug Flow Reactor (PFR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-474
8
Calculation Scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-496
Dissolver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-498
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-498
Particle Size Distribution . . . . . . . . . . . . . . . . . . . . . . . . . .7-502
Material and Heat Balances . . . . . . . . . . . . . . . . . . . . . . . .7-503
Phase Equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-505
Residence Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-505
Concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-505
Solution Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-505
Crystallizer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-506
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-506
Crystallization Kinetics and Population Balance Equations . .7-
508
Material and Heat Balances . . . . . . . . . . . . . . . . . . . . . . . .7-512
Phase Equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-513
Solution Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-514
Melter/Freezer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-516
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-516
Calculation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-516
Chapter 8: Utilities
Phase Envelope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-519
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-519
Calculation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-520
Heating / Cooling Curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-521
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-521
Calculation Options. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-522
Critical Point and Retrograde Region Calculations . . . . . .8-522
VLE, VLLE, and Decant Considerations . . . . . . . . . . . . . .8-523
Water and Dry Basis Properties . . . . . . . . . . . . . . . . . . . . .8-524
GAMMA and KPRINT Options . . . . . . . . . . . . . . . . . . . . .8-524
Availability of Results. . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-525
Binary VLE/VLLE Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-528
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-528
Input Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-529
Output Considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-529
Hydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-531
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-531
Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-531
Check Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-538
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-538
Input Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-538
Calculation Considerations . . . . . . . . . . . . . . . . . . . . . . . . .8-539
10
Heat Input Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11-592
Isentropic Efficiency Considerations . . . . . . . . . . . . . . . . . . . .11-598
Index
Technical Bulletin 627
12
Volume1: Components and Thermody-
namics
General Information
The PRO/II Reference Manual provides details on the basic equations and calculation techniques used in
the PRO/II simulation program and the PROVISION Graphical User interface. It is intended as a reference
source for the background behind the various PRO/II calculation methods.
Specific details concerning the data entry steps required by the program can be found in the main PRO/II
Help. Detailed sample problems are provided in the PRO/II Application Briefs Manual, in the
\USER\APPLIB\ directory, and in the PRO/II Casebooks.
Defined Components
Component Libraries
Fixed Properties
Temperature-dependent Properties
Properties From Structure
Component Libraries
Table 1-1 lists the property data available in the built-in component
libraries for predefined components. These libraries include the
PROCESS library (the physical property library used as the default
in PROCESS, PIPEPHASE, HEXTRAN, and early versions of
PRO/II), the SIMSCI library (a fully documented physical property
Fixed Properties
Specific gravities of permanent gases are often expressed as
relative to air, without any annotations in the output.
Liquid molar volumes may be extrapolated from a condition
very different from 77F (25 C), if the component doesn't natu-
rally exist as a liquid at 77 F.
Also See:
Defined Components
Temperature-dependent Properties
The temperature-dependent correlations available for use in PRO/II
are listed in Table 8-6 in volume I of the PRO/II Component and
Thermodynamic Input Data Manual. The equations that are typi-
cally used to represent a property are listed in Table 1-2. While tem-
perature-dependent library properties are fitted and are usually very
accurate at saturated, sub-critical conditions, caution must be used
in the superheated or super-critical regions.Because of the form of
some of the allowable temperature-dependent equations, extrapola-
tion beyond the minimum and maximum temperatures is not done
using the actual correlation. PRO/II has adopted the rules shown in
Table 1-2, based on the property, for extrapolation of the tempera-
ture-dependent correlations
Table 1-2: PRO/II Temperature-dependent Property Equations and Extrapolation
Conventions
Temperature- Recommended Extrapolation
dependent Equations Method
Property
Vapor Pressure 14, 20, 21, 22 ln(Prop.) vs. 1/T
Liquid Density 1, 4, 16, 32 Prop. vs. T
Petroleum Components
General Information
Property Generation SIMSCI Method
Property Generation CAVETT Method
Property Generation Lee-Kesler Method
Property Generation Heavy Method10
General Information
Petroleum components (often called pseudo-components) are either
defined on a one-by-one basis on PETROLEUM statements or gen-
erated from one or more streams given in terms of assay data. The
processing of assays is described in Assay Processing section. Each
individual pseudo-component is typically a narrow-boiling cut or
From those three basic properties, the program estimates all other
properties needed for the calculation of thermophysical properties.
Assay Characterization
Assay Characterization
Several different sets of characterization methods are provided.
These are known as the SIMSCI (or TWU), CAVETT (API 1963),
Lee-Kesler, CAV8 (API 1980) EXTAPI, and (starting with PRO/II
version 8.2) the HEAVY methods. The Cavett methods developed
in the early 1960s were the default in all versions of PRO/II up to
and including the 3.5 series. The SIMSCI methods use a combina-
tion of published (Black and Twu, 1983; Twu, 1984) and proprie-
tary methods developed by SimSci. These are the default for all
PRO/II versions subsequent to the 3.5 series. The LK option
accesses methods developed by Lee and Kesler in 1975 and
1976.The EXTAPI method is an extension of the method from the
1980 API technical data book with an adjustment for components
that boil below 300F. The most recently added HEAVY method is
an extension of the original Twu correlations. Also know as the
constant Watson K extension, it extrapolates to estimate critical
properties and molecular weight well beyond 1000 Kelvin.
Also See:
Petroleum Components
Equation (1-3):
SGT exp 5 SG o SG 1
Equation (1-4):
where:
SG =specific gravity
Tb = normal boiling point, degrees Rankine
= 1 - Tb / Tc
SG = specific gravity correction
f = correction factor
subscript T refers to the temperature
subscript c refers to the critical conditions
superscript refers to the reference system
The critical volume (in cubic feet per pound mole) and the critical
pressure (in psia) are given by similar expressions:
Equation (1-6):
Vc Vco 1 2 fV / 1 2 fV
2
SGV exp 4 SG o SG 2 1
Equation (1-8):
Equation (1-9):
Equation (1-10):
Equation (1-11):
where:
A7 PR
ln PR A1 A4 A2 A5 / TR A3 A6 ln TR
TR2
where:
ln P R ,b A7 PR ,b / TR2,b f o (TR ,b )
f ' (TR ,b )
where:
subscripts R,b indicate reduced properties evaluated at the nor-
mal boiling point
Functions f o and f are given by:
Equation (1-16):
f o TR A1 A2 / TR A3 ln TR
Equation (1-17):
f ' (TR ) A4 A5 / TR A6 ln TR
Temperature-dependent Properties
The ideal-gas enthalpy (needed for equation-of-state calculations) is
calculated from the method of Black and Twu developed in 1983.
The method was an extension of work done by Lee and Kesler and
involved fitting a wide variety of ideal-gas heat capacity data for
hydrocarbons from the API 44 project and other sources. The equa-
tion (which produces enthalpies in Btu/lb and uses temperatures in
degrees Rankine) is as follows:
Equation (1-20):
A3 2 A4 3
H o A1 A2T T T
2 3
Equation (1-21):
A2 C1 C7 C4
Equation (1-22):
A3 C2 C7 C5
Equation (1-23):
A4 C3 C7C6
C1 0.33886 0.02827 K
Equation (1-25):
C3 1.6658*107
Equation (1-27):
C4 0.26105 0.59332 K
Equation (1-28):
C5 4.92*104
Equation (1-29):
C7 12.8 K 10 K /10 K
2
NBP1/3
K
SG
where:
NBP = normal boiling point in degrees Rankine
SG = specific gravity (typically at 60F/60F)
The constant A1 in equation (1-20) is determined so as to give an
enthalpy of zero at the arbitrarily chosen zero for enthalpy, which is
the saturated liquid at 0 C. The latent heat of vaporization as
described below (to get from saturated liquid to saturated vapor)
and the SRK equation of state (to get from saturated vapor to ideal
gas) are used to compute the enthalpy departure between this refer-
ence point and the ideal-gas state.
The vapor pressure is calculated from the reduced vapor-pressure
equation (1-14) used above in the calculation of the acentric factor.
Petroleum Components
where:
Tc = critical temperature in degrees Fahrenheit
3 log10 Pc
1
7 Tc / Tb 1
PV
Zc c c
0.291 0.08
RTc
Temperature-dependent Properties
Ideal-gas enthalpies (in Btu/lb-mole) are computed with the follow-
ing equations:
Equation (1-36):
H o A BT CT 2 DT 3
Equation (1-37):
A a5 MW a4 a0
Equation (1-38):
B 459.67(1379.01a1 2a2 ) a3
Equation (1-39):
C a2 1379.01a1
Equation (1-40):
where:
T=temperature in degrees Rankine
MW=molecular weight
API =API gravity
K=Watson K-factor defined by equation (1-31).
The constant 0 in equation (1-37) is determined so as to be consis-
tent with the arbitrary zero of enthalpy, which is the saturated liquid
at 0 C.
Vapor pressures (in psia) are computed from a generalized Antoine
equation:
Equation (1-45):
B
ln P A
T 80.0
Equation (1-46):
B
A ln(14.696)
Tb 80.0
Equation (1-47):
ln Pc ln(14.696)
B
1 1
Tc 80.0 Tb 80.0
L A BT CT 2
Equation (1-49):
A 1.328 L ,60
Equation (1-50):
0.3076 L ,60
B
Tc
Equation (1-51):
0.3989 L ,60
C
Tc2
where:
H 0 Tb (7.58 4.571ln Tb )
The critical temperature Tc, normal boiling point Tb, and tempera-
ture T are all in degrees Rankine.
Also See:
Petroleum Components
ln Pc 8.3634 0.0566 / SG
0.24244 2.2898 / SG 0.11857 / SG *10 T 2 3
b
where:
Tc,Tb = critical and normal boiling temperatures (both in
degrees Rankine)
Pc = critical pressure in psia
SG = specific gravity
The acentric factor is estimated from an equation in an earlier work
by Lee and Kesler (1975):
where:
subscripts R, b indicate reduced properties evaluated at the nor-
mal boiling point.
The critical volume then is estimated from the equation:
Equation (1-57):
PV
Zc c c
0.2905 0.085
RTc
where:
K = Watson K-factor defined by equation (1-31).
T = temperature in degrees Rankine.
= acentric factor as calculated by equation (1-56).
The constant of integration is determined so as to give an enthalpy
of zero at the arbitrarily chosen basis for enthalpy, which is the sat-
urated liquid at 0 C.
When the Lee-Kesler characterization option is chosen, the vapor
pressure, saturated liquid density, saturated liquid enthalpy, and
latent heat of vaporization are all calculated by the methods used for
CAVETT characterization, as described in the previous section.
Also See:
Petroleum Components
PRO/II issues warnings when data used with this option are outside
these ranges.
Equation (1-61):
13
SG 1800R = ----------------------------
1800.0 -
K Watson
Equation (1-62):
2
1 2 fM
ln( MW ) ln( MW ) o
1 2 fM
MW
Slope
SG
Reference
Assay Processing
General Information
Cutpoint Sets (Blends)
Inter-conversion of Distillation Curves
Cutting TBP Curves
Gravity Data
Molecular Weight Data
Lightends Data
Generating Pseudocomponent Properties
Vapor Pressure Calculations
Flash Point Calculations
General Information
Hydrocarbon streams may be defined in terms of laboratory assay
data. Typically, such an assay would consist of distillation data
(TBP, ASTM D86, ASTM D1160, or ASTM D2887), gravity data
(an average gravity and possibly a gravity curve), and perhaps data
for molecular weight, light-ends components, and special refining
properties such as pour point and sulfur content. This information is
used by PRO/II to produce one or more sets of discrete pseudo-
components which are then used to represent the composition of
each assay stream.The process by which assay data are converted to
pseudo-components can be analyzed in terms of several distinct
steps. Before each of these is examined in detail, it will be useful to
list briefly each step of the process in order:
The user defines one or more sets of TBP cut points (or accepts
the default set of cut points that PRO/II provides). These cut-
Application Considerations
The selection of cutpoints is an important consideration in the simu-
lation of hydrocarbon processing systems. Too few cuts can result
in poor representation of yields and stream properties when distilla-
tion operations are simulated; moreover, desired separations may
not be possible because of component distributions. On the other
hand, the indiscriminate use of cuts not needed for a simulation
serves only to increase the CPU time unnecessarily. It is wise to
examine the cut definition for each problem in light of simulation
goals and requirements. The default primary cutpoint set in PRO/II
represents, in our experience, a good selection for a wide range of
refinery applications.
In some circumstances, it may be desirable to use more than one
cutpoint set in a given problem. This "multiple blends" functional-
ity is useful when different portions of a flow sheet are best repre-
sented by different TBP cuts; for example, one part of the process
may have streams that are much heavier than another and for which
more cutpoints at higher temperatures would be desirable. It is also
Assay Processing
3000.538 X 6.76156
log10 P for X 0.0022 ( P 2mmHg )
43 X 0.987672
Equation (1-66):
2663.129 X 5.994296
log10 P
95.76 X 0.972546
for 0.0013 X 0.0022 (2 P 760 mmHg )
Equation (1-67):
2770.085X 6.412631
log10 P for X 0.0013 (P 760 mmHg)
36 X 0.989679
where:
P* = vapor pressure in mmHg at temperature T (in degrees
Rankine)
The parameter X is defined by:
Equation (1-68):
Tb
0.0002867Tb
X T
748.1 0.2145Tb
where:
Tb = boiling point (in degrees Rankine) at a pressure of 760
mmHg
TBP(50) SD(50)
where:
TBP(50) true boiling point temperature at 50 volume percent
distilled, Fahrenheit.
SD(50) Simulated distillation temperature at 50 weight percent
distilled, Fahrenheit.
Step 2: Calculate necessary temperature differences between
adjacent cut points.
Equation (1-70):
Wi CVi D
where:
D86 a ( SD)b F c
where:
D86 is the ASTM D86 temperature, and SD is the ASTM
D2887 temperature, both in degrees Rankine at each volume
percent (for D86) and the corresponding weight percent (for
SD). Constants a, b, and c vary with percent distilled according
toTable 1-10.
Table 1-10: Values of Constants a, b, c
Percent
Distilled a b c
0 6.0154 0.7445 0.2879
10 4.2262 0.7944 0.2671
30 4.8882 0.7719 0.3450
50 24.1357 0.5425 0.7132
70 1.0835 0.9867 0.0486
90 1.0956 0.9834 0.0354
95 1.9073 0.9007 0.0625
Equation (1-73):
where:
TP = D86 temperature in Fahrenheit at pressure P
where:
TBP(50) = true boiling point temperature at 50 volume percent
distilled, Fahrenheit.
D86(50) = Observed ASTM D86 distillation temperature at 50
weight percent distilled, Fahrenheit.
Step 2: Calculate necessary temperature differences between
adjacent cut points.
Equation (1-76):
Yi AX iB
where:
Yi = True boiling point temperature difference between two cut
points, Fahrenheit
TBP a ( D86)b
where a and b are constants varying with percent of liquid sample
distilled as given in Table 1-13.
Table 1-13: Values of Constants a, b
Percent Distilled a b
0 0.9167 1.0019
10 0.5277 1.0900
30 0.7429 1.0425
50 0.8920 1.0176
70 0.8705 1.0226
90 0.9490 1.0110
95 0.8008 1.0355
NBP1/3
K
SG
where:
NBP = normal boiling point in degrees Rankine
SG = specific gravity at 60 F relative to H2O at 60 F
Heavy Oil
Developed around 2006, this is the SIMSCI method modified to
better represent components having NBPs above 1000 K. Below
1000 K, molecular weight calculations essentially are identical to
the SIMSCI method.
API63
The unaltered old API method is (API63) is also available.
API80
A newer 1980 API method, called CAV80, is available. This is API
procedure 2B2.1, an extension of the earlier API method that better
matches known pure-component data below 300 F. It has been cor-
related up to 1960 F.
Lee-Kesler
This correlation is based upon Normal Boiling Point (NBP, in Ran-
kine) and specificic gravity versus molecular weight. The complete
method is described in :
Kesler-Lee, Hydrocarbon Processing, March 1976, page 157.
The molecular weight method developed by Lee-Kesler also is
available. See equation (1-58).
EXTAPI
PRO/II additionally supports a composite method (known as
EXTAPI). This option uses the older API63 method for average
boiling temperatures of 300 F and lower. Above this temperature,
EXTAPI uses the CAV80 correlation.
Also See:
Assay Processing
Lightends Data
Hydrocarbon streams often contain significant amounts of light
hydrocarbons (while there is no universal definition of "light," C6 is
a common upper limit). Simulation of such systems is more accu-
rate if these components are considered explicitly rather than being
lumped into pseudocomponents. If the distillation curve is reported
on a lightends-free basis, the light components can be fed to the
flow sheet in a separate stream and handled in a straightforward
manner. Typically, however, the lightends make up the initial part of
the reported distillation curve, and adjustment of the cut-up curves
is required to avoid double-counting the lightends components.
By default, the program "matches" user-supplied lightends data to
the TBP curve. The user-specified rates for all lightends compo-
nents are adjusted up or down, all in the same proportion, until the
NBP of the highest-boiling lightends component exactly intersects
the TBP curve. All of the cuts from the TBP curve falling into the
region covered by the lightends are then discarded and the lightends
components are used in subsequent calculations. This procedure is
illustrated in Figure 2.2 where light end component flows are
Assay Processing
DVPE 0.965 X A
where:
X = the measured total pressure
A = 0.548 psi (3.78 kPa)
This number is then reported as the RVP. Air should be in the com-
ponent list for proper use of this method.
Reference
Correlated Methods
Empirical methods are derived equations based on the lower end
boiling temperatures of distillation curves. Generally, continuous-
component streams are characterized into discrete "cut-points"
using the ASTM D86 method. Depending upon the correlation, the
boiling temperatures ranging between the zero percent and the 10
percent cut points are used and combined using various weighting
strategies to obtain a representative temperature. This temperature
then is incorporated as a variable in an empirical equation that com-
putes the flash point directly.
The two non-proprietary methods available in PRO/II are the SIM-
SCI (or Nelson) method and a modified version of the API meth-
ods. These forms have not been updated since their first appearance
in PRO/II version 3.3. In these forms, both closed cup and open cup
calculations use identical equations.
API Correlation
The equation in PRO/II is an older API method that Simsci has
recast from the original Fahrenheit to Rankine temperatures to elim-
inate zero from the division and LOG terms. It has been superseded
by procedure 2B7.1 of the API technical Data book (2). The form
used in PRO/II is shown in equation (1-78).
Equation (1-78):
where:
TFP = Flash point temperature, Rankine
TBP10% = Boiling temperature of the ASTM D86 10% cut
point, Rankine
SIMSCI Correlation
This implements the method of Nelson (4), which is similar to the
API method and is based on ASTM D86 distillation curve data. It
calculates a weighted average of the 0%, 5%, and 10% cut point
boiling temperatures to compute a representative boiling tempera-
ture. These values then are used in the equation to compute the flash
point temperature directly as shown in equation (1-79).
Equation (1-79):
where:
TFP = Calculated flash point temperature, Fahrenheit
Reference
Basic Principles
General Information
Phase Equilibria
Enthalpy
Entropy
Density
General Information
When modeling a single chemical process, or entire chemical plant,
the use of appropriate thermodynamic methods and precise data is
essential in obtaining a good design. PRO/II contains numerous
Phase Equilibria
When two or more phases are brought into contact, material is
transferred from one to another until the phases reach equilibrium,
and the compositions in each phase become constant. At equilib-
rium for a multi-component system, the temperature, pressure, and
chemical potential of component i is the same in every phase, i.e.:
Equation (2-80):
T T ... T
Equation (2-81):
P P ... P
Equation (2-82):
...
where:
T = system temperature
P = system pressure
= the chemical potential
,,..., represent the phases
The fugacity of a substance is then defined as:
Equation (2-83):
i i0 RT ln fi / f i 0
where:
fi
= fugacity of component i
It follows from (3) and (4) that the fugacities in each phase must
also be equal:
Equation (2-84):
fi f i ... fi , i 1, 2, ... n
K i yi / xi
where:
Ki = K-value, or equilibrium ratio
K Di xiI / xiII
where:
KDi = liquid-liquid distribution coefficient
iV fiV / yi P
where:
Equation (2-88):
fi L iL xi fi 0 L
where:
iL = liquid-phase activity coefficient
fi OL Pi satisat exp P
Pi sat
viL / RTdP
where:
Pi sat = saturated vapor pressure of component i at T
R = gas constant
Equation (2-89) provides two correction factors for the pure liquid
fugacity. The fugacity coefficient, isat,corrects for deviations of the
saturated vapor from ideal-gas behavior. The exponential correction
factor, known as the Poynting correction factor, corrects for the
K i iL fi OL / PiV
K Di iLI / iLII
K i iL / iV
iLII
K Di
iL I
Equations (2-90), (2-91), (2-92), and (2-93) are used to calculate the
distribution of components between phases.
For vapor-liquid equilibria, equation-of-state methods may be used
to calculate the fugacity coefficients for both liquid and vapor
phases using equation (2-92). One important limitation of equation-
of-state methods is that they have to be applicable over a wide range
of densities, from near-zero density for gases to high liquid densi-
ties, using constants obtained from pure-component data. Equations
of state are not very accurate for non-ideal systems unless combined
with component mixing rules and alpha formulations appropriate
for those components. See Mixing Rules (for Equations of State)
Equation (2-90) may be solved by using equation-of-state methods
to calculate vapor fugacities combined with liquid activity methods
to compute liquid activity coefficients. See Liquid Activity-Based
Methods. Liquid activity methods are most often used to describe
the behavior of strongly non-ideal mixtures.
Enthalpy
The enthalpy of a system, H, is defined in terms of the energy of the
system, U as follows:
Equation (2-94):
H U PV
where:
H = enthalpy of the system of nT moles
dU T P / T V , n P dV
T
The enthalpy of the system is then given by:
where:
H* = mixture ideal gas enthalpy = n h i i
0
For low pressure and temperatures well below the lowest critical,
LIBRARY enthalpies are often satisfactory. For high pressures or
temperatures above the critical of a component, it will usually be
better to use an equation of state for vapor and, possibly, liquid
enthalpies. Beware, however, if a liquid activity coefficient method
was selected for K-value; in such systems the traditional cubic
equation of state may not be capable of describing the liquid phase
non-ideality, and it is therefore unlikely that the equation of state
will predict the correct liquid phase enthalpy. In this situation, one
of the more advanced cubic equations using an alpha formulation
which correctly predicts pure component vapor pressures, is a better
choice. As the contribution to the liquid enthalpy of dissolved
super-critical components is usually small, the LIBRARY method
can usually safely be used for liquid enthalpies. Ideal-gas based
enthalpies and saturation enthalpies can be used in combination for
vapor and liquid, respectively, for defined components because the
Entropy
The entropy of a system, S, is defined in terms of the enthalpy, as
follows:
Equation (2-97):
S S R ln R ln P / Pref H H / T
and
Equation (2-98):
S ni si0 R ni ln xi
i i
where:
= fugacity coefficient of mixture
ni = moles of component i
The ideal molar entropy is related to the ideal molar enthalpy by:
T hi0
T
s c dT / T
0
i
pi * dT / T
Tref Tref
T Pconst
where:
Tref = reference temperature, 1 degree Rankine in PRO/II
Density
Cubic equation-of-state methods are generally not very accurate in
predicting liquid densities. More accurate predictive methods have
been developed especially for liquid mixtures. Such methods
include the API and Rackett correlation methods. These methods
are described in detail in Section, Generalized Correlation Methods.
Vapor densities are computed in PRO/II using the following formu-
lae:
Equation (2-100):
v zRT / P
Equation (2-101):
v MW / v
where:
v = vapor density
MW = molecular weight
Application Guidelines
General Information
Refinery and Gas Processes
Natural Gas Processing
Chemical Applications
General Information
Choosing an appropriate thermodynamic method for a specific
application is an important step in obtaining an accurate process
simulation. Normally, there may be any number of thermodynamic
methods suitable for a given application. The user is left to use his
or her best judgement, experience, and knowledge of the available
thermodynamic methods to choose the best method.
It is important to note that for most thermodynamic methods, the
PRO/II databanks contain adjustable binary parameters obtained
from fitting published experimental and/or plant data. The thermo-
dynamic method chosen should ideally be used only in the tempera-
ture and pressure ranges at which the parameters were regressed.
Ideally, for each simulation, actual experimental or plant data
should be regressed in order to obtain the best interaction parame-
ters for the application.
There are several places where the user can find information and
guidelines on using the thermodynamic methods available in PRO/
II. These are:
PRO/II Case books
PRO/II Application Briefs Manual
These show how PRO/II is used to simulate many refinery, chemi-
cal, and petrochemical processing applications using the thermody-
namic methods appropriate to each system.
SourWater Systems
The standard version of PRO/II contains two methods, SOUR and
GPSWATER, for predicting the VLE behavior of sour water sys-
tems. These methods are described in more detail in Special Pack-
Amine Systems
Amine systems used to sweeten natural gas streams may be mod-
eled in PRO/II using the AMINE special package (see Section, Spe-
cial Packages). Data is provided for amines MEA, DEA, DGA,
DIPA, and MDEA. Results obtained for MEA and DEA are accu-
rate enough for use in final design work. However, results for DIPA
systems are not suitable for final design work. For MDEA or DGA
systems, the results may be made to more closely fit plant data by
the use of a dimensionless residence time correction.
The recommended temperature, pressure, and loading ranges
(gram-moles sour gases per gram-moles amine) for each amine sys-
tem available in PRO/II is given in Table 2-21.
Also See:
Application Guidelines
Petrochemical Applications
Common examples of these processes are the following:
Light hydrocarbon applications
Aromatic systems
Aromatic/non-aromatic systems
Alcohol dehydration systems
Aromatic Systems
Mixtures of pure aromatic components such as aniline, and nitro
benzene at low pressures less than 2 atmospheres exhibit close to
ideal behavior. Ideal methods can therefore be used to predict phase
behavior, and compute enthalpies, entropies, and densities. At pres-
sures above 2 atmospheres, the Grayson-Streed, or SRK, or PR
methods provide good results in the prediction of phase equilibria.
The SRK or PR equations of state should provide better results, but
with a small CPU penalty.
Aromatic/Non-aromatic Systems
Systems of mixtures of aromatic and non-aromatic components are
highly non-ideal. Liquid activity methods such as NRTL or UNI-
QUAC, or equation-of-state methods with advanced mixing rules
such as SRKM or SRKS can be used to model these systems. Both
types of methods can be used to successfully model aromatic/non-
aromatic mixtures, provided that all the binary interaction data for
the components in the system are provided. The PRO/II databanks
contain an extensive variety of interaction data for the NRTL and
UNIQUAC, and SRKM methods. One advantage to using the liquid
activity methods NRTL or UNIQUAC however, is that the FILL
option may be used to fill in any missing interaction parameters
using UNIFAC. All library components in the PRO/II databanks
Also See:
Application Guidelines
Ionic Systems
A special version of PRO/II expressly made for aqueous electro-
lytes is recommended when modeling these systems. This version
combines the PRO/II flow-sheet simulator with rigorous electrolyte
thermodynamic algorithms developed by OLI Systems, Inc. Chemi-
cal systems which may be modeled by this special version include
amine, acid, mixed salts, sour water, caustic, and Ben-field systems.
Environmental Applications
These systems typically involve stripping dilute pollutants out of
water. By themselves, liquid activity methods such as NRTL do not
model these dilute systems with much accuracy. A better approach
is to use a liquid activity method in combination with Henry's Law
constants at the process temperature to model these dilute aqueous
systems. PRO/II contains Henry's Law constants for many compo-
nents such as HCl, SO2, and ethanediol in water. Some additional
Henry's Law constants for chlorofluorocarbons (CFCs) and hydro-
fluorocarbons (HFCs) in water are also available in the PRO/II
databanks. Other sources for Henry's Law data include the U.S.
Environmental Protection Agency.
Solid Applications
Solid-liquid equilibria for most systems can be represented in PRO/
II by the vant Hoff (ideal) solubility method or by using user-sup-
plied solubility data. In general, for those systems where the solute
and solvent components are chemically similar and form a near-
ideal solution, the vant Hoff method is appropriate. For non-ideal
systems, solubility data should be supplied. For many organic crys-
tallization systems, which are very near ideal in behavior, the vant
Hoff SLE method provides good results. The VLE behavior can
usually be adequately represented by IDEAL or any liquid activity
methods. Precipitation of solid salts and minerals from aqueous
solutions can be calculated more rigorously by using the electrolyte
version of PRO/II.
Also See:
Application Guidelines
Generalized Correlations
General Information
Ideal (IDEAL)
Chao-Seader (CS)
Grayson-Streed (GS)
Erbar Modification to Chao-Seader (CSE) and Grayson-Streed
(GSE)
Improved Grayson-Streed (IGS)
Curl-Pitzer (CP)
Braun K10 (BK10)
Johnson-Grayson (JG)
Lee-Kesler (LK)
API
Rackett
COSTALD
SRK-Peneloux Density Method
PR-Peneloux Density Method
General Information
Vapor-liquid equilibria can be predicted for hydrocarbon mixtures
using various general correlation methods. Examples of these are
those developed by Chao and Seader, or Grayson and Streed.
Vapor-liquid equilibria can also be predicted by convergence pres-
sure correlations such as the K10 charts developed by Cajander et
Ideal (IDEAL)
Ideal K-values are generally applicable to systems which exhibit
behavior close to ideality in the liquid phase. Mixtures of similar
fluids often exhibit nearly ideal behavior. In an ideal solution at
constant temperature and pressure, the fugacity of every component
is proportional to its mole fraction. For every component i, the fol-
lowing fundamental thermodynamic equilibrium relationship holds:
Equation (2-102):
f i L f iV
where:
superscript L refers to the liquid phase
superscript V refers to the vapor phase
fi = fugacity of component i
fiV yi P
where:
yi = vapor mole fraction
P = system pressure
In the liquid phase for an "ideal" liquid (ignoring correction factors
that are usually small):
Equation (2-104):
fi L xi f pure
L
i xi Pi
sat
where:
xi = liquid mole fraction
L
f pure i
ture
yiP xi Pi sat
K i yi / xi Pi sat / P
Ideal vapor densities are obtained from the ideal gas law:
Equation (2-107):
P / RT
where:
= vapor density of mixture
Ideal-liquid densities are obtained from pure-component saturated-
liquid density correlations. Ideal liquid enthalpies are obtained from
pure-component liquid enthalpy correlations, and the corresponding
vapor enthalpies are obtained by adding in the effect of the known
latent heat of vaporization of the component. Ideal entropies are
calculated from the ideal enthalpy data using the following equation
Equation (2-108):
Si c pi dT / T H i / T P dT / T
where:
Si = ideal entropy
T = temperature of mixture
Also See:
Generalized Correlations
Chao-Seader (CS)
Chao and Seader calculated liquid K-values for the components of
non-ideal mixtures using the relationship:
Equation (2-109):
i fi 0 L
K i yi / xi
i P
where:
fi 0L = the standard-state fugacity of component i in the pure
liquid phase
i = the activity coefficient of component i in the equilib-
rium liquid mixture
i = the fugacity coefficient of component i in the equilib-
rium vapor mixture
It was shown that i could be calculated from molar liquid volumes
and solubility parameters, using the Scatchard-Hildebrand equation,
with regular liquid solution assumed. The Redlich-Kwong equation
of state was used to evaluate . (See General Cubic Equation of
State ) Chao and Seader presented a generalized correlation for
fi0L/P, the fugacity coefficient of pure liquid "I" in real and hypo-
thetical states.
In the development of their correlation for their vapor-liquid K-
value correlation, Chao and Seader used the framework of Pitzer's
modified form of the principle of corresponding states for the pure-
liquid fugacity coefficients, giving values of fi0L/P as a function of
reduced temperature, reduced pressure, and acentric factor for both
real and hypothetical liquids:
ln f i OL / P ln fi OL / P ln f i OL / P
0 1
where:
= acentric factor
The first term on the right hand side of equation (2-110) represents
the fugacity coefficient of simple fluids. The second term is a cor-
rection accounting for the departure of the properties of real fluids
from those of simple fluids.
Limitations of the Chao-Seader method are given below:
For all hydrocarbons (except methane)
Pressure: up to 2000 psia, but not exceeding 0.8 of the critical
pressure of the system.
Temperature: -100 oF to 500 oF, and pseudo-reduced tempera-
ture, Tr, of the equilibrium liquid mixture less than
0.93. The pseudo-reduced temperature is based on the
molar average of the critical temperatures of the com-
ponents.
Concentration: up to 20 mole % of other dissolved gases in the
liquid.
This method is not suitable for other non-hydrocarbon compo-
nents such as N2, H2S, CO2, etc.
Reference
Grayson-Streed (GS)
Grayson and Streed modified the Chao-Seader correlation in 1963
by fitting data over a wider range of conditions and hence deriving
different constants for the equations giving the fugacity coefficients
of the pure liquids. Special coefficients for hydrogen and methane
are supplied because typical application temperatures are far above
Reference
Reference
Curl-Pitzer (CP)
This correlation may be used to predict both liquid and vapor
enthalpies and entropies. It computes the enthalpy deviation using
the principle of corresponding states, i.e. in terms of the reduced
temperature, reduced pressure, and acentric factor. The critical tem-
perature and pressure for the mixture is computed using the mixture
rules of Stewart, Burkhart, and Voo. The mixture acentric factor
used is the molar average value.
The Curl-Pitzer method is limited to nonpolar mixtures, and may be
used for Pr up to 10, and Tr from 0.35 to 4.0 for liquids, and Tr from
0.6 to 4.0 for vapors. For systems containing heavy ends, the satu-
rated vapor is sometimes at a reduced temperature of less than 0.6.
In this case, the CP correlation extrapolates reasonably, producing
satisfactory results.
The Curl-Pitzer method is generally useful for refinery hydrocar-
bons, and in oil absorption gas plants.
Reference
where:
Reference
Johnson-Grayson (JG)
This correlation may be used to predict both liquid and vapor
enthalpies. It is essentially an ideal-enthalpy correlation, using satu-
rated liquid at 0 C as the datum for the correlation (-200 F in ver-
sions 3.5 and earlier). Vapor phase corrections are calculated using
the Curl-Pitzer correlation. Pressure effects are not considered for
the liquid phase.
Johnson-Grayson is useful for systems containing heavy ends
between 0 F and 1200 F. However, it can be extrapolated to higher
temperatures. The correlation should not be used if the mixture is
C4-C5 or lighter.
Reference
Lee-Kesler (LK)
This correlation may be used to predict both liquid and vapor
enthalpies, entropies, and densities. This correlation uses the three-
parameter corresponding-states theory, which essentially states that
all fluids having the same acentric factor must have the same prop-
erties at the same reduced temperature and pressure. Special mixing
rules have been used to calculate the mixture reduced properties.
For most fluids, the Lee-Kesler method is 98% accurate in predict-
ing the gas phase compressibility factors. The method also gives
reasonable results for slightly polar mixtures. This method is not
recommended for highly polar mixtures, or those which form
Reference
API
This correlation may be used to predict liquid densities. An initial
density is calculated at 60 F using the weight average of the compo-
nents. The reduced temperature and pressure of the stream at 60 F
and 14.7 psia are computed using Kay's rule, i.e., the reduced tem-
perature and pressure are assumed to be a linear function of the liq-
uid mole fraction. A density factor C, is then read from Figure
6A2.21 in the API Technical Data Book. A second correction factor
is then determined corresponding to the reduced temperature and
pressure at the actual fluid conditions. The actual liquid density is
then calculated according to:
Equation (2-112):
act
L
60L Cact / C60
where:
Reference
Rackett
This correlation may be used to predict liquid densities. The satu-
rated liquid density is obtained from:
Equation (2-113):
RT ci
V si = ----------- Z rai
P ci
27
i = 1 + 1 ri
where:
Vsi = saturated liquid volume
Reference
COSTALD
The corresponding-states liquid density model for predicts the liq-
uid densities of LNG-like fluids. This accurate and reliable
method is over 99.8% accurate in predicting the densities of light
hydrocarbon mixtures. This model uses two characteristic parame-
ters for each pure component in the mixture - a characteristic vol-
ume, V*, and a tuned acentric factor, . The acentric factor is
chosen such that the SRK equation of state best matches the vapor
pressure data. Typically, this tuned acentric factor varies little in
value from the standard acentric factor. The saturated volume is
given by:
Equation (2-114):
Vs / V * Vr(0) 1 SRKVr( )
Equation (2-115):
4
Vr(0) 1 Ak 1 Tr
k /3
, 0.25 Tr 0.95
1
3
V r
( )
Bk Trk / Tr 1.00001 , 0.25 Tr 1.0
0
where:
Vs = saturated molar volume
V* = characteristic volume
Vr = reduced volume
Tcm xi x j vij * Tcij / Vm*
i j
Equation (2-118):
2/3 1/3
Vm* 1/ 4 xiVi * 3 xi Vi* xi Vi*
i i i
Equation (2-119):
Equation (2-120):
SRK xiSRK i
i
where:
subscript m refers to mixture properties.
For compressed pure liquids and liquid mixtures, the original work
was extended by Thomson et al. in 1982, adding a pressure correc-
tion of the form:
Equation (2-121):
V Vs 1 C ln B P / B Psat
V = molar volume
Reference
A1 = 3.73625
A2 = -2.70717
A3 = 0.642567
Calculate Peneloux Density by using the Peneloux Volume Shift,
and the Compressibility and Density values obtained from the SRK
method.
Equation (2-124):
Where,
c1 = 2.9056e - 01, c2 = 8.775e - 02
c3 = 1.1537e - 01, c4 = 4.4064e - 01
Tci=Critical Temperature for component i, K
Pci=Critical Pressure for component i, Kpa
wi = Acentric Factor for component i
xi = Mole Fraction of component i
N = Total number of components
Vs = Peneloux Volume Shift, m3/Kmol
Use the following correlation to calculate the Peneloux Volume
Shift for water.
Equation (2-126):
A1 = 3.73625
A2 = -2.70717
A3 = 0.642567
Calculate Peneloux Density by using the Peneloux Volume Shift,
and the Compressibility and Density values obtained from the PR
method.
Equation (2-127):
Equations of State
General Information
Soave-Redlich Kwong (SRK)
Peng-Robinson (PR)
SRK Kabadi-Danner (SRKKD)
SRK Panagiotopoulos-Reid (SRKP) and PR Panagiotopoulos-Reid
(PRP)
SRK Modified (SRKM) and PR Modified (PRM)
SRK SimSci (SRKS)
SRK Huron-Vidal (SRKH) and PR Huron-Vidal (PRH)
Hexamer
UNIWAALS
Benedict-Webb-Rubin-Starling
Lee-Kesler-Plcker (LKP)
Twu-Bluck-Coon(TBC)
Predictive Peng-Robinson 78
Predictive Soave-Redlich-Kwong (PSRK)
Fill Options (for Binary Interaction Coefficients)
Free Water Decant
Vapor Phase Fugacities
General Information
Equations of state for phase-equilibrium calculations are applicable
to wide ranges of temperature and pressure conditions. They can
also be used to calculate all the related thermodynamic properties
RT aT
P 2
v b v ubv wb 2
where:
P = the pressure
T = the absolute temperature
v = the molar volume
u, w = constants, typically integers
The values of u and w determine the type of cubic equation of state.
Table 2-30 shows three of the best known of these. The van der
Waals equation developed in 1873 is obtained by setting u = w = 0.
By setting u = 1 and w = 0, the Redlich-Kwong equation (1949) is
obtained. Peng and Robinson developed their equation of state in
1976 by setting u = 2 and w = -1.
The parameters a and b at the critical temperature, (ac and bc) are
found by setting the first and second derivatives of pressure with
respect to volume equal to zero at the critical point. Application of
these constraints at the critical point to equation (2-128) yields:
Equation (2-129):
u 12 u 13 3 2 1 2
u Bc u w Bc
3 27 3 u 1 9 u 12
1 1 1
Bc 0
3 9 u 1 27
Equation (2-130):
Ac 3Z c2 uBc u w Bc2
Equation (2-131):
1 u 1 Bc
Zc
3 3
where:
Ac Pc ac / R 2Tc2
Bc Pc bc / RTc
Reference
Alpha Formulations
The temperature dependent parameter a(T) can be rewritten as:
Equation (2-132):
a T T a Tc
T Tr1/2
01 Soave (1972)
2
1 C1 1 Tr
0.5
02 Peng-Robin-
C1 C2 1 T
2
C3
r
son (1980)
03 Soave (1979)
C
1 1 Tr C1 2
Tr
04 Boston-
exp C1 1 TrC
2
Mathias
(1980)
05 Twu (1988)
Tr2C 1 exp C1 1 Tr2C
2 2
08 Alternative
TrC exp C1 1 TrC
3 2
for form (06)
09 Mathias-
Copeman
(1983)
10 Mathias
1 C1 1 Tr0.5
2
(1983)
C2 1 Tr 0.7 Tr
11 Melhem-
exp C1 1 Tr C2 1 Tr0.5
2
Saini-Good-
win (1989)
Some newer formulations(9) have been added for the temperature
dependent alpha term. These forms do not require the user to supply
values for constants (C1, C2, etc.) Instead, they perform transforms
on the acentric factors of the components of interest.
0 Tr0.201158e
0.14159 1Tr2.29528
and
1 Tr0.660145e
0.500315 1Tr2.63165
16 Twu-Coon-Cun-
0 1 0 ningham (1995)
where :
0 Tr0.171813e
0.125283 1Tr1.77634
and
1 Tr0.607352 e
0.51161 1Tr2.20517
where:
C1 , C2 , C3 = constants
Tr = T / Tc = reduced temperature
= acentric factor
Reference
a xi xi aij
i j
b xi bi
i
where:
xi = mole fraction of component i.
aij ai a j 1 k
1/2
ij
where:
Kij = Kji = binary interaction parameter.
T 1 M 1 Tr1/2
2
Equation (2-138):
= acentric factor
The constants in (2-138) were obtained from the reduction of vapor-
pressure data for a limited number of common hydrocarbons. This
Peng-Robinson (PR)
The form of (T) proposed by Peng and Robinson in 1976 is the
same as that proposed in 1972 by Soave. The numerical values for
the constants in equation (2-138) are different because the volume
function is different and because a somewhat different set of data
was used.
Equation (2-139):
Also See:
General Information
a xi x j ai a j 1 k a
1/2 ' 2
ij x x
wi w i
i j iw
where:
Trw = T/Tcw
Reference
The two adjustable interaction parameters are kij and kji. This
asymmetric definition of the binary interaction parameters signifi-
cantly improves the accuracy in correlating binary data for polar
and non-polar systems. This mixing rule has been used to test sev-
eral systems, including low pressure non-ideal systems, high pres-
sure systems, three-phase systems, and systems with super-critical
fluids. The results in all cases reported are in good agreement with
experimental data.
