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Unit Operations
Reference Manual
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Chapter 1 Introduction
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1
What is in This On-line Manual? . . . . . . . . . . . . . . . . . . . . . .1-1
Finding What you Need . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1
2 Contents
Distillation Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-76
Simple Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-77
Troubleshooting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-85
Liquid-Liquid Extractor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-89
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-89
Basic Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-89
Chapter 7 Reactors
Reactor Heat Balances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-1
Heat of Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-3
Conversion Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-3
Shift Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-4
Methanation Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . . .7-4
Equilibrium Reactor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-5
Shift Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-7
4 Contents
Chapter 9 Stream Calculator
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-1
Feed Blending Considerations . . . . . . . . . . . . . . . . . . . . . . . .9-1
Stream Splitting Considerations . . . . . . . . . . . . . . . . . . . . . . .9-2
Stream Synthesis Considerations . . . . . . . . . . . . . . . . . . . . . .9-3
Chapter 10 Utilities
Phase Envelope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-1
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-1
Calculation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-2
Heating / Cooling Curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-3
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-3
Calculation Options. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-3
Critical Point and Retrograde Region Calculations . . . . . . .10-4
VLE, VLLE, and Decant Considerations . . . . . . . . . . . . . . .10-5
Water and Dry Basis Properties . . . . . . . . . . . . . . . . . . . . . .10-5
GAMMA and KPRINT Options . . . . . . . . . . . . . . . . . . . . . .10-6
Availability of Results. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-7
Binary VLE/VLLE Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-10
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-10
Input Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-11
Output Considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-11
Hydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-13
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-13
Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-13
Exergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-20
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-20
Interpreting Exergy Reports . . . . . . . . . . . . . . . . . . . . . . . .10-20
Chapter 12 Depressuring
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-1
Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-1
Calculating the Vessel Volume . . . . . . . . . . . . . . . . . . . . . . . 12-2
Valve Rate Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-3
Heat Input Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-6
6 Contents
Chapter 1
Introduction
General Information
The on-line PRO/II Unit Operations Reference Help 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.
Basic Principles
(1)
Component Mass Balance:
Fz i = Vy i + L 1 x 1i + L 2 x 2i (2)
Equilibrium:
(3)
(4)
(5)
Summations:
(6)
(7)
Heat Balance:
(8)
(10)
The mole fractions, xi and yi sum to 1.0, i.e.:
(11)
However, the solution of equation (11) often gives rise to conver-
gence difficulties for problems where the solution is reached itera-
tively. Rachford and Rice in 1952 suggested that the following form
of equation (11) be used instead:
(12)
Equation (12) is easily solved iteratively by a Newton-Raphson
technique, with V/F as the iteration variable.
Figure 2.1 shows the solution algorithm for a two-phase isothermal
flash, i.e., where both the system temperature and pressure are
given. The following steps outline the solution algorithm.
1 The initial guesses for component K-values are obtained
from ideal K-value methods. An initial value of V/F is
assumed.
2 Equations (9) and (10) are then solved to obtain xi's and
yi's.
3 After equation (12) is solved within the specified tolerance,
the composition convergence criteria are checked, i.e., the
changes in the vapor and liquid mole fraction for each
component from iteration to iteration are calculated:
(13)
(4)
If the VLE convergence criterion is not met, the vapor and liq-
uid mole fractions are damped, and the component K-values
are re-calculated. Rigorous K-values are calculated using equa-
tion of state methods, generalized correlations, or liquid activ-
ity coefficient methods.
6 A check is made to see if the current iteration step, ITER, is
greater than the maximum number of iteration steps ITER-
max. If ITER > ITERmax, the flash has failed to reach a
solution, and the calculations stop. If ITER <ITERmax, the
calculations continue.
7 Steps 2 through 6 are repeated until the composition con-
vergence criteria and the VLE criterion are met. The flash
is then considered solved.
8 Finally, the heat balance equation (8) is solved for the flash
duty, Q, once V and L are known.