The Panagiotopoulos-Reid mixing rule, however, is fundamentally
inconsistent for multi-component systems. This inconsistency is
exhibited in two (related) flaws:
The dilution of the mixture with additional components (reducing
all the mole fractions xi) nullifies the effect of the second binary
parameter kij. In the limit of an infinite number of components so
that all the xi approach zero, the mixing rule reduces to the original
van der Waals mixing rule, equation(2-136).
The mixing rule is not invariant to dividing a component into a
number of identical pseudo-components. For example, if methane
in a mixture is divided arbitrarily into alpha and beta methane,
the calculated properties of the mixture will be slightly different.
Reference
aij ai a j 1 kij kij k ji xi / xi x j
1/2 cij
Reference
Equation (2-146):
The four adjustable parameters are; k12, k21, 12, and 21. As for the
SRKM equation of state, in binary non-polar systems where devia-
tions from ideality are not large, or are only weakly asymmetric,
only two parameters, k12 and k21 are sufficient to fit the data (i.e.,
12 =21 = 1). For binary polar or polar-nonpolar systems, where
the non-ideality is large or strongly asymmetric, it may be neces-
sary to include the additional parameters 12 and 21. In particular,
for binary polar-nonpolar systems, which have the greatest devia-
tion from ideality, 12 is not set equal to 21. For binary polar sys-
tems however, 12 can generally be set equal to 21.
Twu et al.(1) have derived the activity coefficients from the SRKS
equation of state, and have found that for a binary system, k12 or k21
are directly related to the infinite dilution activity coefficients 1 or
2 respectively. The values of k12 and k21 are therefore determined
when both values of the infinite dilution activity coefficients are
known for a binary system. The physical meaning of the binary
parameters k12 and k21 is that they are used to locate the infinite
dilution activity coefficients in a binary system containing compo-
nents 1 and 2.
After both end points of the liquid activity coefficients are found,
the parameters 12 and 21 are then required to describe the shapes
of the liquid activity coefficient curves for components 1 and 2 in
the finite range of concentration. In general, for real systems, kij is
not equal to kji, and ij and ji are not equal to zero. The conven-
tional mixing rule obtained by setting k12 = k21 and 12 = 21 = 0
for a binary system either results in a compromise of the phase equi-
librium representation, or fails to correlate highly asymmetric sys-
tems.
For a multi-component system, (17) can be generalized as:
Equation (2-148):
3
am xi xj aa
i j 1 kij xi Hij1/3Gij1/3 aai j xj / Gij xj
1/2 1/6
i j i i j
Equation (2-149):
H ij kij k ji
Gij exp ij H ij
g E RT ln xi ln i
i
where:
g E a / b ai xi / bi ln 2
i
Where:
a b ai xi / bi g E / ln 2
i
The excess Gibbs free energy can be calculated by any liquid activ-
ity method. Huron and Vidal chose to use the NRTL liquid activity
method to calculate
Equation (2-154):
cij g ji gii
Equation (2-155):
G ji b j exp a ji c ji / RT
Equation (2-156):
G ji b j exp a ji c ji / RT
The only difference between the classical NRTL equation and equa-
tions (2-154)-(2-155) is the definition of the local composition as
corrected volume fractions, which leads to the introduction of the
volume parameter bj in the calculation of Gji. Substituting for the
excess Gibbs free energy in (25) yields:
Equation (2-157):
a b xi ai / bi 1/ ln 2 x j G ji c ji / xk Gki
i j k
By regressing experimental data to obtain the parameters in the
modified NRTL expression, excellent representation of vapor-liquid
equilibria can be made for several systems. The Huron-Vidal mix-
Reference
Hexamer
Hydrogen fluoride is an important chemical used in many vital pro-
cesses, including HF alkylation, and in the manufacture of refriger-
ants and other halogenated compounds. Unlike hydrocarbons,
however, hydrogen fluoride is polar and hydrogen bonded, and
therefore self-associates not only in the liquid phase, but also in the
vapor phase. Experimental evidence strongly suggests that the HF
vapor exists primarily as a monomer and a hexamer mixture. In
addition, evidence points to the hexamer existing in the form of a
cyclic benzene-like species. This behavior results in significant
departures from ideality, especially in calculating fugacity coeffi-
cients, vapor compressibility factors, heat of vaporization, and
enthalpies.
Twu et al.(1), developed a cubic equation of state with a built-in
chemical equilibrium model to account for HF association. The
cubic equation of state incorporating association is given by:
Equation (2-158):
RT a T
P nr 2
v b v ubv wb2
V
v
n0
where:
a(T) = (T)a(Tc) = Redlich-Kwong equation of state parameter
which refers to the monomer
b = Redlich-Kwong equation of state parameter which refers to
the monomer
v = molar volume
V = total volume
nr = extent of association
The values of a(Tc) and b can be obtained from the critical constants
for the Redlich-Kwong equation of state (see Table 2-31), and the
critical temperature and pressure for HF. The alpha function, (T),
is obtained by matching the equation of state to HF vapor pressure
data. Comparing equation (2-158) to the general two-parameter
equation of state given by equation (2-128), it can be seen that the
only difference is the term nr, which accounts for the contribution
of association. The value of nr is 1.0 when there is no association,
and approaches 1/6 when there is complete hexamerization. As the
temperature increases, the extent of hexamerization should
decrease, i.e., the value of nr should increase.
The total number of moles of monomer and hexamer, nT, and the
total number of moles that would exist in the absence of associa-
tion, n0, are related by:
n0
izi , i 1, 6
nT i
where:
zi = the true mole fraction of species i
6 HF HF 6
6 z6 1
K T
16 z16 P 5
where:
K = equilibrium constant
P = total pressure
1 z1 , K K
RT
K z 6 5 z1
* 6 5 *
1
v b
where K* is the reduced equilibrium constant.
Once the equilibrium constant K is known, equation (2-164) can be
solved to obtain a value for z1 and a corresponding value for z6.
The equilibrium constant for HF hexamerization can be calculated
from the following relationship:
Equation (2-165):
8910
log10 K 43.65
T
where:
K = equilibrium constant, 1/mmHg2
T = temperature, K
Twu et al.(1) have shown that, at the critical point, the values of z1,
the true mole fraction of monomer, and nr, are given by:
Equation (2-166):
z1 Tc 0.7006
Equation (2-167):
nr Tc 0.4005
Reference
a
f PvE / RT ln P v b / RT xi ln P vi bi / RT
RTb i
f xi ai / fi RTbi f g / RT
E
Equation (2-169):
f b/v
Equation (2-170):
fi bi / vi
where:
vE = excess volume
The mixing rule for the a/b parameter contains the mixture (v) and
pure (vi) fluid volumes. The pure component volumes are obtained
for the liquid phase at the given temperature and pressure condi-
tions. Parameter b for the mixture is calculated using the original
mixing rule developed for the RK equation of state (equation (2-
135) on page 97), and UNIFAC is used to calculate gE/RT. Subse-
quently, the van der Waals equation of state and equation (2-170)
are solved simultaneously to obtain the mixture volume, v, and a/
RTb.
Several limitations to this method should be noted:
Reference
Benedict-Webb-Rubin-Starling
The Benedict-Webb-Rubin equation(1) of state was first proposed in
1940 to predict liquid and vapor properties at high temperatures,
and to correlate vapor-liquid equilibria for light hydrocarbon mix-
tures. This original (BWR) equation of state however provided poor
results at low temperatures, and around the critical point. To
improve the accuracy of this equation in predicting thermodynamic
properties for light hydrocarbons in the cryogenic liquid, gas, and
dense fluid regions, and at high temperatures, the BWR equation
was modified by Starling(2) in 1973 to give the following form:
C D E
P RT Bo RT Ao o2 3o o4 2
T T T
d d
bRT a 3 a 6
T T
c 3
2
1 2 exp 2
T
The eleven parameters for pure components (B0 , A0 , etc.) are gen-
eralized as functions of component acentric factor, critical tempera-
ture, and critical density. The mixing rules for the eleven mixture
parameters are analogous to the mixing rules used for the BWR
equation. The single binary interaction parameter for the BWRS
equation of state is built into the mixing rules. The BWRS equation
of state can predict pure-component properties for light hydrocar-
bons very accurately when experimental data covering entire ranges
are available.
Limitations to the BWRS equation of state are given below:
Because the equation is generalized in terms of critical temper-
atures, critical density, and acentric factor, it has difficulty pre-
dicting properties for heavy hydrocarbons and polar systems.
The BWRS equation does not satisfy the critical constraints,
and therefore the equation is inferior to cubic equations of state
when applied to the critical and super-critical regions.
The BWRS equation is less predictive than cubic equations of
state for mixture calculations.
Unlike cubic equations of state, BWRS cannot be solved ana-
lytically, and normally requires more CPU time.
Reference
Lee-Kesler-Plcker (LKP)
The LKP equation(1) is based on the Benedict-Webb-Rubin equa-
tion of state and on Pitzer's(3) extended theory of corresponding
states. Thermodynamic data are correlated as a function of critical
temperature and pressure and the acentric factor as follows:
Equation (2-172):
z z o z r zo
r
where:
Z = compressibility factor
= acentric factor
subscripts o, r denote Simple and Reference fluids, respec-
tively.
The work of Plcker et al.(4) introduces new mixing rules which are
purported by the authors to better handle mixtures of asymmetric
molecules. This is accomplished by the introduction of an exponent,
into the mixing rules.
The mixing rules proposed here are:
Equation (2-173):
Tc ,mix
Pc , mix .2905 0.085mix R
Vc ,mix
Equation (2-174):
Vc , mix zi zkVcjk
i k
Equation (2-175):
mix z j j
j
where:
Vc = the molar critical volume
Tcjk TcjTck
1/ 2
K jk
Equation (2-177):
1 1/3
Vcj Vck1/3
3
Vcjk
8
where:
Kjk is an adjustable binary parameter, characteristic of the j-k
binary, independent of temperature, density, and composition.
The pseudo-critical temperature is found by:
Equation (2-178):
1 n
T c mix = --------------- z i z j V cij T cij
V c mix
i j
Twu-Bluck-Coon(TBC)
The previous SRK and PR mixing rule modifications included com-
position-dependence for applying these equations of state to com-
plex mixtures. A more rigorous way to represent the phase behavior
of strongly non-ideal systems is to develop the relationship between
the mixing rule and excess free energy model such that the zero-
pressure Gibbs free energy could be expressed by a NRTL-like
method (see Section, Liquid Activity Methods). Such approach had
been extended by Twu, Bluck and Coon(1) in 1998 with a newly
developed zero-pressure-based mixing rule which would accurately
reproduce the excess Gibbs model and allow the available activity
coefficient models at low pressures be used directly.
The general Helmholtz free-energy departure function is given by:
AE Avdw
E
A Avdw
At zero pressure, equation (2-179) may be derived as:
Equation (2-180):
A0E A0Evdw b a a
ln vdw Cv0 vdw
RT RT b b bvdw
where:
avdw
1 A0E A0Evdw b
a b ln vdw
bvdw Cv0 RT RT b
and
Equation (2-182):
b bvdw
GE n x j ji G ji
xi
j
n
RT i
x Gk
k ki
where:
Aji
ji and G ji exp ji ji
T
By regressing experimental data to obtain the parameters in the
NRTL expression, excellent representation of vapor-liquid equilib-
ria can be made. The prediction of equilibria at low densities is rea-
sonable, and the equation of state can be expected to yield better
results at higher pressures, because the mixing rules have been
derived at the zero pressure limit of the excess Gibbs free energy.
The TBC equation of state overcomes the limitation of infinite-
pressure based models, such as Huron-Vidal (SRKH, PRH,) that
it can directly utilize parameters for the NRTL method correlated
from low temperature data.
Reference
Predictive Peng-Robinson 78
The Predictive Peng-Robinson equation of state (PPR78) method
can be used for the prediction of phase equilibria of binary mixtures
in both the subcritical and critical regions very accurately.
This model uses temperature-dependent binary interaction parame-
ter, kij , to predict the critical locus of the binary systems and the
phase behavior of asymmetric systems with high accuracy.
PPR78 uses a group contribution method to estimate the kij(T)
parameters.
Limitations
Functionality
Technical Information:
Functionality
The following functionality is provided for PPR78 Thermo:
User will be able to select the PPR78 method for Equilibrium,
Enthalpy, Entropy, and Density.
All properties relevant to PPR78 will be provided, e.g., fugac-
ity, fugacity coefficient, compressibility, molar volume, partial
molar properties, etc.
All properties that represent derivatives will be calculated ana-
lytically. This is customary for other methods in Thermo.
Technical Information:
The technical information for PPR78 Thermo is given below :
In 1976, Peng and Robinson proposed a two-constant equation
of state, the well-known PR EOS. In 1978, they proposed an
improved version of their equation of state for the heavy hydro-
carbons. This improved equation is called PPR78.
For a pure component, the PPR78 EOS is given by:
Equation (2-185):
RT ai T
P
v bi v v bi bi v bi
where
Equation (2-188):
N
b zi bi
i 1
Bk ,l
Ng Ng 1
1 298.15 A
2 k 1 l 1
i ,k j ,k i ,l j ,l Ak ,l
T
k ,l
ki , j T
ai T a j T
2
bi b j
2
a T a j T
i
bi bj
ai T a j T
2
bi b j
Reference
E
g0 a i RT b-
a = b -------- + x i ---- + ------- x i ln ---
A1 bi A1 bi
Equation (2-191):
b = xi bb
Where:
A1=-0.64663
ai and bi are parameters of the pure substances. Their mole fractions
are given by xi and the excess Gibbs energy (gE). The excess Gibbs
energy is calculated by a modified UNIFAC model.
Applications
This model yields good results for vapor-liquid-equilibria
(VLE) of non-polar and polar mixtures.
This model can be used for VLE predictions at high tempera-
tures and pressures.
This model can predict phase equilibria of the mixtures con-
taining supercritical components.
Limitations
The SRK EOS describes the vapor densities of pure compo-
nents and mixtures quite well, but predicts the liquid density
poorly.
Reference
General Information
In many hydrocarbon-water mixtures, including those found in
refinery and gas processing plants, the water phase formed is nearly
immiscible with the liquid hydrocarbon phase. For such systems,
the water phase can be assumed to decant as a pure aqueous phase.
This reduces the number of computations involved with rigorous
VLLE methods. The water-decant method as implemented in PRO/
II follows these steps:
Water vapor is assumed to form an ideal mixture with the
hydrocarbon vapor phase.
The water partial pressure is calculated using one of two meth-
ods.
The pressure of the system, P, is calculated on a water-free
basis, by subtracting the water partial pressure.
A pure water liquid phase is formed when the partial pressure
of water reaches its saturation pressure at that temperature.
The amount of water dissolved in the hydrocarbon-rich liquid
phase is computed using one of a number of water solubility
correlations.
Note: The free water decant option may only be used with the
Soave-Redlich-Kwong, Peng-Robinson, Grayson-Streed, Chao-
Seader, Improved Grayson-Streed, Erbar modifications to Grayson-
Streed and Chao-Seader, Braun K10, or Benedict-Webb-Rubin-
Starling methods. Water decant is automatically activated when
either one of these methods is selected.
Calculation Methods
The amount of water dissolved in the hydrocarbon-rich liquid phase
can be computed once the water K-values, , are known. These
are calculated using the following relationship:
K w Pw / Pxw
where:
Pw = water partial pressure at temperature T
P = system pressure
The water partial pressure is calculated using the ASME steam
tables, or Chart 20-4 in the 12th edition of GPSA Data Book or
WICHERT Method. The GPSA Data Book option is recommended
for natural gas mixtures above 2000 psia. The WICHERT method is
based on the article with the title New charts provide accurate esti-
mations for water content of sour natural gas by Gordon C.Wichert
and Edward Wichert from the Oil and Gas Journal dated Oct. 27,
2003. This method is recommended for low pressures. Three sets of
steam tables can be used:
Water properties can be calculated assuming saturated vapor
and liquid conditions.
Steam tables for superheated water vapor based on the Keenan
and Keyes equation of state.
IF 97 Steam Tables - International Association for the Proper-
ties of Water and Steam - Industrial Formulation 1997 steam
tables are used for the property calculations.
GASO Gasoline
JP3 JP-3 fuel
JP4 JP-4 fuel
General Information
In vapor-liquid equilibrium calculations, it becomes necessary to
calculate separately the fugacity of each component in the vapor
and liquid phases. Each of the two phases usually requires different
techniques. For example, liquid-phase non-idealities may be
described by activity coefficients, while deviations from ideal gas
behavior in the vapor phase are described by fugacity coefficients.
The vapor phase fugacity coefficients may be obtained through the
use of an equation of state. The fugacity coefficients are obtained
from classical thermodynamics as follows:
Equation (2-193):
1
P RT
ln i
RT V
ni T ,V , n j V
dV ln z
Equation (2-194):
i f i / yPi
where:
i = fugacity coefficient of component i
fi = fugacity of component i
R = gas constant
T = system temperature
P = system pressure
ni = number of moles of component i
V = volume of system
z = compressibility factor of the mixture
Equations of State
Equations of state are powerful methods for calculating vapor-
phase fugacities at low and high densities. The analytical expres-
sion of the fugacity coefficient can be derived from a cubic equation
of state. The derivation of the fugacity coefficient from a cubic
equation of state is straightforward because the cubic equation of
state in pressure is volume-explicit. Cubic equations of state are
usually applied to systems comprising mixtures of nonpolar or
weakly polar components. The usefulness of a cubic equation of
state can be greatly enhanced by using an advanced alpha function,
and an advanced mixing rule. Modified cubic equations of state can
be suitable for systems containing polar components. See General
Cubic Equation of State
Additionally, a cubic equation of state (incorporated with a chemi-
cal theory of association) is suitable for systems containing polar
and hydrogen-bonding molecules. These include carboxylic acids
which form monomer-dimer pairs and hydrogen fluoride. Such
methods include the Associating Equation of State and the Hayden
O'Connell method. See Hayden-O'Connell .
The equation-of-state methods are generally more reliable for cal-
culating vapor phase fugacity coefficients than any other method,
except for dimerizing components where the Hayden-O'Connell
method should be used.
Pv B C D
z 1 2 3 ...
RT v v v
z 1 BP / RT
The compositional dependence of B for a mixture containing N
components is given by:
Equation (2-197):
N N
B yi y j Bi , j
i j
where:
Reference
Hayden-O'Connell
The truncated virial equation of state described above is useful for
predicting deviations from ideality in those systems where moder-
ate attractive forces yield fugacity coefficients not far removed
from unity. However, in systems containing carboxylic acids, two
acid molecules tend to form a dimer, resulting in large negative
deviations from vapor ideality even at very low pressures.
To account for dimerization, Hayden and O'Connell(1) developed a
fugacity coefficient expression based on a chemical theory of vapor
imperfection. The chemical theory assumes dimerization equilib-
ria exist for a binary mixture of components A and B:
Equation (2-198):
K K
A1 A1
A2
A2
B1 B1
B2
B2
Equation (2-199):
AB
A1 B1
K AB
where:
A1, B1 = monomers
A2, B2 = dimers
AB = cross dimer
Hayden and O'Connell related second virial coefficients to the
dimerization equilibrium constants, KA2, KB2, and KAB, and devel-
oped generalized second virial coefficients for simple and complex
systems. Properties required to use this correlation are; the critical
temperature, critical pressure, mean radius of gyration, dipole
moment, association parameter, and solvation parameter. Associa-
General Information
Liquid activity coefficient methods for phase equilibrium calcula-
tions differ at a fundamental level from equation of state (EOS)
methods. In EOS methods, fugacity coefficients (referring to an
ideal-gas state) are computed for both vapor and liquid phases. In
activity coefficient methods, the reference state for each component
in the liquid phase is the pure liquid at the temperature and pressure
of the mixture. It is often more convenient and accurate to use this
fi L i xi f i oL
where:
oL
The standard-state fugacity fi is defined as that of the pure liquid
i at the temperature and pressure of the mixture. With this defini-
tion, gi approaches one in the limit xi 1. The standard-state
fugacity may be related to the vapor pressure of component i as fol-
lows:
Equation (2-201):
Pisat
where:
P = system pressure
sat
Pi = vapor pressure of component i at system temperature
R = gas constant
T = system temperature
When liquid activity coefficients are used, any method may be used
to compute the vapor-phase fugacity. An ideal gas is often assumed,
but in general vapor fugacities may be written as:
Equation (2-203):
f iV iV yi P
where:
f i V = fugacity of component i in vapor phase
yi = mole fraction of component i in vapor
iisat Pi sat
Ki
iV P
Unless there is vapor-phase association (as is the case with carbox-
ylic acids, for example), the fugacity coefficients may also be
ignored at low and moderate pressures. Equation (2-204) then sim-
plifies to
Equation (2-206):
i Pi sat
Ki
P
For most low-pressure systems, the regression of experimental
vapor-liquid equilibrium data will produce essentially the same
parameters if equation (2-205) or (2-206) is used in place of the full
equation (2-204). This is not necessarily the case at higher pressures
and for systems where vapor-phase non-ideality is important. Sig-
nificant errors can be introduced when the regression and calcula-
tions using the regressed parameters employ differing sets of
simplifying assumptions. In general, calculations should be per-
formed using the same assumptions about vapor fugacities and the
Poynting factor as those employed in fitting the parameters. An
important exception to this rule is the case where parameters were
fitted at low pressure but the calculations are at a substantially
higher pressure; in such a case it is best to employ non-ideal vapor-
phase fugacities and the Poynting correction in the calculation even
if they were not used in the original fit.
Liquid activity coefficients are derived from expressions for the
excess Gibbs energy of a liquid mixture. The defining equation is:
Equation (2-207):
1 G E
ln i
RT ni T , P ,n
ji
Reference
Margules Equation
Table 2-5: Margules Equation
Required Pure
Application Guidelines
Component Properties
Vapor pressure Temperature: Use at or near
temperatures where parameters were
fitted
ln i 1 xi Ai 2 Bi Ai Di xi 3Di xi2
2
where:
N N
Ai x j aij / 1 xi Bi x j a ji / 1 xi
j 1 j 1
N
Di x j d ij / 1 xi dij d ji
j 1
Reference
Another old correlation which is still frequently used is the van Laar
equation. It may be obtained by discarding ternary and higher order
terms in an alternative expansion of the excess Gibbs energy
(known as Wohl's equation), though that is not how van Laar
derived it originally. The resulting expression for the activity coeffi-
cient is:
where:
xl
Zl
a
j x j ail
li
Two parameters, aij and aji, are required for each binary. As with
the Margules equation, no method is included for making the
parameters temperature dependent. It should also be noted that the
van Laar equation, because of its functional form, is incapable of
representing maxima or minima in the relationship between activity
coefficient and mole fraction. In practice, however, such maxima
and minima are relatively rare.
Reference
j
L
xv
j j j L
xk vk
k
where:
Vi L = liquid molar volume of component i
Reference
Flory-Huggins Theory
Table 2-8: Flory Huggins Theory
Required Pure
Component Properties Application Guidelines
Vapor pressure Components Best for components that
Liquid molar volume are chemically similar and differ
Solubility parameter only in size (e.g. polymer
solutions)
viL viL
ln i ln i
reg
ln L 1 L
v v
where:
ireg = activity coefficient from regular solution theory
Reference
Wilson Equation
Table 2-9: Wilson Equation
Required Pure
Component Properties Application Guidelines
Vapor pressure Components: Useful for polar or associating
Liquid molar volume components in nonpolar solvents
and for completely miscible liquids
where:
L
v a ij
i
A ij = ------ exp ------ (when unit of a ij is K)
L T
v
j
L
v a ij
i
A ij = ------ exp ------- (when unit of a ij is KCal/KMol or KJ/KMol)
L RT
v
j
L
and v i is the liquid molar volume of component i.
aij represents a characteristic energy of interaction between species
i and j. While there is no explicit temperature dependence in the
Wilson equation's parameters, the derivation is such that the equa-
tion may be used with some confidence over a wider range of tem-
peratures than either the Margules or van Laar equations. It is also
much more successful in correlating mixtures containing polar
components. The Wilson equation cannot describe local maxima or
minima in the activity coefficient. Its single significant shortcom-
ing, however, is that it is mathematically unable to predict the split-
ting of a liquid into two partially miscible phases. It is therefore
Reference
NRTL Equation
Table 2-10: NRTL Equation
Required Pure
Component Properties Application Guidelines
Vapor pressure Components: Useful for strongly non-
ideal mixtures and for partially
miscible systems.
j ji G ji x j x j G ij k x k kj G kj
- + ------------------- ij -------------------------
In i = ---------------------- -
k G ki x k k G kj x k k G kj x k
j
When unit is K:
b C
ij = a ij + -----ij + ------ij- + d ij InT + e ij T + f ij TInT
T T2
b ij c ij
ij = a ij + ------
- + -----------
-
RT R 2 T 2
G ij = exp ji ij ji = ji + ji T
Three parameters, ij, ji, and ij = ji are required for each binary.
These parameters may be made temperature dependent as described
above. If tij is to be represented with only one constant, it has been
found empirically that better results over a range of temperatures
are obtained if only bij is used and aij = cij = 0. The parameter
does not vary greatly from binary to binary, and it is often satisfac-
tory to fix it at 0.3 for vapor-liquid systems and 0.2 for liquid-liquid
systems.
Reference
UNIQUAC Equation
Table 2-11: UNIQUAC Equation
Required Pure
Application Guidelines
Component Properties
Vapor pressure Components:Useful for non-electrolyte
van der Waals area mixtures containing polar or
van der Waals volume nonpolar components and for
partially miscible systems
ln i ln iC ln iR
Equation (2-216):
z i i M
ln iC ln i qi ln li x l
i
j j
xi 2 xi j 1
Equation (2-217):
M
M
ln iR qi 1 ln j ji M j ij
j 1 j 1
k 1
k kj
U ij
ij = exp -------
- (when the unit is K)
T
U ij
ij = exp -------- (when the unit is KCal/KMol or KJ/KMol)
RT
xi ri xi qi
i = --------------------- i = ----------------------
M M
xj rj xj qj
j=1 i=1
A wi
r i = V wi q i = --------------------
-------------
15.17 2.5 10 9
U ij = a ij + b ij T Z = 10
Z
l i = --- r i q i r j 1
2
Two parameters, Uij and Uji, are required for each binary; they may
be made temperature dependent as described above. If no tempera-
ture dependence is used for Uij, better results over a range of tem-
peratures are normally obtained by using aij and setting bij = 0.
UNIFAC
Table 2-12: UNIQUAC Equation
Required Pure
Component Properties Application Guidelines
Vapor Pressure Pressure up to 100 atmospheres
van der Waals area Temperature 32 300F
van der Waals volume
Components: All components well below
their critical points
ln i ln iC ln iR
z i i M
ln iC ln i qi ln li x l
i
j j
xi 2 xi j 1
where:
xi ri xi qi
i NOG
i NOG
xr
j 1
j j xq
j 1
j j
z
li ri qi rj 1
2
NOG NOG
ri vki Rk
k 1
qi v Q
k 1
i
k k
where:
NOC = number of components
NOG = number of different groups in the mixture
z = lattice coordination number = 10
The group volume and area parameters are obtained from the
atomic and molecular structure.
Vwk
Rk
15.17
Equation (2-219):
Awk
Qk
2.5*109
where:
Vwk = van der Waals volume of group k
Equation (2-220):
NOG
ln iR ln
k 1
k ln ik
where:
k = residual activity coefficient of group k in the mixture
ik = residual activity coefficient of group k in a reference solu-
tion containing only molecules of group type i. This quantity is
required so that:
iR 1 as xi 1
The residual activity coefficient is given by:
Equation (2-221):
m
ln k Qk 1 ln m mk
m m n nm
n
amk
mk exp
RT
Reference
1 Derr, E.L., and Deal, C.H., 1969, Inst. Chem. Eng. Symp.
Ser., 32(3), 40.
2 Fredenslund, Aa., Jones, R.L., and Prausnitz, J.M., 1975,
Group Contribution Estimation of Activity Coefficients in
non-ideal Liquid Mixtures, AIChE J., 27, 1086-1099.
3 Skjold-Jrgensen, S., Kolbe, B., Groehling, J., and Rasmus-
sen, P., 1979, Vapor-Liquid Equilibria by UNIFAC Group
Contribution. Revision and Extension, Ind. Eng. Chem.
Proc. Des. Dev., 18(4), 714-722.
4 Gmehling, J., Rasmussen, P., and Fredenslund, Aa., 1983,
Vapor-Liquid Equilibria by UNIFAC Group Contribution.
Revision and Extension, Ind. Eng. Chem. Proc. Des. Dev.,
22(10), 676-678.
5 Hansen, H.K., Rasmussen, P., Fredenslund, Aa., Schiller,
M., and Gmehling, J., 1991, Vapor-Liquid Equilibria by
UNIFAC Group Contribution. 5. Revision and Extension,
Ind. Eng. Chem. Res., 30(10), 2352-2355.
Also See:
Liquid Activity-Based Methods
Modifications to UNIFAC
The UNIFAC method provides good order-of-magnitude estimates.
The accuracy of the method can be improved by incorporating a
temperature-dependent form for the binary group energy interaction
parameter.
Amk
mk exp
RT
Equation (2-224):
T
Amk amk bmk T To cmk T ln o T To
T
where:
amk , bmk , cmk = binary interaction parameters
To = 298.15 K
wi w
ln ic ln 1 i
xi xi
Equation (2-226):
ri 2/3 xi
wi NOG
r
i 1
i
2/3
xi
Reference
wi w zq ln i
ln ic ln 1 i i 1 i
xi xi 2 i Qi
Equation (2-229):
ri3/4 xi
wi NOG
r
i 1
i
3/4
xi
where:
xi ri xi qi
i NOG
i NOG
xr
j 1
j j xq
j 1
j j
Reference
UFT3
For this modified UNIFAC method, the temperature-dependent
form of Amk is given by:
ln i ln iC ln iR ln iFV
Equation (2-232):
V 1/3
i 1
V 1
ln FV
3Ci ln 1/3 Ci i 1 / 1 1/3
i
V m 1 Vm V i
where:
Vwi 1 NOG i
Vi
15.17bri
ri vk Rk
Mi k1
i i Vj wj
Vw
Vm b 1.28
15.17b rw
i i rj wj
where:
Vi = volume per gram of solvent i
Fill Options
The ability of a liquid activity method to accurately predict vapor-
liquid equilibria and/or vapor-liquid-liquid equilibria depends to a
great degree on whether or not binary interaction parameters are
available for that method. PRO/II contains a proven mechanism for
filling in missing binary interaction parameters for liquid activity
methods. When a liquid activity method such as NRTL is selected
for phase equilibrium calculations, and the FILL option is selected,
PRO/II uses the following mechanism in order to obtain the binary
interaction data the model needs:
1 Any user-supplied binary interaction parameters, or mutual
solubility, infinite dilution, or azeotropic data are used in
preference to any other data.
2 The VLE and LLE databanks which contain binary interac-
tion parameters are then searched for data.
3 The SimSci azeotropic databank is searched for appropriate
azeotropic data, which are then regressed to provide binary
interaction data.
4 For VLE calculations, if steps 1 through 3 do not supply the
required parameters, then the group contribution methods
UNIFAC or its modification UFT1, or the regular solution
method, or the Flory-Huggins or CIUNIFAC method may
be used to provide estimates for the interaction parameters.
For LLE calculations, UNIFAC or CIUNIFAC or the modi-
fied UNIFAC method UFT1 is used to supply the parame-
ter estimates.
5 Finally, if binary interaction parameters are still missing
after steps 1-4 are followed, then all missing parameters are
set equal to zero.
fi
H ij lim
xi 0 x
x 1 i
j
H ij
Ki
P
This relationship is strictly true only in the infinite-dilution limit,
but K-values from Henry's law generally remain accurate at solute
mole fractions up to approximately five percent.
PRO/II correlates Henry's constants to the following functional
form:
Equation (2-235):
C2
ln H ij C1 C3 ln T C4 P
T
The temperature dependence in equation (2-232) is that expected
from a thermodynamic analysis provided the solvent's critical point
is not approached too closely. Thermodynamics also predicts that
the effect of pressure on the effective Henry's constant at conditions
beyond infinite dilution is linear in pressure (with C4 proportional
to the solute's partial molar volume). The pressure correction is neg-
where the sum is taken over all solute species j, and the mole frac-
tions xj used in the sum are computed on a solute-free basis.
Gamma Method
Thermodynamics allows the excess enthalpy to be computed
directly from the activity coefficients in a mixture and their temper-
ature dependence. This is known as the GAMMA option, and the
equation is:
Equation (2-237):
ex In i
RT 2 ------------
H = i
x
T
i
where:
Hex = excess heat of mixing
Despite the attractiveness of this direct thermodynamic computa-
tion, experience has shown that the activity-coefficient parameters
which correlate phase equilibria do not in general produce very
accurate values for excess enthalpies. GAMMA is a viable option
when no other method is available, but the resulting heats of mixing
may only be accurate to within a factor of two.
Also See:
Redlich-KisterExpansion
Experimental data for heats of mixing for binary systems are most
often represented by an expansion about an equi-molar mixture:
Equation (2-238):
where:
X = x1 - x2
X xi x j (form RK1)
xi x j
X (form RK2)
xi x j
Also See:
Heat of Mixing Calculations
Special Packages
General Information
General Information
PRO/II contains a number of thermodynamic methods specifically
developed for special industrial applications. Data packages are
available for the following applications:
Alcohol systems
Glycol systems
Sour water systems
Amine systems
For many applications, databanks containing binary interactions
specifically regressed for components commonly found in the
application have been developed and incorporated into PRO/II. For
example, for alcohol systems, a special alcohol databank, in combi-
nation with the NRTL K-value method is used to calculate the K-
values. For other applications, such as the SOUR or GPSWAT
method for sour systems containing NH3, H2S, CO2, and H2O, a
K-value method has been specifically developed for phase equilib-
rium calculations.
This system uses a special set of SRKM binary interaction data and
alpha parameters for systems containing glycols, water, and other
components. The binary parameters and alpha parameters have
been obtained by the regression of experimental data for glycol sys-
tems.
Figure 2-5 shows the binary interaction parameters, denoted by
"x", present in the glycol databank.
pH 2 S H H 2 S * CH 2 S
Equation (2-241):
where:
pi = partial pressure of component i
ln H CO2 18.33 2.48951*104 / T 2.23996*107 / T 2
9.0918*109 / T 3 1.2601*1012 / T 4
Equation (2-243):
ln H H 2 S 100.684 2.46254*105 / T 2.3902*108 / T 2
1.01898*1011 / T 3 1.5973*1013 / T4
5.0*102 CNH3 0.965 486 / T CCO2
where:
T = system temperature, degrees Rankine
The Henry's Law constant for water was obtained by correlating
H2O vapor pressure data from the A.S.M.E. steam tables over the
range 25 C to 150 C:
Equation (2-244):
ln H H 2O 14.466 6.9966*103 / T 77.67
The Henry's Law constant for NH3 was taken from data published
by Edwards et al.:
Equation (2-245):
6.0*102 2CCO2 CH 2 S
The chemical equilibria of all the main reactions in the liquid phase
due to the dissociation of the sour gas molecules are considered in
the model. The reaction equilibrium constants, Ki, are correlated as
functions of temperature, composition of undissociated sour gas
molecules in the liquid phase, and ionic strength.
where:
Ki = equilibrium constant of reaction i
ln K io A B / T C / T 2 D / T 3 E / T 4
where:
A, B, C, D, E = constants
The constants used in the SWEQ model for equations () and (2-
246), obtained by the regression of experimental data, are given in
the original EPA report. The original SWEQ method was developed
for pressures less than 50 psia where non-idealities in the vapor
phase are not important. Corrections for vapor-phase non-idealities
using SRKM have been incorporated PRO/II, thus extending the
applicable pressure range to 1500 psia.
The phase behavior of all other components present in the system is
modeled using the SRKM equation of state (see Section, Equations
of State). The following limits apply to the SOUR method as imple-
mented in PRO/II:
Temperature: 67-300 F
Pressure: up to 1500 psia
Composition: wNH 3 wCO2 wH 2 S 0.30
where: wi = weight fraction of component i
Note: NH3 and water must be present when using the SOUR
method.
Ammonia:
Equation (2-248):
Hydrogen Sulfide:
Equation (2-249):
Bisulfide:
Equation (2-250):
Carbon Dioxide:
Equation (2-251):
Bicarbonate:
Equation (2-252):
Equation (2-254):
z 1 B / v C / v2
where:
B, C are the second and third virial coefficients
v = molar volume
z = compressibility factor
Phase equilibria for all other components present in the system are
modeled using the SRKM equation of state (see Section, Equations
of State).
The following limits apply to the GPSWATER method:
Temperature: 68-600 F
Pressure: up to 2000 psia
Composition: wNH3 < 0.40
Note: NH3, CO2, H2S, and water must be present when using the
GPSWATER method.
Reference
Hydrogen Sulfide:
Equation (2-258):
Carbon Dioxide:
Equation (2-260):
Bicarbonate:
Equation (2-261):
Alkanolamine:
Equation (2-262):
where:
Ki = equilibrium constant for reaction i
RRNR = alkanolamine
R represents an alkyl group, alkanol, or hydrogen
In addition to the acid-base reactions above, CO2 also reacts
directly with primary and secondary alkanolamines to form a stable
carbamate, which can revert to form bicarbonate ions.
Carbamate Reversion to Bicarbonate:
Equation (2-263):
Tertiary amines such as MDEA are not known to form stable carba-
mates. In an aqueous solution with MDEA, CO2 forms bicarbonate
ions by reaction (22) only.
Note: CO2, H2O, and H2S must be present when using the AMINE
method.
ln K i A B / T C / T 2 D / T 3
H r ln KT1 / KT2 R / 1/ T1 1/ T2
where:
Hr = heat of reaction
R = gas constant
KT1, KT2 = K-values at temperatures T1 and T2
The vapor phase enthalpy and density, and liquid and vapor phase
entropy are calculated using the SRKM equation of state (see Sec-
tion, Equations of State). Ideal methods are used to calculate the liq-
uid-phase density (see Section, Generalized Correlation Methods).
For MEA and DEA systems, data have been regressed from a large
number of sources, resulting in good prediction of phase equilibria
for these systems. For systems containing DIPA, a limited amount
of experimental data was available, and so the DIPA results are not
recommended for final design purposes. For MDEA and DGA sys-
tems, the user is allowed to input a residence time correction to
allow the simulation results to more closely match plant data. The
following application ranges are suggested for amine systems:
Reference
1 Kent, R. L., and Eisenberg, B., 1976, Better Data for Amine
Treating, Hydrocarbon Processing, Feb., 87-90.
2 Maddox, R. N., Vaz, R. N., and Mains, G. J., 1981, Ethanol-
amine Process Simulated by Rigorous Calculation, Hydro-
carbon Processing, 60, 139-142.
Related Topics:
Glycol Package (GLYCOL)
GPA Sour Water Package (GPSWATER)
Sour Package (SOUR)
Amine Package (AMINE)
Also See:
Special Packages
Electrolyte Methods
Electrolyte Mathematical Model
Discussion of Equations
The mathematical model employed in PRO/II Electrolytes is a
deterministic set of nonlinear algebraic equations. The equation set
always includes equilibrium expressions and an electroneutrality
equation. These are discussed below. It also may include additional
equations for liquid-liquid equilibria.
Equilibrium Expressions
For each vapor-liquid, liquid-liquid, solid-liquid, and liquid intra-
phase equilibrium, there is an equation of the form:
Equation (2-266):
m
niP niP
iP iP
K iP
niR niR
m
iR
iR iR
where:
K = thermodynamic equilibrium constant: a function of tem-
perature and pressure
iP , iR =activity coefficient or, for vapors, fugacity coefficient
of the ith product and reactant, respectively; a function of tem-
perature, pressure, and composition
niP , niR =stoichiometric coefficient of the ith product and reac-
tant, respectively
miP , miR =molality or, for vapors, partial pressure of the ith
product and reactant, respectively.
An electroneutrality equation
Equation (2-267):
NC NA
Z
i 1
i mi Z i mi
i 1
where:
Zi = species charge
aiA aiO i 1, NM
where:
ai = activity of ith species.
Modeling Example
To better understand this modeling concept, consider the aqueous
system represented by H2O-CO2-NACL. The reactions considered
will be:
Equation (2-269):
H 2Ovap H 2O
Equation (2-270):
H 2Oaq H 1 OH 1
Equation (2-272):
NaCl ppt Na 1 Cl 1
NaCl ppt Na 1 Cl 1
Based upon the general model described earlier, this leads to:
Equilibrium Expressions
Equation (2-275):
H O
K H 2Ovap 2
H Ovap yH Ovap P
2 2
Equation (2-276):
CO aq mCO aq
K CO2vap 2 2
H Ovap yH Ovap P
2 2
Equation (2-277):
H mH OH mOH
1 1 1 1
K H 2Oaq
a H 2O
Equation (2-278):
H mH HCO mHCO
1 1 1 1
K CO2 aq 3 3
CO aq mCO aq aH O
2 2 2
Equation (2-279):
Na mNa Cl mCl
1 1 1 1
K NaClppt
aNaClppt
Electro-neutrality Equation
Equation (2-280):
yH 2Ovap yCO2vap 1
where:
y = mole fraction for vapor species
Sodium balance
Equation (2-283):
Chlorine balance
Equation (2-284):
CO2in H 2O / 55.51 mCO2 mHCO 1 mCO2 aq VyCO2vap
3
mHCO1 , mNa1 , mCl 1 , mCO2 aq , moles NaCl ppt and moles of water
3
Also See:
General Information
Equilibrium Constants
Equilibrium Constants
By considering basic thermodynamic relationships and assuming a
constant heat capacity of reaction, the following general equation
can be derived:
Equation (2-286):
G o H o 1 1 CPo Tr Tr
ln K T ln 1
RTr R T Tr R T T
where:
T = temperature in Kelvin
Tr = reference temperature, 298.15 K
R = gas constant
The derivation of the relationship given in equation (2-286) can be
found in the Handbook of Aqueous Electrolyte Thermodynamics
(Ref. 1). Values of Gf, Hf, and Cp for reaction species are usu-
ally available in the critically evaluated data compilations of the
National Bureau of Standards (Ref. 2) or the Russian Academy of
Sciences (Ref. 5).
The chosen standard states for the thermodynamic framework are as
follows:
Aqueous solutes - hypothetical, infinitely dilute solution at
unit molality;
Solvent - pure fluid;
Gaseous species - hypothetical 1 bar ideal gas;
Solid species - pure solid.
These are the same standard states as used by the NBS (Ref. 4).
The original implementation now is referred to as the "Old Frame-
work". For some reactions, where sufficient measurements are
available, it uses empirically fitted functions for K values as a func-
tion of temperature instead of equation (1). The "Old Framework"
is used for all models supplied by SIMSCI and by the PUBLIC
library.
A new framework was introduced in the PUBNEW library starting
with PRO/II 5.11. This new form uses an equation of state to predict
K values as a function of both temperature and pressure. Starting
with version 8.0, PRO/II no longer supports the old framework or
Also See:
Electrolyte Thermodynamic Equations
Ionic Species
For ions the formulation used is:
Equation (2-287):
ln i DH i BZ i Pi
NI
1 2
ionic strength = I = --- Z i m i
2
i=1
where: m = molality,
ij
0.06 0.6B Z Z ij i j
Bij Cij I Dij I 2
1 1.5 / Z Z I
2
i j
NM
Z2
Pi BPij 12 BPS j m j
j 1 4I
where:
Equation (2-291):
BPij ij 0 ij 0 1 2 I 1/2 1 exp 2 I 1/ 2 / 2 I
and
and
Equation (2-293):
where:
NM = number of molecular species in solution
NS = number of species in solution
jk0=, jk1 two interaction coefficients for each ion-molecule or
molecule-molecule interaction.
Also See:
Electrolyte Thermodynamic Equations
where:
bi = Setschenow coefficient for the neutral species
where
BPij is defined by equation (2-291) above.
Also See:
Electrolyte Thermodynamic Equations
Aqueous Phase Activity Coefficients
Water Activity
The water activity for multi-component systems is obtained from an
integrated form of the Gibbs-Duhem equation, together with a mix-
ing rule suggested by Meissner and Kusik (Ref. 10). The formula-
tion can be represented as:
Equation (2-296):
1 NC NA NM
NS
ln aH2O
AZ i 1 j 1
Zi Z j ij mi m j 0.01801 m j 2 BPWij mi
i 1 j 1
where:
Equation (2-297):
NC NA
AZ Z i2 mi Z i2 mi
i 1 i 1
Equation (2-298):
Nothnagel Method
Nothnagel et al.(Ref. 11) developed a method for calculating fugac-
ity coefficients in mixtures at moderate pressures. The main feature
of the method is the inclusion of dimerization effects on the second
virial coefficient.
The equation of state is written as:
Equation (2-299):
nT RT
P
V nT bm
where:
P = pressure, atmospheres
nT bm ni bi
i
where:
1 1/3 1/3 3
bi
8
bA bB
Values of b for monomers are tabulated in the original reference.
For component j, the fugacity coefficient is given by:
Equation (2-302):
zj
j exp b j P / RT
yj
where:
bj = size parameter for monomer j, cm3 / mole
The true mole fractions zj are computed from the dimerization equi-
libria. Each dimerization is described by an equilibrium constant
Kij:
Equation (2-303):
zij ij
K ij P
zi z j i j
Equation (2-304):
The dimerization equilibrium constants are related to the enthalpy
and entropy of dimerization:
ln RTK ij H ij / RT Sij / R
where:
Hij = enthalpy of dimerization, cal/mole
Nakamura Method
Nakamura et al. (Ref. 12) proposed the following perturbed-hard-
sphere equation of state for gas mixtures:
Equation (2-306):
RT 1 2 3 a
P
1 v v c
3
v
where:
P = pressure, atmospheres
R = gas constant, 0.082056 liter atm/mole K
T = temperature, Kelvins
v = molar volume, liter / mole
e = reduced density, b/4v
b = parameter signifying the hard-core size of the molecule,
liter / mole
a = parameter signifying the attractive force strength, atm/mole
4 3 2 b 4 2 2
ln k 2
k 3
1 bM 1
5 1 cM
m m
2 n
j kj
y a 1
RTv j 1 m 1 m 1 v
a c 4 1m m 1 c m 1
M k
M
ln z
RTv m 1 m2 v 2
bk exp 2.30259 T
where:
g = pure-component parameter
d =pure-component parameter
Equation (2-309):
n
bM yi bi
i 1
where:
yi = vapor mole fraction of i
ck = pure-component parameter
Equation (2-310):
n
cM yi ci
i 1
Pv
z compressibility factor
RT
Equation (2-312):
n n
aM yi y j aij
i 1 j 1
Equation (2-313):
ij
aij ij
T
where:
a = pure-component parameter
aij = interaction parameter
Equation (2-314):
ij ij0 ij1
Equation (2-315):
ij ij0 ij1
Equation (2-316):
ij1 i1 1j
Equation (2-317):
ij1 i1 1j
Equation (2-318):
1 0
ij0
2
i 0j
Equation (2-319):
ij = interaction parameter
SRK Method
Calculation of fugacity coefficients from the Soave-Redlich-Kwong
equation of state is described in Soave-Redlich Kwong (SRK).
Also See:
Electrolyte Thermodynamic Equations
Vapor Phase Fugacities
Enthalpy
The pressure dependence of the enthalpy for vapor, liquid, and solid
phases is neglected in this thermodynamic framework. However,
this does not introduce significant uncertainties in enthalpy calcula-
tions over the stated model validity ranges for temperature (0 to 200
C) and pressure (up to 200 bars). Because enthalpy is treated as
pressure-independent, PRO/II Electrolytes users will receive a
warning about potential failure of the flash when pressure is varied
to meet a duty specification.
Also See:
Electrolyte Thermodynamic Equations
where:
Hio , yi = the standard state molar enthalpy and the mole frac-
tion, respectively, of the ith vapor or solid component
NC = the total number of components present in the vapor or
solid phase.
At the temperature of interest, Hio is evaluated using:
Equation (2-321):
T
H io H ofi ,Tr CPoi dT
Tr
where:
CPoi , H ofi ,Tr = the standard state, isobaric, molar heat capacity,
and the standard state molar enthalpy of formation for the ith
vapor or solid component.
Tr = the reference temperature of 298K.
Values of CPo for vapor and solid species are obtained from empiri-
i
cal functions of temperature, which are given by:
Equation (2-322):
where:
Ai, Bi, Ci = temperature-independent, but phase-dependent
constants of the ith vapor or solid component.
Also See:
Electrolyte Thermodynamic Equations
where:
Hw = the molar enthalpy of pure water at the temperature of
interest and at the vapor/liquid saturation pressure of H2O
xi = the mole fraction of the ith solute species
Equation (2-325):
ln i
H i H io RT 2
T
where:
Vapor Phase
The density of the vapor phase is evaluated using the equation of
state which corresponds to the chosen vapor fugacity method.
where:
vw = the molar volume of pure water at the temperature and
pressure of interest, as given by the HGK(Ref. 13) equation of
state.
vio,Tr = the standard-state molar volume of the ith molecular or
ionic aqueous solute species, at the reference temperature.
Solid Phase
The molar volume of the solid phase, vsol, at the temperature of
interest is evaluated using:
where:
vio,Tr = the standard state molar volume of the ith pure solid
component at the reference temperature.
Reference
1 Zemaitis, J.F. Jr., Clark, D.M., Rafal, M., and Scrivner, N.C., 1986,
Handbook of Aqueous Electrolyte Thermodynamics, AIChE.
2 Wagman, D.D., et al., 1968-1973, Selected Values of Chemical Ther-
modynamic Properties, NBS Tech Note, 270-3 to 8.
3 Chase, M.W. Jr., Davies, C.A., Downey, J.R. Jr., Frurip, D.J.,
McDonald, R.A., and Syverud, A.N., 1985, JANAF Thermodynamic
Tables, 3rd edn., J. Phys. Chem. Ref. Data, 14, Supplement no. 1,
1856 pp.
4 Wagman. D. D., et al., 1982, The NBS Tables of Chemical Thermo-
dynamic Properties, J. Phys. Chem. Ref. Data, 11, Supplement no. 2,
392 pp.
5 Glushko, V.P., editor, 1965-1981, Thermal Constants of Compounds,
Russian Academy of Sciences, Vols. I-X.
6 Zemaitis, J.F., Jr., 1980, Predicting Vapor-Liquid-Solid Equilibria in
multi-component Aqueous Solutions of Electrolytes, Thermodynam-
ics of Aqueous Systems with Industrial Applications, S.A. Newman,
ed., ACS Symposium Series, 133, 227-246.
7 Bromley, L.A., 1973, Thermodynamic Properties of Strong Electro-
lytes in Aqueous Solutions, AIChE J., 19, 313-320.
8 Pitzer, K.S., 1979, Theory: Ion Interaction Approach, Activity Coef-
ficients in Electrolyte Solutions, 1, 157-208, R.M. Pytkowicz, ed.,
CRC Press, Boca Raton, FL.
9 Pitzer, K.S., 1980, Thermodynamics of Aqueous Electrolytes at Vari-
ous Temperatures, Pressures and Compositions, Thermodynamics of
Aqueous Systems with Industrial Applications, S.A. Newman, ed.,
ACS Symposium Series, 133, 451-466.
10 Meissner, H.P., and Kusik, C.L., 1973, Aqueous Solutions of Two or
More Strong Electrolytes - Vapor Pressures and Solubilities, Ind.
Eng. Chem. Proc. Des. Dev., 12, 205-208.
Thermodynamic Properties
Solid-Liquid Solubility
Transport Properties
Solid-Liquid Solubility
General Information
Solubility Data
General Information
The solubility of solids in liquids can be described by the van't Hoff
(ideal-solubility) equation. This is sufficient for many systems
where non-idealities are small. Alternatively, solubility data, corre-
lated as a function of temperature, may be entered directly. Precipi-
tation of solid salts and minerals from aqueous solutions may be
calculated rigorously using PRO/II Electrolytes. These capabilities
are described in separate sections of Electrolyte Methods.
H m T CP Tt CP Tt
ln xi 1 1 ln
RT Tt R T R T
where:
Hm = enthalpy change of melting
Tt = triple-point temperature
Solubility Data
For systems where sufficient data exist, solid solubilities may be
entered by the user in the form of a correlation of solubility versus
temperature. This correlation has the same functional form as the
van't Hoff equation:
where:
xij = the equilibrium solubility of solute i in solvent j at temper-
ature
For solubility of a solid solute i in a mixed solvent, theory dictates
that the mixing rule should have the following form:
Equation (2-332):
ln xi Z j ln xij
j
In equation (2-332) the sum is over all solvent species, and Zj is the
mole fraction of solvent component j normalized to a solute-free
basis. If the normal liquid mole fractions are denoted by z, this is
written as:
Equation (2-333):
zj
Zj
1 zi
Also See:
General Information
Note: When the van't Hoff equation is used as a FILL option, the
Cp terms are ignored.
The FILL = ONE option uses values of one (complete miscibility) for
the solute's solubility in the missing solvents. The FILL = FREE
option causes the missing solvent or solvents to be ignored in the
solubility calculation. In other words, if a solvent k is missing solu-
bility data for the solute, the sum in equation (2-332) is only taken
zj
Zj
1 zi z k
k
In equation (2-334) the sum is over all solvents k for which there
are no solubility data. Note that equation (2-334) is meaningless if
no solvent in the mixture has solubility data. If FILL = FREE is spec-
ified in such a case, the calculations are defaulted to the van't Hoff
equation.
Reference
Transport Properties
General Information
PURE Methods
PETRO Methods
TRAPP Correlations
Liquid Diffusivity
PURE Methods
PRO/II provides options to compute transport properties as a
weighted average of pure-component values. These PURE methods
(also known as LIBRARY methods) require an available property
value for each component in a mixture. An exception to this
requirement is any petroleum pseudo-components. For a pseudo-
component, a missing property value (not supplied by the user) is
calculated using the PETRO method below. The pure-component
properties (at the temperature of interest) are combined to calculate
stream average properties according to the mixing rules listed in
y MW
1/3
i i i
m i
yi = Mole fraction (2)
y MW
1/3
i i
i
Liquid Viscosity
3
m xi i1/3 xi = Mole fraction (3)
i
Vapor Viscosity
y MW
1/ 2
i i i
m i
yi = Mole fraction (4)
y MW
1/2
i i
i
Surface Tension
Liquid Viscosity
The method selected for liquid viscosity is dependent on the
reduced temperature, which is in turn calculated by Kay's rule.
When the system is near the critical point (0.98<Tr<1.0), the
method developed by Letsou and Steil is used. For the range
0.76<Tr<0.98, equations relating viscosity to reduced temperature
and acentric factors developed by Letsou and Steil (as cited in sec-
tion 9-12 in Reid, Prausnitz and Poling, (Ref. 7)) are used. These
methods were developed from data on simple liquid hydrocarbons.
For low temperatures in which the temperature is below the normal
boiling point, a method based on the Arrhenius relation and the
Thomas equation was developed by SimSci. This method relates
liquid density at the normal boiling point, the critical temperature,
and the system temperature. The density at the normal boiling point
is estimated using the equation of Gunn and Yamada. (Ref. 2)
For intermediate ranges (Tb<T<0.76<Tc), the Andrade equation
(Ref. 1) is used to determine the viscosity, based on reference values
at the normal boiling point and a reduced temperature of 0.76. The
reference values are computed by the methods described above.
After the mixture viscosity has been estimated using one of the
above methods, it is corrected for the effects of pressure using the
method of Kouzel (also see the API Technical Data Book, pp. 11-
47, 2nd edition). Vapor pressure (needed for this method) is esti-
mated using the Reidel equation (Ref. 8).
When water decant is active, water viscosities are taken from the
component data library. A wet viscosity is then calculated for
water/hydrocarbon streams by combining the hydrocarbon and
water viscosities with the following mixing rule:
Equation (2-335):
3
wet xaqaq
1/ 3
xhchc
1/ 3
where:
= viscosity
x = mole fraction
Reference
1
wet
w whc hc2
2 1/2
aq aq
where:
= thermal conductivity
w = weight fraction in the liquid phase
Subscripts aq and hc refer to the aqueous (water) and hydrocarbon
portions of the stream.
Reference
Surface Tension
The surface tension for hydrocarbon liquids is estimated with pro-
cedure 10A3.1 in the API Technical Data Book (3rd edition). Sur-
face tension for water is extracted from the component data library.
Wet surface tension values for decant hydrocarbon systems are
computed with the formula:
Equation (2-337):
where:
= surface tension
x = mole fraction in the liquid phase
Subscripts aq and hc refer to the aqueous and hydrocarbon por-
tions of the stream.
where:
= mole fraction in the vapor phase
MW = molecular weight
subscripts aq and hc refer to the aqueous and hydrocarbon por-
tions of the stream
Reference
where:
y = mole fraction in the vapor phase
MW = molecular weight
Subscripts aq and hc refer to the aqueous and hydrocarbon por-
tions of the stream.
Reference
TRAPP Correlations
The TRAPP method predicts viscosities and thermal conductivities
for pure hydrocarbon components and mixtures of hydrocarbons
and light inorganics for both vapor and liquid phases.
Note: Since this method does not predict surface tension, this prop-
erty is computed from the PETRO correlation described earlier in
this section
x , T o o , To F
, T o' o , To F" , T
where:
= viscosity
= thermal conductivity
F = a dimensional factor
= the fluid density
Subscripts x and o denote unknown and reference fluids.
Superscript ' refers to the potential or translational contribution.
Superscript " refers to the contribution due to internal degrees
of freedom.
This method is applicable to the full range of densities and tempera-
tures, from the dilute gas to the dense liquid. The required constants
for each component are the critical constants (Tc, Pc and Vc) and
the acentric factor.
Note: The method originally was developed for, and was restricted
to, the list of components given in Table 2-19.
Reference
SG
2
f2 x SG 21.1141
Tb1/2
Equation (2-344):
56.7394
x 1.99873
Tb1/2
Equation (2-345):
SG SG SG o
SG
2
f1 1.33932 x SG 21.1141
Tb1/2
ln ln Z A B ln T
Equation (2-349):
Z 0.7 e
1.47 1.84 0.51
2
Equation (2-350):
ln ln Z1 ln ln Z 2
B
ln T1 ln T2
ln ln Z ln ln Z1 B ln T ln T1
where:
= kinematic viscosity
Reference
M m ln m 0.7 xi M i ln i 0.7
i
i = defined + lumped
where:
M, molecular weight
m (subscript) represents the mixture and
i (subscript) sums over all defined (library) component and the
single (lumped) petro component.
is dynamic viscosity, mPa S
Reference
API API r1
ln ln r1 ln r1 ln r 2
r1
API API
r2
where:
= kinematic viscosity of the petroleum fraction
API = API gravity
Superscripts r1, r2 refer to reference fluids 1 and 2.
1/2 K 10
r2
r1
r1
where:
K = the Watson Characterization factor.
The viscosity of the reference fluid (either fluid 1 or fluid 2) can be
expressed as:
Equation (2-355):
C2
ln r C1 C3 ln Tb C4Tb C5Tb3 C6Tb6
Tb
where:
C1, C2, C3, C4, C5, C6 = empirical constants.
Reference
Liquid Diffusivity
PRO/II's Dissolver unit requires the diffusivity of the solute in the
solvent liquid if the user does not supply mass transfer data. PRO/II
can calculate these diffusivities based on user-input data or can esti-
mate them from the Wilke-Chang correlation.
ln Dij c1 c2 / T c3 ln T
where:
T = temperature in Kelvins
c1, c2, c3 = constants
ln Di , m X j ln Dij
j
where:
Di,m = diffusivity (in m2/sec) of solute i in solvent mixture
Wilke-Chang Correlation
Wilke and Chang (1955) developed a method for estimating the dif-
fusivity of a solute at infinite dilution in a binary mixture. SimSci
has adapted this method slightly and put it in multi-component
form. The Wilke-Chang correlation is of limited accuracy, but it
will generally provide a diffusivity that is good to within 50%. The
correlation should not be used in cases where the solute is water or
where the solute is electrolytic. The equation is as follows:
Equation (2-358):
1/2
7.4*102 j X j j M j T
Di ,m
mVi 0.6
where:
Di,m = diffusivity (in m2/sec) of solute i in solvent mixture
T = temperature in Kelvins
m= viscosity of solvent mixture in centipoise
Also see:
Transport Properties
where:
m = surface tension of the mixture, in dynes per centimeter
n = number of components in the mixture
Pi = parachor for component i.
L = density of the liquid mixture, in grams per millimeter
V = density of the vapor mixture, in grams per millimeter
ML = molecular weight of the liquid mixture
MV = molecular weight of the vapor mixture
xi = mole fraction of component i in liquid
yi = mole fraction of component i in vapor
where:
= Surface tension of the liquid, in dynes per centimeter
Tc = Critical or pseudo critical temperature, in degrees Rankine
T = Temperature of system, in Rankine
K = Watson characterization factor
Reference
1 API Technical Data Book - Chapter 10, page no - 23, 1982.
Acentric factor , 1-2, 1-8, 1-9, 1-11, 1-12, 1-13, 1-16, American Petroleum Institute , 2-78, 2-81, 2-82
1-18, 2-75, 2-76, 2-78, 2-80, 2-83, 2-84, 2-94, 2-96, American Society , 1-25, 1-44
2-110, 2-111, 2-112, 2-129, 2-210 Testing , 1-25
ACH , 2-160 AMINE , 2-64, 2-65, 2-66, 2-173, 2-174, 2-175
ACS Symp , 2-99 Amine data package , 2-172
ACS Symposium Series , 2-198 Amine Package , 2-172
Activity Coefficients , 2-145, 2-198 Amine Systems , 2-62
Group Contribution Estimation , 2-145 Methods Recommended , 2-62
Activity-coefficient , 2-157 Amine Treating , 2-169, 2-175
Index-222
Better Data , 2-169, 2-175 ASME , 2-125
Amines , 2-49, 2-63, 2-65, 2-172, 2-173 ASOG , 2-145
Amines diethanolamine , 2-172 Assay Processing , 1-21, 1-22, 1-25, 1-40, 1-41
Amines MEA , 2-62 Assay streams , 1-22
Amines monoethanolamine , 2-172 Associating equation of state , 2-104
Amk , 2-148, 2-149, 2-150 Association , 2-104, 2-105
Ammonia , 2-169 extent , 2-105
Analytical Solution , 2-145 ASTM , 1-25, 1-29, 1-31, 1-33
following , 2-145 ASTM D1160 , 1-21
And/or , 2-95, 2-203 ASTM D2887 , 1-21
And/or vapor-liquid-liquid , 2-152 ASTM D323-73 , 1-42
Anderson , 2-145 ASTM D49 , 1-41
Andrade , 2-205, 2-206 ASTM D5191-91 , 1-42
Ann , 2-139 ASTM D86 , 1-21, 1-25, 1-46
Annual Book , 1-25 converting , 1-33
ASTM Standards , 1-25, 1-44 ASTM Standards , 1-25
Antoine , 1-4, 1-14 Annual Book , 1-25
API , 1-10, 1-12, 1-14, 1-16, 1-19, 1-20, 1-25, 1-26, 1-27, Azeotrope , 2-77
1-29, 1-31, 1-32, 1-33, 1-36, 1-38, 2-49, 2-58, 2-81, Azeotropes , 2-80
2-82, 2-126, 2-165, 2-205, 2-206, 2-207, 2-212,
azeotropic data , 2-152
2-215, 2-216
Azevedo , 2-54, 2-135, 2-157, 2-202
Flash point correlation , 1-46
API gravity , 1-12, 1-14, 1-36, 1-38, 2-215, 2-216
API liquid density , 2-49, 2-50, 2-81 B
API Method , 2-215
API Technical Data Book , 1-25, 1-33, 1-38, 1-42, 2-81,
Backfill , 2-153
2-124, 2-205, 2-206, 2-207, 2-212
PRO/II , 2-152, 2-153, 2-154
API/EPA , 2-166
Banks , 2-139
APINAPHTHA , 1-42, 1-44
Benedict-Webb-Rubin , 2-109, 2-111
Application Guidelines , 1-41, 2-75, 2-76, 2-77, 2-78,
Benedict-Webb-Rubin-Starling , 2-109, 2-124
2-80, 2-81, 2-82, 2-83
BENZENE , 2-211
application ranges , 2-76, 2-155
Bicarbonate , 2-172
Applications , 2-50
Carbamate Reversion , 2-173
Phase Equilibria , 2-54, 2-135
Bii , 2-129
Applied Hydrocarbon Thermodynamics , 1-20, 1-44
Bij , 2-100, 2-129, 2-142, 2-144, 2-185, 2-191
Applying , 1-6
setting , 2-144
Rackett , 1-12
Binary , 2-136
Aqueous Electrolyte Thermodynamics , 2-182
Thermodynamic Evaluation , 2-137
Handbook , 2-183
Binary Fill options , 2-152
Aqueous Liquid Phase , 2-178, 2-196, 2-197
binary interaction databank , 2-159, 2-164
Aqueous Phase Activities , 2-184, 2-185, 2-187, 2-188
Binary Mixtures , 2-137
Aqueous Solutions , 2-197
Two , 2-198 Bisulfide , 2-169, 2-172
Aqueous Solutions Containing Volatile Weak BK10 , 2-60, 2-61, 2-79
Electrolytes , 2-169 Black , 1-10
Aqueous Sour Water Systems , 2-169 Blending , 1-23
Aromatic Systems , 2-66, 2-67 Example , 1-23, 1-24, 1-25
Index-224
CO2 , 2-62, 2-63, 2-64, 2-76, 2-77, 2-79, 2-97, 2-126, Critical Review , 2-83
2-159, 2-160, 2-164, 2-166, 2-169, 2-171, 2-172, Equations , 2-83
2-173, 2-194, 2-211
Critical temperature , 1-2, 1-7, 1-9, 1-12, 1-15, 1-16,
Coal-tar Liquids , 1-20, 1-45 1-19, 2-56, 2-78, 2-82, 2-90, 2-105, 2-109, 2-110,
Coker fractionators , 2-60 2-111, 2-112, 2-129, 2-130, 2-155, 2-205
Complex Mixtures , 2-95 Critical volume , 1-2, 1-7, 1-13, 1-17, 2-85, 2-111,
2-129
Component Data , 1-1, 1-5, 2-205, 2-206, 2-207, 2-208
Cross-references , 1-1
Component Libraries , 1-1, 2-203, 2-205
Cubic , 2-91, 2-98, 2-100
Component Name , 2-211
New Generalized Alpha Function , 2-91
Component properties-extrapolation
cubic equation forms , 2-89
conventions , 1-3
Component properties-temperature correlation Cubic equation-of-state , 2-58
equations , 1-3 Cunningham , 2-95, 2-102, 2-107
Component Solutions , 2-113 Cup
Components Available , 2-126 Closed cup , 1-45
Open Cup , 1-45
components in databank , 2-159, 2-164
Curl-Pitzer , 2-58, 2-60, 2-78, 2-80
Composition Curve
Ideal Liquid Mixtures , 2-206 Curves , 1-25
distillation cutpoints , 1-33
Composition-dependence , 2-102
TBP , 1-25
Compressed Liquids , 2-85
Cutpoint , 1-22, 1-23, 1-24, 1-40, 1-41
Compressibility , 2-54, 2-58, 2-80, 2-104, 2-111, 2-127,
2-128, 2-169, 2-191 Cutpoint Sets , 1-23
Compressibility Factors , 1-20 Cutpoints , 1-21, 1-22, 1-35
Defining , 1-22
Contents , 1-1, 1-21, 2-60
distillation curves , 1-33
Table , 1-1
set , 1-22, 1-23, 1-24, 1-34, 1-35
Convert
use , 1-24
ASTM D86 , 1-25
Cutpoints-application guidelines , 1-22
D86 , 1-25
TBP , 1-25 Cutpoints-multiple sets , 1-22
Coon , 2-95, 2-102, 2-107 Cutpoints-secondary set , 1-22
Copeman , 2-95 CYCLOHEXANE , 2-161, 2-164, 2-211
Correlation , 1-47 CYCLOPENTANE , 2-161, 2-211
API Flash Point , 1-46
SIMSCI flash point , 1-47
Correlations , 2-212 D
Predicting Liquid Viscosities , 2-212
Corresponding States , 2-111 D.M. Rafal , 2-197
Multicomponent Mixtures , 2-111 D1160 Curves , 1-25
Corresponding States Correlation , 2-113 D2887 , 1-25, 1-27, 1-29, 1-30
Saturated Liquid Volume , 2-206 D2887 Curves , 1-25
Corresponding-states , 2-83 D2887 Simulated Distillation , 1-29
COSTALD , 2-67, 2-73, 2-84, 2-85 D323 , 1-41
COSTALD liquid density , 2-67, 2-83 D323 RVP , 1-44
Critical compressibility factor , 1-2, 2-82 D4953 , 1-42, 1-44
Critical pressure , 1-2, 1-7, 1-12, 1-16, 2-76, 2-79, D5191 , 1-41, 1-44
2-129, 2-130
D86 Curves , 1-25
Critical Properties , 1-6, 1-12
Danner , 2-83, 2-97, 2-98
Index-226
Empirical Correlation , 2-128 Erbar-modified Grayson-Streed , 2-77
Second Virial Coefficients , 2-130 Estimates , 2-98, 2-216
Empirical Equation , 2-110 diffusivity , 2-216, 2-217
Thermodynamic Properties , 2-109 Gi , 2-98
Englewood Cliffs , 2-135, 2-157, 2-202 water/hydrocarbon , 2-98
Enthalpy , 1-3, 1-6, 1-12, 1-21, 1-40, 2-49, 2-50, 2-54, Ethanediol , 2-71
2-57, 2-60, 2-72, 2-73, 2-78, 2-80, 2-88, 2-104, Ethanolamine Process Simulated , 2-175
2-157, 2-159, 2-164, 2-166, 2-169, 2-172, 2-182,
Ethylbenzene , 2-164
2-189, 2-191, 2-194, 2-195, 2-196, 2-199
ETHYLCYCLOHEXANE , 2-164
Improved Prediction , 2-80
ETHYLCYCLOPENTANE , 2-212
Enthalpy-ideal-gas , 1-16, 1-19
Entropic , 2-139 ETHYLENE , 2-212
Ethylene Glycol , 2-164
Entropy , 2-49, 2-50, 2-57, 2-72, 2-73, 2-78, 2-80, 2-88,
2-137, 2-159, 2-164, 2-166, 2-169, 2-172, 2-189, ETLN , 2-212
2-191 EtSH , 2-169
Environmental Applications , 2-69 Excess Free Energy , 2-141
Equation New Expression , 2-139
API flash point , 1-46 Excess Gibbs Free Energy , 2-145
Nelson flash point , 1-47
New Expression , 2-145
SIMSCI flash point , 1-47
Extent , 2-104
Equation of state incorporating , 2-104
association , 2-104
equation of state water solubility method , 2-124 extent of association , 2-104
Equation-of-state , 1-10, 2-53, 2-63, 2-67, 2-68, 2-69,
Extrapolation Conventions , 1-3
2-70, 2-126, 2-128
Equations For Electrolyte LLE , 2-177
Equations For Solutions Involving F
Second Liquid Phase , 2-176
Equations of State , 1-6, 1-20, 2-49, 2-50, 2-54, 2-57,
FCCU , 2-60, 2-61
2-58, 2-60, 2-62, 2-69, 2-75, 2-82, 2-83, 2-88, 2-89,
2-91, 2-95, 2-96, 2-97, 2-98, 2-99, 2-100, 2-102, including , 2-60
2-104, 2-108, 2-109, 2-111, 2-124, 2-127, 2-128, Feeds , 1-22
2-130, 2-155, 2-157, 2-159, 2-164, 2-166, 2-169, flowsheet , 1-23, 1-24, 1-25
2-172, 2-182, 2-189, 2-191, 2-194, 2-196, 2-197 FILL , 1-5, 2-69, 2-201
Fill options , 2-121
Fill
Equilibrium constant K , 2-107 Equations of state , 2-121
Equilibrium constant Kij , 2-189 Liquid Activity methods , 2-152
Equilibrium Constants , 2-94, 2-104, 2-167, 2-168, Fill Options for _Solubility Data , 2-201
2-174, 2-177, 2-182, 2-190 Fitting
Equilibrium Expressions , 2-176, 2-179 Distillation Curves , 1-33
Equilibrium Flash Vaporization Calculations , 1-41 Fixed Properties , 1-3
Equilibrium Ratios , 2-80 Flash , 1-45
equilibrium reactions , 2-130, 2-172 Flash Point
Equimolar , 2-158 API Correlation , 1-46
Calculations , 1-45
Equlibrium , 2-174
Correlated Methods , 1-46
Erbar , 2-77, 2-124
Definition , 1-45
Erbar Modification , 2-77 Empirical methods , 1-46
Chao-Seader , 2-77 Index and User Mixing methods , 1-45
Erbar modification to Chao-Seader , 2-77 Library component Properties , 1-2
Erbar modification to Grayson-Streed , 2-77 Nelson Correlation , 1-47
Index-228
GLYCOL , 2-63, 2-64, 2-164 H
Glycol data package , 2-164
Glycol data package uses , 2-164
H.K. Rasmussen , 2-145
GLYCOL databank , 2-64, 2-164
H.P. , 2-198
Glycol Dehydration Systems , 2-64
H2O , 2-77, 2-159, 2-164, 2-166, 2-167, 2-169, 2-173,
Glycol Package , 2-165 2-176, 2-177, 2-178, 2-180, 2-194, 2-196
Glycols , 2-49, 2-164 correlating , 2-167
Glycols tri-ethylene , 2-64 pressure , 2-196
involving , 2-63, 2-64 H2O-alcohol , 2-160
Gmehling , 2-148, 2-150 oF , 2-159, 2-160
Gomes , 2-54, 2-135, 2-157, 2-202 H2O-CO2-NACL , 2-178
Goodwin , 2-95 H2S , 2-62, 2-63, 2-64, 2-76, 2-77, 2-79, 2-97, 2-126,
2-159, 2-164, 2-166, 2-169, 2-171, 2-172, 2-173,
GPA Research Report RR-118 , 2-172
2-194, 2-211
GPA Sour Water Equilibria Correlation , 2-172
H2S Volatility Data , 2-169
GPA Sour Water Package , 2-169
H2S/C3H8 , 2-77
GPSA Data Book , 2-124
H2S-CO2-DEA-H2O , 2-166
GPSWAT , 2-159, 2-169
H2S-CO2-MEA-H2O , 2-166
GPSWATER , 2-64, 2-65, 2-171
Haar , 2-196, 2-199
GPSWATER data package , 2-169
Halogenated , 2-104
Gravity
Handbook , 2-182
specific , 1-15
Aqueous Electrolyte Thermodynamics , 2-182
Gravity data , 1-21, 1-36
Hankinson , 2-85
Grayson , 1-16, 2-72, 2-76, 2-77, 2-80
Hanley , 2-209, 2-212
Grayson-Steeed , 2-124
Hansen , 2-148
Grayson-Streed , 2-60, 2-61, 2-67, 2-76, 2-77, 2-78,
Harris , 2-142
2-124
Grayson-Streed Erbar , 2-60 Harvey , 2-100
Index-230
binary Fill options , 2-121, 2-152 Keyes , 2-125
Interconversion , 1-25 K-factor , 2-125
Interconversion of Distillation Curves , 1-25 K-free , 2-202
Internally Consistent Correlation , 2-214 Kinematic , 2-212, 2-213, 2-214, 2-215
Predicting , 1-20, 1-45 Kister , 2-135, 2-136
Predicting Liquid Viscosities , 2-214 Kistiakowsky , 1-15
Intraphase , 2-176
Kistiakowsky-Watson , 1-10
Introduction , 1-1, 2-54, 2-103, 2-111, 2-135
Knapp , 2-113
Ion Interaction Approach , 2-198 Kolbe , 2-148
Ionic Chemical Systems , 2-69
Krevelen , 2-166, 2-169
Methods Recommended , 2-70, 2-71
Kusik , 2-188, 2-198
Ions , 2-173, 2-185, 2-186, 2-187, 2-197
K-value , 2-50, 2-54, 2-73, 2-75, 2-79, 2-124, 2-155,
Isobutane , 2-164 2-157, 2-159
ISOPENTANE , 2-160, 2-164 compute , 2-156
selected , 2-56
K-values , 2-49, 2-53, 2-60, 2-73, 2-74, 2-75, 2-77, 2-79,
J 2-97, 2-124, 2-126, 2-155, 2-159, 2-174
Kwong , 2-91
J.Chem.Phys , 2-139
J.E. Cunningham , 2-91
J.H. Prausnitz , 2-137
L
J.M. Lichtenthaler , 2-155, 2-201
JANAF Thermochemical Tables , 2-198 Larsen , 2-149
Joback , 1-5 Latent heat of vaporization , 1-6, 1-12, 1-18, 2-54, 2-73
Lee , 1-5, 1-10, 1-16, 1-20, 2-81
John Wiley , 2-54, 2-135
Lee-Kesler , 1-6, 2-60, 2-73, 2-80, 2-81
Johnson , 1-16, 2-80
Johnson-Grayson , 2-80 Lee-Kesler characterization , 1-17, 1-18
Lee-Kesler-Plcker , 2-111
Jones , 2-145, 2-148
Leiden , 2-91
Leland , 2-112, 2-113, 2-209, 2-212
K Lenior , 2-80
LIBID , 2-160, 2-164
K.H. Abrams , 2-197 LIBRARY , 2-54, 2-203
Kabadi , 2-97, 2-98 use , 2-55, 2-56
Kabadi-Danner , 2-64, 2-194 LIBRARY enthalpies , 2-56, 2-57
Kabadi-Danner SRK , 2-97 Lichtenthaler , 2-54
Kansas City , 2-78 Light Gases , 2-159
Kay s , 2-81 Light Hydrocarbon Applications , 2-66
Keenan , 2-125 Light Hydrocarbons , 2-67, 2-109, 2-110
Kell , 2-196, 2-199 Light Petroleum Systems , 2-110
Kelvin , 2-68 Fluid Thermodynamic Properties , 2-110
Index-232
Example , 2-179 Naphthenes , 2-126
modeling , 2-49 Natural Gas Processing , 2-62
Modifications , 2-148 Natural Gas Systems , 2-62
UNIFAC , 2-148, 2-149, 2-150, 2-151 Methods Recommended , 2-62
Modifications to UNIFAC , 2-148 NBP , 1-5, 1-6, 1-11, 1-35, 1-37, 1-38, 1-39, 1-40
Modified , 2-92, 2-94, 2-95, 2-98 equal , 1-40
function , 1-6
modified UNIFAC , 2-148
UFT3 , 2-148 NBS Tables , 2-198
Chemical Thermodynamic Properties , 2-197
Modified UNIFAC Group Contribution Model , 2-149
Prediction , 2-149, 2-150 NBS Tech Note , 2-197
Modified UNIFAC Model , 2-150 NBS2 , 2-183
Molalities , 2-178 N-butane , 2-164
Molality , 2-176, 2-177, 2-183, 2-185 NC4 , 2-164
Molar Volume and Density , 2-197 NC5 , 2-161, 2-164
Molecular Thermodynamics , 2-54, 2-155, 2-202 NC6 , 2-161, 2-164
Fluid-Phase Equilibria , 2-54, 2-202 NC7 , 2-161, 2-164
FluidPhase Equilibria , 2-135, 2-157 N-DECANE , 2-211
Molecular weight , 1-1, 1-5, 1-6, 1-12, 1-21, 1-40, 2-58, N-DODECANE , 2-211
2-62, 2-148, 2-164, 2-216
Nelson flash point , 1-47
Molecular weight data , 1-22, 1-38
NEOPENTANE , 2-211
Molecular weight value , 1-38
New Alpha Function , 2-95, 2-102
Molecular-weight , 1-38
New Correlation , 2-85, 2-169
Molecule-molecule , 2-187 NH3 , 2-166, 2-167, 2-168, 2-169
Molecules , 2-209 Saturated Densities , 2-85
Different Sizes , 2-212 New Expression , 2-141, 2-142
Monomer-dimer , 2-128 Excess Free Energy , 2-139
Mueller , 2-113 Excess Gibbs Free Energy , 2-142
Multicomponent , 2-50, 2-96, 2-98, 2-99, 2-100, 2-135, New Generalized Alpha Function , 2-95
2-157, 2-188, 2-201, 2-216 Cubic , 2-92, 2-94, 2-95
Multicomponent Aqueous Solutions , 2-198 New Group-Contribution , 2-109
Multicomponent Equilibria , 2-141 New Mixing Rules , 2-102
Multicomponent Mixtures , 2-113 New Two-constant , 2-91
Corresponding States , 2-111, 2-113 Newman , 2-169, 2-198
Multicomponent Phase Equilibria , 2-142 NH3 , 2-126, 2-159, 2-166, 2-169, 2-171, 2-194
Calculation , 2-145 containing , 2-159
Multiple cutpoint , 1-22 involving , 2-169
M-XYLENE , 2-164, 2-211 New Correlation , 2-166
N-HEPTADECANE , 2-211
N-HEPTANE , 2-161, 2-211
N N-HEXADECANE , 2-211
N-HEXANE , 2-161, 2-211
NACLppt , 2-180 Ni , 2-57, 2-127, 2-128, 2-135, 2-187, 2-189, 2-196
Nakamura , 2-191, 2-194 N-NONANE , 2-211
Nakamura Method , 2-189, 2-191 NOC , 2-146
N-alkanes , 2-212 N-OCTANE , 2-211
Naphthalenes , 2-79, 2-80 NODIME , 2-139
Index-234
work , 2-111 PRO/II Keyword Input Manual , 1-3
Poling , 2-206 PRO/II s databanks , 1-41, 2-130
Polymer Solutions , 2-138 PRO/II Temperature-dependent Property
Equations , 1-3
Polymer Solutions Using , 2-152
Probability-curve , 1-34
Polymer/solvent , 2-139
maintain , 1-34
Poynting , 2-133, 2-134
PROII databanks , 2-68
Poynting correction , 2-52, 2-53, 2-69, 2-134, 2-169,
2-171 PROPADIENE , 2-211
PR , 1-9, 2-61, 2-62, 2-63, 2-67, 2-69, 2-78, 2-89, 2-91, PROPANE , 2-211
2-97, 2-98, 2-102, 2-124 Properties , 2-205
Prausnitz , 2-54, 2-100, 2-112, 2-113, 2-129, 2-130, Properties From Structure , 1-5, 2-203
2-135, 2-141, 2-142, 2-145, 2-148, 2-152, 2-157, Property Generation CAVETT Method , 1-12
2-169, 2-199, 2-200, 2-202, 2-205, 2-206
Property Generation SIMSCI Method , 1-6
Predicting , 1-16, 1-19, 1-41, 2-62, 2-197, 2-205
Internally Consistent Correlation , 1-20, 1-45 Property GenerationLee-Kesler Method , 1-16, 1-19
vapor-liquid-liquid , 2-64 PROVISION Graphical User , 1-1
Vapor-Liquid-Solid Equilibria , 2-197 PRP , 2-98
Predicting Liquid Viscosities , 2-212 Pseudocomponent , 1-1, 1-5, 1-21, 1-22, 1-40, 2-82,
Correlation , 2-212, 2-214, 2-215 2-83, 2-203
Internally Consistent Correlation , 2-212 define , 1-22
Predicting Saturated Liquid Density , 2-82 Pseudocomponent Properties , 1-40
Predicting Second Virial Coefficients , 2-131 Generating , 1-40
Generalized Method , 2-131 Pseudo-components , 2-125
Predicting Viscosities , 2-216 Pseudocomponents , 1-1, 1-5, 1-21, 1-22, 1-23, 1-24,
Generalized Method , 2-216 1-25, 1-33, 1-35, 1-38, 1-39, 1-40, 2-99, 2-203
Prediction , 1-20, 2-82, 2-148 Pseudo-critical , 2-112
Improved Equation , 2-82 Pseudo-Critical Constants , 2-78
Modified UNIFAC Group Contribution Mixtures , 2-78
Model , 2-148
Pseudocritical Constants , 2-113
Thermodynamic Properties , 1-20
Pseudoreduced , 2-76
Pressure , 1-25, 2-104, 2-176, 2-196
Pseuodoreduced , 2-76
760 , 1-26, 1-27, 1-29, 1-30, 1-31
H2O , 2-196 Pure , 2-203
HF , 2-104, 2-105, 2-107 PURE Methods , 2-203
Pressure-explicit , 2-129 P-XYLENE , 2-164, 2-211
Pressure-independent , 2-194 Pytkowicz , 2-198
PRH , 2-102
Primary TBP Cutpoint Set , 1-22
PRLN , 2-211
Q
PRM , 2-62, 2-64, 2-68, 2-70, 2-99
QUADRATIC , 1-34, 1-36
PRO/II Application Briefs Manual , 1-1
Quasichemical , 2-142
PRO/II back-calculates , 2-82
PRO/II Casebooks , 1-1
PRO/II databanks , 2-61, 2-62, 2-67, 2-82, 2-85 R
PRO/II Electrolytes , 2-176, 2-182, 2-185, 2-194, 2-199
PRO/II flowsheet , 2-70 RACKETT , 1-6, 2-58, 2-82, 2-197
PRO/II Help , 1-1 applying , 1-12
use , 2-82
Index-236
SO2 , 2-71, 2-126, 2-194, 2-212 Specific gravity , 1-2, 1-6, 1-7, 1-11, 1-15, 1-22, 1-36,
Soave , 2-92, 2-94, 2-96, 2-97 1-37, 1-38, 2-82, 2-85, 2-212
Soave-Redlich-Kwong , 2-49, 2-61, 2-96, 2-98, 2-99, Specific heat capacity , 1-16, 1-19
2-100, 2-102, 2-124, 2-126, 2-189, 2-194 Spencer , 2-83
Soave-Redlich-Kwong Huron-Vidal , 2-102 Spline , 1-34
Soave-Redlich-Kwong Kabadi-Danner , 2-97, 2-126 SRK , 1-11, 1-12, 2-57, 2-61, 2-62, 2-63, 2-66, 2-67,
Soave-Redlich-Kwong modified , 2-99 2-70, 2-83, 2-84, 2-92, 2-97, 2-98, 2-102, 2-126,
2-165, 2-194
Soave-Redlich-Kwong Panagiotopoulos-Reid , 2-98
SRK databank , 2-165
Soave-Redlich-Kwong Panagiotoupolos-Reid , 2-98
SRK HEXAMER , 2-104
Soave-Redlich-Kwong SimSci , 2-100
SRK Method , 2-194
Solid , 2-183
SRK/PR , 2-61, 2-62
Solid Applications
Methods Recommended , 2-69 SRKH , 2-102
Solid Cp , 1-4 SRKKD , 2-63, 2-64, 2-97
Solid Phase , 2-178, 2-195, 2-197 SRKM , 2-58, 2-62, 2-64, 2-66, 2-67, 2-70, 2-99, 2-101,
2-160, 2-164, 2-165, 2-168, 2-171, 2-172, 2-174
Solid Thermal Conductivity , 1-4
SRKM/PRM , 2-62, 2-63
Solid-Liquid Equilibria , 2-199, 2-200, 2-201