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 Composition Convergence
Tolerance is not protected and may be changed by users. Table 2-1
shows the values of the tolerances used in the algorithm for the
(5)
The bubble point temperature or pressure is to be found by trial-
and-error Newton-Raphson calculations, provided one of them is
specified.
The K-values between the liquid and vapor phase are calculated by
the thermodynamic method selected by the user. Equation (16) can,
however, be highly non-linear as a function of temperature as K-
values typically vary as exp(1/T). For bubble point temperature cal-
culations, where the pressure and feed compositions has been given,
and only the temperature is to be determined, equation (16) can be
rewritten as:
(6)
Equation (17) is more linear in behavior than equation (16) as a
function of temperature, and so a solution can be achieved more
readily.
Equation (16) behaves in a more linear fashion as a function of
pressure as the K-values vary as 1/P. For bubble point pressure cal-
culations, where the temperature and feed compositions have been
given, the equation to be solved can be written as:
(8)
For dew point pressure calculations, equation (19) can be linearized
by writing it as :
(9)
For dew point temperature calculations, equation (19) may be
rewritten as:
(10)
The dew point temperature or pressure is then found by trial-and-
error Newton-Raphson calculations using equations (20) or (21).
(11)
An iterative Newton-Raphson technique is used to solve the Rach-
ford-Rice equation (12) simultaneously with equation (22) using V/
F and temperature as the iteration variables.
Note: The free-water decant option may only be used with the
Soave-Redlich- Kwong, Peng-Robinson, Grayson-Streed, Gray-
son-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.
The water-decant flash method as implemented in PRO/II follows
these steps:
1 Water vapor is assumed to form an ideal mixture with the
hydrocarbon vapor phase.
2 Once either the system temperature, or pressure is speci-
fied, the initial value of the iteration variable, V/F is
selected and the water partial pressure is calculated using
one of two methods.
3 The pressure of the system, P, is calculated on a water-free
basis, by subtracting the water partial pressure.
4 A pure water liquid phase is formed when the partial pres-
sure of water reaches its saturation pressure at that tempera-
ture.
5 A two phase flash calculation is done to determine the
hydrocarbon vapor and liquid phase conditions.
6 The amount of water dissolved in the hydrocarbon-rich liq-
uid phase is computed using one of a number of water solu-
bility correlations.
7 Steps 2 through 6 are repeated until the iteration variable is
solved within the specified tolerance.
Reference
(12)
(13)
where:
(14)
(15)
(16)
Equations (23) through (27) are solved iteratively using a Newton-
Raphson technique to obtain L1 and L2. The solution algorithm
developed by SimSci is able to rigorously predict two liquid phases.
This algorithm works well even near the plait point, i.e., the point
on the ternary phase diagram where a single phase forms.
Table 2-2 shows the thermodynamic methods in PRO/II which are
able to handle VLLE calculations. For most methods, a single set of
binary interaction parameters is inadequate for handling both VLE
and LLE equilibria. The PRO/II databanks contain separate sets of
binary interaction parameters for VLE and LLE equilibria for many
Valve
Splitter
Compressor
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 3-1 shows the thermody-
namic systems which may be used to generate entropy data. User-
added subroutines may also be used to generate entropy data.
Basic Calculations
For a compression process, the system pressure P is related to the
volume V by:
(1)
where:
n = exponent
Figure 3.1 shows a series of these pressure versus volume curves as
a function of n.
(2)
where:
k = ideal gas isentropic coefficient
= specific heat at constant pressure
= specific heat at constant volume
For a real gas, n > k.
The Mollier chart (Figure 3-2) plots the pressure versus the
enthalpy, as a function of entropy and temperature. This chart is
used to show the methods used to calculate the outlet conditions for
the compressor as follows:
(3)
(5)
Ws = (H 2 − H 1 )J = (∆H ad )J (6)
where:
J = mechanical equivalent of energy
In units of horsepower, the isentropic power required is:
(7)
(9)
where:
GHP = work in hP
H = enthalpy change in BTU/lb
F = mass flow rate, lb/min
= Adiabatic Head, ft
The factor 33000 is used to convert from units of ft-lb/min to units
of hP.