SRKP , 2-99
Solubility Data , 2-199, 2-200, 2-201, 2-202
SRKS , 2-64, 2-66, 2-67, 2-69, 2-101, 2-107
Solubility Parameter , 1-2
SRKS/SRKM , 2-69
Solubility parameter (Hildebrand) , 1-6, 1-16, 1-19,
2-138 Starling , 2-109, 2-110
solute components , 2-156 Starling s BWRS , 2-111
Solutions , 2-89, 2-136, 2-139 State , 1-11, 2-49, 2-51, 2-52, 2-53, 2-55, 2-56, 2-58,
Classification , 2-136 2-59, 2-60, 2-63, 2-66, 2-67, 2-75, 2-83, 2-88, 2-89,
Thermodynamic Properties , 2-139 2-90, 2-91, 2-92, 2-94, 2-95, 2-96, 2-97, 2-98, 2-99,
2-101, 2-102, 2-103, 2-104, 2-105, 2-106, 2-107,
Thermodynamics , 2-91
2-108, 2-109, 2-110, 2-111, 2-125, 2-126, 2-127,
Solvation , 2-130 2-128, 2-129, 2-130, 2-131, 2-133, 2-155, 2-156,
Solve , 2-156 2-157, 2-160, 2-164, 2-165, 2-168, 2-171, 2-172,
C1 , 2-156 2-174, 2-182, 2-183, 2-184, 2-189, 2-191, 2-194,
2-196, 2-197
Solvent , 2-60, 2-62, 2-183
Associating Equation , 2-128
Solvent Activities , 2-138, 2-152 equation , 1-8, 1-9, 1-11, 1-12, 1-16, 1-17, 1-18,
Generalized Correlation , 2-138 1-20, 1-42, 1-43, 2-49, 2-52, 2-53, 2-55, 2-56,
Solvent De-asphalting Units , 2-60, 2-62 2-58, 2-59, 2-60, 2-63, 2-69, 2-75, 2-76, 2-82,
SOUR , 2-62, 2-64, 2-65, 2-159, 2-166, 2-167, 2-168, 2-83, 2-88, 2-89, 2-90, 2-91, 2-92, 2-94, 2-95,
2-169 2-96, 2-97, 2-98, 2-99, 2-101, 2-102, 2-103,
2-104, 2-105, 2-106, 2-107, 2-108, 2-109, 2-110,
Sour Package , 2-166
2-111, 2-112, 2-125, 2-127, 2-128, 2-129, 2-130,
Sour water data package , 2-166 2-131, 2-132, 2-133, 2-134, 2-155, 2-156, 2-157,
Sour Water EQuilibrium , 2-166 2-158, 2-160, 2-164, 2-165, 2-168, 2-171, 2-172,
2-174, 2-182, 2-183, 2-184, 2-189, 2-191, 2-194,
Sour Water Systems , 2-64
2-196, 2-197
Methods Recommended , 2-63, 2-65
General Cubic Equation , 2-89, 2-95, 2-102
Special Methods , 2-212
Statistical Thermodynamics , 2-145, 2-212
Liquid Viscosity , 2-212
Mixtures , 2-209, 2-212
Special Methods for LiquidViscosity , 2-212
Statistical-mechanical , 2-142
Special Packages , 2-62, 2-159, 2-164, 2-166, 2-169,
2-172 Steil , 2-205
Stewart , 2-78
Index-238
Torres-Marchal , 2-151 UNIQUAC , 2-67, 2-68, 2-69, 2-70, 2-142, 2-143, 2-145,
TR , 1-9, 2-55, 2-76, 2-78, 2-182, 2-195 2-146
UNIQUAC Equation , 2-143, 2-145, 2-146
Trans-2-BUTENE , 2-211
UNIWAALS , 2-70, 2-91, 2-108, 2-109
Trans-2-PENTENE , 2-211
UNIWAALS equation-of-state , 2-70
Transport Properties , 2-203, 2-205, 2-209, 2-212, 2-216
Transport properties-API method , 2-212 Unsaturated Hydrocarbons , 2-126
Use , 1-22, 1-37, 2-54, 2-61, 2-70, 2-71, 2-80, 2-82,
Transport properties-thermal conductivity , 2-209
2-166, 2-171
Transport properties-TWU method , 2-212 cutpoints , 1-22, 1-23, 1-24
Transport properties-viscosity , 2-205 LIBRARY , 2-55, 2-56
Transport properties-Wilke-Chang method , 2-216 PHI , 2-69, 2-70
TRAPP , 2-203 Rackett , 2-82, 2-83
Triethylene Glycol , 2-164 SimSci , 2-62
SWEQ , 2-166, 2-169
Triple Point Pressure , 1-2
three-parameter corresponding-states , 2-80
Triple-point temperature , 2-200
USER , 1-1
True Boiling Point , 1-21
User-supplied Diffusivity Data , 2-216
True vapor pressure (TVP) , 1-41
Utilities , 2-182
True vapor pressure (TVP)-application
guidelines , 1-41
Truncated Virial , 2-128, 2-130, 2-169 V
TVIRIAL , 2-128
TVP
van der Waals , 2-89, 2-90, 2-91, 2-95, 2-99, 2-108,
function , 1-42
2-112, 2-142, 2-146, 2-147
TVP Methods , 1-43
van der Waals area and volume , 1-2, 2-142, 2-146
Two-Parameter Cubic , 2-89, 2-90
Van der Waals mixing , 2-112
Twu , 1-6, 1-10, 2-92, 2-95, 2-100, 2-101, 2-102, 2-104,
van Laar , 2-136, 2-137, 2-140
2-107, 2-212, 2-214, 2-216
Van Laar Equation , 2-136, 2-137
Twu-Bluck-Coon , 2-113
Van Ness , 2-54, 2-135
Twu-Bluck-Cunningham-Coon , 2-93
Van Nostrand Reinhold Co , 2-138
Twu-Coon-Cunningham , 2-94
Van t Hoff , 2-69, 2-199
Type , 1-25
Distillation Curves , 1-25 Van t Hoff SLE , 2-69
van't HoffEquation , 2-199, 2-200, 2-201
VANT HOFF Method , 2-71
U VAPOR , 2-195
Vapor and Solid Phases , 2-195
UFT1 , 2-152 Vapor fugacity , 2-49
UFT1 Lyngby , 2-148 Vapor Phase , 2-197
UFT2 Dortmund , 2-149 Vapor Phase Fugacities , 2-128, 2-131, 2-189, 2-191,
UFT3 , 2-150 2-194
UNDC , 2-211 Vapor Phase Imperfections , 2-169
UNFV , 2-151 Vapor pressure , 1-2, 1-3, 1-4, 1-10, 1-11, 1-12, 1-26,
2-52, 2-55, 2-74, 2-79, 2-83, 2-85, 2-96, 2-105,
UNIFAC , 2-69, 2-108, 2-145, 2-148, 2-155
2-132, 2-135, 2-136, 2-137, 2-138, 2-139, 2-141,
Free volume modification , 2-151 2-142, 2-156, 2-167
UNIFAC Group Contribution , 2-148 Vapor Pressure Calculations , 1-41
UNIFAC Structure Vapor Pressure Equations , 1-4, 1-16, 1-19
petro , 2-68
Vaporization , 1-4, 1-10, 1-11, 1-12, 1-15, 2-55, 2-74 Water Activity , 2-188
latent heat , 1-6, 1-12, 1-18, 2-55, 2-57, 2-74 Water decant , 2-63, 2-124
Vapor-Liquid Equilibria , 1-20, 2-75, 2-76, 2-77, 2-91, water partial pressure , 2-124, 2-125
2-109, 2-145, 2-169 Water/hydrocarbon , 2-97
Generalized Correlation , 2-75, 2-76 estimates , 2-97
High Temperature , 2-77
Water-hydrocarbon , 2-97, 2-98, 2-126
Systems Containing Polar Components , 2-94
Water-Hydrocarbon Phase Equilibria , 2-98
VaporLiquid Equilibria , 2-145, 2-148
Watson , 1-12, 1-16, 1-19, 2-124, 2-212
Vapor-Liquid Equilibrium Calculations , 2-130 expresses , 2-212
VaporLiquid Equilibrium XI , 2-141 function , 2-125
Vapor-liquid-liquid , 2-62 Watson characterization , 1-11, 2-216
predict , 2-63, 2-64
Watson K , 1-37, 2-68
Vapor-Liquid-Solid Equilibria , 2-198
Watson K-factor , 1-14, 1-37
Predicting , 2-198
WATSONK , 1-37
Vapor-phase fugacity , 2-182
WCO2 , 2-65
Vapor-phase nonidealities , 2-171
Webb , 2-110
Various Mineral Oils
Weidlich , 2-150
Specific Heat , 2-207
Weight-fraction , 1-35
Versatile Phase Equilibrium , 2-95
Vidal , 2-102, 2-103, 2-104 WH2S , 2-65
Wien , 2-136
Virial , 2-128, 2-129, 2-130, 2-131, 2-171, 2-189
Wilke , 2-217
Viscosity , 2-205, 2-206, 2-208, 2-209, 2-210, 2-212
Nonpolar Gas Mixtures , 2-205 Wilke-Chang , 2-216, 2-217
Technical Gas Mixtures , 2-208 Wilke-Chang Correlation , 2-216, 2-217
VL , 1-10 Wilke-Chang method , 2-216
VLE , 2-62, 2-69, 2-108, 2-148 WILSON , 2-69, 2-139, 2-141, 2-142, 2-166, 2-169
VLE databank , 2-154 Wilson Equation , 2-140, 2-141
VLLE , 2-124 Wilson Equation Used , 2-141
Vloeistoftoestand , 2-91 Predict Vapor Compositions , 2-141
Volume-averaged , 1-37 Winkle , 2-141
Volume-explicit , 2-128 Wiss , 2-136
Volume-fraction , 1-35 WNH3 , 2-65, 2-171
Volumetric , 2-113 Wohl , 2-137
Volumetric Data , 2-111 Wohl s , 2-136
Gas Mixtures , 2-113 Work , 2-111
Volumetric Properties , 2-113 Plcker , 2-111
Wright , 2-213, 2-214
W
Y
Walas , 2-135
Wamine , 2-65, 2-66 Yamada , 2-205, 2-206
Index-240
Yoon , 2-208 Z
Zipperer , 2-208
Basic Principles
Figure 1-1: Three-phase equilibrium flash
MESH Equations
Water Decant
MESH Equations
The Mass balance, Equilibrium, Summation, and Heat bal-
ance (or MESH) equations may be written for a three-phase
flash as:
Total Mass Balance:
Equation (1-1):
F V L1 L2
Equilibrium:
Equation (1-3):
yi K1i x1i
Equation (1-4):
yi K 2i x2i
Equation (1-5):
K 2i
x1i x2i
K1i
Summations:
Equation (1-6):
y x
i
i
i
1i 0
y x
i
i
i
2i 0
Heat Balance:
Equation (1-8):
FH f Q VH v L1 H1i L2 H 2i
Also See:
Basic Principles
zi
xi
V
Ki 1 1
F
The corresponding vapor mole fraction is then given by:
Equation (1-10):
yi K i xi
x y
i
i
i
i 1.0
Ki 1 zi
y x
i i
V
TOL
i i i
Ki 1 1
F
Equation (1-12) is easily solved iteratively by a Newton-Raphson
technique, with V/F as the iteration variable.
yi , ITER yi , ITER 1
TOL
yi
Equation (1-14):
xi , ITER xi , ITER 1
TOL
xi
y x
i i ITER yi xi ITER 1 TOL
Also See:
Basic Principles
Flash Tolerances
The flash equations are solved within strict tolerances. Most
of these tolerances are built into the PRO/II flash algorithm
and cannot be modified by the user. However, the Composi-
tion Convergence Tolerance is not protected and may be
changed by users. Table 1-20 shows the values of the toler-
ances used in the algorithm for the Rachford-Rice equation (),
Also See:
Basic Principles
K z y
i
i i
i
i 1.0
ln K i zi 0
i
K z 1 0
i
i i
Also See:
Basic Principles
z
i
i / K i xi 1.0
i
z
ln i 0
i Ki
For dew point temperature calculations, equation (1-19) may
be rewritten as:
Equation (1-21):
zi
1 0
i Ki
Hv V Hl
1 1 TOL
Hf F Hf
Water Decant
The water decant option in PRO/II is a special case of a three-
phase flash. If this option is chosen, and water is present in the
system, a pure water phase is decanted as the second liquid
phase, and this phase is not considered in the equilibrium
flash computations. This option is available for a number of
thermodynamic calculation methods such as Soave-Redlich-
Kwong or Peng-Robinson.
Note: The free-water decant option may only be used with the
Soave-Redlich- Kwong, Peng-Robinson, Grayson-Streed,
Grayson-Streed-Erbar, Chao-Seader, Chao-Seader-Erbar,
Improved Grayson-Streed, Braun K10, or Benedict-Webb-
Rubin-Starling methods. Note that water decant is
automatically activated when any one of these methods is
selected.
Reference
1. Perry R. H., and Green, D.W., 1984, Chemical Engi-
neering Handbook, 6th Ed., McGraw-Hill, N.Y.
2. Rachford, H.H., Jr., and Rice, J.D., 1952, Journal of
Petroleum Technology, 4 sec.1, 19, sec. 2,3.
3. Prausnitz, J.M., Anderson, T.A., Grens, E.A., Eckert,
C.A., Hsieh, R., and O'Connell, J.P., 1980, Computer
Calculations for Multicomponent Vapor-Liquid and
Liquid-Liquid Equilibria, Prentice-Hall, Englewood
Cliffs, N.J.
Also See:
Basic Principles
f1 L1 , L2 a z
i
i i / d i Tolerance
Equation (1-24):
f1 L1 , L2 b z
i
i i / di Tolerance
where:
Equation (1-25):
ai 1 K1i
Equation (1-26):
bi 1 K 2i K1i / K 2i
Equation (1-27):
di K1i ai L1 bi L2
Also See:
Basic Principles
Flash Drum
The flash drum unit can be operated under a number of differ-
ent fixed conditions; isothermal (temperature and pressure
Also See:
Equilibrium Unit Operations
Mixer
Figure 1-1: Mixer Unit
The mixer unit is, like the valve unit operation, solved in a
similar manner to that of an adiabatic flash unit. In this unit,
the temperature of the single outlet stream is computed for a
specified outlet pressure and a duty specification of zero. The
number of feed streams permitted is unlimited. The outlet
product stream will not be split into separate phases.
Splitter
Figure 1-1: Splitter Unit
Flash Calculations
General Information
PRO/II contains calculations for single stage, constant entropy
(isentropic) operations such as compressors and expanders. The
entropy data needed for these calculations are obtained from a num-
ber of entropy calculation methods available in PRO/II. These
include the Soave-Redlich-Kwong cubic equation of state, and the
Curl-Pitzer correlation method. Table 2-23 shows the thermody-
namic systems which may be used to generate entropy data. User-
added subroutines may also be used to generate entropy data.
Compressor
Once entropy data are available, the condition of the compressor
outlet stream is computed. These results may be used alone, or in
conjunction with (optional) user-specified adiabatic or polytropic
efficiency to compute the compressor power requirements.
Basic Calculations
ASME Method
GPSA Method
Basic Calculations
For a compression process, the system pressure P is related to the
volume V by:
Equation(2-1):
PV n constant
where n = isentropic coefficient
n k CP / Cv
where:
k = ideal gas isentropic coefficient
Cp = specific heat at constant pressure
Cv = specific heat at constant volume
For a real gas, n > k.
The Mollier chart (Figure 2-2) plots pressure versus enthalpy, as
functions of entropy and temperature. This chart is used to show the
methods used to calculate the outlet conditions for the compressor
as follows:
H ad H 2 H1
H ac H ad * ad
H 3 H1 H ac
WS H 2 H1 J H ad J
where:
J = mechanical equivalent of energy
In units of horsepower, the isentropic power required is:
Equation(2-7):
HEADad H ad *778
where:
GHP = work in horsepower
H = enthalpy change in BTU/lb
F = mass flow rate, lb/min
HEADad = Adiabatic Head, ft
ASME Method
The ASME method is more rigorous than the GPSA method, and
yields better answers over a wider rage of compression ratios and
feed compositions. For these reasons, it is now the default when no
preference is specified. The GPSA method was the default prior to
PRO/II version 4.1.
For a real gas, as previously noted, the isentropic volume exponent
(also known as the isentropic coefficient), ns, is not the same as the
compressibility ratio, k. The ASME method distinguishes between
k and ns for a real gas. It rigorously calculates ns, and never back-
calculates it from k.
Adiabatic Efficiency Given
Polytropic Efficiency Given
nS ln P2 / P1 / ln V1 / V2
where:
V1 = volume at the inlet conditions
nS 1
WS 144 nS / nS 1 fPV
1 1 2 1 S 1
P / P n
n ln P2 / P1 / ln V1 / V3
where:
V3 = volume at the outlet pressure and actual outlet enthalpy
conditions
The polytropic work, i.e., the reversible work required to compress
the gas in a polytropic compression process from the inlet condi-
tions to the discharge conditions is computed using:
Equation(2-13):
n 1
W p 144 n / n 1 fPV
1 1 P2 / P1
n 1
where:
Wp = polytropic work
Wp Wp Wp
p ad
Wac Ws / ad Ws
Note: This polytropic efficiency does not agree with the value cal-
culated using the GPSA method which is computed using p = {(n-
1)/n} / {(k-1)/k}
Reference
American Society of Mechanical Engineers (ASME), 1965, Power
Test Code, 10, 31-33.
Also See: Isentropic Calculations
GPSA Method
The GPSA method is commonly used in the chemical process
industry, but is less rigorous than the default ASME method.
Note: The GPSA method was the default prior to PRO/II version
4.1. Currently, the ASME method is the default.
HEADad z1 z2 / 2 RT1 / k 1 / k P2 / P1
k 1 / k
1
R = gas constant
T1 = temperature at inlet conditions
k 1 / k
T2 z1 / z2 T1 P2 / P1
HEAD p z1 z2 / 2 RT1 / n 1 / n P2 / P1
n 1 / n
1
HEADad HEAD p
ad p
n / n 1
p
k / k 1
Reference
GPSA, 1979, Engineering Data Book, Chapter 4, 5-9 - 5-10.
Also See:
Isentropic Calculations
Expander
General Information
Basic Calculations
General Information
The methods used in PRO/II to model expander unit operations are
similar to those described previously for compressors. The calcula-
tions however, proceed in the reverse direction to the compressor
calculations. Also, the expander model currently does not support
polytropic calculations.
Also See:
Isentropic Calculations
H ad H 2 H1
If the adiabatic efficiency, ad, is given as a value less than
100%, the actual enthalpy change (ac) is calculated from:
Equation(2-22):
H ac H ad * ad
The actual outlet stream enthalpy is then calculated using:
Equation(2-23):
H 3 H1 H ac
WS H 2 H1 J H ad J
where:
J = mechanical equivalent of energy
In units of horsepower, the isentropic expander power output is:
Equation(2-25):
HEADad H ad *778
where:
GHP = work in horsepower
H = enthalpy change in BTU/lb
HEADac z1 z2 / 2 RT1 / k 1 / k P2 / P1
k 1 / k
1
where:
z1, z2 = compressibility factors at the inlet and outlet condi-
tions
R = gas constant
T1 = temperature at inlet conditions
Equation(2-29):
HEAD p z1 z2 / 2 RT1 / n 1 / n P2 / P1
n 1 / n
1
Adiabatic head is related to polytropic head by:
Equation(2-30):
HEADad HEAD p
ad p
n / n 1
p
k / k 1
Also See:
Isentropic Calculations
Pipes
General Information
Basic Calculations
General Information
PRO/II contains calculations for single liquid or gas phase or mixed
phase pressure drops in pipes. The PIPE unit operation uses trans-
port properties such as vapor and/or liquid densities for single-
phase flow, and surface tension for vapor-liquid flow. The transport
property data needed for these calculations are obtained from a
number of transport calculation methods available in PRO/II. These
include the PURE and PETRO methods for viscosities. Table 3-24
shows the thermodynamic methods which may be used to generate
viscosity and surface tension data.
dP / dL t dP / dL f dP / dL e dP / dL acc
total friction elevation acceleration
dP / dL f f v 2 / 2 gc d
Equation (3-3):
dP / dL e g sin / gc
Equation (3-4):
dP / dL acc v / g c dv / dL
where:
l and g refer to the liquid and gas phases
P = the pressure in the pipe
L = the total length of the pipe
f = friction factor
= fluid density
v = fluid velocity
gc = acceleration due to standard earth gravity
For two-phase flow, the density, velocity, and friction factor are
often different in each phase. If the gas and liquid phases move at
the same velocity, then the "no slip" condition applies. Generally,
however, the no-slip condition will not hold, and the mixture veloc-
ity, , is computed from the sum of the phase superficial veloci-
ties:
Equation (3-5):
vm vsl vgl
where:
sl = superficial liquid velocity = volumetric liquid flow rate/
cross sectional area of pipe
dP / dL f f tp tp vtp2 / 2 g c d
Equation (3-7):
dP / dL e g tp sin / g c
Equation (3-8):
Beggs-Brill-Moody (BBM)
This method is the default method used by PRO/II, and is the rec-
ommended method for most systems, especially single phase sys-
tems. For the pressure drop elevation term, the friction factor, f, is
computed from the relationship:
Equation (3-9):
f / f n f tp / f n exp s
y ln L / H L2
where:
fn = friction factor obtained from the Moody diagram for a
smooth pipe.
L = no-slip liquid holdup = vsl / (vsl + vsg)
The liquid holdup term, HL, is computed using the following corre-
lations:
Equation (3-13):
H L 0 aLb / N Fr
c
H L H L0 when 0
H L H L 0 when 0
where:
Equation (3-14):
where:
NFr = Froude number
a, b, c, d, e, f, g = constants
The BBM method calculates the elevation and acceleration pressure
drop terms using the relationships given in equations (3) and (4) (or
equations (7) and (8) for two-phase flow).
else
Ek 0.95
vm = mixture velocity
vsonic = sonic velocity of the fluid
P
v sonic = g c ---
s
gc = 32.2 (in FPS), or 1.0 (in SI)
= ratio of specific heats of the fluids
P = pressure at prevailing conditions
= density at prevailing conditions
Beggs-Brill-Moody-Palmer (BBP)
This method uses the same elevation, and acceleration correlations
described above for the Beggs-Brill-Moody (BBM) method. The
equation for the friction pressure drop term is the same as that given
for the BBM method in equations (9) through (12). For this method,
however, the Palmer correction factors given below are used to cal-
culate the liquid holdup.
Equation (3-16):
H L 0.541H L , BBM 0
H L 0.918H L , BBM 0
where:
HL,BBM = liquid holdup calculated using the BBM method
Dukler-Eaton-Flanigan (DEF)
This method uses the Dukler correlation to calculate the friction
term. The friction factor is given by:
Equation (3-17):
y ln L
Equation (3-19):
f n 0.0056 0.5 N Re
where:
NRe = Reynolds number
H L 1/ 1 0.326v1.06
sg
Wl vl Wg vg
2 2
dP
dL acc 2 g c qm L
where:
W = mass flow rate
v = fluid velocity
vsg = superficial gas velocity
Mukherjee-Brill (MB)
The Mukherjee-Brill method is recommended for gas condensate
systems. In the MB method, a separate friction pressure drop term is
dp / dL f f g vg2 / 2 g c d
dP / dL f f m vm2 / 2 g c d
dP / dL f ff fr g vg2 / 2 g c d
where:
ffr = factor calculated from a correlation
For bubble, slug, and mist flows, the elevation pressure drop is
computed using equation (7), but for stratified flows, the fluid den-
sity used is the gas phase density.
The acceleration pressure drop term is given by:
Equation (3-25):
dP / dL acc vmvsg g tp / g c P dP / dL t
where:
vs = slip velocity
The density, tp, is equal to the gas density for stratified flows only.
A separate expression is used to calculate the holdup for each flow
pattern. These are given as:
< 0 Bubble, Slug, Mist flow
Equation (3-26):
N 0.371771
H L e H 2 , H 2 H1 GV0.393962
N LV
Equation (3-27):
N GV
0.079961
H L e , H 2 H1 0.604887
H2
N LV
Equation (3-29):
H1 1.330282 4.171584s in 4.171584sin2 56.262268NLV
2
N 0.475686
H L e H 2 , H 2 H1 GV0.288657
N LV
Equation (3-31):
where:
Nlv = liquid viscosity number
Gray Method
The Gray method has been especially developed for gas condensate
wells, and should not be used for horizontal piping. The recom-
mended ranges for use are:
Angle of inclination, = 70 degrees
Velocity, v < 50 ft/s,
Pipe diameter, d < 3.5 inches
Liquid condensate loading ~ 50 bbl/MMSCF
The friction pressure drop term is computed from equations (2) or
(6), where the friction factor used is obtained from the Moody
charts. The elevation term is calculated using equations (3) or (7),
while the acceleration term is given by equation (24).
The liquid holdup term, HL is given by:
Equation (3-32):
HL 1 Hg
Equation (3-34):
B1
205
A1 2314 N v 1
Nc
Equation (3-35):
0.730 R
B1 0.0814 1 0.05554 ln 1
R 1
Equation (3-36):
VsL
R
Vsg
Equation (3-37):
m2 vsm
2
Nv
g L L g
Equation (3-38):
g l g D 2
ND
L
Equation (3-39):
0 q0 0.617 w qw
L
q0 0.617 qw
where:
= surface tension
q0 = in situ oil volumetric flow rate
ND = diameter number
Oliemens Method
This method uses the Eaton correlation previously described above
to calculate the liquid holdup. The friction factor is obtained from
the Moody diagrams, and the friction pressure term is computed
using:
Equation (3-40):
G q1 1 qg g / 1 BL A
Equation (3-42):
OLI tp / 1 BL
Equation (3-43):
BL H L H Lns
where:
G = mass flux
HLns = no-slip liquid holdup
dP / dL e s g sin / g c144
s 1 H1 g H g , 0
s g , 0 and H L 1.0
Equation (3-45):
s 1 , 0 and H L 1
Hagedorn-Brown (HB)
This method is recommended for vertical liquid pipelines, and
should not be used for horizontal pipes. The liquid holdup term is
calculated from a correlation of the form:
Equation (3-46):
H L function of N LV , N GV , N D
where:
NLV , NGV , ND are the dimensionless liquid velocity number, gas
velocity number, and diameter number.
The friction factor is obtained from the Moody diagrams, and the
friction pressure term is computed using equations (2) or (6),
depending on whether there is single- or two-phase flow.
Reference
Pumps
General Information
Basic Calculations
General Information
The PUMP unit operation in PRO/II contains methods to calculate
the pressure and temperature changes resulting from pumping an
incompressible fluid.
Also See:
Pressure Calculations
Basic Calculations
The GPSA pump equation is used to relate the horsepower required
by the pump to the fluid pressure increase:
Equation (3-47):
HP qP / 1714.3e
where:
HP = required pump power, in horsepower
q = volumetric flow rate, gal/min.
P = pressure increase, psi
Note: The PUMP unit should only be used for incompressible flu-
ids. Compressible fluids may be handled using the COMPRESSOR
unit operation.
Reference
GPSA Engineering Data Book, 9th Ed., 5-9
Also See:
Pressure Calculations
General Information
This chapter presents the equations and methodology used in the
solution of the distillation models found in PRO/II. It is recom-
mended reading for those who want a better understanding of how
the distillation models are solved. This chapter also explains how
the intermediate printout relates to the equations being solved.All of
the distillation algorithms in PRO/II are rigorous equilibrium stage
Mathematical Models
There are many different approaches to solving the distillation
equations. This is evident from the large number of articles on the
subject in the chemical engineering literature. There are many
classes of distillation problems; wide and narrow boiling, azeo-
tropic, homogeneous and heterogeneous liquid phases, electrolytic
and reactive. Unfortunately, no one algorithm is yet available which
can reliably solve all of these problems. PRO/II provides different
algorithms which excel in solving certain classes of problems and
often provide solution capability over a very wide range of prob-
lems. Eldist is designed to solve a specific class of problems,
KV
Sj b
L j
where:
Sj = the Stripping Factor for stage j
LSS
H1 f S1 , S 2 ,...., S n , 0
L k
LSS
H 2 f S1 , S 2 ,...., S n , 0
L k
........................................................
LSS
H n f S1 , S 2 ,...., S n , 0
L k
LSS
SPk f S1 , S 2 ,...., S n , 0
L k
LSS VSS
H j H Lj L j 1 H j V j 1
V
L j V j
NF NQ
H Lj 1 L j 1 H Vj 1V j 1 H iF Fi Qi 0
i 1 i 1
LSS VSS
f j = l j 1 + l j 1 + ---------- + v j 1 + ---------- vj + 1
Lj Vj
j j
where:
l = the component liquid rate, moles/time
v = the component vapor rate, moles/time
f = the component feed rate, moles/time
Given the equilibrium relationship it is possible to remove v from
equation (4). This is done as follows:
K ij v j lij
vij yij v j K ij xij v j
Lj
Bi ,1 Ci ,1 li,1 fi ,1
1 B Ci,2 l f
i ,2 i ,2 i,2
1 Bi ,3 Ci ,3 li,3 fi ,3
. . . . .
. . . . .
. . . . .
1 Bi,n1 Ci ,n1 li ,n1 fi,n1
1 Bi,n li ,n fi,n
K 1V 1
Cij ij j
L 1
j
Side stream withdrawal factors are defined as:
LSS
RL j 1
L j
VSS
RV j 1
V j
K ij ij K b
1 1
ln K b A B ref
T T
In equation (4-12) Tref is a reference temperature. Using this defini-
tion of the simple K-value model and the side stream withdrawal
factors, the material balance () can be rewritten as:
Equation (4-13):
Outer Loop
The outer loop in the Inside/Out algorithm updates the simple ther-
modynamic model parameters and checks for convergence. In the
inner loop, the distillation equations are solved for the current sim-
ple thermodynamic models. The convergence check in the outer
loop therefore compares the rigorously computed enthalpies and
ln K b wi ln K i
i
ti
wi
t i
i
ln K i
ti yi
1
T
The simple K-values can be calculated very quickly for a given
temperature. Also, once new molar flows are computed in the inner
loop, a new bubble point temperature can be easily computed. Once
the molar flows are computed, the mole fractions are obtained from:
Equation (4-16):
lij
xij
l i
ij
y K
i
ij
i
x 1
ij ij
Equation (4-18):
1
Kb
xi
i i
H v H v0 H v
H L H L0 H L
where:
Hv = the vapor enthalpy
H v A B T T ref
H L C D T T ref
where the departures are modeled in terms of energy per unit mass.
The I/O algorithm has four different levels of intermediate iteration
printout. These are None, Part, Estimate, and All. None results in no
iteration printout. Part results in partial intermediate printout, and is
useful to monitor the progress of the algorithm toward solution.
Estimate should be used to debug a non-converged column. Esti-
mate prints the initial column estimate and more information on
actual equation errors to help determine what the convergence diffi-
culty is. All prints out the column temperature, liquid and vapor
profiles at each iteration and the same comprehensive intermediate
printout as Estimate.
Table 4-26:
Iteration E(ENTH+SPEC) Tolerance
1 0.01
0.001, (if E(ENTH+SPEC) error from iteration 1
2
was below 0.001, then the tolerance = 2.0E-5)
3 2.0E-5
Reference
Russell, R.A., A Flexible and Reliable Method Solves Single-tower
and Crude-distillation -column Problems, 1983, Chem. Eng., 90,
Oct. 17, 53-9.
Also See:
Rigorous Distillation Algorithms
Chemdist Algorithm
The Chemdist algorithm in PRO/II is a Newton based method
which is suited to solving non-ideal distillation problems involving
a smaller number (10 vs. 100) of chemical species. These condi-
tions are generally encountered in chemical distillations as opposed
to crude fractionation where the I/O algorithm would be a better
choice. Chemdist is designed to handle both vapor-liquid and
Basic Algorithm
Figure 4-1 shows a schematic of an equilibrium stage for the case of
two phase distillation with no chemical reaction. The equations
which describe the interior trays of the column are as follows:
Energy Balance:
Equation (4-23):
Qij Yij X ij ln K ij , i 1, NT ; j 1, NC
Equation (4-26):
NC
Si' 1 exp Yij i 1, NT
j 1
where:
Fi =total feed flow to tray i
Ti = temperatures of tray i
NC = number of components
NT = number of trays
subscripts:
i = tray index
j = component index
superscripts:
F = refers to a feed
D = refers to a draw
Vapor-Liquid-Liquid Algorithm
The equations describing the VLLE system are derived by substitut-
ing the bulk liquid flows and transformed bulk liquid mole frac-
tions, Li and Xi,j, for the single liquid phase flows and the
transformed liquid mole fractions, Li and X ij , in the above equa-
tions (22-26).
That is, Li becomes Li and Xi,j becomes X ij
where:
Equation (4-27):
Li L'i L"i
and:
L'ij , L"ij = total liquid flows of the first and second liquid phases,
respectively.
l ij' , l ij"
= component liquid flows in the first and second liquid
phases, respectively.
The new equations which are identical in form to those listed in the
basic algorithm section above, equations (22-26), will not be
repeated here. The K-values which are used in the VLE equations
are calculated by performing a LLE flash. That is, the K-value is
evaluated at the composition of one of the liquid phases produced
by the LLE flash. Chemdist uses the K-value derivatives with
respect to the two liquid phases, the chain rule, and the definition of
a total derivative to calculate the derivatives of the VLE equation
with respect to the bulk liquid flow and composition. That is, the
bulk liquid flows are subject to the all of the constraints imposed by
the LLE equations.
The equations are solved in a two-step approach. After initialization
and calculation of the Jacobian matrix, the Newton-Raphson algo-
rithm calculates new values for the iteration variables (X,Y,L,V,T)i.
Reference:
Basic Algorithm
Figure 4-1 shows a schematic of an equilibrium stage for the case of
two phase distillation with chemical reaction. The equations which
describe the interior trays of the column on which reactions occur
are essentially the basic equations which have terms added for gen-
eration and consumption of chemical species. The equilibrium
equations will be affected only indirectly through the formation or
disappearance of chemical species. Similarly, the energy balance
equation is affected through the enthalpies of the species enthalpies.
If two chemicals react to form a third and produce heat in doing so,
then the enthalpy of the reaction product must be low enough to
account for the disappearance of the moles of the reacting species
and the heat of reaction.
where:
V = the reaction volume
A, B = denote chemical species A and B
a,b = the stoichiometric coefficients of chemical species A and
B in the stoichiometric equation, respectively
exp(-A/RT) = the Arrhenius rate expression for temperature
dependence
= denotes the product of the concentrations of the chemicals
raised to their stoichiometric coefficients.
The only place the reaction volume is used in the distillation calcu-
lations is in the kinetic rate expression (equation (30)). It is
extremely important that the tray reaction volumes are consistent
with the volume basis used in determining the kinetic rate expres-
sion. If the reaction is a homogeneous liquid phase reaction, and the
rate expression is based on liquid phase reactions done in a CSTR,
then the liquid volume should be used. This volume corresponds to
the liquid volume on the tray and in the downcomer. Do not use the
entire mechanical volume between trays unless the rate expression
was determined from pilot plant data and the entire volume was
used to characterize the rate equation. Similarly, if the reaction is
catalyzed by a metal on a ceramic support and the rate equation was
based on the entire cylindrical volume of the packed bed holding
the catalyst, then this should be used.
such that:
Equation (4-32):
H x 0 , 0 g x 0 0
H x , 0 f x 0
H x, t tf x 1 t g x 0
Reference
User-provided Estimates
Ideally, the only estimates the user has to provide is either the over-
head rate or the bottoms rate with the product information. On the
other extreme, the user can provide the complete estimates for the
temperature, flow rates, and composition profiles. PRO/II's initial
estimate generation (IEG) algorithms generate these numbers rela-
tively well and the user need not provide any initial estimates
except for difficult simulations.
PRO/II could interpolate the temperature, liquid and vapor rates,
and phase compositions estimates, if the end point values for these
variables are available. These end point values could either be pro-
vided by the user or estimated by PRO/II. When these values are
provided by the user, we require that the user provide at least two
endpoint values (first and last theoretical stage). The first theoreti-
cal stage is the condenser or the top tray for the no condenser
case. The last theoretical stage is the reboiler or the bottom tray for
the no reboiler case.
Temperatures
Tray temperatures are relatively easy to estimate. The reboiler and
condenser temperatures represent the bubble points and/or dew
points for the products. These may be estimated by the user or cal-
culated using the shortcut fractionator model.
The top and bottom tray temperatures may be estimated by addition
or subtraction of a reasonable temperature difference from the con-
denser and reboiler temperatures.
Estimate Generator
The temperature, rate, and composition profiles not provided by the
user are generated by PRO/II using one of the built-in estimate gen-
erator models. When using the estimate generator, product rates are
still provided with the product information.
Various models used for the estimate generation are shown below in
Table 4-27 with the column algorithm.
Electrolyte Default*
Recommendations
Provide reasonable estimates with the product information.
Provide a reasonable reflux estimate.
Provide temperature guesses for sub-cooled products (the esti-
mate generator would use the saturated values).
Provide the side cooler/heater estimates, if possible.
Also See:
Rigorous Distillation Algorithms
Distillation and Liquid-Liquid Extraction Columns
Basic Algorithm
Column mesh equations are solved by a Newton-Raphson algo-
rithm in the outer loop while liquid phase speciation along with K-
value computations are handled by the inner loop, as shown in Fig-
ure 4-1.
CO aq * mCO aq * aH Oaq
2 2 2
Equation (4-36):
where:
=activity coefficients
K = equilibrium constants
Activity coefficients and equilibrium constants are functions of
temperature, pressure and molarities of components or ions.
In addition, there are four independent atom balance equations and
one electroneutrality equation.
Sodium Balance:
Equation (4-37):
Carbon Balance:
Equation (4-39):
CO2 in mCO3ion mHCO3ion mCO2aq * MolesH2O * MWH2O /1000 0
H+ Balance:
Equation (4-40):
H 2O in MolesH 2O MolesH 2O * MWH 2O /1000
* mCO3ion mOHion mHCO3ion 0
Electroneutrality Equation:
Equation (4-41):
The inside loop solves these eight equations for eight unknowns
using Newton's method. Once these unknowns are computed, and
true (aqueous) mole fractions of aqueous components are deter-
mined, all ions are combined to translate them in terms of aqueous
mole fractions of the original components. These components are
referred to as Reconstituted Components. Overall mole fractions for
these components would be the aqueous mole fractions (true mole
fraction) plus reconstitution of ions. Hence, for a given set of input
liquid mole fractions (x), the inside loop returns two sets of liquid
mole fractions, namely the true mole fractions (x), and the reconsti-
tuted mole fractions (xRC).
Once the speciation equations are solved, vapor-liquid equilibrium
constants (K-values) and its derivatives are computed as a function
of T, P, Xt, and y.
Table 4-28:
a. Natural log of liquid mole fractions, ln(x) NC
b. Natural log of vapor mole fractions, ln(y) NC
c. Tray liquid rate L 1
d. Tray vapor rate V 1
e. Tray temperature T 1
2NC + 3
The equations to be solved on each tray are:
mb n, j x n 1, j L n 1 y n 1, j V n 1
f n, j y n, j V n SV n x n, j L n SL n
vle n, j ln y n, j ln k n, j x n, j 0
Eb n F n Hf n V n 1 H n 1 L n 1 h n 1
V n SV n H n L n SL n h n Q n 0
Summation x: (1)
SX n x n, j 1 0
j
Summation y: (1)
Equation (4-46):
SY n y n, j 1 0
j
Reference:
Variables
Each non equilibrium (rate based) tray or segment introduces
5*NOC + 3 equations and variables (where NOC is the number of
components). The equilibrium stage model used by RATEFRAC
uses only 2*NOC+1 equations and variables. Because of the
increased number of equations and variables, RATEFRAC must
Equations
Vapor Phase Component Material Balances
Liquid Phase Component Material Balances
Vapor Phase Enthalpy Balance
Calculation of Partial Molar Enthalpy
Liquid Phase Enthalpy Balance: (1 Equation)
vi , j N i , j vi , j 1 1 rv j 1 viF, j viPA
,j
NF NPA
i = 1..NOC, j = 1..NT
where
i is the component
j is the segment
Total vapor flow rate of component i leaving
vi , j
segment j
Pump around
PA
NF Number of feeds
NPA Number of pumparounds
NOC Number of components
NT Number of trays or segments
li , j N i , j li , j 1 1 rl j 1 liF, j liPA
,j
NF NPA
i = 1..NOC, j = 1..NT
where
v
NOC
i, j H j N i , j H i , j q vj vi , j 1 svi , j 1 H j 1
NOC NOC NOC
PA
viF, j H Fj viPA
, j H j Q j
v
Equation (4-50):
qvj htcjv T jv T jI
v Vapor Temperature
Tj
I Interface Temperature
Tj
Total Enthalpy nT H j
nT H j
H i, j , k 1..c, k i
ni , j T , P , n
k
H j
H j nT , k 1..c, k i
ni , j T , P ,n
k
(H j )
is determined by perturbing ni , j
ni , j
( n i, j i , j
x i, j when i is perturbed ( i , j
nT , j i , j
( n k, j
x k, j when i k , k 1..c
nT , j i , j
v
NOC
i, j N i , j H i , j q vj vi , j 1 svi , j 1 H j 1
NOC NOC
PA
viF, j H Fj viPA , j H i, j Q j
v
l
NOC
i, j h j li , j 1 sli , j 1 h j 1 N i , j h j 1 q j
NOC NOC NOC
PA
liF, j h Fj liPA
, j hj Q j Q j
L L
where
Equation (4-56):
q Lj htcjL T jI T jL
I Interface Temperature
Tj
L Liquid Temperature
Tj
L
lij Nij hij = lij 1 slij 1 hij 1 + q j
NOC NOC
F F PA PA L
+ l ij h j + l ij h ij Q j +
NF NOC
NPA NOC NQ
LPA
Q j
Equilibrium Relationships
Vapor Liquid Equilibrium Relationships
Rate Relationships in the Vapor Phase
where:
In general,
The K-values are functions of the interface temperature, vapor
phase mole fractions and the liquid phase mole fractions
where:
k Component index
N
NOC
i. j H i , j q vj N
NOC
i. j hi , j q Lj
Equation (4-62):
N i. j H i , j htcjv T jv T jI N i. j hi , j htcjL T jI T jL
NOC NOC
k Component Index
x
NOC
L
i, j 1.0 i 1, 2....NOC
y
NOC
I
i, j 1.0 i 1, 2....NOC
where:
J y yI
1 1
L
B v v exp v I bulk
j j j j j
B v 1
j
Matrix of multi component mass
transfer coefficients on segment j.
exp I
v
j
v 1
Correction factors for finite mass
transfer fluxes. Elements of the matrix
are given by equations (24 &
v
25)
Equation (4-69):
1 1
Bin yibulk
,j i 1, 2..... NOC 1 , i n
kin , j kic , j
where:
Diagonal element
Bij
Off-diagonal element
Bin
Ni , j c N n, j
i, j i 1, 2.... NOC 1
kic , j n 1 kin , j
n i
Equation (4-71):
1 1
in N i , j i 1, 2..... NOC 1 , i n
kin , j kic , j
where:
Diagonal element
ij
Off-diagonal element
in
N i , j J iv, j yiave
, j NTj
where:
Equation (4-73):
, j yi , j
yibulk I
y ave
i, j
2
The diffusion flux of any component i is proportional to only its
own concentration gradient. Thus:
eieffv 1 y yiI, j
1
J iv, j kieff
v
ieff
v bulk
i, j
Liquid phase
Equation (4-75):
where:
L L 1 1 I bulk
J j = B j j j exp j exp I j x x j
xijI C xnI , j
Bi , j i 1, 2.... NOC 1
kiC n 1 kin , j
n i
where
ln i
in in xi i, n 1, 2... NOC 1
xn
where:
Ni , j NOC N n, j
i, j i 1, 2.... NOC 1
kic , j n 1 kin , j
n i
Equation (4-81):
1 1
in N i , j i 1, 2..... NOC 1 , i n
kin , j kic , j
where
Diagonal element
ij
Off-diagonal element
in
where
Equation (4-83):
ln yi j
ieff j eieff 1 j xiI, j xibulk
,j
1
J iL, j kieff
L
1 xi
xi
where:
k
v
ic , j
Vapor phase binary mass transfer coefficient
of species i and C forming the binary pair on
segment j
y ave i , j y I i , j y bulk i , j
2
(b) The interfacial area available for mass transfer in packed col-
umns is calculated using [ref 2].
Equation (4-86):
0.05 0.2
0.75
aw a 1 exp Re0.1 Fr We
L L L
c
where
ReL L
apL
WeL L2
a p L
L Liquid Viscosity
L Liquid Density
Surface tension
L L 1/3 L2/3
ScinL a p d 1p
1/ 2 0.4
in
k 0.0051
g L aw L
ScinL L / L Din
L Liquid Viscosity
htc
kav Sc pr
2/3 2/3
Cpmix
where
Sc Schmidt number
r Prandtl number
r
c mix mix / ktmix
c mix
Mass heat capacity
Diffusion Coefficients
0.000143T 1.75
DAB 2
P M AB v A v B
1/3 1/3
where
P Pressure
M A, M B Molecular weights
M AB
2 1
MA MB
1 1
C 15.9
H 2.31
O 6.11
N 4.54
F 14.7
Cl 21.0
Br 21.9
I 29.8
S 22.9
Aromatic Ring -18.3
Heterocyclic Ring -18.3
B M B T
o
DAB 7.4*108
BVA0.6
T Temperature
Viscosity of solvents B
DA, B DAB D
o 1 xB xi /2 o 1 xi x j /2
BA
Reference
1. R. Krishnamurthy, R. Taylor, A non equilibrium stage model
of multi component separation processes. Part 1: model
description and method of solution, AIChEJ., Vol 31(1985),
pp. 449-456.
2. Onda, K., Takeuchi, H., and Okumoto, Y. J., Journal of Chemi-
cal Eng, Japan, 1(1) 56, (1968).
Column Hydraulics
General Information
Tray Rating and Sizing
Random Packed Columns
Structured Packed Columns
General Information
PRO/II contains calculation methods for rating and sizing trayed
distillation columns, and for modeling columns packed with ran-
dom or structured packing. Trayed columns are preferable to
packed columns for applications where liquid rates are high, while
packed columns are generally preferable to trayed columns for vac-
uum distillations, and for corrosive applications. All tray rating and
packed column calculations require viscosity data. A thermody-
namic method for generating viscosity data from Table 4-32 should
therefore be selected by the user for these applications.
Table 4-32: Thermodynamic Generators for
Viscosity
Method Phase
PURE V, L, VL
PETRO V, L, VL
TRAPP V, L, VL
Capacity
The capacity of a trayed column is defined in terms of a vapor flood
capacity factor, at zero liquid load, CAF0. Nomographs are used to
obtain the capacity factors based on tray spacing and vapor density.
Foaming on trays is taken into account by using a so-called system
factor. Table 4-33 shows the system factors to be used to correct
the vapor capacity factors.
For sizing an existing trayed column, or for calculating the percent
of flood for a given column diameter, the column vapor load is
used. The vapor load may be determined by using:
Equation (4-92):
Vload ACFS G / L G
0.5
where:
Vload = vapor load capacity
G = vapor density
L =liquid density
Pressure Drop
For valve, sieve, or bubble cap trays the total tray pressure drop is a
sum of the dry tray pressure drop, and the pressure drop due to the
liquid holdup on the trays:
P Pdry Pl
where:
P = total pressure drop, inches liquid
Pdry = dry tray pressure drop, inches liquid
where:
Cv = discharge coefficient
For bubble cap trays, the dry tray pressure drop is calculated by the
method of Bolles:
Equation (4-95):
Pdry 1.20 G / L G
0.2
hsh vG0.4 K 2 G / L vG2
where:
hsh =bubble cap slot height
The dry cap coefficient, K2, in equation (4) is a function of the ratio
of the annular to riser areas.
For valve trays, the pressure drop through the liquid is given by:
Pl 0.4 L / lw hw
2/3
where:
L = total liquid flow rate, gpm
lw = weir length, inches
The pressure drop through the liquid on the sieve or bubble cap tray
is given by:
Equation (4-97):
Pl hds
where:
hds = calculated height of clear liquid over trays (dynamic seal)
hw = weir height
hs = static slot seal (weir height minus height of top slot above
plate floor)
how = height of crest over weir
Table 4-34: Random Packing Types, Sizes, and Built-in Packing Factors
(ft2/ft3)
T Random (mm.) 6.3 9.5 12.7 15.9 19 25.4 31.7 38.1 50.8 76.2 88.9
Y Packing (in) 0.25 0.375 0.5 0.62 0.75 1.0 1.25 1.5 2.0 3.0 3.5
PE Type (size) 5 #25 #40 #50 #70
#15
IMTPR
1 51 41 24 18 12
(Metal)
Hy-Pak TM
2 45 29 26 16
(Metal)
Super Intalox
R
3 60 30
Saddles
(Ceram)
Super Intalox
4 Saddles 40 28 18
(Ceram)
Pall Rings
5 95 55 40 26 17
(Plastic)
Pall Rings
6 81 56 40 27 18
(Metal)
Intalox
7 Saddles 725 1000 580 145 92 52 40 22
(Ceramic)
Raschig Rings
8 1600 1000 580 380 255 179 125 93 65 37
(Ceramic)
Raschig Rings
9 700 390 300 170 155 115
(1/32" Metal)
Raschig Rings
10 410 300 220 144 110 83 57 32
(1/16" Metal)
Capacity
The capacity of a randomly packed column is determined by its
flood point. The flood point is defined as the point at which the
slope of the pressure drop curve goes to infinity, or the column effi-
ciency goes to zero. For random packing, the flood point as given
by the superficial vapor velocity at flood, vGf, is determined by
Eckart's correlation:
Equation (4-100):
Fp = packing factor
= w/L
w = density of water
G = density of vapor
L = density of liquid
gc = gravitational constant
L = liquid viscosity
Pressure Drop
The column pressure drop may be calculated by one of two meth-
ods. The Norton method uses a generalized pressure drop correla-
tion:
Equation (4-101):
G L G
0.5
P function1 FP vL0.1vG2 ,
L G G L
where:
L = L/L = liquid kinematic viscosity
The Tsai method uses the following correlation for computing pres-
sure drop:
Equation (4-102):
C 2 F v L 0.5
P function2 s P L , G
g c G L
where
Cs = operating capacity factor
0.5
Cs vG G
L G
Efficiency
The column efficiency may be measured by the Height Equivalent
to a Theoretical Plate (HETP). The HETPs for most chemical sys-
tems are generally close in value for a fixed packing size, regardless
of the application. By default, therefore, the HETP values are deter-
mined by a Rules-of-thumb method suggested by Frank. Only the
D ' a z p 1/3
/ 737.34GL f f f
0.5 b
H G t
ScG
0.3048 3.048
where:
HG = height of vapor phase transfer unit, m
= packing parameter
f = (L/w)0.16
f = (L/w)-1.25
f = (L/w)-0.8
H L C fl z p / 3.048 ScL
0.15 0.5
where:
= packing parameter
Cfl = function of Fr
HETP H G H L ln / 1
where:
= ratio of slope of equilibrium line to operating line = mV/L
Packing factors for the various random packing types are given in
Table 4-34.
Also See:
Column Hydraulics
Capacity
The capacity of a packed column is generally limited by the onset of
flooding, or maximum column vapor load. The flooding point,
however, is difficult to measure. For structured packing, the limit of
capacity is generally used to indicate the flood point. The limit of
capacity (100% capacity) is defined as the vapor load that corre-
sponds to a column pressure drop of 12 mbar/m.
Furthermore, the column capacity is expressed in terms of the
capacity factor. The capacity factor or load factor, cG, of the vapor
phase is defined as:
Equation (4-106):
cG VG G / L G
1/2
L / G G / L
1/2
where:
L = liquid flow, kg/s
G = vapor flow, kg/s
The liquid phase capacity factor, cL, is defined by:
Equation (4-108):
cL VL L / L G
1/2
where
VL = superficial liquid velocity, m/s
cL is related to the vapor capacity factor by:
Equation (4-109):
cG1/2 mcL1/2 n
Pressure Drop
The pressure drop model used in PRO/II for structured packing is a
sum of three separate correlations as shown in Figure 4-1.
F factor VG G
1/2
Efficiency
The column efficiency or separation performance for Sulzer pack-
ing is measured by the number of theoretical stages per meter
where:
aI LVL
0.2
For metal packing types such as the MELLAPAK series, the factor
m in equation (20) usually has a value of 0.8. For gauze packing
such as BX or CY, the factor m has a value closer to 1, i.e., indepen-
dent of the liquid load. This is because gauze packing are more
completely wetted, regardless of the liquid load, while for metal
packing the wetted area increases with increasing liquid load. The
NTSM correlations are obtained by substituting equations (20) and
(21) into equation (19).
Shortcut Distillation
General Information
Fenske Method
Underwood Method
Kirkbride Method
Gilliland Correlation
General Information
PRO/II contains shortcut distillation calculation methods for deter-
mining column conditions such as separations, minimum trays, and
minimum reflux ratios. The shortcut method assumes that an aver-
age relative volatility may be defined for the column. The Fenske
method is used to compute the separations and minimum number of
trays required. The minimum reflux ratio is determined by the
Underwood method. The Gilliland method is used to calculate the
number of theoretical trays required and the actual reflux rates and
condenser and reboiler duties for a given set of actual to minimum
reflux ratios. Finally, the Kirkbride method is used to determine the
optimum feed location.
The shortcut distillation model is a useful tool for preliminary
design when properly applied. Shortcut methods will not, however,
work for all systems. For highly non-ideal systems, shortcut meth-
ods may give very poor results, or no results at all. In particular, for
columns in which the relative volatilities vary greatly, shortcut
methods will give poor results since both the Fenske and Under-
wood methods assume that one average relative volatility may be
used for calculations for each component.
Fenske Method
The relative volatility between components i and j at each tray in
the column, is equal to the ratio of their K-values at that tray, i.e.:
Equation (4-114):
yiN / xiN K iN
N
i, j N N N
yj / xj Kj
where:
y = mole fraction in the vapor phase
x = mole fraction in the liquid phase
iave
, j i , j i , j
1 N
xi , D x j , B
log
x j , D xi , B
N min
log iave
,j
where:
subscripts B, D refer to the bottoms and distillate respective.
Also See:
Shortcut Distillation
Underwood Method
The values of the relative volatilities of the feed components deter-
mine which components are the light and heavy key components. It
is recommended that the most volatile component found in mean-
ingful concentrations in the bottom product is selected as the light
key component. Similary, the least volatile component found in
meaningful concentrations in the overhead product is selected as the
heavy key component.
The relative volatility of each component can therefore be
expressed in terms of the volatility of the heavy key, i.e.,
Equation (4-117):
Kj
j
K hk
xJF, F hk 1 xhkF , F hk 1 xhkF , F
If the value of the ratio given by equation (5) is less than -0.01 or
greater than 1.01 for any component J, then that component will
likely not distribute between both products. Therefore to test if the
correct key components are selected, equation (5) should be applied
to those components lighter than the light key, and heavier than the
heavy key. If they fail the test described above, then new key com-
ponents should be selected.
It should be noted that an exact value of Rmin is not needed. This
value is necessary only to provide an estimate of the product com-
position, and to determine if the specified reflux ratio is reasonable.
The Underwood equations assume a constant relative volatility, as
well as a constant liquid/vapor rate ratio throughout the column.
The first equation to be solved is:
Equation (4-119):
N J xJ , F
1 q
i 1 J
HG H F
q
Hv
where:
q = thermal condition of feed
= heat to convert to saturated vapor/heat of vaporization
HG = molar enthalpy of feed as a saturated vapor
where:
Rmin = minimum reflux ratio = (L/D)min
m B x xlk , B
2
log 0.206 log hk , F
p D xlk , F xhk , D
where:
m = number of theoretical stages above the feed tray
p = number of theoretical stages below the feed tray
Also See:
Shortcut Distillation
Gilliland Correlation
The Gilliland correlation is used by PRO/II to predict the relation-
ship of minimum trays and minimum reflux to actual reflux and
corresponding theoretical trays.
The operating point selected by the user (expressed as either frac-
tion of minimum reflux or fraction of minimum trays) is selected as
the mid-point for a table of trays and reflux. Based on the corre-
sponding reflux ratio, the column top conditions are calculated and
the associated condenser duty determined.
The reboiler load is computed from a heat balance. Note that the
selection of the proper condenser type is vital to accurate calcula-
tion of heat duties. Also, the condenser type selected will have no
effect whatsoever on the separations predicted. Figure 4-1 shows
Distillation Models
There are two shortcut distillation models available in PRO/II, as
shown in Figure 4-1. In the first method (CONVENTIONAL),
which is the default, total reflux conditions exists in the column. In
the second method (REFINE), the shortcut column consists of a
Complex Columns
For complex columns (in which there are more than two products) it
becomes impossible to select key components to define the frac-
tionation within the various sections. For such columns, the separa-
tion is defined indirectly in terms of stream properties. The PRO/II
program allows a wide variety of such properties.
As mentioned above, two models are available for complex col-
umns. For the CONVENTIONAL model, Fenske relationships
defining the column sections (each section having two products) are
solved simultaneously, thus the interaction of reflux between the
sections is considered. For the REFINE model, each section is
solved independently, starting from the bottom. This model closely
approximates typical oil refinery columns in which total liquid
draws are sent to side strippers and little (if any) liquid is returned to
the next lower tray.
As the number of products increases, the difficulty in definition of
nonconflicting specifications also increases. There are often upper
and lower limits for each specification. For example, the total prod-
uct rate cannot exceed the feed rate. Furthermore, for specifications
such as ASTM/TBP temperatures, the selection of the components
to represent the feed streams can be very important. For example, it
would not be reasonable to attempt to separate ten components into
six products, etc. Care should be exercised that the specifications
Troubleshooting
Simple Columns
Simple columns are defined as consisting of one feed and two prod-
ucts, with reboilers and condensers. Systems with two overhead
products (partial condensers) are simulated with one combined
overhead product, with the separation to vapor and liquid products
being accomplished in an ensuing flash drum.
Troubleshooting is usually simple for such columns. Fenske calcu-
lation failures are usually caused by:
Impossible or conflicting specifications which result in impos-
sible material balances. (In particular, look for this situation
when component mole fractions are specified).
Complex Columns
For complex columns (more than two products), a series of two
product columns are used to represent the separations with the feed
introduced into the bottom section. The default model type one con-
siders the effect of reflux between the sections; model two assumes
to reflux between the sections. The second model type is very use-
ful for simulation of petroleum refinery heavy ends columns.
For these columns, it is impossible to select key components to
define the fractionation within the various sections. Therefore, the
separations must be indirectly defined using product stream proper-
ties. As the number of products increase, it becomes increasingly
difficult to define non-conflicting product specifications. There are
also usually upper and lower limits for each specification based on
material balance considerations and feed representation. Care must
be exercised to define specifications which result in unique rates for
all products (either directly or indirectly).
Calculation failures are always related to specifications. Some pos-
sible problems include:
Conflict of fractionation indices with intensive stream property
specifications. In general, this combination of specifications
should be avoided and fractionation index used only in con-
junction with stream bulk properties such as rates and gravities.
Reference
General Information
Liquid-liquid extractions are modeled in PRO/II using the general
trayed column model in conjunction with the LLEX algorithm. The
LLEX algorithm in PRO/II is a Newton based method which is
suited to solving non-ideal distillation problems involving a smaller
number (10 vs. 100) of chemical species. LLEX is designed to solve
liquid-liquid equilibrium problems with more than one equilibrium
stage.
Basic Algorithm
Figure 4-6 shows a schematic of an equilibrium stage with a lighter
liquid (denoted as liquid-1) and a heavier liquid (liquid-2) in equi-
librium.
M i , j exp X iI, j LIi exp X iII, j LIIi exp X iII1, j LIIi 1 LDII
i 1
exp X i 1, j LIi 1, j Fi , j i 1, NT
i 1, NT
Si 1 exp X iI, j i 1, NT
Equation (4-127):
where:
Fi = total feed flow to tray i
Ti = temperatures of tray i
Reference
Murphree Efficiency
This is the most common form of tray efficiency, and is supported
by the IO and enhanced IO algorithms. The RATEFRAC algo-
rithm supports Murphree tray efficiencies only on equilibrium
stages; not on non-equilibrium rate-based segments. Murphree effi-
ciencies may be greater than 1.0 for a given component or group of
components. The equation for Murphree efficiency has the form:
Equation (4-128):
i ,n i ,n 1
EiM, n
i*,n i ,n 1
where:
Vaporization Efficiency
The IO, Enhanced IO, LLEX, and CHEMDIST algorithms support
vaporization efficiency. IN the LLEX model, the vaporization effi-
K ieff,n
,n
Eivap
K ieq,n
where:
Equilibrium Efficiency
Only the IO and Enhanced IO algorithms support equilibrium effi-
ciency. The equation form is:
Equation (4-130):
K ieff,n 1
E
eq
i,n
,n 1
K ivap
General Information
Heat exchangers are used to transfer heat between two process
streams, or between a process stream and a utility stream such as air
or steam. For all three heat exchanger models, the following basic
design equation holds:
Equation (5-1):
U U o T A
where:
q = heat transferred in elemental length of exchanger dz
Uo = overall heat transfer coefficient
T = overall bulk temperature difference between the two
streams
A = element of surface area in exchanger length dz
Q U om Ao Tm H out H in
where:
Q = total exchanger heat duty
Uom = overall mean heat-transfer coefficient
Calculation Methods
The simple heat exchanger model in PRO/II may be used to simu-
late heat exchange between two process streams, heat exchange
between a process stream and a utility stream, or to heat or cool a
single process stream. The simple model does not rigorously rate
the exchanger, i.e., pressure drops, shell and tube side heat transfer
coefficients, fouling factors are not calculated.
Tlm LMTD
T 1
in Tout
2
Tout1 Tin2
T1 T 2
ln in1 out2
Tout Tin
For co-current flows,
Equation (5-4):
Tlm LMTD
T 1
in Tin2 Tout
1
Tout
2
T1 T 2
ln 1in in2
Tout Tout
where:
Tlm = LMTD = logarithmic mean temperature difference
superscript 1 denotes one side of the heat exchanger
where:
h = sensible heat transfer coefficient
H = enthalpy of utility stream
For steam or refrigerant utilities, only latent heat is considered
in the heat transfer. Either the saturation temperature (Tsat) or
saturation pressure (Psat) must be supplied.
Equation (5-6):
Q m
where:
m = mass flowrate of utility stream
= latent heat at Tsat
Zones Analysis
General Information
Calculation Methods
General Information
Conventionally for a simple heat exchanger, the logarithmic mean
temperature difference is calculated using the stream temperatures
at the inlet and outlet of the unit (equations (5-3) and (5-4) in the
previous section - Simple Heat Exchangers). Optionally, PRO/II
can compute a duty-averaged LMTD. This option becomes increas-
ingly useful when phase changes occur along the length of the
exchanger. Under these conditions, the LMTD calculated as
described for the simple heat exchanger may often be inadequate
because of the non-linearity of the enthalpy-temperature character-
istics of the stream changing phase. Zone analysis may therefore be
extremely useful for locating internal temperature pinches.
Also See:
Zones Analysis
Calculation Methods
In this method, the heat exchanger is divided into a number of
zones, and the heat exchanger design equation is then applied to
each zone separately. The number of zones may be specified by the
user, or be automatically selected by PRO/II. Automatic selection
Q U om Ao LMTDzones H out H in
Q
LMTDzones n
Qi
i 1 LMTDi
where:
Q = total exchanger duty
Qi = heat duty in zone i
The LMTD values for the individual zones are computed using the
temperatures of the streams entering and leaving each zone.
For counter-current flows in zone i,
Equation (5-9):
LMTD
T 1
in ,i Tout
2
,i Tout ,i Tin ,i
1 2
i
T1 T 2
ln in1,i out2,i
Tout ,i Tin ,i
For co-current flows in zone i,
Equation (5-10):
LMTD
T 1
in ,i Tin2,i Tout
1
,i Tout ,i
2
i
T1 T 2
ln 1in ,i in2,i
Tout ,i Tout ,i
Example
An example of a zones analysis of a counter-current heat exchanger
is given next, and shown in Figure 5-1.
General Information
PRO/II contains a shell-and-tube heat exchanger module which will
rigorously rate most standard heat exchangers defined by the Tubu-
lar Exchanger Manufacturers Association (TEMA). Shell and tube-
side heat transfer coefficients, pressure drops, and fouling factors
Shell Side
The basic correlations used for phase change (i.e Modified Chen
Vaporization method, or HEX5 method) or no phase change cases
are as follows:
The heat transfer coefficient for an ideal tube bank, Hideal, is
obtained from the following relationships:
Equation (5-11):
0.8
0.037 N Re G N Pr
N Nu (tur )
1 2.443 N Re G N Pr2/3 1
0.1
Equation (5-12):
N Nu (lam ) 0.664 N Re
0.5 1/3
G N Pr
Equation (5-13):
Equation (5-14):
kN Nu ( bund )
hideal
L
NReG = WL
F DS lb b
c
b
NPr = Prandlt number = --------
k
W = total mass flow rate in shell side
c = specific heat of fluid
lb = baffle spacing
h hideal J c J l J b J s J r
where:
h = average shell side heat transfer coefficient
hideal = shell side heat transfer coefficient for an ideal tube bank
Tube side
The basic correlations used for phase change (i.e Modified Chen
Vaporization method, or HEX5 method) or no phase change cases
are as follows:
For turbulent flow in circular tubes, the tube side heat transfer coef-
ficient is obtained from the Sieder-Tate equation:
Equation (5-16):
0.14
hD 0.8 1/3 w
N Nu 0.023 N Re N Pr
k b
where:
w = fluid viscosity at the wall temperature
The above relationship holds for the following flow regimes:
Equation (5-17):
N Re 10000
0.7 N Pr 700
L
60
D
where:
DW
NRe = Reynolds number = -----------
At b
L = tube length
D = effective tube diameter
W = total mass flow rate in tube side
At = cross sectional tube area
D
N Gz N Re N Pr
L
For NGz < 100, a relationship first developed by Hausen is used:
Equation (5-19):
0.14
0.085 N Gz b
N Nu 3.66 2/3
1 0.047 N Gz w
For NGz > 100, the Sieder-Tate relationship is used:
Equation (5-20):
0.14
b
N Nu 1.86 N 1/3
Cadj
w
Gz
where:
3
D b gc
N Gr = --------------------------
-
2
b
2 2
b w
= ----------------------
-
2 w
For transition flow regimes where 2000 < NRe < 10000, the tube
side film coefficient is obtained by interpolation between those val-
ues calculated for the laminar and turbulent flow regimes:
Equation (5-21):
htrans
hturb hlam N Re 2000 h
lam
8000
where:
htrans = heat transfer film coefficient for the transition regime
26bW N cw lb W2
Pwi ' 2
g c Sm S w Do Dw g c Sm S w
0.5 0.5
W 2 2 0.6 N cw
Pwi
2 gc Sm S w
The pressure drop for an ideal cross flow section is then calculated:
Equation (5-24):
0.14
4 f W 2 Nc w
Pbi k
2 g c Sm2 b
where:
Pwi= pressure drop for an ideal window section
fk = the friction factor for the ideal tube bank calculated at the
shell side Reynolds number
N
Ps N b 1 Pbi Rb N b Pwi Rl 2Pbi RB Rs 1 cw
Nc
where:
Ps = actual shell side pressure drop
0.6856 S w
1.9 exp
Sm
Rw
2 S w2
Equation (5-28):
Rt func Rt b , Rs b
Equation (5-31):
W
Ww 0.5
R Rc
1 w
Rl
Equation (5-32):
Pc RcWw2
Equation (5-33):
Pw RwWw2
Equation (5-34):
Pc / Rc
0.5
Fc
W
where:
Sc = cross flow area
Fc ,iter Fc ,iter 1
0.01
Fc ,iter
The shell side end space pressure drops at the inlet and outlet of the
exchanger, Ps,in, and Ps,out, and the actual shell side pressure
drop, Pss, are then calculated using the equations:
Equation (5-36):
Ps ,in Rs ,inWin2
Equation (5-37):
Rs ,in function Rc , lb , S m , S w ,
Equation (5-38):
Ps ,out Rs ,outWout
2
Equation (5-39):
Rs ,out function Rc , lb , S m , S 2 ,
Equation (5-40):
Ps ,in N b 1 Pc Pw Ps ,out
Pss
gc
where:
Ps,in = mean shell side end space pressure drop at exchanger
inlet
Ps,out = mean shell side end space pressure drop at exchanger
outlet
Rs,in = end space resistance at exchanger inlet
FGt2 Ln
Pt
4.35*109 Di S p c
Equation (5-42):
2nGt2
Pr
2.741*10 S
6 2
p
Equation (5-43):
Pts Pt Pr
where:
Pt = pressure drop in tubes
F = friction factor
Gt = mass flux
L = tube length
n = number of tube passes
For transition flow regimes, 2100 < NRe < 2800, F and c are
obtained by interpolation between the laminar and turbulent values:
Equation (5-48):
c
c ,tur c ,lam N Re 2100
c ,lam
700
Equation (5-49):
F
Ftur Flam N Re 2100 F
lam
700
Number of Passes
The static head effect on tube side is considered if there is only 1
tube pass. Similarly, the static head effect on shell side is considered
if there is only 1 shell pass (E, J, K, X type of shells). The
exchanger height (tube length) is considered in the static head cal-
culations.
Bundle weight
Equation (5-50):
AS AT / N S / N P
Equation (5-51):
A 12 L / Di 2.5
0.537
B Di
1.611
Equation (5-55):
Equation (5-56):
Z AB / C
Equation (5-57):
WS 2.205*63.0545 / 489.54 DS Z
Equation (5-58):
VS L Di / 2 /144.0
2
Y1 0.5C1 Di / 2
2
Equation (5-61):
Y2 0.192 Di / 2
3
Equation (5-62):
Y3 Di / 2 Y1 Y2
2
Equation (5-63):
VS L Y3 /144.0
Equation (5-64):
VT LN d o2 di2 / 4*144.0
WW DW VS VT
Equation (5-66):
WSW WB WS WW
where:
AS = Area per shell (ft3)AT = Total Area (ft3)
Fouling Factors
In most exchanger applications, the resistance to heat transfer
increases with use as a result of scaling caused by crystallization or
deposition of fine material. These factors may or may not increase
the pressure drop in the exchanger. For both the tube side and shell
side, the user may input separate factors to account for thermal and
Reference
General Information
The PRO/II LNG (Liquefied Natural Gas) heat exchanger model is
also called a Cold Box. It simulates the exchange of heat between
any number of hot and cold streams. An advantage of this type of
exchanger is that it can produce close temperature approaches
which is important when cooling close boiling point components.
Typically, LNG exchangers are used for cryogenic cooling in the
natural gas and air separation industries.
where:
qcell = heat transferred in exchanger cell
Hout = enthalpy of stream leaving the cell
Hin = enthalpy of stream entering the cell
The following specifications may be set for a LNG cell:
Outlet temperature, Tout.
Cell duty, dqcell.
Phase of outlet stream.
Hot-cold stream temperature approaches.
Minimum internal temperature approach (MITA).
Note: The last three specifications listed above (outlet phase, tem-
perature approach, and MITA) can only be accomplished using a
feedback controller unit.
Zones Analysis
When phase changes occur within the LNG heat exchanger, PRO/II
can perform a Zones Analysis to locate and report any internal tem-
perature pinches or crossovers. For the LNG exchanger, the UA and
Also See:
LNG Heat Exchanger
Heat Exchangers
General Information
Air Cooled Heat Exchanger (ACE) is Heat Transfer equipment,
which uses air as the cooling fluid. Air cooled Heat exchangers are
used in many process industries, especially in Petro chemical indus-
tries.
Air Cooled Heat Exchanger have two sides, one is tube side, which
is a process side and the other one is shell side, which is basically
air side. Air is supplied to the unit operation using fans.
Two calculation options available in PRO/II for simulating Air
Cooled Heat Exchanger are
1 Rating mode
2 Design mode
N R N EU FR WF2
ps
1.2*1011
Equation (5-69):
F2
N EU N EUI W
Equation (5-70):
WF DOT
N Re
12K
Equation (5-73):
C 1
4 pt / DOT
Equation (5-74):
DOT DO 2tf1
A) In-line arrangement:
For 2.9 < NRe 2 x 103
Equation (5-75):
E1 0.272
1.02
86.7
N Re
E2 0.263
N Re
1.0*1010
9.27 *106
N Re
2.49*103
N Re
E1 0.267
N Re
2.74*1013
3.12*1010
N Re
1.24*107
N Re
1.97 *103
N Re
E2 0.235
N Re
1.83*104
6.01*10 3
N Re
6.46*10
2
N Re
5.66*101
N Re
E3 0.188
N Re
1.37 *1018 N Re
3
3.96*1025 N Re
4
A1 1.009 F30.744
A2 1.007 F30.655
A3 1.004 F30.539
0.0265
0.297
F3
A4 1.218
F3
AK1 A4
A4 A3 N Re 1.0*105
AK1 A3
106 105
For 1.0x104 < NRe 1.0 x 105
Equation (5-81):
A3 A2 N Re 1.0*104
AK1 A2
105 104
For 1.0x103 < NRe 1.0 x 104
Equation (5-82):
A2 A1 N Re 1.0*103
AK1 A1
104 103
AK1 A4
NR
1 2 3 4 5
FR1 3.3405 2.4903 2.0068 1.7551 1.6041
FR2 1.2497 1.1897 1.1397 1.1048 1.0838
FR3a 1.895 1.1575 1.02 1.025 1.02
FR4a 2.6543 1.8216 1.5325 1.1480 0.9139
NR
6 7 8 9 10
FR1 1.5034 1.4315 1.3775 1.3356 1.3021
FR2 1.0698 1.0598 1.0524 1.0466 1.0419
FR3a 1.0167 1.0143 1.0125 1.0111 1.01
FR4a 0.3704 0.4603 0.5278 0.5803 0.6222
FR FR 4 a
For 1.0x104 < NRe 1.0 x 106
Equation (5-85):
FR 4a FR 3a N Re 1.0*104
FR FR 3a
106 104
FR 3a FR 2 N Re 1.0*102
FR FR 2
105 104
FR 2 FR1 N Re 1.0*102
FR FR1
102 101
For NRe 10
Equation (5-88):
FR FR1
B) Staggered arrangement:
For 2.9 < NRe 2 x 103
Equation (5-89):
3
3 2.41 10
1.55 10 + -------------------------
2 N Re
3.35 10 + ------------------------------------------------------------------
2 N Re
2.47 10 + ------------------------------------------------------------------------------------------------- -
N Re
E 1 = 0.795 + ---------------------------------------------------------------------------------------------------------------------------------
-
N Re
5.49*1012
1.32*1010
N Re
9.84*106
N Re
3.39*103
N Re
E1 0.245
N Re
5.74*102
4.26*104
N Re
97.3
N Re
1.11*10 2
N Re
E2 0.683
N Re
For 2 x 103 < NRe 2.01 x 106
Equation (5-92):
4.82*1012
1.04*1010
N Re
7.58*106
N Re
2.48*103
N Re
E2 0.203
N Re
For 6.99 < NRe 101.0
Equation (5-93):
3.80*108
8.80*106
N Re
7.17 *104
N Re
3.03*102
N Re
E3 0.343
N Re
8.72*1015
1.65*1012
N Re
7.92*107
N Re
1.81*103
N Re
E3 0.162
N Re
8.62*107
1.92*10 6
N Re
1.48*10
4
N Re
98.9
N Re
E4 0.330
N Re
4.63*1014
2.51*10 11
N Re
5.07 *10
7
N Re
4.98*103
N Re
E4 0.119
N Re
pt
F3
pl
Equation (5-99):
A1 0.93F30.48 if F3 1.6
F30.048 if F3 1.6
A2 0.951F30.284
0.113
0.55
F3
0.708
F3
A3 1.28
F3
A4 2.016 1.675F3 0.949 F32 0.234 F33 0.021F34
For F3 1.6
Equation (5-101):
0.113
0.55
F3
0.708
F3
A2 1.28
F3
A3 2.016 1.675F3 0.949 F32 0.234 F33 0.021F34
AR1 A4
For 104 < NRe 105
A4 A3 N Re 104
AR1 A3
105 104
A3 A2 N Re 103
AR1 A2
104 103
For 102 < NRe 103
Equation (5-105):
A2 A1 N Re 102
AR1 A1
103 102
For NRe 102
Equation (5-106):
AR1 A1
NR
1 2 3 4 5
FR1 0.8089 0.8841 0.9227 0.9421 0.9536
FR2 0.2595 0.4946 0.6562 0.7422 0.7937
FR3 0.450 0.6701 0.780 0.8351 0.8680
FR4 1.1593 1.1044 1.0696 1.0522 1.0418
FR5 1.50 1.335 1.230 1.1725 1.1380
NR
6 7 8 9 10
FR1 0.9614 0.9669 0.9710 0.9742 0.9768
FR2 0.8281 0.8527 0.8711 0.8854 0.8969
FR3 0.890 0.9057 0.9175 0.9267 0.9340
FR4 1.0348 1.0298 1.0261 1.0232 1.0209
FR5 1.115 1.0986 1.0863 1.0767 1.069
FR FR 5
FR 5 FR 4 N Re 104
FR FR 4
105 104
For 103 < NRe 104
Equation (5-109):
FR 4 FR 3 N Re 103
FR FR 3
104 103
For 102 < NRe 103
FR 3 FR 2 N Re 102
FR FR 2
103 102
For 10 < NRe 102
Equation (5-111):
FR 2 FR1 N Re 102
FR FR1
102 101
For NRe 10
Equation (5-112):
FR FR1
B1 1.25
Equation (5-114):
B3 2.0
Equation (5-115):
B2 1.5
Equation (5-116):
E2 E2
Equation (5-117):
E1 E1
Equation (5-118):
E3 E3
In-line arrangement
Equation (5-120):
B1 1.5
Equation (5-121):
B2 2.0
Equation (5-122):
B3 2.5
Equation (5-123):
E1 E2
Equation (5-124):
E2 E3
Equation (5-125):
E3 E4
E2 if E3 104
Equation (5-126):
N EUK E3 if ptc B3
( E3 E2 )( ptc E2 )
E3 if ptc B2 and ptc B3
( E3 E2 )
E1 if ptc B1
ps ps K1
Equation (5-128):
K f Gs2YC1C2
ps
5.22 1010 sDv
Equation (5-129):
K1 0.42 N Re
0.075
1
In-line arrangement
K1 1.0 Staggered arrangement
Equation (5-130):
0.00806
Kf 0.1321
N Re1
Equation (5-131):
W
Gs
AF
Equation (5-132):
0.4
12 Dv
C1
pt
Equation (5-133):
0.6
Y
C2 l
pt
Equation (5-134):
4( XYZ N TTLTV )
Dv
ABX
Equation (5-135):
ABX TL N T DO F
Equation (5-137):
s
62.5
Equation (5-138):
W
WF
AF
Equation (5-139):
WF Dv
N Re1
K
Equation (5-140):
2 N F H FTF )
N TTL ( DOT
AF XZ
12 N R
Equation (5-141):
where
Kf = Friction factor
s = Specific gravity
tfl = Air side fouling layer thickness (inch)
H air H C H R AT H W AW AT
Equation (5-143):
(1 t )( gTC4 gTW4 )
HR
2(TC TW )
Equation (5-144):
3
T
H W 9.46 W
1000
Calculation of HC
1) Bare Tubes
2) Finned Tubes
1) Bare Tubes
Equation (5-145):
N Nu(cal) N Nu(row) F1 F2
N Nu(lam) 0.664 N Re
0.5
N Pr0.33
Equation (5-149):
0.8
0.037 N Re N Pr
N Nu(tur) 0.1
1 2.443N Re ( N Pr0.667 1)
Equation (5-150):
WF DOT
N Re
12 k
Equation (5-151):
W
WF
ZXC
Equation (5-152):
C 1
4 pt / DOT
Equation (5-153):
DOT Do 2tfl
Equation (5-154):
N Pr
F1 0.25
N Pr N Pr(wall)
N Pr(wall)
N Pr
0.11
N Pr N Pr(wall)
N Pr(wall)
Equation (5-155):
1 ( N R 1) F3
F2
NR
0.667
F3 1 Staggered arrangement
pl
p
0.7 l 0.3
1 pt Inline arrangement
2
1.5 pl
C 0.7
pt
Equation (5-157):
pl
pl
DOT
Equation (5-158):
pt
p t
DOT
Equation (5-159):
2Y ( X Z )
AW
N T DOTL
Equation (5-160):
AT 1.0
2) Finned Tubes
Equation (5-161):
N Nu(cal) N Nu(row) F2
N 0.625
0.3 Re0.375
( N Pr )0.333
F
F
Inline arrangement
Equation (5-164):
pl
pl
DOT
Equation (5-165):
( N R 1)
F 2 0.5
NR
Equation (5-166):
pt
pt
DOT
Equation (5-167):
DOR 2tfl
DOT
Equation (5-168):
WF DOT
N Re
12k
Equation (5-169):
W
WF
AF
Equation (5-170):
2 N F H FTF )
N TTL ( DOT
AF XZ
12 N R
A1
FF
A2
Equation (5-172):
A1 A3 A4
Equation (5-173):
A2 0.2618 Do
Equation (5-174):
DOR (1 A5 ) ( DOR 2 H F ) A5
A3
12
Equation (5-175):
A4
2 N F ( DOR 2 H F ) 2 DOR
2
48
Equation (5-176):
A5 N FTF
Equation (5-177):
A6 0.2618 Di
Equation (5-178):
2Y ( X Z )
AW
N T DORTL
Equation (5-179):
DOR
AT
Di FF
Equation (5-180):
A1
FF
A6
g = Emissivity (0.17)
Major Specifications
Modes of Operation
The furnace model makes no explicit distinction between rating and
design modes. However, depending upon the data supplied by the
user, the simulation solves implicitly on one or the other of these
modes.
Design mode: Supply operating values for the following measur-
able parameters:
Process-side outlet temperature or duty (not both).
Tube skin temperature.
Wall temperature.
Ambient temperature (with wall temperature, for heat loss).
The model computes the heat transfer coefficients for radiation,
conduction through the tube walls, and conductive heat losses
through the furnace walls.
Where:
Rr = Molar flow rate of reactant r in the feed to the combus-
tion side.
Rfuel = Molar flow rate of total merged feed to combustion side
Xr = Mole fraction of reactant r in the feed to the combustion
side.
War = Atomic weight of reactant r
Only nitrogen, oxygen, carbon, hydrogen, sulfur, and argon partici-
pate in the combustion process. All library components that consist
only of these elements are decomposed to obtain the available
amount of reactants. The model analyzes the chemical formulae of
these components to determine the stoichiometric content of each
reactant. The decomposition process reduces binary molecules O2,
N2, and H2 to their elemental forms. Renormalization of the feed
redefines the composition using the reactant species in place of the
decomposed components. The model treats non-library and other
components in the feed as inert species that do not participate in
combustion, and they exit intact in the flue gas. Additionally, solids
and assay components should not be present in the combustion -side
fluid.
Air is a unique component that receives special consideration.
When argon is present, it displaces a fraction (0.00934) of the nitro-
gen from air. In addition, the decomposition of air releases its water
content as water vapor. When analysis determines insufficient oxy-
gen is available to achieve complete combustion, the model intro-
duces additional nitrogen and oxygen (simulating air) to eliminate
the oxygen deficiency. It also issues a warning to notify the user of
this action.
The following relationships determine the stoichiometric amount of
each reactant available in the combustion-side feed.
RN = Rfuel * XN / 14.0067 Moles of atomic nitrogen.
RO = Rfuel * XO / 15.9994 Moles of atomic oxygen.
RO2 = Rfuel * XO2 / 31.999 Moles of molecular oxygen.
RC = Rfuel * XC / 12.01115 Moles of carbon.
RH = Rfuel * XH / 1.00797 Moles of atomic hydrogen.
RS = Rfuel * XS / 32.064 Moles of sulfur.
RSO2 = RS
Where:
RCO2 = Moles of carbon dioxide in the flue gas
RH2O = Moles of water in the flue gas
RSO2 = Moles of sulfur dioxide in the flue gas
RO2 = Moles of molecular oxygen in the flue gas
RN2 = Moles of molecular nitrogen in the flue gas
RAir = Mole flow rate of air
XH2O/Air = Mole fraction of water in air
XO2/Air = Mole fraction of molecular oxygen in air
XN2/Air = Mole fraction of molecular nitrogen in air
Where:
Rflue = Mole flow rate of flue gas
Rp = Moles of combustion product p
Where:
dHfiring = Firing duty
Where:
Hfuel = initial enthalpy of the fuel feed
Equation (5-189):
%dHloss rad = Qloss rad / dHfiring
Equation (5-190):
Qloss atm = HTCwall-atm * (Twall Tatm)
Combustion-Side Duty
Equation (5-191):
Hcombust = Qprocess + Qloss
LMTD Calculations
dT1 = Ttskin avg Tproc in
Equation (5-192):
LMTD = (dTlo - dThi ) / log(Tratio )
Process-Side Calculations
The process side of the furnace is much simpler (from a calculation
viewpoint) than is the combustion side. The process stream under-
goes simple heating with no reactions. In a rating mode, once the
heat duty from the combustion side is available on the process side,
it is not difficult to calculate the final outlet conditions.
In a design mode, the user supplies either process outlet tempera-
ture or duty. It then requires only a straightforward application of a
temperature-pressure (T, P) flash or a pressure-enthalpy (P,Q) flash
Equation (5-195):
dTskin = Tskin max Tskin avg
Duty H 2 H1 H r H 4 H 3
The total reactor duty is the sum of the individual path duties. This
process is completely independent of enthalpy datum, hence users
can supply enthalpy values at any arbitrary datum with good results.
For vapor phase reactions, the reference pressure is taken as 1 atm.
Should the reference phase condition (checked by the flash opera-
tion) be found to be liquid for either the reactants or products, the
pressure is lowered further until only vapor is present. Similarly, for
the liquid phase reactions, the reference pressure of reactants or
products is increased until only liquid is present.
Reactors 6-454
When the ADIABATIC option is active, duty may be supplied on
the OPERATION statement. (Unlike the FLASH unit operation, the
reactor also has reference state enthalpies H2 and H3 and heat of
reaction Hr which can be changed, and which will change the outlet
enthalpy. An adiabatic reactor will actually be a fixed-duty reactor.)
The outlet temperature is determined by trial and error to satisfy the
duty.
The reactor duty can be calculated from equation (6-1).
The heat balance will be printed in the reactor summary if the
PRINT PATH statement is input.
Also See:
Reactors
Heat of Reaction
The heat of reaction may be furnished by the user as a function of
the moles of base component reacted. Alternatively, the heat of
reaction will be computed by PRO/II if not supplied, through the
following relationship:
Equation(6-2):
H r H f , products H f , reactants
where:
Hf = heat of formation of each component at 25 C
Conversion Reactor
Shift Reactor Model
Methanation Reactor Model
The CONREACTOR unit operation is a simple conversion reactor.
No kinetic information is needed nor are any reactor sizing calcula-
tions performed. The desired conversion of the base component is
specified and changes in the other components will be determined
where:
T is in problem temperature units
C0, C1, C2 are constants
Reactors 6-456
Shift Reactor Model
The purpose of the shift reactor model is to simulate the shift con-
version of carbon monoxide into carbon dioxide and hydrogen with
steam:
Equation(6-4):
CO H 2O CO2 H 2
Also See:
Conversion Reactor
CO 3H 2 CH 4 H 2O
CO H 2O CO2 H 2
Also See:
Conversion Reactor
Equilibrium Reactor
The EQUREACTOR unit operation is a simple equilibrium reactor.
No kinetic information is needed nor are any reactor sizing calcula-
tions performed. Equilibrium compositions are calculated based on
equilibrium constant data. Approach data, if specified, are used to
compute approach to equilibrium.
The reactor may be operated isothermally at a given temperature,
adiabatically (with or without heat duty specified), or at the feed
temperature. For adiabatic reactors, heat of reaction data must be
given or should be calculable from the heat of formation data avail-
able in the component library databank. Temperature constraints
can be specified. For isothermal reactors, the heat of reaction data is
optional. If supplied, the required heat duty will be calculated.
aA bB cC dD
The equilibrium constant is:
For liquid with Activity as activity base:
Equation(6-7):
c d
C D
K eq = ------------------
-
a b
A B
for vapor or liquid with Fugacity as activity base:
Equation(6-8):
c d
fC fD
K eq = ---------------
a b
fA fB
for vapor or liquid with Molar Concentration as activity base:
Equation(6-9):
c d
CC CD
K eq = ------------------
-
a b
CA CB
for vapor or liquid with Mole Fraction as activity base:
Equation(6-10):
c d
xC xD
K eq = -----------------
a b
xA xB
where:
p = the partial pressure of the component
= the activity of the component
Reactors 6-458
f = the fugacity of the component in either liquid or vapor
C = the molar concentration of the component in liquid
x = the mole fraction of the component in liquid
Note: Keq is dimensionless for liquid phase reactions and has the
dimension of (pressure unit) with = c + d - a - b for vapor phase
reactions
B
ln Keq A C ln T DT E T 2 F T 3 GT 4 H T 5
T
where:
Keq = reaction equilibrium constant
CB BF BR BF BE
where:
= C0 + C1T + C2T2
CO H 2O CO2 H 2
B
ln K eq A
T
Reactors 6-460
where:
A and B are functions of temperature
T = absolute temperature, R
and
Equation(6-15):
P CH4 P H2 O
K eq = -----------------------
-
3
P CO P H2
where:
p = partial pressure in any units
If desired, users may override the NBS data and supply their own
constants A and B in the above equations.
The approach to equilibrium can also be indicated either on a frac-
tional conversion basis or by a temperature approach.
Also See:
Equilibrium Reactor
CO 3H 2 CH 4 H 2O
CO H 2O CO2 H 2
Just as for the shift reaction, the National Bureau of Standards data
are available for methanation reaction. The methanation equilib-
rium is given by:
Equation(6-17):
PCH 4 PH 2o
K eq
PCO PH32
Gibbs Reactor
General Information
General Information
The Gibbs Reactor in PRO/II computes the distribution of products
and reactants that is expected to be at phase equilibrium and/or
chemical equilibrium. Components declared as VL or VLS phase
type can be in both chemical and phase equilibrium. Components
declared as LS or S type are treated as pure solids and can only be
Reactors 6-462
in chemical, but not phase, equilibrium. The reactor can be at either
isothermal or adiabatic conditions. Reaction and product specifica-
tions can be applied to impose constraints on chemical equilibrium.
Available constraints include fixed product rates, fixed percentage
of feed amount reacted, global temperature approach, and reaction
extent or temperature approach for each individual reaction. The
mathematical model does not require the knowledge of reaction
stoichiometry from the user except when the reaction extent or a
temperature approach is to be specified for the individual reaction.
Phase Split
NS G OC NP NC G
G
j n cj jp n jp
RT j 1 RT p 1 j 1 RT
where:
NS = number of solid components
NP = number of fluid phases
NC = number of fluid components
1
G N G n GT n N n N n 2G N n
T
2
When a temperature approach is applied for all reactions (global
approach) or for individual reactions (individual approach), the
standard state free energies of formation are modified in a way that
the relation between the reaction equilibrium constant and change
of Gibbs free energy of formation is satisfied (see equation ()). The
standard state Gibbs free energy is defined as at reactor tempera-
ture, 1 atm, and ideal gas state for all fluid components, and at reac-
tor temperature, 1 atm, and solid state for all solid components
Equation(6-20):
K j = exp G j RT
j = 1 NR
where:
NR = number of reactions
T' = T + T
T = temperature approach
The second part of the objective function is the conservation of ele-
ment groups and mass balance equations created from the con-
straints on chemical equilibrium. For each element group, the
output flow rate has to be equal to the feed flow rate, i.e.:
Equation(6-21):
NS NP NC
bk m jk n m jk nmp
c
j k 1,..., NE
j 1 p 1 j 1
Reactors 6-464
where:
bk = feed quantity of element group k
d j n cj j 1,..., NSFIX
NP
d j n jp j 1,..., NCFIX
j 1
where:
dj = specified or derived fixed product rate
NS NR NS
NP
r arj ncj nj arj n jp n 0j r 1,..., NR
j 1 j 1 p i
where:
In equation (6-24) above, 's are the Lagrange multipliers for the
conservation of elemental groups and various mass balance equa-
tions.
F n
0 j 1,..., NS
n cj
F n
0 j 1,..., NC ; p 1,..., NP
n cjp
F n
0 k 1,..., NE
k
F n
0 r 1,..., NR
r
F n
0 j 1,..., NSFIX
j
F n
0 j 1,..., NCFIX
j
Note that since these are the necessary, but not the sufficient, condi-
tins for Gibbs free energy minimization, a local minimum Gibbs
free energy can be obtained. Multiple solutions may be found when
multiple fluid phases coexist in the mixture. Providing different ini-
tial estimates for different runs can be used as a way to check
whether solution corresponding to a local minimum Gibbs free
energy has been reached.
Reactors 6-466
The new solution point in each calculation iteration is determined
by:
Equation(6-26):
N ' n N n
where:
n = the solution point from previous iteration
G r G r 1 if G r 1 2
or
Equation(6-28):
G r G r 1
if G r 1 2
G r 1
and
Equation(6-29):
r r 1
ncj ncj r r 1
c r 1
if n cj n cj 0.01
n j
and
n rjp n rjp1
if n rjp n rjp1 0.01
n rjp1
Phase Split
When a fluid phase condition of either vapor, liquid, vapor-liquid,
liquid-liquid, or vapor-liquid-liquid, is specified for the reactor, the
Gibbs free energy of fluid components is calculated based on the
specified fluid phases. On the other hand, if the fluid phase is
unknown or not specified for the reactor, phase split trials can be
performed to evaluate the number of fluid phases in the reactor. The
starting iteration number and the frequency of phase split trial can
be adjusted by the user. In each phase split trial, a new fluid phase is
added to the current fluid phases. If the Gibbs free energy is
reduced as a result of adding this new phase, the new fluid phase is
accepted.
The reactor modeling generally follows the algorithm described in
the papers of Gautam et al. (1979) and White et al. (1981). Addi-
tional information can be found in the book by Smith (1991).
Reference
Reactors 6-468
Gibbs Reactor
Mass balance:
Equation(6-1):
M
Fj Fjf ij i T , P, C1 , C2 ,..., CN V
j 1
Energy balance:
Equation(6-2):
N N M
Fjf H T f Fjf H T H i jV Q 0
*
j 1 j 1 i 1
where:
Cj = exit concentration of jth component
P = reactor pressure
ij = stoichiometric coefficient of jth species for ith reaction
Tf = feed temperature
T = reactor temperature
Hi = molar heat of reaction for the ith reaction
Reactors 6-470
subroutines feature in PRO/II. For further details, refer to Chapter 7
of the PRO/II User-added Subroutines User's Manual. The result-
ing general expression for the rate of the ith reaction is:
Equation(6-3):
E N
i Ai exp i T C j j
RT j 1
where:
Ai = Arrhenius frequency factor
R = gas constant
T = temperature
= temperature exponent
Cj = concentration of jth species
N = total number of reacting components
j = exponents of concentration
i
= reaction rate for reaction i.
For multiple, simultaneous reactions, the overall reaction rate for
each reacting component is:
Equation(6-4):
M
E N
*j ij Ai exp i T C j j
i 1 RT j 1
where:
*j = net rate of production of species j.
Solution of a CSTR involves the simultaneous solution of the mass
and energy balance equations (6-1) and (6-2).
Also See:
Continuous Stirred Tank Reactor (CSTR)
Reactors 6-472
Also See:
Continuous Stirred Tank Reactor (CSTR)
Design Principles
PFR Operation Modes
Available Methods
Also See:
Reactors
Design Principles
The steady state mass and energy balance for the one-dimensional
PFR for M simultaneous reactions can be derived as follows:
Reactors 6-474
Mass balance:
Equation(6-5):
d i
G i 1 , 2 ,..., M , P, T
dz
Energy balance:
Equation(6-6):
dT
G J * 1 , 2 ,... M , P, T Q
dz
where:
G = mass flow per unit area through the reactor
= extent of reaction per unit mass
i = rate or reaction for the ith reaction
Q
Q
C P
where
H R
CP
where
C = mean heat capacity of the species in the reactor
P
dT d Q
J
dz dz G
or
Equation(6-10):
z Q
T To J dz
0 G
where:
T To , 0 at z 0
Reactors 6-476
(b) Tc governed by a further differential equation. Here, the
issues to be considered are: the form of coolant flow (cocur-
rent or countercurrent) and whether the cold feed itself is to
be used as the coolant.
Also See:
Plug Flow Reactor (PFR)
Reference
Smith, J.M., 1970, 2nd Ed., Chemical Engineering Kinetics,
McGraw-Hill, NY.
Also See:
Plug Flow Reactor (PFR)
DP G 1
3 150 1 1.75G
DL g c D p Dp
where:
P = pressure, lb/ft2
Reactors 6-478
change is negligible over the length of a finite segment we can
develop the following:
As the reactor is operated at steady state the mass flow rate at any
point down the reactor, m(kg/s) is equal to the entering mass flow
rate, m0 (equation of continuity).
m0 = m
r0v0 = v
Since volume of the fluid is changing with temperature and pres-
sure, we have
Equation(6-12):
v vo 1 AXA Po P T To
vo To 1 P
o o
v T 1 A Po
From equation (6-5) and (6-7) we have:
Equation(6-14):
dP G 1 PT
3 150 1 1.75G o 1 A X
dL o g c DP Dp To P
Where,
Reactors 6-480
Chapter 7:Solids Handling Unit Oper-
ations
The equations used by the following types of solids handling equip-
ment are discussed in this chapter.
Dryer
General Information
Calculation Methods
General Information
PRO/II has the capability of simulating a simple continuous solids
dryer in which the drying gas and solid streams flow counter-cur-
rent to each other. The liquid (typically water) content of the solid
stream is reduced by contact with the hot gas stream. The dryer unit
is simulated in much the same way as the flash drum unit is. If the
stream composition and rate are fixed, then there are 2 degrees of
freedom that may be fixed. Any one of the following combination
of specifications may be used when defining the dryer unit opera-
tion:
DRYER
SPECIFICATION 1 SPECIFICATION 2
OPERATION
Calculation Methods
The design specification is used along with mass balance equations
to calculate the operating dryer temperature or pressure (the other is
specified). A two-phase (VL) flash is performed to determine the
vapor and liquid phase distributions. The details of the calculation
flash algorithm may be found in Chapter 1, Flash Calculations.
Also See:
Dryer
General Information
In solid-liquid separations, horizontal rotary drum filters are often
used to decrease the liquid content of a stream containing solids.
For a given filter diameter and width (rating calculations), PRO/II
will compute the pressure drop, cake thickness, average cake satu-
ration, as well as determine the rates of the solid cake and filtrate
product streams. For design calculations, PRO/II will determine the
drum diameter and width required for a given pressure drop.
Equation(7-1):
K g c d p2 A B
where:
K = permeability of filter cake
gc = acceleration due to gravity
a
A and B assume different values in different sphericity ranges:
For > 1.5,
Equation(7-2):
0.4942
A exp 1.8780
0.5144
B exp 1.1069
The pressure drop across the filter cake is then given by:
Equation(7-4):
2 L L Skc
Pc
D 2W 2 Atot2
where:
L = liquid volumetric flow rate through the cake
L = liquid viscosity
= angle of filtration
D = diameter of filter drum
W = width of filter drum
= drum rotational speed in rad/s =2(RPM)/60
RPM = rotational speed of drum in revolutions/min
Atot = total filter area =2DW
The actual pressure drop across the drum filter is then given by:
Equation(7-5):
1/ 1 C f
Pact Pc
where:
Cf = filter cake compressibility factor
The value of the filter cake compressibility factor can vary from 0
for an incompressible cake to 1.0 for a highly compressible cake.
Industrially, the value of Cf is typically 0.1 to 0.8.
S
t
D W s 1
2
The filter bed will never become completely dry, but will always
contain a certain amount of liquid which cannot be removed by fil-
tration. This liquid remains in the spaces between particles, and is
held in place by the surface tension of the liquid. This residual cake
saturation is a function of a dimensionless group known as the cap-
illary number, Nc. The capillary number is given by:
Equation(7-7):
P
K L act
t
Nc
where:
L = liquid density
s0 101.80.299log Nc
s0 102.7590.957 log Nc
L
Nc K
0.275
hD
ND
where:
t
z
hD
Pact
2
1/3
y ln 0.453K 1
t L
Reference
1 Treybal, R. E., 1980, Mass-Transfer Operations, 3rd Ed.,
McGraw-Hill, N.Y.
2 Dahlstrom, D.H., and Silverblatt, C.E., 1977, Solid/Liquid
Separation Equipment Scale Up, Uplands Press.
3 Brownell, L.E., and Katz, D.I., 1947, Chem. Eng. Prog.,
43(11), 601.
4 Dombrowski, H.S., and Brownell, L.E., 1954, Ind. Eng.
Chem., 46(6), 1207.
5 Silverblatt, C.E., Risbud, H., and Tiller, F.M., 1974, Chem.
Eng., 127, Apr. 27.
Also See:
Rotary Drum Filter
Solids Handling Unit Operations
General Information
An alternate solid-liquid separating unit to the rotary drum filter is
the filtering centrifuge. In this type of unit, the solid-liquid mixture
is fed to a rotating perforated basket lined with a cloth or mesh
insert. Liquid is forced through the basket by centrifugal force,
while the solids are retained in the basket. PRO/II contains five
types of filtering centrifuges as indicated in Table 7-39.
Calculation Methods
For rating applications, the basket diameter, rotational speed in rev-
olutions per minute, and centrifuge type are specified. The centrifu-
gal force is then computed using:
Equation(7-13):
r 2
g cent
gc
where:
gcent = centrifugal force
If Centrifuge type is not given and RPM value is not supplied then
the RPM is calculated based on expression 8-14 and a centrifugal
force of 1200 kg-m/sec2 .
The amount of solids remaining the basket is computed from:
Equation(7-14):
M s r 2 rcake
2
hs 1
where:
Ms = mass of solids remaining in the basket
h = height of basket
s = solid density
tcake r rcake
The surface area of the filter basket, and the log-mean and arithme-
tic mean area of the filter cake are given by:
Equation(7-16):
2 htcake
Acake ,lm
ln r / rcake
Acake ,mean r rcake h
Afilter 2 rh
where:
Acake,lm = log-mean surface area of filter cake
K d p2
A B
where:
K = permeability of filter cake
dp = diameter of cake particle
0.4942
A exp 1.8780
0.5144
B exp 1.1069
K L g cent
Nc
g c
where:
L = liquid density
s0 101.80.299log Nc
For Nc > 0.03,
Equation(7-22):
s0 102.7590.957 log Nc
s0 0.072
The cake drain number and height are calculated from the cake per-
meability, centrifugal force, and the liquid density and surface ten-
sion:
Equation(7-24):
K L g cent
ND
gc
0.275
hd
ND
t h h
sav s0 cake D D
tcake tcake
where:
sav = average filter cake saturation
L
X cake sav
1 s
Finally, the actual rate of filtrate through the basket is given by:
Equation(7-27):
where:
Acake ,lm K
L 2 r 2 rL2 m
Acake,mean Afilter
Fmax
2 L K c M s
where:
Reference
1 Treybal, R. E., 1980, Mass-Transfer Operations, 3rd Ed.,
McGraw-Hill, N.Y.
2 Grace, H.P., 1953, Chem. Eng. Prog., 49(8), 427.
3 Dombrowski, H.S., and Brownell, L.E., 1954, Ind. Eng.
Chem., 46(6), 1207.
Also See:
Solids Handling Unit Operations
Filtering Centrifuge
Countercurrent Decanter
General Information
Calculation Methods
Calculation Scheme
General Information
Mixtures of solids and liquids may be separated by counter-current
decantation (CCD). This unit operation consists of several settling
Calculation Methods
The equations describing the model are as developed below.
U N TS / PS
ON U N 1 ON 1 U N
where:
U = decanter underflow rate from a stage
PS = solid fraction in underflow
TS = total solids flow through CCD
O = total overflow rate from a stage
Subscripts N, N-1, N+1 refer to stage N, and the stages below
and above stage N.
Component Balance:
Equation(7-31):
where:
xiU, N 1
EN
xiO, N
where:
Equation(7-36):
U1 O1 R1
R2 1 O2U1
Y1
1
D1
Equation(7-37):
O2 R2
1
D1
Equation(7-38):
F1C fi ,1C
Fi ,1
D1
Equation(7-39):
D1 O1 R1 1
Equation(7-40):
N 1
Equation(7-41):
R N + 1 1 O N + 1 U N
U N + O N R N ------------------------------------------------- -
yN
N = -------------------------------------------------------------------------------------
DN
Equation(7-42):
yN U N
Equation(7-43):
ON 1 RN 1
N
DN
FNC fi ,CN
Fi , N
DN
Equation(7-45):
DN U N 1 RN 1 ON
Equation(7-46):
1
RN
EN
The underflow and overflow stream temperatures from each stage
are the same and are assumed equal to the stage temperature, i.e.,
the stage is in thermal equilibrium.
Also See:
Countercurrent Decanter
Calculation Scheme
For the rating calculations, the total mass balances are solved easily
once the total solids and percent solids underflow at each stage are
specified. The calculation procedure is given below.
First the underflow rates are calculated from equation (7-29). The
wash water rate to the last stage is known, and the last stage over-
flow rate is then calculated using:
Equation(7-47):
ON F2 U N 1 U N
The remaining overflow rates are then calculated from the last stage
backwards to the first stage using equation (7-30).
Once UN and ON are calculated for all stages, the component bal-
ance equations are then solved using the Thomas algorithm, a ver-
sion of the Gaussian elimination procedure. This method of solving
the tri-diagonal equations (7-33) through (7-34) avoids matrix
inversion, buildup of truncation errors, and avoids negative values
of xi, N being produced. The tri-diagonal equations can be reduced
to:
1 p1 0 0 . . . 0 xi ,1 qi ,1
0
1 p2 0 . . . 0 xi ,2 qi ,2
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
. . . . . . . . . .
0 0 0 0 . . . pN 1 xi , N 1 qi , N 1
0 0 0 0 . . . 1 xi , N qi , N
where:
Equation(7-49):
1
p1
1
Equation(7-50):
Fi ,1
qi ,1
1
Equation(7-51):
N
pN
N N pN 1
Equation(7-52):
Fi , N N qN 1
qi , N
N N pN 1
The solution of this matrix results in the immediate solution of the
last stage composition xi, N, using the last row of the matrix, i.e.,
Equation(7-53):
xi , N qi , N
xi , N 1 qi , N 1 pN 1 xi , N
Reference
1 Scandrett, H.E., Equations for Calculating Recovery of
Soluble Values in a Countercurrent Decantation Washing
System, 1962, Extractive Metallurgy of Aluminum, 1, 83.
Also See:
Countercurrent Decanter
Solids Handling Unit Operations
Dissolver
General Information
Particle Size Distribution
Material and Heat Balances
Solution Procedure
General Information
Dissolution of solids into liquid solutions is a mass transfer opera-
tion which is widely used in the chemical industry in both organic
as well as inorganic processes. A unit operation that utilizes mass
transfer controlled dissolution is the stirred tank dissolver. The con-
tents of the stirred tank dissolver are well-mixed using an agitator,
and when it is operated in a continuous manner, the unit can be
called a continuous stirred tank dissolver or CSTD. The PRO/II dis-
solver is of the CSTD type.
p V p t V p t t Ap k L L S C t
where:
p = density of solid particle, kg/m3
Vp = volume of particle, m3
dV p
p Ap k L L S C
dt
Equation(7-57):
4
V p r 3 , Ap 4 r 2
3
where:
r = radius of solid particle, m and
Equation(7-58):
dr
p kL L S C
dt
Equation (7-58) describes the mass transfer rate per unit area as
dependent on two factors; the mass transfer coefficient and concen-
tration difference. The mass transfer coefficient is the liquid phase
coefficient, since diffusion of the solute from the particle surface
through the liquid film to the bulk of the liquid solution is the dom-
inant or rate-controlling step. The concentration difference is the
difference between the equilibrium concentration at the solid-liquid
interface and the solute concentration in the dissolver liquid.
Integrating equation (7-58) for constant kL,
Equation(7-59):
kL
r pL S C
p
where:
dp = solid particle diameter, m
di = impeller diameter, m
a b
kL 0.1733
dp dp
where:
a, b are mass transfer coefficient parameters
dcut = solid particle cut-off diameter, m
r2 dr
L S C / p
r1 kL
Note: Both r (radius) and dp (diameter) are used for particle size
here, but inter-conversion between r and dp is done in the program.
Also See:
Dissolver
kL
rip rif L S C
p
Equation(7-65):
r
3
1 mif
ip
r
i
if
3
kL
1 1
r
L S C mif
i
p if
Overall
Equation(7-66):
F EB
where:
F = mass rate of feed, kg/sec
E = mass rate of overhead product, kg/sec
B = mass rate of bottoms product, kg/sec
Component
solute,
Equation(7-67):
solvent,
Equation(7-68):
inerts,
Fi Ei Bi , i 1, 2,..., N
where:
solute refers to the solute component
solvent refers to the solvent component
i refers to the inert component
Fsolute Fsolute
Liq
PF
Equation(7-71):
Bsolute Bsolute
Liq
P
where:
Liq
Fsolute = mass rate of solute component in feed liquid, kg/sec
PF = mass rate of solid in feed, kg/sec
Liq
Bsolute = mass rate of solute component in bottoms product liquid,
kg/sec
P = mass rate of solid in bottoms product, kg/sec
E
Esolute Ysolute MWsolute
MWvapor
where:
MWsolute = molecular weight of solute component kg/kgmol
Phase Equilibria
Solid-liquid Phase Equilibrium
Equation(7-74):
X solute f1 temperature
Yi f 2 X i
Residence Time
Equation(7-76):
V /Q
where:
= residence time in the dissolver, sec
Concentration
Equation(7-77):
C Cf / Q
Solution Procedure
The solution procedure or algorithm using the above equations per-
forms sequential calculations of the solid-liquid problem through
mass transfer kinetics and vapor-liquid equilibrium calculations
along with heat and material balances. This iteration loop is
repeated until product stream compositions do not change and con-
vergence is obtained.
Crystallizer
General Information
Crystallization Kinetics and Population Balance Equations
Material and Heat Balances
Solution Procedure
General Information
The crystallizer is used for separation through the transfer of the
solute component from a liquid solution to the solid phase. The
crystallization process depends on both phase equilibria as well as
kinetic or non-equilibrium considerations.Solid-liquid equilibrium
is defined in terms of solubility, which is the equilibrium composi-
tion of the solute in a liquid solution containing the solvent compo-
nent. Solubility is a function of temperature, and is calculated from
either the van't Hoff equation or user-supplied solubility data. The
solubility is rigorously calculated if electrolyte thermodynamic
methods are used. Crystallization can occur only in a supersaturated
liquid solution. A supersaturated liquid is one in which the solute
concentration exceeds the equilibrium solubility at the crystallizer
temperature. Supersaturation is generally created by cooling the liq-
uid and/or evaporation of the solvent. Additionally, for crystalliza-
tion systems where evaporation of solvent occurs, the vapor phase
and liquid solution satisfy vapor-liquid equilibrium.
The quantity of crystals formed depends on the residence time in
the crystallizer and is determined by the kinetics of the crystalliza-
tion process. Crystals are generated from supersaturated solutions
by formation of nuclei and by their growth. The primary driving
G kG S GEXP
where
G = growth rate of crystals, m/sec
kG = growth rate constant, m/sec
eq
X solute X solute
S = supersaturation ratio= ------------------------------------------
eq
X solute
Xsolute = Actual mole fraction of solute in liquid
Nucleation Rate:
Equation(7-79):
where:
Bo = crystal nucleation rate, number/sec.m3
Bo
no
G
where:
no = nuclei number density, number/m/m3 slurry
dn
q f n f qn GV
dr
where:
q = volumetric rate of bottoms product slurry, m3/sec
qf = volumetric rate of feed, m3/sec
V = operating volume of crystallizer, m3
r = characteristic length of crystal, m
Equation(7-82):
Gr q f 1 r
q G f dr
d e n n e G
where:
c = density of crystals, kg crystal/m3 crystal
M T 6 c kv no G
4
Also See:
Crystallizer
Overall
Equation(7-90):
F EB
where:
F = feed rate, kg/sec
E = overhead product rate, kg/sec
B = bottom product rate, kg/sec
Component
Equation(7-91):
F i = E i + B i i = 1 2 N
where: subscripts solute, solvent, and i refer to the solute, sol-
vent and inert components, respectively.
Fsolute Fsolute
Liq
PFc
Equation(7-95):
Bsolute Bsolute
Liq
Pc
E
Esolute Ysolute MWsolute
MWvapor
where:
Ysolute = vapor phase mole fraction of solute
Phase Equilibria
Solid-liquid Phase Equilibrium
Equation(7-98):
X solute f1 temperature
where:
eq
X solute = equilibrium mole fraction of solute in crystallizer liquid
at crystallizer temperature.
Yi f 2 X i
Solution Procedure
The solution procedure for the crystallizer model uses the above
equations to perform solid-liquid calculations through crystalliza-
tion kinetics in a supersaturated liquid solution, and VLE calcula-
Reference
1 Treybal, R.E., 1980, Mass Transfer Operations, 3rd Ed.,
McGraw Hill, N.Y.
General Information
Solid melting and freezing units are important operations in many
industries, including food, glass, and edible oil manufacture. Solid
components in a mixture may be melted and transformed into a liq-
uid component, and liquid components may be frozen and trans-
formed into solids in the PRO/II melter/ freezer unit operation.
Calculation Methods
The operating temperature and pressure of the melter/freezer is
specified by the user. The unit may operate in one of two modes:
The temperature is specified and PRO/II determines which
components are to undergo phase transformation based on the
normal melting temperature of each component
The component and fraction to be frozen or melted is specified.
This is the only criteria used for determining which compo-
nents undergo phase transformation. The melting temperature
is ignored for the calculations, and components not specifically
given by the user do not undergo a solid-liquid phase change.
The resulting product streams are then flashed isothermally at the
given temperature and pressure conditions to determine their ther-
modynamic properties. Only the distribution between vapor and liq-
uid (and/or water) phases is considered in the flash calculations.
True solid-liquid equilibrium is not considered.
Phase Envelope
General Information
Calculation Methods
General Information
The PHASE ENVELOPE module generates a phase envelope or
constant liquid fraction curve (in tabular or plot form) for streams
using the equation of state methods.
Note: The phase envelope module is currently limited to the equa-
tion of state methods only. Up to five separate curves or tables may
be specified for each phase envelope module. Figure 8-1 shows a
typical phase envelope:
Calculation Methods
Flash computations often fail at the critical conditions. However,
for the Phase Envelope module, the true critical point, criconden-
therm, cricondenbar, and points of the phase envelope are deter-
mined with the method of Michelsen. This method provides a direct
solution for the mixture critical point, and encounters no difficulties
in the critical region. Regions of retrograde condensation are also
accurately predicted.
Reference
1 Michelsen, M.L., 1980, Calculations of Phase Envelopes
and Critical Points for Multi-component Mixtures, Fluid
Phase Equil., 4, pp. 1-10.
2 The Phase Envelope calculations are always performed
after the flow sheet has fully converged, and therefore does
not affect the convergence calculations. Also, like the
Utilities 8-520
HCURVE, this unit is not accessible via the CONTROL-
LER, MVC, or CASESTUDY.
Also See:
Phase Envelope
Utilities
General Information
The HCURVE module provides a variety of options to calculate and
report properties of process streams in a PRO/II simulation. In gen-
eral, a heating/cooling curve is generated for a process stream
between two defined points or states: the user must provide infor-
mation that defines both the initial point and end point of the pro-
cess stream being investigated. The physical state of the stream
must be fully defined at these two limiting points. The information
presented here is intended to extend user understanding and provide
insight into the capabilities and limitations of the HCURVE mod-
ule. Several different types of curves may be requested, and each
type of curve offers a number of options for defining the end-point
states of the stream. Examples of data that sufficiently define a
stream state include:
Specifying both temperature and pressure, or
Specifying enthalpy content and either temperature or pressure.
The stream itself always supplies all composition information.
Calculation Options
Any number of heating / cooling curves may be requested in each
HCURVE unit, but you must identify the process stream for each
curve. Alternatively, instead of explicitly identifying a process
stream, the HCURVE module allows you to specify a stream by
describing a configuration of a unit operation such as a heat
exchanger, flash drum, or distillation column. For example, you
may elect to instruct the HCURVE module to generate a curve with
points spaced at equal temperature and pressure increments
between the inlet and outlet conditions on the hot side of a heat
exchanger in the simulation. When using any of these options, the
end-point states of the desired stream are obtained from the con-
verged solution of the unit operation, and in general cannot be mod-
ified by supplying additional input data for the curve.All
calculations use the standard thermodynamic, flash, and transport
techniques discussed in earlier sections of this manual and in the
PRO/II Keyword Input Manual and PROVISION User's Guide. A
single thermodynamic method set is used in each HCURVE mod-
ule. When more than one thermodynamic method set is present in
the simulation, a unit-specific method may be used to choose the
one set that will be used for all curves in the HCURVE module.
When the unit-specific method is not specified, the default thermo-
dynamic data set will be used.
The GAMMA option available for most heating cooling curves is
valid only when the thermodynamic method set being used employs
a liquid activity K-value method.
Also See:
Heating / Cooling Curves
Utilities 8-522
correctly finds both solutions when retrograde phenomena are pres-
ent.
Utilities 8-524
as the KVALUE option and adds more data to the report. For this
reason, there is no benefit to including both options for a single
heating/cooling curve.Both GAMMA and KVALUE generate a
report for each component in the stream at each point of the heating/
cooling curve. Table 8-1 summarizes the information reported at
each point.
Availability of Results
Heating/Cooling units always perform their calculations during the
output pass of the flow sheet convergence module whenever PRO/II
executes. This means that HCURVE modules are not considered
until after the completion of all calculations needed to solve the
flow sheet. For this reason, the following applies to data generated
by HCURVE units:
HCURVE data are not available to CONTROLLERs or OPTI-
MIZERs to control or modify flow sheet calculations,
HCURVE data are not accessible through the SPECIFICA-
TION feature
HCURVE data cannot be used to affect flow sheet convergence
calculations.
However, HCURVE results are stored in the problem database files
and appear in the standard output reports of the simulation. In addi-
tion, HCURVE results may be retrieved through facilities of the
PRO/II Data Transfer System (PDTS) for use in user-written appli-
Utilities 8-526
The statement above identifies the data as an isothermal (ISO) heat-
ing/cooling curve generated by HCURVE unit HC00 for stream
F100. The remaining entries on this line are included for use by
PRO/II utility functions such as IMPORT, and are not described
here.
The subsequent lines of information in Table 8-3 present a limited
subset of data generated for this stream by the HCURVE calcula-
tions. Each point of the curve is summarized on two lines of the list-
ing. Table 8-3 interprets the data for a typical point of the curve.
Table 8-3: Data For an HCURVE Point
----------- Enthalpy, K*Kcal/h -------------
All the data are expressed in the dimensional units used to supply
input data in the original problem definition. For example, Table 8-
3 indicates temperature is presented in degrees Celsius. Alterna-
tively, if the dimensional unit of temperature in the original input
file had been, for example, Rankine, then the temperatures pre-
sented in Table 8-2 and Table 8-3 would represent Rankine temper-
atures. This reasoning also applies to the enthalpy and rate data.
Note: The information available in the .ASC file always is limited
to the data shown in Table 8-3, regardless of the type of heating/
cooling curve or the printout options included in the HCURVE unit.
Also See:
Heating / Cooling Curves
General Information
The Binary VLE/VLLE Data module (BVLE) may be used to vali-
date binary vapor-liquid or vapor-liquid-liquid equilibrium data for
any given pair of components. This unit operation generates tables
and plots of K-values and fugacity coefficients versus liquid and
vapor composition at a specified temperature or pressure. A number
of plot options are available.Any thermodynamic VLE or VLLE K-
value method may be used to validate the VLE or VLLE data. For
liquid activity thermodynamic methods, the following are calcu-
lated by the BVLE module:
K-values
Liquid activity coefficients
Vapor fugacity coefficients
Vapor pressures
Poynting correction.
For non-liquid activity methods such as the SRK cubic equation of
state, the following are calculated by the BVLE module:
K-values
Liquid fugacity coefficients
Vapor fugacity coefficients.
Only selected input and output features of the Binary VLE / VLLE
Data module are discussed in this reference manual.
The BVLE unit operation does not affect flow sheet convergence. It
is always executed during the output calculations phase of simulator
execution, after the flow sheet has fully converged, and therefore
does not affect the convergence calculations. Also, like the
HCURVE, this unit is not accessible via the CONTROLLER,
MVC, or CASESTUDY.
Also See:
Binary VLE/VLLE Data
Utilities 8-528
Input Considerations
One feature worth discussing further is the XVALUE option of the
EVALUATE statement. Quite often, tables of generated data
bracket, but do not exactly match, points of great interest such as
experimental compositions. The XVALUE option allows the user to
specify exact component mole fraction values so these points can be
very closely investigated.The XVALUE entry accepts liquid/vapor
mole fractions for component i, one of the two components
declared on the COMP entry (on the same EVAL statement). If
only one value is given, it is assumed to be the starting value, with
the number of points determined by the DELX and POINTS
entries. If two values are given, they are assumed to be the starting
and terminal values, with the number of points to generate specified
by the POINTS entries. The default starting and ending (mole frac-
tion) values are 0.0 and 1.0. When three or more points are sup-
plied, only those specific points are generated.
Also See:
Binary VLE/VLLE Data
Output Considerations
Results of each EVALUATE statement are printed as tables or
optional plots. The format of the report tables changes depending
upon whether the thermodynamic methods set that is being used is
able to predict two liquid phases (VLLE) or only a single liquid
phase (VLE). The tables of results are clearly labeled and only two
additional notes are presented here:
1 In the mole fraction results tables, X(1) in the header repre-
sents the molar liquid fraction and Y(1) represents the
molar vapor fraction of component one. X(2) and Y(2)
identify the same quantities for the second component of
the binary. In VLLE results listings only, the first and sec-
ond liquid phase columns are distinguished by asterisks.
For example, X(1)* represents mole fractions of compo-
nent 1 in the first liquid phase while X(1)** is used for frac-
tions of component 1 in the second liquid phase. Since at
most only a single vapor phase exists, asterisks never
appear with vapor data headings (such as Y(1) or Y(2)).
2 In VLLE results listings of activity coefficients and vapor
fugacity coefficients, an additional column appears labeled
Distribution Coefficient. The distribution coefficients are
liquid-liquid equilibrium analogs of vapor-liquid equilib-
K Di xiI / xiII
where:
KDI = liquid-liquid distribution coefficient of component i
Utilities 8-530
Hydrates
General Information
Theory
General Information
PRO/II contains calculation methods to predict the occurrence of
hydrates in mixtures of water and hydrocarbons or other small com-
pounds. PRO/II can identify the temperature/pressure conditions
under which the hydrate will form, as well as identify the type of
hydrate that will form (type I or type II). The effect of adding an
inhibitor (either methanol, sodium chloride, ethylene glycol, di-eth-
ylene glycol, or tri-ethylene glycol) on hydrate formation can also
be predicted by PRO/II.
Theory
Hydrates are formed when water acts as a host solid lattice to
guest molecules which occupy a certain portion of the lattice cav-
ity. Only molecules which are small in size, and of a certain geome-
try may occupy these guest cavities. These hydrates are a form of an
inclusion compound known as clathrates, and no chemical bonds
form between the water lattice and enclosed gas molecules. Two
different types of hydrates can be identified, as illustrated in Figure
8-3. Their characteristics are given in Table 8-4. Table 8-5 lists the
gas molecules which may occupy the cavities of these hydrates.
Utilities 8-532
Equation (8-2):
H
= RT v i ln 1 Y ki
W
i k
i = 1, 2, ..., Ncav
k = 1, 2, ..., Ncomp
where:
Cki f k
Yki
1 C ji f j
j
j = 1, 2, ..., Ncomp
k = 1, 2, ..., Ncomp
where:
fk = fugacity of hydrate-forming component k
H
= RT v i ln 1 + C ki f i
W
i k
1 W r
Cki exp 4 r dr
2
kT 0
kT
where:
k = Boltmann's constant = 1.38 x 10-16 erg/K
T = temperature, K
W(r) = spherical cell potential, erg
r = radial coordinate,
The spherical cell potential, W, is a function of the radius of the unit
cell, the coordination number of the cavity containing the gas mole-
cule, and sum of the interactions between the enclosed gas molecule
and the water molecules in the lattice wall.
The Kihara potential between a single gas molecule and one water
molecule in the lattice wall is given by:
Equation (8-6):
12 6
r 4 for r > 2
r 2 r 2
Equation (8-7):
r for r 2
where:
= Kihara potential, ergs
= characteristic energy, ergs
= core radius,
+ 2 = collision diameter,
Summing the gas-water interactions over the entire lattice yields:
Utilities 8-534
Equation (8-8):
12 6
W r 2 z 11 10 11 5 4 5
Rc r Rc Rc r Rc
and,
Equation (8-9):
r
N
r
N
1 1
Rc Rc Rc Rc
N N 4,5,10,11
N
where:
z = coordination number of cavity
Rc = cell radius
When liquid water is present with the hydrate, the chemical poten-
tial difference between water in the liquid phase and the empty
hydrate is given by:
Equation (8-10):
L
= RT v i ln 1 + C ki f i + RTInx w
W
i k
where:
Utilities 8-536
Equation (8-11):
wL RT k 1 3 k 1 yk2 2 k 1 yk3
i h 1 Cki f k RThxw
i k
where:
k = binary interaction parameter between the most volatile
component and component k
yk = mole fraction of component k in the vapor phase
Reference
1 Munck, J., Skjold-Jorgensen, S., and Rasmussen, P., 1988,
Computations of the Formation of Gas Hydrates, Chem.
Eng. Sci., 43(10), pp. 2661-2672.
2 Ng, H.-J., and Robinson, D.B., 1976, The Measurement
and Prediction of Hydrate Formation in Liquid Hydrocar-
bon-Water Systems, Ind. Eng. Chem. Fundam., 15(4), pp.
293-298.
3 Parrish, W. R., and Prausnitz, J.M., 1972, Dissociation
Pressures of Gas Hydrates Formed by Gas Mixtures, Ind.,
Eng., Chem. Proc., Des. Develop., 11(1), pp. 26-35.
4 Peng, D. Y., and Robinson, D.B., 1979, Calculation of
Three-Phase Solid-
Liquid-Vapor Equilibrium Using an Equation of State,
Equations of State in Engineering and Research, Advances
in Chemistry Series, No. 182, ACS, pp. 185-195.
Also See:
Hydrates
General Information
The Check Solids unit operation is a Simsci Add-on module that
tests specified streams for the formation of a solid phase for a lim-
ited list of components: CO2, H2S, and benzene. The unit checks for
conditions under which these components freeze and form solids.
No solids form when the stream temperature is above the melting
point of the potential solids former.
Input Considerations
Feeds
Each feed stream must have a positive flow rate with 2 or more
components having positive (non-zero) compositions. Pure (single)
component streams are bypassed, and the unit issues an error.
The unit requires one feed stream and allows up to 10. Because the
PROVISION Graphical User Interface does not allow a single
stream to feed more than one unit operation, a typical strategy is to
lay down additional streams to feed the Check solids unit. These
streams should reference other process streams in the flow sheet
that are candidates for solids formation. Refer to section 9.3, Ref-
erence Streams, in the PRO/II Keyword Input Manual.
Products
There are no product streams from this unit operation. Since the
unit operation does not affect the thermodynamic state of the feed
streams, it does not participate in the material balance of the flow
sheet simulation in which it is embedded.
Components
The three components tested for formation of a solid phase are:
Utilities 8-538
hydrogen sulfide H2S 16020140
benzene C6H6 12010010
Calculation Considerations
The algorithm in this unit uses correlations derived by D. Y. Peng of
Robinson and Associates to compute the properties of solids. It also
uses the Peng-Robinson form of the generalized cubic equation of
state to model the fluid properties during the analysis. The solid
property correlations are similar to the property correlations used by
the hydrates package in PRO/II. Unlike the hydrate calculations,
solids form by freezing, not by forming a complex with water. In
this model, solid formation calculations are performed on a dry
(water-free) basis.
The presence of certain other specific components (that may inter-
act with the solid-forming components) cause adjustments to the
data and coefficients of the Peng-Robinson equation of state:
Additional adjustments are made to the alpha terms (ijs) and the
overall temperature-dependent a(T) term in the equation of state to
account for the departure of the fluid from ideal behavior as the
operating temperature diverges from the critical temperature.
Algorithm
Each feed stream is processed individually. The phase state of the
stream is determined by a flash calculation at stream temperature
Report Considerations
The output report consists of a single table that includes one line of
information for each feed stream. Reported data include the stream
temperature and pressure and the results for each of the three possi-
ble solids-forming components.
Example
Test stream T60 for solids formation at one degree temperature
increments between 40 K and 44 K.
TITLE PROJECT=CHKSOLID, PROBLEM=ST2
DESC CHECK SOLID FORMATION (AT 27.2 ATM)
PRINT INPUT=NONE, STREAM=NONE
DIMENSION ENGLISH, TEMP=K, PRES=ATM, LIQVOL=CUFT, VAPVOL=CUFT, &
XDENSITY=SPGR, CONDUCT=BTUH, SURFACE=DYNE
SEQUENCE ASENTERED
COMPONENT DATA
LIBID 1, C1/ 2, C2/ 3, C3/ 4, CO2/ 5, H2S, BANK=PROII_8.2:SIMSCI, PROCESS
ASSAY CONVERSION=API94, CURVEFIT=IMPROVED, KVRECONCILE=TAILS
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, SET=SRK01
STREAM DATA
PROPERTY STREAM=T060, TEMPERATURE=60, PRESSURE=27.2, &
PHASE=M, COMPOSITION(M,LBM/H)=1, 66 / 2, 3 / 3, 1 / 4, 8 / 5, 22
Utilities 8-540
PROPERTY STREAM=T040, TEMPERATURE=40, REFSTREAM=T060
PROPERTY STREAM=T041, TEMPERATURE=41, REFSTREAM=T060
PROPERTY STREAM=T042, TEMPERATURE=42, REFSTREAM=T060
PROPERTY STREAM=T043, TEMPERATURE=43, REFSTREAM=T060
PROPERTY STREAM=T044, TEMPERATURE=44, REFSTREAM=T060
UNIT OPERATIONS
SOLCHK UID=UT04X, Name = Solids-Check Sample
FEED T040, T041, T042, T043, T044
END
The output report for this input is:
SIMULATION SCIENCES INC. R PAGE P-1
PROJECT CHKSOLID PRO/II VERSION 9 ELEC V6.6
PROBLEM ST2 OUTPUT
SOLIDS CHECKING SUMMARY MARCH 2007
========================================================================
UNIT 1, 'UT04X'
SOLID FORMERS
------------------------------------
TEMP, PRES,
STREAM IDS K ATM CO2 - MOL% C6H6 - MOL% H2S - MOL%
----------- -------- --------- ----------- ----------- -----------
T040 40.0000 27.2000 YES 8.000 NSF N/A YES 21.995
T041 41.0000 27.2000 YES 8.000 NSF N/A YES 21.994
T042 42.0000 27.2000 YES 8.000 NSF N/A YES 21.993
T043 43.0000 27.2000 YES 8.000 NSF N/A YES 21.992
T044 44.0000 27.2000 YES 8.000 NSF N/A YES 21.990
Utilities 8-542
Exergy
General Information
Interpreting Exergy Reports
General Information
Exergy (or availability) calculations may be requested by the user
by supplying the EXERGY statement in the General Data Category
of input. All entries are optional. When requested, exergy calcula-
tions are performed in the final stages of writing the PRO/II output
report. As such, exergy calculations are not available during, and in
no way whatsoever affect, flow sheet convergence. Exergy results
appear after the Stream Summary reports in the PRO/II output
report.The availability function, B, is defined as:
Equation (8-12):
B H TS
where:
H = enthalpy
T = temperature
S = entropy
The external work done by the unit operation (W-ext), and the heat
duty of the unit operation (Duty) are also given in the exergy report.
Reference
1 Venkatesh, C.K., Colbert, R.W., and Wang, Y.L., Exergy
Analysis Using a Process Simulation Program, presented at
National Convention of the Mexican institute of Chemical
Engineers, October 17, 1980.
2 de Nevers, Noel, and Seader, J.D., Mechanical Lost Work,
Thermodynamic Lost Work, and Thermodynamic Efficien-
Utilities 8-544
cies of Processes, presented at 86th AIChE National Meet-
ing, Houston, Texas, April 1979.
Also See:
Exergy
General Information
Feed Blending Considerations
Stream Splitting Considerations
Stream Synthesis Considerations
General Information
The Stream Calculator is a multi-purpose module intended to facili-
tate the manipulation of process streams in a PRO/II simulation
flowsheet. There are two distinctly different modes of operation
available: stream splitting and stream synthesis. A single Stream
Calculator module may operate in either of these two modes exclu-
sively, or may be configured to operate in both modes simultane-
ously. When configured to operate in both modes, a single set of
feed streams and feed blending factors is utilized by both the split-
ting and synthesis calculations. However, each mode uses the feed
streams and blending factors independently. In no way do the split-
ting calculations affect the synthesis calculations. In a completely
complementary manner, the synthesis calculations never in any way
affect the splitting calculations.
Also See:
Stream Calculator
Note: The XOVHD and XBTMS splitting factors specify only the
relative composition of components in the overhead and bottoms
products respectively. This means they do not and cannot be used
Also See:
Stream Calculator
Note: The XPROD splitting factors specify only the relative com-
position of components in the synthesized product. This means
they do not and cannot be used as a basis for calculating the
rate of the synthesized product; some splitting factor that estab-
lishes an absolute basis for calculating product flow rate is
required. For this reason, the rate of at least one component must
be specified using an FPROD or RPROD separation factor.
Also See:
Stream Calculator
General Information
PRO/II solves process flow sheets using a Sequential Modular
Solution Technique. This technique solves each individual process
unit, applying the best solution algorithms available. Additionally,
PRO/II applies several advanced techniques known as Simultane-
ous Modular Techniques, to enhance simulation efficiency.
Methodology
Any given simulation is equivalent to a large system of nonlinear
simultaneous equations. This system of equations includes the eval-
uation of all necessary thermodynamic properties for all streams in
the flowsheet, as well as all rates and compositions using the
selected thermodynamic and unit models. In principle, it is possible
to solve all these equations simultaneously, but PRO/II utilizes a
General Information
PRO/II performs an analysis of the flowsheet and determines the
recycle streams and the loops of units with which they are associ-
ated. Then, tear streams and a solving sequence are determined. The
user can override all these calculations and define his/her own cal-
culation sequence. Initial estimates for the tear streams are desirable
but not mandatory. If good estimates are provided, convergence will
be achieved faster.
Tearing Algorithms
Two calculation sequence methods are available:
Minimum Tear Streams (SimSci Method)
This default sequencing method uses improved algorithms devel-
oped by SimSci to determine the best sequence for calculation pur-
poses. This method provides a calculation sequence featuring a
minimum number of tear streams.
Alternate Method (Process Method)
This method determines the sequence based partially on the order in
which the unit operations were placed during the construction of the
flowsheet. The units which were placed first are likely to be solved
earlier than the units which were placed at a later time.
Both methods determine the independent calculation loops in the
flowsheet, moving all calculations not affected by the recycle
streams outside these independent loops. These units will not be
calculated until the loops are solved. Then, for each loop, a tear set
is determined. In the case of the SimSci Method, a minimum tear
set based on the algorithm developed by Motard and Westerberg
(1979) is used. If more than one choice is available for the tear set,
the Simsci Method will pick the stream that has been initialized by
the user. In the case of the Process Method, an algorithm that pre-
serves as much as possible the order in which the user placed the
units is used.
Reference
Motard, R.L. and Westerberg, A.W., 1979, DRC-06-7-79.
Also See:
Calculation Sequence and Convergence
Convergence Criteria
Convergence is defined as being met when the following three
requirements are achieved for two successive determinations of the
recycle streams: Component molar flow convergence test:
Equation (10-1):
Error in Temperature
Tn Tn 1 eT
temperature tolerance
Pressure convergence test:
Equation (10-3):
Error in Pn Pn 1 Temperature
eP
pressure Pn tolerance
Default component molar flow, temperature and pressure tolerances
of c = 0.01, eT = 1.0 F (0.55 C) and ep = 0.01 will be assigned by
PRO/II. These tolerances may also be redefined in the General Data
category of input or on the LOOP statement.
These convergence tests are applied to all streams, but the user has
the option to apply them to the tear streams only.
Also See:
Calculation Sequence and Convergence
Flowsheet Solution Algorithms
Acceleration Techniques
General Information
Wegstein Acceleration
Broyden Acceleration
General Information
Unless acceleration techniques are requested by the user, PRO/II
will use direct substitution for closure of all recycle streams. This
method usually works well; however, for loops in which closure is
asymptotic an acceleration technique becomes desirable to reduce
the number of trials required.
Wegstein Acceleration
The Wegstein acceleration technique takes advantage of the result
of the previous trials, but ignores the interaction between different
components. To use this technique, at least one trial must be made
with direct replacement. Let xk represent the estimated rate of a
xk 1 qxk 1 q xk 1
w
q
w 1
where:
xk 1 xk
w
xk xk 1
Reference
Wegstein, J. H., 1958, Comm. ACM, 1, No. 6, 9.
Also See:
Acceleration Techniques
Broyden Acceleration
Broyden's method is a Quasi-Newton method. It consists of updat-
ing the inverse of the Jacobian at each iteration instead of calculat-
ing it or approximating it numerically. This method takes
specifically into account all interactions between component rates
and temperature of all streams included in the recycle loop. Let
represent the estimated rate of all components in a recycle stream at
the beginning of trial k and the calculated rate after trial k.
Broyden uses an approximation to the inverse of the Jacobian
which is being updated at every iteration. Broyden's procedure pro-
vides as follows:
Equation (10-6):
xk 1 xk d k xk
where:
dk=a damping factor
xk H k xk 1 xk
The update of Hk is performed using the following formula:
H k H k 1
H k 1 yk d k xk 1 xkT1 H k 1
xkT1 H k 1 yk
where:
Equation (10-9):
yk xk 1 xk xk xk 1
The algorithm starts with Ho=I, avoiding thus expensive numerical
calculations and inversion of the Jacobian. The damping factor has
a default value dk=1 at every iteration, and it is reset to a smaller
value automatically to prevent the new estimates xk 1 from becom-
ing negative.
Reference
Broyden, C.G., 1965, Math Comp., 19, pp 577-593.
Also See:
Acceleration Techniques
Flowsheet Solution Algorithms
General Information
PRO/II allows both feedback controllers and multi variable control-
lers to be included within a flowsheet. These units, which are
described in more detail below, allow specifications on process
units or streams to be met by adjusting upstream flowsheet parame-
ters. If there is a one-to-one relation between a control variable and
a specification, it is best to use a feedback controller. If, on the other
hand, several specifications and constraints are to be handled simul-
taneously, the multi variable controller should be used.Both the
feedback and multi variable controllers terminate when the error in
the specifications is within tolerance. By default, the general flow-
sheet tolerances are used as shown in Table 10-2.
Feedback Controller
General Information
Recommendations
General Information
The PRO/II CONTROLLER is analogous to a feedback process
controller; it varies a particular parameter (control variable) in order
Recommendations
When defining control variables and specifications, it is important
to note that the value of a control variable must remain fixed unless
it is changed by the CONTROLLER. Typical control variables
include inlet feed rates, specified heat duties of heat exchangers and
adiabatic flash drums as well as specified reflux ratios of distillation
columns. Conversely, the CONTROLLER specifications must be
defined as calculated results of the flowsheet simulation e.g. outlet
flow rates, column heat duties or temperatures of intermediate
streams. However, it is meaningless for the CONTROLLER to
specify the temperature of an isothermal flash.
For best performance, the functional relationship between the con-
trol variable and the controller specification should be continuous
and monotonically increasing or decreasing as illustrated in region
III of Figure 11-6. Functions that are discontinuous (region I),
exhibit local maxima or minima (region II), or are invariant (region
IV) may cause convergence problems. Frequently, these difficulties
can be overcome by including upper and/or lower bounds on the
control variable to restrict its range (for example VMIN1 and
VMAX1 in Figure 11-6).
General Information
The Multi-variable feedback controller (MVC) in PRO/II allows
control variables to be varied to satisfy an unlimited number of
flowsheet specifications. The specifications can include stream and
unit operating conditions as well as CALCULATOR results. The
control variables can be defined as stream or unit operating condi-
tions, thermodynamic properties and CALCULATOR results. The
number of variables must equal the number of specifications. If
desired, upper and lower bounds as well as maximum step sizes can
also be included for each control variable.Figure 11-8 shows an
example of a simple MVC application. There are three input
streams, S1, S2 and S3, all of which contain the three gaseous com-
ponents C1, C2 and C3 as well as inert gas C4. The flow rates and
compositions of the three streams are known. They are mixed to
form stream S4 and the MVC is used to specify the total flow rate
of S4 as well as the final ratio of C1 to C2 and of C2 to C3. The
MVC specifications are to be met by varying the flow rates of the 3
input streams.
The Algorithm
The MVC uses a first-order unconstrained optimization method to
simultaneously converge all the specifications. The objective func-
tion to be minimized consists of the sum of the squared errors in the
specifications. If bounds on the control variables are defined, these
are included in the objective function as penalty terms. Figure 11-9
illustrates the solution procedure for an MVC with 2 variables and
specifications.
Flowsheet Optimization
General Information
Solution Algorithm
General Information
The optimization algorithm within PRO/II is a powerful tool which
allows the operating conditions of a single unit or an entire process
flowsheet to be optimized. Typical applications are the minimiza-
Typical Application
depicts a typical optimization application:
Objective Function
Exactly one objective function is required in the OPTIMIZER; it
must be defined so that it is the result of a calculation within PRO/II
and not a value which is fixed by the user.
The OPTIMIZER objective may be either a design or performance
objective. It may be expressed as an operational criterion (e.g.,
maximum recovery or minimum loss) or an economic criterion
(e.g., minimum cost or maximum profit). The CALCULATOR can
be used to develop more complex objective functions which
account for a variety of design and economic factors.
Finally, the objective function may also be defined via a user-writ-
ten subroutine.
Note that the objective function should be continuous in the region
of interest. The OPTIMIZER will perform best if the objective
function shows a good response surface to the variable; it should
neither be too flat nor too highly curved. Unfortunately, in practice,
many objective functions tend to be quite flat which may cause the
optimizer to terminate at different solutions when different starting
points are used. These solutions, which are all valid within toler-
ance will have similar objective function values but the values of
the variables may be quite different.
Optimizer Variables
Any flowsheet value which is defined as a fixed input parameter
can be used as a variable for the PRO/II optimizer. This includes
stream rates or properties, unit operating conditions, thermody-
namic properties and CALCULATOR results.
Certain restrictions apply; for example, if the location of COLUMN
feeds, draws, heaters or coolers are used as variables within the
OPTIMIZER, the rate and/or heat duty cannot also be used.
If the variables to be manipulated by the optimizer are specifica-
tions made on the flowsheet base case, the simplest specifications
should be chosen if possible since this speeds up the solution time.
For example, suppose a splitter specification is an optimization
variable. The base case specification on the splitter should be a
molar rate or ratio, this being the simplest specification possible.
The optimizer varies the value of this specification and resolves the
flowsheet. Making a more complex specification on the splitter
Recommendations
When solving an optimization problem, the following points should
be noted:
Always solve the base case separately. Check the results care-
fully to ensure that the problem setup and solution are exactly
what is required.
Carefully select the bounds and constraints to ensure that the
flowsheet is physically well-defined over the entire solution
space. The flowsheet will not solve if, for example, flow rates
or absolute temperatures are allowed to go negative.
Flowsheet tolerances should be tightened for improved accu-
racy. This is necessary in order to obtain good first order deriv-
atives and is particularly important when the flowsheet
contains columns or recycle loops.
Solution Algorithm
Introduction
PRO/II uses Successive Quadratic Programming (SQP) to solve the
nonlinear optimization problem. The algorithm consists of the fol-
lowing steps. To simplify the notation, define xk=(x1,k,x2,k,...xn,k)
as the vector of the optimization variables which define the state of
the system.
1. Set the cycle counter k=1 and solve the flowsheet at x1.
2. < >Perturb each optimizer variable by some amount hi and
resolve the flowsheet. Use the base case flowsheet solution and
the n additional flowsheet solutions to approximate the first
derivatives of the objective function, specifications and con-
straints via finite differences.
3. If the
kuse 2 first order derivatives at the previous and current
cycles to approximate the second order derivatives.
f f xi hi f xi
xi hi
To obtain the best derivative information, the step size hi for each
variable xi should be small enough so that the higher order terms
which are neglected in the above formula are minimized. However,
hi R xi ,typical
where:
R = the relative accuracy with which the functions are evalu-
ated.
For simple functions this is on the order of machine precision (~
10E-6); for complex flow sheets with sufficiently tight tolerances
the relative accuracy is on the order of 10E-3 to 10E-4.
To aid the user in selecting appropriate step sizes, a full diagnosis is
printed when the keyword DERIV is included on the OPTPARAM
statement of keyword input. To activate this through PROVISION,
on the main Data Entry Window for the Optimizer, press the
Options button. From the Options DEW, press the Advanced
Options button. From the Advanced Options DEW, turn Deriva-
tive Analysis: to ON. This is independent of the number of opti-
mizer cycles. In addition to the forward difference formula given
above, the derivatives are also calculated using backward differ-
ences and central differences.
The information shown in Table 10-3 is then displayed for each
variable for the objective function and each specification and con-
straint.
Unless a variable has no effect, the first line displays the sign of the
backward, central and forward derivatives. If the maximum differ-
ence between the central derivative and forward or backward deriv-
atives is greater than 1%, it is reported on line 3. The perturbation
size should be chosen so as to minimize this difference. The current
value of the absolute perturbation is reported on line 4 and a sug-
gested perturbation, calculated assuming that the accuracy of the
flowsheet solution is 10-4, is printed on the last line. Note that this
value is only intended as a guideline; the change in the maximum
deviation should be monitored when the perturbation size is modi-
fied. Note also that if the magnitude of a variable changes by sev-
eral orders of magnitude, the perturbation size determined at the
initial point will no longer be appropriate.
To ensure consistent flowsheet solutions it may also be necessary to
invoke the COPY option (an OPTPARAMETER keyword). Here,
the entire PRO/II database is stored which allows the flowsheet
variables to be initialized identically for each perturbation evalua-
tion rather than at the final value from the previous perturbation.
STEP Sizes
By default, the OPTIMIZER variables are not allowed to move
more than 30, 60 and 90 percent to their upper or lower bound dur-
ing optimization cycles 1, 2 and 3, respectively. This is intended as
a safety feature; it prevents the optimizer from moving too far,
particularly when the derivatives are inaccurate. The STEP key-
word is used to override this default by providing an absolute limit
for the maximum change in a variable during one optimization
cycle. Providing a value for STEP which is larger than MAXI-MINI
for a particular variable allows that variable to move through its full
range at every optimization cycle.
Termination Criteria
The following conditions are tested at every optimizer cycle:
1. Is the relative change in the objective function at consecutive
cycles less than 0.005 (or the user defined value RTOL for the
objective function)?
2. Is the relative change in each variable at consecutive cycles less
than 0.0001 (or the user defined values RTOL for each vari-
able)?
3. Has the maximum number of cycles been reached?
4. Does the scaled accuracy of the solution fall below 10-7 (or the
user defined value SVERROR)? The scaled accuracy, which is
also known as the Kuhn-Tucker error, is calculated from:
Equation (10-14):
KTE f T d i hi i gi
i i
where:
f = a vector which contains the first derivatives of the objec-
tive function
d = the search direction from the QP subproblem
h and g = specifications and constraints, respectively.
The weights on the specifications and constraints, and are deter-
mined automatically when the QP subproblem is solved (step 3 in
the algorithm previously described). These weights are referred to
as multipliers or shadow prices (see the following section).
If none of the above conditions are satisfied, the optimizer contin-
ues to the next cycle. If at least one of conditions 1 to 4 is satisfied,
the following conditions are also tested.
5. Is the relative error for each specification less than 0.001 (or the
user defined value RTOL or ATOL for each specification)?
Reference
1 Fletcher, R., 1987, Practical Methods of Optimization,
Wiley.
2 Gill, P.E., Murray, W., and Wright, M.H., 1981, Practical
Optimization, Academic Press.
General Information
Theory
Calculating the Vessel Volume and Surface Area
Valve Rate Equations
Orifice Rate Equations
Heat Input Equations
Isentropic Efficiency Considerations
General Information
All unit operation calculation methods described in previous chap-
ters of this manual relate to process units operating under steady-
state conditions. PRO/II also provides a model for one unsteady-
state process unit -- the depressuring unit. This unit operation may
be used to determine the time-pressure-temperature relationship
when a vessel containing liquid, vapor, or a vapor-liquid mixture is
depressured through a relief or control valve. The user may input
the valve flow characteristics. This unit operation also finds appli-
cation for problems relating to refrigeration requirements in storage
vessels. Product streams may be generated as a user option, but the
calculations are not performed until output time. A heat input may
also be described by the user to simulate the pressuring of the vessel
by a fire or other means.
Theory
The depressuring calculations begin by mixing the feed streams adi-
abatically to give the composition, xi,0, temperature, T0, and pres-
sure P0 of the vessel at time t=0. The initial composition of the
liquid and vapor inside the vessel is calculated following the guide-
lines below.If a liquid holdup is specified:
For a mixed-phase feed, the composition of the liquid phase,
will be set equal to the composition of the liquid portion of the
feed, and the vapor-phase composition set equal to the feed
vapor composition.
Note: For a vapor only feed, PRO/II will give an error message if a
liquid holdup is specified.
After the initial composition of the vapor and liquid portion of the
vessel contents is determined, the initial total number of moles for
each component, Fi,0, in the vessel is calculated using:
Equation (11-1):
Fi ,0 xiL,0V0L 0L xiV,0V0V 0V
where:
Fi,0 = moles of component i at time t=0
xLi,0 = mole fraction of component i in liquid
xVi,0 = mole fraction of component i in vapor
VL0 = initial liquid volume in vessel
VV0 = initial vapor volume in vessel
If no liquid holdup is specified:
The composition of the vessel contents is set equal to the com-
position of the feed, and the temperature and pressure of the
vessel are set equal to that of the feed stream. The total number
of moles of each component in the vessel at time t=0, Fi,0, is
calculated using:
Equation (11-2):
Fi ,0 xifeedV0 f ,mix
where:
Fi,0 = moles of component i at time t=0
xifeed = mole fraction of component i in feed
V0 = volume of vessel
f,mix = mixture density of feed stream
Depressuring 11-584
Also See:
Depressuring
Equation (11-4):
For Spherical Head:
1 2
V end = --- 0.5 r 3 1.25 r 0.5 r
3
For Hemispherical Head:
2
V end = 3 L 3 r L
For Ellipsoidal Head (2:1 Ellipsoidal Head):
2
V end = 6 L 3 r L
Depressuring 11-586
For Spherical Head:
1 2
V end = --- 0.5 r 3 1.25 r 0.5 r
3
For Hemispherical Head:
2
V end = 3 h 3 r h
For Ellipsoidal Head (2:1 Ellipsoidal Head):
2
V end = 6 h 3 r h
For Flat Head:
V end = 0
Vertical Cylinder Vessel Surface Area
A v = 2 rL + 2 A end
where:
Av = total surface area of the vessel
r = radius of the vessel
Aend = end cap of the total surface area, which is given by:
Equation (11-8):
For Spherical Head:
A end = 2 1.25 r 0.5 r
For Hemispherical Head:
A end = 2 r 2
For Ellipsoidal Head (2:1 Ellipsoidal Head):
A end = 4 1.084 r 2
For Flat Head:
A end = r 2
Spherical Vessel Volume
Equation (11-9):
4
Vv r 3V fac
3
r = radius of the vessel
P 0.5C 2f P1
where:
Cf = critical flow factor, dimensionless
P = actual pressure drop = P1 - P2, psia
P1 = upstream pressure, psia
P2 = downstream pressure, psia
The valve rate for sonic flow is given by:
Equation (11-12):
W 2.8Cv C f P1 G f
Depressuring 11-588
where:
W = vapor flow rate through valve, lbs/hr
Cv = valve flow coefficient, dimensionless
Gf = specific gravity at temperature T(oR)
The gas specific gravity can be written as:
Equation (11-13):
520 MW
Gf
MWairT
where:
MW = molecular weight of discharge stream
MWair = molecular weight of air
T = temperature of stream, oR
The stream molecular weight is given by:
Equation (11-14):
v
MW zRT
Pi
where:
z = gas compressibility factor
R = gas constant = 1.98719 BTU/lb-molR
v = vapor density, lb/ft3
Substituting equations (9) and (10) in equation (8) gives the follow-
ing expression for the vapor rate through a valve under sonic flow
conditions:
Equation (11-15):
W C1 P1 v
where:
Equation (11-16):
520 zR
C1 2.8Cv C f
MWair
Subsonic Flow:
P 0.5C 2f P1
W 3.22Cv PPG
1 f
Again, substituting equations (9) and (10) into (13), the valve rate
for subsonic flow becomes:
Equation (11-19):
W C1 P v
where:
Equation (11-20):
520 zR
C1 3.22Cv
MWair
W Constant
Masolenian Model:
The user may also specify a more general valve rate formula:
Equation (11-22):
W AC f CvY f P1 v
where:
A = a constant with units of (weight.volume/pressure.time2)1/2.
Depressuring 11-590
Values for the constant A in equation (16) in English, SI, or Metric
units are given in Table 11-2.
Yf is given by:
Equation (11-23):
Y f Y 0.148Y 3
and,
Y is given by:
Equation (11-24):
0.5
P
1.63
P1
Y
Cf
Where
Pcf = Critical flow nozzle pressure
P1 = Upstream relieving pressure
Orifice Subsonic flow:
2
D2
The valve rate (weight/time) = C --------- ----------------- 2 P Pb
4 4
1
---------
1
2
--- Pb
------ 2---
1
P
Pb Pb
= ------ --------- ------------------------------- 1 1 ------
4 4
where 1 P
Pb
1 ------
P
Pb = Value down stream pressure
= Ratio of Orifice diameter to Pipe diameter
Orifice Sonic Model: + 1
----------
2 1
The valve rate (weight/time) = C A ---------- p
+ 1
where is specific heat ratio.
Also see:
Depressuring
Depressuring 11-592
Fire Relief Model
Gas Blowdown Model
User-defined Model
This heat model is given by:
Equation (11-26):
v Vt 4
Q = C 1 + C 2 t + C 3 C 4 T t + C 5 ----- + C 6 T v
Vi
where:
Q = heat duty in millions of heat units/time
C1, C2, C3, C4, C5 , C6 = constants in units of millions of heat
units/time
t = time (elapsed since start of depressuring)
TV = vessel temperature at time t
Vt = volume of depressuring vessel at time t
Vi = volume of depressuring vessel at initial conditions
If values for the constants are not provided, the general heat model
defaults to Q = 0.0, i.e., to adiabatic operation.
The User-Defined model allows up to six coefficients while the
Blowdown model allows five coefficients. In these two models,
each coefficient Ci is used as a separate term. By omitting or pro-
viding zero as the value of coefficient effectively removes it from
the equation (i.e. the contribution of the term is zero). Therefore, by
selecting non-zero values for different combinations of coefficients,
these two equations will support wider variety of equation forms.
For example, the sixth coefficient in the User-Defined model allows
a modelling called NORSOK correlation.
Q C1 At
C2
where:
C1, C2 = constants whose values are given in Table 11-3
Vt
At Ai Afac
Vi
APISCALE Model
This heat model is similar to the API 2000 heat model, except the
heat duty is scaled and is given by:
Equation (11-29):
Vt
Q C1 At
C2
Vi
ANSI/API 521
This heat model applies to uninsulated vessels above ground level
and is the recommended model for pressure vessels. The heat model
is given by:
Equation (11-30):
Q 21000 At
0.82
Depressuring 11-594
Again, an area scaling factor may or may not be specified. If Afac is
used, At is given by equation (12-23). If Afac isn't specified, At is
set equal to the initial wetted area.
Vt
Q 21000 At
0.82
Vi
Q C1C2 At
C3
where:
C1, C2, C3 = user-supplied constants
Vt
Q C1 C2t C3 C4 Twall C5
Vi
The heat transfer to the fluid inside the vessel is computed using:
Equation (11-34):
T Twall T fluid
0.13kv N Gr N Pr h fac
1/3
hv
r
where:
kv = thermal conductivity of vapor phase
NGr = dimensionless Grashof number
NPr = dimensionless Prandtl number
hfac = heat transfer coefficient factor (=1.0 by default)
The Grashof and Prandtl numbers are given by the following rela-
tionships:
Equation (11-37):
r 3 v2 g c T
N Gr
v2
Equation (11-38):
cpv v
N Pr
kv
where:
= volumetric coefficient of thermal expansion, 1/oF
gc = acceleration due to gravity
Depressuring 11-596
v = viscosity of vapor
T = Twall - Tfluid
cpv = heat capacity of vapor
The heat transfer coefficient between the vessel and the liquid phase
of the fluid, hl, is determined in a similar manner using the follow-
ing relationships.
Equation (11-39):
0.13kl N Gr N Pr h fac
1/3
hl
r
where:
kl = thermal conductivity of liquid phase
The Grashof and Prandtl numbers are given by the following rela-
tionships:
Equation (11-40):
r 3 l2 g c T
N Gr
l2
Equation (11-41):
cpl l
N Pr
kl
where:
l = viscosity of liquid
where:
qfluid = change in specific enthalpy of the fluid, BTU/lb-mole
qisen = isentropic specific enthalpy change as the gas expands
where:
E isen is the specified isentropic efficiency.
H init is the initial enthalpy of the fluid at the start of the step.
H isen is the fluid enthalpy computed by the isentropic flash.
Work isen is the energy consumed as isentropic work.
H fluid is the final adjusted enthalpy change of the fluid.
Depressuring 11-598
Removing work in this manner eliminates the energy lost to isentro-
pic expansion from the overall energy balance. This means subse-
quent heat transfer calculations do not need to consider losses due
to isentropic work.
Reference
2 Masoneilan Handbook, 1977, 6th Ed., Masoneilan Ltd.,
London, GB.
3 Perry, R.H., and Green, D.W., 1984, Chemical Engineering
Handbook, 6th Ed., McGraw-Hill, N.Y., pg. 10-13.
Also See:
Depressuring
Equation (12-1):
1 1
K b A B ref
T T
dH1
V2 1 R D F1
dt
Reboiler
Equation (12-4):
dH n
LN 1 VN Fn B Wvn
dt
Overall
Equation (12-5):
n N 1
dH n N N
D Fj WL j Wv j
n 1 dt j 1 j 2 j 2
dH1 X i1
1 R DX i1 K i 2V2 X i 2 f i1
dt
where i = 1, , n (n no. of components)
dH n X iN
Ln 1 X in 1 ( K in vn B) X iN f i1
dt
where i = 1, , n (n no. of components)
Equation (12-9):
Ln Ln WLn
Equation (12-10):
Vn Vn Wvn
where
B Bottom residual
D Distillate
Hi Holdup of tray i
R Reflux ratio
Condenser
Equation (12-11):
dH1hL1
V2 hv 2 (1 R) DhL1 Qc F1hF 1
dt
Reboiler
Equation (12-13):
dH n hL N
QR LN 1hLN 1 VN hVN FN hFN BhLN Wvn H vn
dt
Overall
Equation (12-14):
N N 1
dH n hL N N N
QR Qc DhL1 Fj H Fj WLJ H LJ WVJ hVJ
n 1 dt j 1 j 2 j 2
Where
Qc Condenser duty
QR Reboiler duty
Equilibrium relation
Equation (12-15):
(K
i
in 1) X in 0
Equation (12-16):
Yij
K ij
X ij
comp
Y
i 1
ij 1
VLE
Equation (12-17):
yin K in X in
State
Equation (12-18):
Gn n
Hn
Mn
where
n Density
Mn Molecular weight
Mn
n
XM
i i(T i)
i n
M n X in M i
i
Equation (12-21):
hLn hLn Tn , n , xn
Equation (12-22):
hvn hvn Tn , n , yn
Equation (12-23):
kin kin Tn , n , xn yn
dH
D W
dt
or
Equation (12-25):
dH X i
DX i1 W X i
dt
Index-610
Calculation Options , 8-281 column specifications , 4-131
Calculation Procedure , 6-221 Columns
Equilibrium , 6-221 simple , 4-132
Calculation Scheme , 7-255, 7-276, 7-277 Complex Columns , 4-133, 4-140
Calculation Sequence , 10-314, 10-315 Complex Distillation Column , 4-50, 4-51
Calculation Sequence and Convergence , 10-314, 10- Component Balance , 4-77, 7-252
316 COMPONENT ERROR , 4-54
CalculationOptions , 8-281 Component Libraries , 6-216
CalculationProcedure forEquilibrium , 6-221 Component library databank , 6-215, 6-216
CALCULATOR , 10-322, 10-326, 10-331, 10-332, 10-334 Component Mass Balance , 1-3, 4-62
Carbon Balance , 4-77 Composition Convergence , 1-8, 1-9
CASESTUDY , 8-280, 8-287 Compostion sensititve K-values , 4-54
Cat Fractionators , 4-135, 4-138 Compressibility , 2-23, 2-25, 2-28, 7-242, 11-345
Caustic Regenerator , 4-109 Compression , 2-19, 2-20, 2-21
Caustic Wash , 4-109 Compressor , 2-19, 2-22, 2-23, 2-27, 3-46
CCD , 7-252, 7-253 Compressor work , 2-23
Ceram , 4-112 CONREACTOR , 6-214
CG , 4-119 Constraints , 10-330, 10-334, 10-335
Chao-Seader , 1-11 Contents , 1-1, 1-14, 7-240, 7-241, 7-246, 7-257, 7-266, 8-
Chao-Seader-Erbar , 1-11 280, 11-343
Characteristics , 4-54, 7-242, 7-244, 11-342 Table , 1-1
function , 7-242, 7-244 Continuation Method , 4-72
Chemdist , 1-1, 4-48, 4-50, 4-62, 4-67, 4-73, 4-77 Functional Equations , 4-67
Simple Stage , 4-62 Continuous Stirred Tank Crystallizer , 7-266
Chemical Engineer s Handbook , 4-117 Continuous Stirred Tank Dissolver , 7-258
Chemical Engineering Handbook , 1-12, 5-173, 11-355 Continuous stirred tank reactor , 6-228
Chemical Engineering Kinetics , 6-236 Continuous Stirred Tank Reactor (CSTR) , 6-228, 6-
Chemical Engineers , 7-264, 8-303 229, 6-231, 6-232
Chemical Reaction Equilibrium Analysis , 6-222 CONTROLLER , 4-49, 8-280, 8-284, 8-287, 10-321, 10-
322, 10-323, 10-324, 10-325, 10-326
Chilton , 4-123, 5-174
sequence , 10-323
Chlorine Balance , 4-77
Controllers , 10-310
Clarified Oil , 4-138
CONVENTIONAL , 4-75, 4-76, 4-133
Clathrates , 8-290
Convergence Criteria , 1-5, 10-316
CO , 6-216, 6-220
Convergence Region , 10-318
CO2 , 4-78
Conversion Reaction , 4-52
CO2 Absorber , 4-109
Conversion Reactor , 6-214, 6-215
CO2 Regenerator , 4-109
Cooler/heater , 4-76
Cocurrent , 5-152, 5-153, 5-155, 6-233, 6-236
Cooling Curves , 8-280
Cold Box , 5-176
Correlations , 4-118, 4-120, 4-121, 4-122, 4-123
COLUMN , 10-331, 10-332, 10-333, 10-334, 10-335
Countercurrent Decantation Washing System , 7-257
Column
Countercurrent Decanter , 7-251, 7-252, 7-255
Equilibrium Efficiency , 4-148
Murphree Efficiency , 4-147 Cpv , 11-349
Tray Efficiency , 4-146 Cpvess , 11-354
Vaporization Efficiency , 4-147 Cricondenbar , 8-279
Column Hydraulics , 4-107, 4-108, 4-112, 4-117 Cricondentherm , 8-279
Index-612
Dissolver-mass balance , 7-262 EnVironmental State , 8-302
Dissolver-mass transfer coefficient correlations , 7-258 Equations
Dissolver-mass transfer rate , 7-258 Depressuring unit
Index-614
G GPSA method , 2-23, 2-24, 2-25
GPSA pump , 3-45
GAMMA , 8-281, 8-283, 8-284 Graetz , 5-163
GAMMA and KPRINT Options , 8-283 Grashof , 11-353
Gas Blowdown Gray correlation , 3-35
depressuring model , 11-352 Grayson-Streed , 1-11
Gas Hydrates , 8-296
Grayson-Streed-Erbar , 1-11
Formation , 8-290
Green , 1-12, 11-355
Gas Hydrates Formed , 8-290
Grossell , 4-123
Dissociation Pressures , 8-296
Growth Rate , 7-267
Gas Mixtures , 8-290
GSE , 1-14
Gas Oil , 4-138, 4-139, 4-141
Gas Wells , 3-44
Gases , 8-290 H
Hydrate-forming , 8-291, 8-292, 8-295
Gas-Liquid Flow , 3-45 H.E. Equations , 7-255
Gasoline Calculating Recovery , 7-257
Light Cycle , 4-131 H2O , 4-78
Gaussian , 7-255 H2S Stripper , 4-109
Gautam , 6-227 Hagedorn , 3-45
Gear , 6-236 Hagedorn-Brown , 3-44
General Column Model , 4-50 Hagedorn-Brown correlation , 3-35
General Data , 10-316, 10-317 Hausen , 5-163
General Flowsheet Tolerances , 10-321 HCURVE , 8-280, 8-281, 8-282, 8-283, 8-284, 8-287
General Stream , 1-15 HCURVE Point , 8-284
GeneralInformation , 1-1, 2-27, 4-48, 4-107, 4-124, 4- Data For , 8-284
143, 5-150, 5-154, 5-158, 5-176, 6-221, 7-240, 7-241, HCURVE-DBASE option , 8-284
7-246, 7-251, 8-278, 8-280, 8-287, 8-290, 8-297, 8-
HCURVE-GAMMA option , 8-281
302, 10-310, 10-314, 10-317, 10-321, 10-326, 10-329,
11-342 HCURVE-output , 8-284
Gibbs , 6-222 HCURVE-Using PDTS with , 8-284
change , 6-223, 6-226, 6-227 Heat , 1-3, 4-67, 6-212, 6-214, 6-216, 6-229, 6-233, 7-265
Gibbs Free Energy Minimization , 6-222 fire relief model , 11-351
Objective Function , 6-222, 6-223, 6-224 Formation , 6-212, 6-214, 6-216
Gibbs Reactor , 6-221, 6-222 fusion , 7-265
gas blowdown model , 11-352
Gilliland , 4-124, 4-142
reaction , 4-68, 4-69, 4-70, 4-71, 4-72, 6-212, 6-213,
Gilliland Correlation , 4-129 6-214, 6-215, 6-217, 6-218, 6-229, 6-230, 6-234, 6-
Glitsch , 4-52, 4-108 235
Glitsch Bulletin No , 4-123 Heat Balance , 1-3, 7-264, 7-272
GLYCOL , 1-14 Heat Exchanger Temperature Profiles , 5-152
Glycol Contactors , 4-109 Heat Exchanger Types , 5-159
Glycol Stills , 4-109 Heat exchangers , 4-53, 5-150, 5-153, 5-154, 5-158, 5-
176, 7-265, 8-281
Glycol Synthesis Gas , 4-109
Heat Input Equations , 11-349
Gnielinski , 5-161, 5-174
Heat of formation , 6-212, 6-214, 6-216
GPSA , 2-25, 2-27
GPSA Engineering Data Book , 2-23, 3-46 Heat of fusion , 7-266
Index-616
K Liquid-Liquid Equilibria , 1-12
Liquid-Liquid Equilibrium Equations , 4-146
Katz , 7-245 Liquid-Liquid Extraction Columns , 4-48
KERAPAK , 4-119 Liquid-Liquid Extractor , 4-53, 4-143
Kern , 5-174 Liquids , 4-50
Kero , 4-138 Liquid-Vapor Equilibrium Using , 8-296
key component identification , 4-125 Liquified Natural Gas , 5-176
Kihara , 8-293 LKP , 1-14
Kinematic , 4-115 LLE , 1-13, 4-62
Kinetic Reaction , 4-52 performing , 4-62
Kinetic Reaction Homotopy , 4-67 LLEX , 4-49, 4-52, 4-54, 4-67, 4-70, 4-75, 4-143
Kirkbride , 4-129, 4-142 Simple Stage , 4-143
Kirkbride Method , 4-124, 4-129 LMTD , 5-152, 5-154, 5-155, 5-156, 5-157, 5-179
Index-618
Norton Bulletin IHP-1 , 4-123 Overhead - Light Gas Oil , 4-131
NOSCALE , 10-337
NOTSEPARATE , 4-53
NRTL , 1-13
P
Nucleation Rate , 7-267 Packed Column , 4-52
Nucleii Number Density , 7-268 Packing , 4-112
Number , 4-133, 4-138, 5-165, 5-166, 5-169, 10-326, 10- Type , 4-112
330, 10-334, 10-335, 10-337, 10-339, 10-340 Pall Rings , 4-112
crossflow , 5-165, 5-166, 5-167
Palmer corection , 3-37
Fenske , 4-132, 4-133, 4-134, 4-138
flowsheet , 10-326 Pang , 7-265
optimizer , 10-330, 10-331, 10-332, 10-334, 10-335, Parikh , 7-265
10-336, 10-337, 10-338, 10-339, 10-340 Parrish , 8-296
Nusselt , 5-161, 5-163, 11-352 Particle Size , 7-261
Particle Size Distribution , 7-261, 7-268, 7-269, 7-270
Patterns , 3-39, 3-45
O
PDTS , 8-284
Objective Function , 6-222, 10-330, 10-332 Peng , 8-296
Gibbs Free Energy Minimization , 6-222 Peng-Robinson , 1-11, 2-18, 8-278, 8-282
Oil Reclaimer , 4-109 Performance Characteristics
OLI Systems , 4-50 Correlations , 4-117
Oliemens correlation , 3-35 Performing , 4-66, 4-67
LLE , 4-66
Olsen , 4-123
Perry R , 1-12
Optimization , 10-335
Practical Methods , 10-340 Petro , 3-32, 4-107, 6-212
Optimization Variables , 10-333 Petrochemical Plants , 4-142
Optimizer , 4-48, 4-50, 10-328, 10-329, 10-335 PFR Operation Modes , 6-236
cause , 10-332, 10-335 Phase , 6-227
Number , 10-329 Phase Envelope , 8-278, 8-279
prevents , 10-338
Phase Equilibria , 7-262
value , 10-336, 10-337, 10-338, 10-339, 10-340
Phase Split , 6-227
Optimizer Variables , 10-332
Physical Continuation Approaches , 4-67
Optimizer-objective function , 10-329
Solving Reactive Distillation Problems , 4-62
Optimizer-recommendations , 10-329 Pipe , 3-32, 3-33, 3-34, 3-36, 3-41, 3-43, 3-44
OPTIMIZERs , 8-284, 10-315, 10-329, 10-335
Pipe Flow , 3-35
number , 10-335 Friction Factors , 3-35
respect , 10-336
Pipelines , 3-44, 3-45
Optimizer-shadow prices , 10-335
Pipes , 3-32, 3-33, 11-344
OPTPARAMETER , 10-337, 10-338, 10-340
Platteeuw , 8-291
OR , 11-346, 11-347
Plug flow reactor , 6-233, 6-236
Order , 10-314, 10-315, 10-335, 10-336, 10-337
Plug Flow Reactor (PFR) , 6-233, 6-236
OSCIL , 7-246
Polytropic , 2-23, 2-24, 2-25, 2-26, 2-27
Outer Loop , 4-54, 4-58
Polytropic compressor , 2-26
Outer Newton-Raphson Loop , 4-79
Polytropic efficiency , 2-18, 2-19, 2-23, 2-24, 2-25, 2-27
Output Considerations , 8-288
Polytropic Efficiency Given , 2-24, 2-27
OutputConsiderations , 8-288
Polytropic efficiency gp , 2-25, 2-28
Index-620
Random packed column hydraulics-Norton pressure Reports , 8-302
drop correlation , 4-112 Research , 8-296
Random packed column hydraulics-packing factors , 4-
Resid , 4-139
112
Residence Time , 7-264
Random packed column hydraulics-Tsai pressure drop
correlation , 4-112 Resolve , 10-328, 10-329, 10-335
Random Packed Columns , 4-112 flowsheet , 10-328, 10-329, 10-331, 10-332, 10-333,
10-334, 10-335, 10-336, 10-337, 10-338, 10-340
Random Packing Types , 4-112, 4-117
Retrograde Condensation , 8-282
Rankine , 8-286
Retrograde Region Calculations , 8-281
Raschig , 4-112
Revolutions/min , 7-243, 7-247, 7-267
Raschig Rings , 4-112
Reynolds , 3-38, 5-161, 5-162, 5-163, 7-260
Rasmussen , 8-296
Rice , 1-4, 1-12
Reaction , 4-67, 6-212, 6-214, 6-216, 6-229, 6-233
heat , 4-68, 6-212, 6-213, 6-214, 6-215, 6-216, 6-229, Rif , 7-261
6-234, 6-235 Rigorous Distillation Algorithms , 4-48, 4-50, 4-53, 4-
54, 4-62, 4-67, 4-73
Reaction Data , 4-70, 6-212, 6-213
Reactive Distillation , 4-67, 4-68, 4-70, 4-71 Rmin , 4-126, 4-127
solve , 4-125
Reactive Distillation Algorithm , 4-71
value , 4-126, 4-127
Reactive distillation algorithm uses , 4-71
Robinson , 8-296
Reactor Heat Balances , 6-212, 6-214
Rotary Drum Filter , 7-241, 7-242, 7-246
Reactor models , 6-219, 6-222
Rubin-Starling , 1-11
Reactor sizing , 6-214, 6-216
Rules-of-thumb , 4-112
Reactors , 4-67, 6-212, 6-215, 6-216, 6-219, 6-220, 6-221,
Runge-Kutta , 6-236
6-222, 6-228, 6-229, 6-231, 6-232, 6-233, 6-236, 9-
308, 10-323 Russell , 4-54, 4-62
Reactors-CSTR , 6-228
Reactors-equilibrium , 6-216
S
Reactors-heat balances , 6-212
Reactors-PFR , 6-233 Sample HCURVE , 8-285
Reboiler , 4-50, 4-51, 4-73, 4-74, 4-124, 4-129, 4-132, 10- Scandrett , 7-257
331
ScG , 4-116
Reboilers , 4-139
Schmidt , 4-116, 4-117, 7-260
Recommendations , 4-76, 10-323, 10-335
Seader , 8-303
Recommended Uses , 10-319, 10-320
Seider , 6-227
Broyden , 10-319, 10-320
Separation Columns
Wegstein , 10-317, 10-318, 10-319
Distillation , 4-123
Reconstituted Components , 4-79
Sequence , 10-323, 10-328
Recycle , 10-311, 10-314, 10-315
CONTROLLER , 10-323
Recycle acceleration-acceleration factor , 10-317 Sequencing-PROCESS , 10-314
Recycle acceleration-recommendations , 10-317, 10-319
Sequential Modular Solution Technique , 10-310, 10-
Recycle Loop , 10-325 311, 10-313
REFINE , 4-133 Series-parallel , 6-215
Refinery Heavy Ends Columns , 4-135 Shadow Prices , 10-339, 10-340
Refining , 4-75, 4-76 Shadow prices-Optimizer , 10-335
Refluxes , 4-138 Shell weight (dry) , 5-171
relative volatility , 4-58, 4-124, 4-125, 4-126, 4-131 Shell weight (with water) , 5-172
Report Information , 8-284
Index-622
SRKH , 1-14 Subcooled , 4-76, 4-132, 5-157
SRKH UFT1 , 1-14 containing , 5-156, 5-157
guesses , 4-76
SRKKD , 1-14
Subsurface Controlled Safety Valve Sizing Computer
SRKM , 1-14, 2-19
Program , 3-44
SRKP , 1-14
Successive Quadratic Programming , 10-335
SRKP UFT1 , 1-14
Sulfur hexafluoride , 8-290
SRKP UFT2 , 1-14
Sulzer , 4-117
SRKS , 1-14
Sulzer Brothers , 4-51, 4-117
SRKS UFT2 , 1-14
Sulzer Packings Available
SRKS UFT3 , 1-14 Types , 4-118, 4-119, 4-121, 4-122, 4-123
State , 2-18, 8-278, 8-282, 8-287, 8-296 SUM , 4-61, 4-62
equation , 1-4, 1-5, 1-6, 2-18, 8-278, 8-282, 8-287, 8-
Super Intalox , 4-112
291, 8-292, 8-295, 8-296
Super Intalox R , 4-112
STEPSIZES , 10-329, 10-337, 10-339
Supersaturation , 7-265, 7-266, 7-267
Stirred Tank Dissolver , 7-265
Design , 7-265 Superset , 8-283
KVALUE , 8-284
Stirred Tank Reactor , 6-228
Supplying , 8-302
Stoichiometric , 4-67, 6-212, 6-216, 6-222, 6-229
EXERGY , 8-302
corresponding , 6-215
Sure , 4-49, 4-52, 4-75
Stoichiometric Reactor , 6-219
Sure Algorithm , 4-62
Stoichiometry , 6-222
Surface Tension , 3-32
Straightforward , 4-67, 9-308
Switzerland , 4-117
Stream Calculator , 9-306, 9-307, 9-308, 9-309
Sulzer Brothers , 4-117
Stream Calculator allows , 9-307
System Factors , 4-108
Stream Splitting Considerations , 9-308
Stream Summary , 8-302
Stream Synthesis Considerations , 9-309 T
Streams , 10-310
flowsheet , 10-310 Tablular , 8-278
TORSION , 7-246
Total Mass Balance , 1-3, 7-252
U
TPSPEC , 1-15
Tracking , 4-71 Underpinings , 4-70
homotopy , 4-67 Underwood , 4-124, 4-125, 4-131
Transport Properties , 3-32 invalidate , 4-131
TRAPP , 3-32 Underwood Method , 4-126
TRAY , 4-54 UnderwoodMethod , 4-125
Tray UNIFAC , 1-13
efficiency , 4-146 UNIQUAC , 1-13, 1-14
Tray Rating , 4-108 Unit Cell , 8-290
Tray Rating and Sizing , 4-108 Hydrate Types , 8-290
Tray Rating/Sizing , 4-52 Unit grouping , 10-312
Trayed , 4-48, 4-107, 4-108, 4-109, 4-143 UNIWAALS , 1-14, 2-18
sizing , 4-107 UNIWAALS FLORY , 1-14
Treaction , 6-218 UNIWAALS REGULAR , 1-14
Treybal , 4-142, 7-245, 7-251, 7-260, 7-265, 7-274 Uom , 5-151
Triagonal , 7-255 Uphill Flow , 3-44
solving , 7-255 Effect , 3-44
Trial-and-error Newton-Raphson , 1-9, 1-11 Use , 3-35, 10-311, 10-312
Tridiagonal , 4-57, 4-58 Controllers , 10-312
form , 4-54, 4-57, 4-58 Dukler , 3-37, 3-45
Tri-ethylene , 8-290 Eaton , 3-38, 3-43, 3-45
Index-624
USER , 1-1 Fenske , 4-131
User Manual , 3-35 Viscosity , 4-107
User-defined Model , 11-349 Thermodynamic Generators , 4-107
User-provided Estimates , 4-73 VL , 2-18, 2-19, 4-120, 6-221, 7-241
Utilities , 5-150, 5-153, 8-284 VLE , 1-4, 1-8, 1-13, 1-15, 4-54, 4-62, 7-273, 8-282, 8-283,
flowrate , 5-153 8-287, 8-288
VLLE
and DecantConsiderations, 8-282
V VLE Convergence , 1-9
VLE K-value , 8-283
V & L , 3-32
VLLE , 1-13, 1-15, 4-62, 8-282, 8-287, 8-288
V Total , 6-232
describing , 4-66
Vacuum Towers , 4-108
VLLE Data , 8-287
Vacuum Units , 4-135, 4-138 VLLE K-value , 8-283, 8-287
Valve , 1-16
VLLE Predefined Systems , 1-14
Valve Rate Equations , 11-345
Vload , 4-109
Valve RateEquations , 11-345 VLS , 6-221
Valve Unit , 1-16
VMAX1 , 10-323
van der Waals , 8-291
VMIN1 , 10-323
van't HoffEquation , 7-265 Volume Based , 4-67
VAPOR , 8-303
Vapor fugacity , 8-287
Vapor Mole Fractions , 4-74 W
Vapor pressure , 8-283
Wang , 8-303
Vapor Profiles , 4-74
WATER , 8-283
Vapor/heat , 4-127
Water and DryBasis Properties , 8-283
Vapor/liquid , 4-50
Water decant , 1-11, 4-49
Vaporization , 4-127
from flash , 1-2
latent heat , 4-127
water partial pressure , 1-12
Vaporization Efficiency , 4-147
Water/hydrocarbon , 4-49
Vapor-Liquid Equilibrium , 4-65, 4-79, 7-262, 7-264, 7-
272 Wegstein , 10-310, 10-317
Vapor-liquid-liquid , 4-62, 6-222, 8-287 Recommended Uses , 10-317
Wegstein Acceleration , 10-317, 10-318
Vapor-Liquid-Liquid Algorithm , 4-66
Weight.volume/pressure.time2 , 11-345
Vapor-liquid-liquid equilibrium (VLLE) , 1-2, 1-13
Variables , 10-335, 10-336, 10-337, 10-338, 10-339 Weight/time , 11-345
Westerberg , 10-314, 10-316
Various Two-Phase Flow Regimes , 3-39
White , 6-227
VARY , 10-339
Varying , 10-326 WIDE , 7-246
flowrates , 10-326 Wiley , 10-340
Venkatesh , 8-303 Willis , 5-166, 5-174
Vertical Cylinder Vessel , 11-344 Wright , 10-340
Vertical Flow Correlation , 3-44
Vessel Volume , 11-344
Calculating , 11-344
X
Violate , 4-131 XOVHD , 9-308
Y
Yadav , 7-265
Ysolute , 7-272
Z
Zones Analysis , 5-154, 5-156, 5-178
Zp , 4-116
Index-626
Volume3: Technical Bulletin
General Information
The PRO/II Reference Manual provides details on the basic equations and calculation techniques used in
the PRO/II simulation program and the PROVISION Graphical User interface. It is intended as a reference
source for the background behind the various PRO/II calculation methods.
PRO/II predefines more than one set of values for standard vapor
conditions and standard vapor volume. In the English system, these
values are 60F (15.555C) and 14.696 psia (1 atm), yielding a stan-
dard vapor volume of 379.49 ft3/lb_mole (23.690 m3/kg-_mole). In
the metric and SI systems, the values are 0C (32F), 1.01325 bar (1
atm) and a standard vapor volume of 22.414 m3/kg_mole (259.04
ft3/lb_mole). These differences cause a simulation to reach different
solutions when re-run using a different system of units of measure.
PRO/II allows users to change the vapor standard conditions of
temperature and pressure. These conditions were used in the ideal
gas equation (PV = nRT) to calculate a standard vapor volume.
Users could alternatively specify the standard vapor volume (STD-
VAP), which would always be inconsistent with the (default) stan-
dard vapor conditions. No user-supplied values affected liquid
standard conditions or standard liquid volume, which caused
chronic problems for the users.
PRO/II Version 8.3.2 introduced significant enhancements that
address the problems mentioned above. This chapter describes the
following enhancements and many more.
Usage and options for user-supplied standard temperature and
pressure (STP) have changed.
User-supplied values now constitute new adjusted standard
conditions. These now apply to liquid as well as vapor, and are
in addition to the standard conditions.
Adjusted standard vapor volumes are computed using the vapor
density method of a thermodynamic METHOD set at user-sup-
plied standard temperature and pressure.
Adjusted standard liquid volumes are computed using the liq-
uid density method of a thermodynamic METHOD set at user-
supplied standard temperature and pressure.
Standard volumes are computed at default standard conditions,
not from the user-supplied values. Standard vapor volume still
may be supplied (STDVAP), or computed from the ideal gas law.
mp
Note: Altered standard volume rates are available only for stream
bulk rates, and not for rates of individual components in a multi-
component stream.
Select Total Fluid Rate as the property and ensure that the
Unit of Measure is a liquid volume or gas volume unit.
Select the Adjusted Standard Basis checkbox.
Assay Stream:
Click the Flowrate and Assay button for a stream that has
assay data instead of composition. The Stream Data
Keyword Interface
Generic syntax:
SPEC STREAM=sid, <property 1>, <modifiers 1> &
{<operator> <reference 2>, <property 2>, modifiers 2>} &
VALUE=value, {miscellaneous modifiers}
Standard liquid volume rates:
SPEC STREAM=sid, RATE(LV, uLvol), {PHASE=T or L or V
or S,} {WET or DRY}, & {<operator>, <reference 2>, <prop-
Flash Drum
Below figure shows the main Data Entry Window of a flash drum
after declaring an adjusted standard flow rate specification on
product stream 3L1 (shown in blue text).
Figure SS2 uses the flash drum of Figure SS1 to illustrate the proce-
dure used to create the product specification.
All DEFINE constructs that allow a second reference are able to refer
to stream flow using an ASTD basis. In keywords, the second refer-
ence must appear after an operator (PLUS, MINUS, DIVIDE or
MULTIPLY). The operator must appear after the primary reference
and before the second reference. It acts as a delimiter between the
two reference constructs.
<operator> is required whenever a second reference is present.,
Otherwise, <operator> is not allowed.
<reference 2>, <property 2>, and <modifiers 2> represent a refer-
ence to the second datum. They may refer to a flow rate, including
another ASTD rate, as does <property 1>, or they may refer to a dif-
ferent type of datum.
Refer to chapters 10.3 through 10.6 of the PRO/II Keyword Manual
for a thorough discussion of the syntax of SPECIFICATION state-
ments.
GUI Interface
The PROVISION Graphical User Interface utilizes different Data
Entry Windows for each unit operation that supports DEFINE con-
structs. The following sections present a series of figures that illus-
trate the interface windows modified to support adjusted standard
rates in DEFINE constructs. Similar cascading windows are typical
in other SPECIFICATIONs and DEFINEs.
UAS/PDTS Functionality
Interface subroutines UDENS and DUDENS may be called from user-
added subroutines and PRO/II Data Transfer System applications.
These subroutines compute actual flowing liquid volume, not stan-
dard liquid volume. However, adjusted standard volumes are com-
Keyword Interface
A keyword option on the PRINT statement allows users to include
adjusted standard volume rates in the standard stream reports.
TITLE
PRINT , ASTD,
COMPONENT DATA
Graphical Interface
On the PRO/II Stream Property Report Options window, select
the Include Adjusted Standard Flowrates check box to report
adjusted standard volume flowrates.
1. Navigate to the PRO/II Stream Property Report Options win-
dow by clicking Output menu > Report Format > Stream Prop-
erties.
(1) STD LIQUID VOLUME AT 60 F AND 14.696 PSIA USING PURE COMPONENT SPGR
(2) ADJ STD LIQUID VOLUME AT 65 F AND 29.696 PSIA USING STREAM THERMO SET
(1) STANDARD VAPOR VOLUME IS 189.61 FT3/LB-MOLE (65 F AND 29.696 PSIA)
(2) ADJUSTED VAPOR VOLUME AT 65 F AND 29.696 PSIA USING STREAM THERMO SET
Stream Summary
There are several changes to Stream Summary reports to consider.
Changes in each section are discussed separately below.
(1) STD LIQUID VOLUME AT 60 F AND 14.696 PSIA USING PURE COMPONENT SPGR
(2) ADJ STD LIQUID VOLUME AT 65 F AND 29.696 PSIA USING STREAM THERMO SET
STD LIQ RATE: Addition of this row for wet standard liquid rate
corrects an omission. Previously, the Stream Summary never dis-
played the standard flowing rate. Now it does. This wet standard
rate is computed in the traditional manner, at the default standard
conditions, using specific gravity values of all components, includ-
ing water. Recall that component specific gravity data are scalar
values typically furnished at 60F and 14.696 psia. Refer to the first
footnote in the table above.
(3) STANDARD VAPOR VOLUME IS 189.61 FT3/LB-MOLE (65 F AND 29.696 PSIA)
(4) ADJUSTED VAPOR VOLUME AT 65 F AND 29.696 PSIA USING STREAM THERMO SET
STD VAP RATE: The calculation logic has been modified. Now
when users adjust standard temperature and standard pressure, the
adjusted values are applied to the ideal gas law to obtain a standard
specific volume. The footnote shows the new standard conditions
and the corresponding standard vapor volume. Refer to footnote 3
in the table above. When user-adjusted standard temperature and
pressure are absent, the standard vapor volume rate is reported in
the traditional manner (at default standard temperature and pres-
sure.) Note that the default standard conditions in the English sys-
tem(and therefore the standard vapor volume) are different from
those in the metric and SI dimensional systems.
ADJ VAP RATE: This row reports the adjusted standard vapor rate
calculated as an actual rate. These values are obtained by solving
the vapor density method associated with each stream. The calcula-
tions use actual stream compositions at the user-adjusted standard
temperature and user-adjusted standard pressure. Comparing foot-
note 4 with footnote 3 confirms that the same temperature and pres-
sure are used for standard vapor rate and adjusted standard vapor
rate. The differences in rate values reveal the extent to which the
actual vapor density departs from the ideal gas law results.
(1) STD LIQUID VOLUME AT 60 F AND 14.696 PSIA USING PURE COMPONENT SPGR
(2) ADJ STD LIQUID VOLUME AT 65 F AND 29.696 PSIA USING STREAM THERMO SET
(1) STD LIQUID VOLUME AT 60 F AND 14.696 PSIA USING PURE COMPONENT SPGR
(3) STANDARD VAPOR VOLUME IS 189.61 FT3/LB-MOLE (65 F AND 29.696 PSIA)
(1) ADJ STD LIQUID VOLUME AT 65 F AND 29.696 PSIA USING STREAM THERMO SET
(2) ADJUSTED VAPOR VOLUME AT 65 F AND 29.696 PSIA USING STREAM THERMO SET
Readme First
Definitions
The DIPPR Library
Distribution Protocol and Software Compatibility
Library Contents
Rights and Limitations
Bank Name and Library Registration
Naming Convention for DIPPR Components
User Customizations
Parameter Fill-in
Enthalpy Correlations
Entropy Values
User Modifications to the DIPPR Correlations
Readme First
Legal Attributions
Definitions
Legal Attributions
Design Institute for Physical Property Data and its acronym
DIPPR are registered trademarks of the American Institute of
Chemical Engineers (AIChE) and are used by permission.
DIPPR Design Institute for Physical Properties, a division of the American Institute
of Chemical Engineers (AIChE)
DIPPR Database Refers to the Microsoft Access database that DIPPR distributes as part of
the DIPPR 801 Project: Thermophysical Property Database for Pure
Chemicals
SimSci Library Refers to the lb1/lb2 files distributed with SimSci products.
Library Contents
The following fixed properties are available in the DIPPR library,
provided they are available in the DIPPR database:
Notes:
"DIPPR Name" is the actual name appearing in the DIPPR doc-
umentation.
"SimSci Name" is the attribute-mnemonic appearing in the
XML files used to generate the lb1/lb2 files.
Conversion factor formula: (SimSci value) = Factor * (DIPPR
value)
The following temperature-dependent properties are available in the
DIPPR library, provided they are available in the DIPPR database:
DIPPR Name SimSci Name Is Cp? DIPPR UOM SimSci UOM Temp Unit
LDN LiquidDensity N kmol.m-3 kg-mole /m3 K
Notes:
"DIPPR Number" is the actual correlation number appearing in
DIPPR documentation.
"SimSci Number" is the corresponding SimSci correlation
number.
User Customizations
SimSci Products allow the creation and use of User Libraries con-
taining User Databanks (See TDM Documentation). Users cannot
modify an existing value in the DIPPR Library directly. However, a
copy of the component with all the existing data can be included in
a User Databank in a User Library. Then, the data becomes avail-
Parameter Fill-in
The DIPPR database provides a significant amount of pure compo-
nent parameters that are of direct use in process simulators.
Depending on the situation, however, this amount of data may not
be sufficient to support the needs of process simulators. When data
deficiency is indicated by the simulator, the user can enable cascade
databank search to allow automatic fill-in using values available in
the standard databanks. Although cascade databank search is effec-
tive, the DIPPR library contains extensions to the original DIPPR
database contents to reduce or even eliminate the need for cascade
databank search order in many situations. More specifically, the fol-
lowing items are included in the DIPPR library whenever feasible,
even though most of them are not a part of the original DIPPR data-
base:
Enthalpy Correlations
The DIPPR database provides heat capacity correlations for the
ideal gas, saturated liquid, and solids. The SimSci library by con-
trast stores enthalpy correlations. These enthalpy correlations are
obtained by integrating the corresponding heat capacity correla-
tions. Once the integrated form is obtained, an additional parameter
shows up in each one. It is called the constant of integration.
For process calculations, the actual values of the constants of inte-
gration are not important because the values that matter are the dif-
ferences in enthalpy values. Although this is conceptually clear and
well-known to users of process simulators, an interesting usability
situation is introduced when users change the component search
order so that DIPPR is searched before the SimSci banks: A compo-
nent previously found in say the SIMSCI bank is now found in the
DIPPR library. Although not strictly necessary for process calcula-
tions, the user probably expects the enthalpy values obtained using
the DIPPR components to be similar or close to the values obtained
using the SIMSCI components.
Since enthalpy values are a standard and very visible part of PRO/II
reports, the integration constants for the enthalpy correlations found
in the DIPPR library are adjusted, whenever possible, so that
DIPPR component predicts values similar to the SimSci values.
This procedure is called Enthalpy Reconciliation." This is not a fun-
damental requirement to do energy balances but it is done to facili-
tate human understanding of the results.
Entropy Values
There are no entropy correlations in the DIPPR database or the
DIPPR library. Instead, entropy is a calculated quantity, based on
various terms. The ideal gas heat capacity plays a key role in the
calculation because Cp/T is integrated from a very low reference
temperature of 1 R to the system temperature. It is important for
the users of the DIPPR library to know that entropy values calcu-
lated using DIPPR components and SimSci components can have,
and often will have, significant differences between them. These
significant differences though surprising and unavoidable are
explainable. Most of the difference in values is due to two reasons:
The minimum temperature for the ideal-gas heat capacity cor-
relations in SimSci may be different from that in DIPPR.
Extrapolation is required to handle the integration of Cp/T from
1 R to the correlation's minimum temperature. The fact that
minimum temperature in SimSci is different from that in
DIPPR may introduce a significant difference in the Cp value
used in the extrapolation range.
Shell side
Tubeside
Shell side
Modified Chen Vaporization Method
A1) Shellside Vaporization (Except Kettle Reboiler):
Equation (A-1):
HF
(HLIQ H NB) (QREB QLIQ QWAT) HVAP (QVAP QSTE )
QR
QCHF
if (TSAT H F ) QCHF
TSAT
Equation (A-2):
H LIQ H LIQ FF
HLIQ and HVAP are calculated using the Shell side heat transfer cor-
relations listed in equations from (5-11) to (5-15) in Chapter 5 of
Volume 2, Unit Operations.
Equation (A-3):
FF 1 if XTT 10
0.7
1
2.25 0.113 if XTT 10
XTT
Equation (A-4):
0.9 0.5 0.1
(1 X V )
XTT V L
XV L V
(WAV WAS )
XV
WTOT
Equation (A-6):
(WVi WVo )
WAV
2
Equation (A-7):
(WLi WLo )
WAL
2
Equation (A-8):
(WWi WWo )
WAW
2
Equation (A-9):
(WSi WSo )
WAS
2
Equation (A-10):
DOTL TL
12
C1
A
Np
Equation (A-12):
TSAT 144
PSAT
TTP
Equation (A-16):
1 1
TC 144
V L
TTP
778 L
Equation (A-17):
1
Fbs
(1 1.17
N Re tp
10 5 )
Equation (A-18):
2.5
TSAT
FONB
T
W CT
Equation (A-19):
FWBT e ( 0.009(TD TB ))
1 if FWBT 1
0.2 if FWBT 0.2
Equation (A-20):
N Re tp N Re L FF1.25
Equation (A-21):
DW GT
N Re L
12 L
Equation (A-22):
(WAL WAW )
GT
N p AF
AC
AF
144
Equation (A-24):
QREB QR QTOT
Equation (A-25):
QLIQ Cp L T WAL
Equation (A-27):
QVAP Cp V T WAV
Equation (A-28):
QWAT Cp W T WAW
Equation (A-29):
Equation (A-32):
0.25
140.963 K L d o L TB Cp L
3 2
H1b
d o L K L
d o d o (tf 2)
Equation (A-34):
L2
2
L
TB L L
Equation (A-35):
FWBT e ( 0.009(TD TB ))
1.0 if FWBT 1
0.2 if FWBT 0.2
1.0 if (WHCL H HCV 1 and WS WW 1)
B) Shellside Condensation:
Equation (A-38):
1
H F
1 QF
H F C1 H VAP
Equation (A-39):
QVAP QSTE
QF
QR
A
C2 0.5 C1 ( A )1
e 1 1
Equation (A-41):
WTOT A2 Cp VS
A1
H VAP
Equation (A-42):
H F T BWFd
A2
WTOT L
Equation (A-43):
T BW 0.5 (Ti To ) TW
Equation (A-44):
QCOND
Fd
QR
Equation (A-45):
Cp VS
WAV Cp WAS Cp
V S
WAV WAS
Assign C2 value to C1 and repeat calculation of HF till
C2 C1
10 6
C1
Equation (A-46):
2
H F H LI 2
Q H SHL
0.5
Equation (A-47):
0.78
1
H LIQ 1.26 H LIQ
XTT
HLIQ and HVAP are calculated using the shell side heat transfer cor-
relations listed in equations from (5-11) to (5-15) in Chapter 5 of
Volume 2, Unit Operations.
(WAV WAS )
XV
WTOT
Equation (A-50):
a2
H SHL 1.51
a1
Equation (A-51):
L2 1 3
--------------------------------------------------------------------
L L v 4.17312 10 8
a 1 = ---------------------------------------------------------------------------------
KL
Equation (A-52):
( 1 / 3)
4 Wx
a2
L
Equation (A-53):
Equation (A-54):
WTOT (1 X V )
Wx
N p N pp
HEX5 Method
C1) Shellside Vaporization (except Kettle Reboiler):
HLIQ and HVAP are calculated using the Shell side heat transfer cor-
relations listed in equations from (5-11) to (5-15) in Chapter 5 of
Volume 2, Unit Operations.
Equation (A-56):
0.6667
H F 749.0 RJ KL L
L
H F F if shell type is ' X' and orientation is vertical
Equation (A-57):
X 1 ln N Pr
Equation (A-59):
X 2 Log10 N Re
Equation (A-60):
Cp L L
N Pr
KL
Equation (A-61):
3.993 Cr
N Re
L
Equation (A-62):
C1 Log10 (C2 )
A N = 0.87 N T
d o d o (tf 2)
Equation (A-68):
QREB QR QTOT
Equation (A-69):
QLIQ C p L T WAL
Equation (A-71):
QVAP C p V T WAV
Equation (A-72):
QWAT C p W T WAW
H F H1 FC
Equation (A-74):
H1 ( H1a H1b )
Equation (A-75):
0.69 0.31 0
QTOT Cp L 144 PAV K L
H1a 0.225 L 1
A L TS V
0.7 0.17
Q P
2.99 TOT AV
Area 3208.0
if (WHCL H HCV ) 1 and (WS WW ) 1
Equation (A-76):
0.25
140.963 K L d o L TB Cp L
3 2
H1b
d o
L K L
0 if (WHCL H HCV ) 1 and (WS WW ) 1
Equation (A-77):
L2
2
L
TB L L
Equation (A-78):
TB TW TC
Equation (A-79):
Fc e ( 0.015(To Ti ))
1 if (WHCL H HCV 1 and WS WW 1)
D) Shellside Condensation:
Equation (A-80):
QR
H F
QCOND QLIQ QWAT QVAP QSTE
H H H VAP
F LIQ
Equation (A-84):
X V 1 X L
Equation (A-85):
1
XL
(WAV WAS ) WF
1
(WAL WAW )
Equation (A-86):
0.1111 0.5556
WF V L
L V
X 1 ln N Pr
Equation (A-89):
X 2 Log10 N Re
Equation (A-90):
Cp L L
N Pr
KL
Equation (A-91):
3.993 Cr
N Re
L
Equation (A-92):
C1 Log10 (C2 )
Equation (A-94):
AN 0.87 N T
1.38 AN if layoutis Triangular(30 ) or Rotated square(4
QCOND QR QTOT
Equation (A-98):
QLIQ C p L T WAL
Equation (A-100):
QVAP C p V T WAV
Equation (A-101):
QWAT C p W T WAW
Equation (A-102):
Tubeside
Modified Chen Vaporization Method
A) Tubeside Vaporization:
Equation (A-103):
HF
( H LIQ H NB ) (QREB QLIQ QWAT ) H VAP (QVAP QSTE
QR
GR Cp V V
0.2
0.056 K V N Re if (TSAT H F ) QCHF
V
KV
Equation (A-104):
H LIQ H LIQ FF
HLIQ and HVAP are calculated using the Tube side heat transfer cor-
relations listed in equations from (5-16) to (5-21) in Chapter 5 of
Volume 2, Unit Operations.
Equation (A-105):
FF 1 if XTT 10
( FF 1) FWBT 1 if XTT 10
(WAV WAS )
XV
WTOT
Equation (A-109):
(WVi WVo )
WAV
2
Equation (A-110):
(WLi WLo )
WAL
2
Equation (A-111):
(WWi WWo )
WAW
2
Equation (A-112):
(WSi WSo )
WAS
2
Equation (A-113):
L V 4.17312 10
F CHF F CHF 1 B V ----------------------------------------------------------
L
Q CHF = -----------------------------------------------------------------------------------------------------------------------------
41.5
Equation (A-114):
86.4 0.5658
FCHF 5.622
Pcp Pcp2
Equation (A-115):
FCHF1 1 N Re L 10 6
Pav
Pcp
Pcrit
0.001 if Pcp 0.001
1.0 if Pcp 1.0
Equation (A-117):
B (1 X V ) L
Equation (A-118):
TSAT 144
PSAT
TTP
Equation (A-120):
1 1
TC 144
V L
TTP
778 L
Equation (A-121):
1
Fbs
(1 1.17
N Re tp
2.53 10 6 )
Equation (A-122):
2.5
TSAT
FONB
T
W CT
Equation (A-123):
FWBT e ( 0.009(TD TB ))
1 if FWBT 1
0.2 if FWBT 0.2
Equation (A-124):
N Re tp N Re L FF1.25
d i GT
N Re L
12 L
Equation (A-126):
(WAL WAW )
GT
AT
Equation (A-127):
5.45 10 3 d i2 N T
AT
N tp
Equation (A-128):
QREB QR QTOT
Equation (A-129):
QLIQ Cp L T WAL
Equation (A-131):
QVAP Cp V T WAV
Equation (A-132):
QWAT Cp W T WAW
Equation (A-133):
d i GT
N Re V
12 V
Equation (A-135):
W WAS
GT AV
AT
GTOT C2
VSG
C1
Equation (A-139):
8 0.5
V L V 4.17312 10 d o
C 1 = -------------------------------------------------------------------------------------
12
Equation (A-140):
C3
C2
(C3 XTT1.111 )
Equation (A-141):
0.555 0.111
C3 V L
L V
Equation (A-142):
0.9 0.5 0.1
(1 X V )
XTT V L
X V L V
Equation (A-143):
WTOT N tp
GTOT
5.454 10 3 d i2 N t N p
Equation (A-144):
0.25
a
H STR b1 1
a2
1
b2
1 X 0.6667
1 V
V
X V L
Equation (A-147):
WAV WAS
XV
WTOT
Equation (A-148):
3 8
a1 = KL L L V 4.17312 10 L
Equation (A-149):
L d o TBW
a2
12
Equation (A-150):
H CAL H CAL1 if Si 0
H CAL2 if Si 0
Equation (A-151):
ff 1 (1 850.0 ff 2) ff 3
Equation (A-153):
ff 4
0.5
ff 2 V L 0.9
L V Re g
Equation (A-154):
(-0.2)
ff 3 0.046 Re g
0.0379 N
0.4
ff 4 0.707 N Re 0.9 2.5
0.5 2.5
Re
Equation (A-156):
G tot 1 X V d inside
N Re = ---------------------------------------------------------
-
12 L
Equation (A-157):
V VG d o
Re g
12 V
Equation (A-158):
GTOT X V
VG
V
Equation (A-159):
0.5
H CAL2 1.41 N Re if N Re 50.0
( Z1 Z 2 ) (1 / Z 3 ) if N Re 50.0
Equation (A-160):
Z3
1.41
Z1 0.5
N Re
Equation (A-161):
Z3
0.5
0.071 N Pr
Z 2
0.04167
N Re
Equation (A-162):
N Pr 3
Z3
2
Equation (A-163):
Cp L L
N Pr
KL
8 L
2 13
m 1 = K L 4.17312 10 ------
L
Equation (A-166):
2 8 23
L L 4.17312 10
m 2 = -----------------------------------------------------------------------
L
Assume Y1 Si and calculate
Equation (A-167):
0.5
Y
Y2 H CAL2 m1 1
m2
Equation (A-168):
Y2 TBW VG Fd
Y3
L Si
Equation (A-169):
Si Y3
Y4
1 e ( Y3 )
Equation (A-170):
QCOND
Fd
QR
Y4 Y1
10 6
Y
1
4 Wx
N Re
L
Equation (A-175):
W tot 1 X V N TP 12
W x = ----------------------------------------------------------------
-
N T d inside
Equation (A-176):
(WAV WAS )
XV
WTOT
Equation (A-177):
2 13
L
-------------------------------------------------------------------8-
L * L V *4.17312 10
a 1 = --------------------------------------------------------------------------------
-
KL
Equation (A-178):
0.22
0.756 N Re
H LAM2
a1
Equation (A-179):
0.25 0.5
0.023 N Re N Pr
H turb
a1
Equation (A-180):
Cp L L
N Pr
KL
Z3
1.41
Z1 0.5
N Re
Equation (A-184):
Z3
0.5
0.071 N Pr
Z 2
N 0.04167
Re
Equation (A-185):
N Pr 3
Z3
2
Equation (A-186):
Si
b1
b2
Equation (A-188):
Si 0.5 ff 1 V VG2
Equation (A-189):
8 23
L * L V * L * 4.17312 10
b 2 = -----------------------------------------------------------------------------------------------
-
L
Equation (A-190):
ff 1 (1 1400.0 ff 2 (1 e J1 )) ff 3
ff 3 0.046 Re (-0.2)
g
Equation (A-193):
0.0379 N
0.4
0.9 2.5
ff 4 0.707 N Re
0.5 2.5
Re
Equation (A-194):
V VG d o
Re g
12 V
Equation (A-195):
(1 1400.0 ff 2)1.5
J1
(13.2 ff 5 ff 2)
Equation (A-196):
8
L 4.17312 10 d o
ff5 = ------------------------------------------------------
-
2
12 V ff3 V G
Equation (A-197):
0.5
S
H CAL1 H CAL2 m1 i
b2
Equation (A-198):
1
m1
a1
Y2 TBW VG Fd
Y3
L Si
Equation (A-201):
Si Y3
Y4
1 e ( Y3 )
Equation (A-202):
QCOND
Fd
QR
Y4 Y1
10 6
Y1
HEX5 Method
C) Tubeside Vaporization:
Equation (A-203):
HF
(H F QREB ) H LIQ (QLIQ QWAT ) H VAP (QVAP QSTE ) if Q
QR
H F H LIQ H VAP if QR 0
3
H F d i
if orientation is Horizontal
do
HLIQ and HVAP are calculated using the Tube side heat transfer cor-
relations listed in equations from (5-16) to (5-21) in Chapter 5 of
Volume 2, Unit Operations.
Equation (A-204):
0.6667
HF 749.0 RJ KL L
L
HF F if shell type is ' X' and orientation is vertical
X 1 ln N Pr
Equation (A-207):
X 2 Log10 N Re
Equation (A-208):
Cp L L
N Pr
KL
Equation (A-209):
3.993 Cr
N Re
L
Equation (A-210):
C1 Log10 (C2 )
Equation (A-212):
(WAL WAW )
Cr if orientation is Horizontal
N TTL X V Np
Equation (A-214):
X V 1 X L
1
XL
(WAV WAS ) WF
1
(WAL WAW )
Equation (A-217):
0.1111 0.5556
WF V L
L V
Equation (A-218):
QREB QR QTOT
Equation (A-219):
QLIQ C p L T WAL
Equation (A-221):
QVAP C p V T WAV
Equation (A-222):
QWAT C p W T WAW
Equation (A-223):
D) Tubeside Condensation:
Equation (A-224):
QR
H F
QCOND QLIQ QWAT QVAP QSTE
H Q QVAP
F LIQ
HLIQ and HVAP are calculated using the tube side heat transfer cor-
relations listed in equations from (5-16) to (5-21) in Chapter 5 of
Volume 2, Unit Operations.
1
b2
X 0.6667
1 L V
X V L
Equation (A-228):
X V 1 X L
Equation (A-229):
1
XL
(WAV WAS ) WF
1
(WAL WAW )
Equation (A-230):
0.1111 0.5556
WF V L
L V
Equation (A-231):
X 1 ln N Pr
Equation (A-233):
X 2 Log10 N Re
Equation (A-234):
Cp L L
N Pr
KL
Equation (A-235):
3.993 Cr
N Re
L
Equation (A-236):
C1 Log10 (C2 )
Equation (A-238):
WCOND QTOT N tp
Cr
QCOND N T F VTL N p
Equation (A-240):
QCOND QR QTOT
Equation (A-242):
QLIQ C p L T WAL
QVAP C p V T WAV
Equation (A-245):
QWAT C p W T WAW
Equation (A-246):
where
QR Duty, region
V Vapor density
L Liquid density
L Liquid viscosity
V Vapor viscosity
TL Tube length
L Latent heat
ST Surface tension
TW Temperature, wall
TC Temperature, average
N Re Reynolds number
AF Flow area
GT Mass velocity
T TB
tf C
2
L Density of liquid at tf
L Viscosity of liquid at tf
WS Flowrate, steam
WW Flowrate, water
Ti Inlet temperature
To Outlet temperature
Si Interfacial Shear
Vg Velocity, gas