The isentropic and polytropic coefficients, polytropic efficiency,
and polytropic work are calculated using one of two methods; the
method from the GPSA Engineering Data Book, and the method
from the ASME Power Test Code 10.
ASME Method
The ASME method is more rigorous than the GPSA method, and
yields better answers over a wider rage of compression ratios and
(10)
where:
= volume at the inlet conditions
= volume at the outlet pressure and inlet entropy conditions
The compressor work for a real gas is calculated from equation (8),
and the factor f from the following relationship:
{ }
Ws = 144[(n s − 1) / n s ] fP1V1 (P2 / P1 ){(ns −1) / ns } − 1
(11)
The ASME factor f is usually close to 1. For a perfect gas, f is
exactly equal to 1, and the isentropic coefficient ns is equal to the
compressibility factor k.
The polytropic coefficient, n, is defined by:
(12)
where:
= volume at the outlet pressure and actual outlet enthalpy con-
ditions
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:
{
W p = 144[n /(n − 1)] fP1V1 (P2 / P1 ){(n−1) / n } − 1 } (13)
where:
= polytropic work
(14)
Note: This polytropic efficiency will 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.
Note: The GPSA method was the default prior to PRO/II version
4.1. Currently, the ASME method is the default.
( k −1)
HEAD ad = {[(z1 + z 2 ) 2 ] RT1 {( k − 1) k }} (P2 P1 ) k
− 1
(15)
where:
= compressibility factors at the inlet and outlet conditions
R = gas constant
= temperature at inlet conditions
This trial and error method of computing k produces inaccurate
results when the compression ratio, (equal to P2/P1) becomes low.
PRO/II allows the user to switch to another calculation method for k
if the compression ratio falls below a certain set value.
If the calculated compression ratio is less than a value set by the
user (defaulted to 1.15 in PRO/II), or if k does not satisfy
. ≤ k ≤ 166667
10 . , the isentropic coefficient, k, is calculated by
trial and error based on the following:
( k −1)
T2 = ( z1 z 2 )T1 (P2 P1 ) k
(16)
The polytropic compressor equation is given by:
( n −1)
HEAD p = {[(z1 + z 2 ) 2 ] RT1 {( n − 1) n}} (P2 P1 ) n
− 1 (17)
γp =
[n (n − 1)]
[k ( k − 1)] (19)
(20)
Reference
GPSA, 1979, Engineering Data Book, Chapter 4, 5-9 - 5-10.
Expander
General Information
The methods used in PRO/II to model expander unit operations are
similar to those described previously for compressors. The calcula-
Basic Calculations
The Mollier chart (Figure 3-3) plots the pressure versus the
enthalpy, as a function of entropy and temperature. This chart is
used to show the methods used to calculate the outlet conditions for
the expander as follows:
(1)
(2)
(3)
(4)
where:
J = mechanical equivalent of energy
In units of horsepower, the isentropic expander power output is:
(5)
(6)
(7)
where:
GHP = work in hP
H = enthalpy change in BTU/lb
F = mass flow rate, lb/min
= Adiabatic Head, ft
The factor 33000 is used to convert from units of ft-lb/min to units
of hP.
(8)
where:
= compressibility factors at the inlet and outlet conditions
R = gas constant
= temperature at inlet conditions
The polytropic expander equation is given by:
(9)
The adiabatic head is related to the polytropic head by:
(10)
The polytropic efficiency n is calculated by:
(11)
The polytropic coefficient, n, the polytropic efficiency p, and the
polytropic head are determined by trial and error using equations
(9), (10), and (11) above. The polytropic gas horsepower output by
the expander (which is reported as work in PRO/II) is then given
by:
(12)
Pipes
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 4-1
shows the thermodynamic methods which may be used to generate
viscosity and surface tension data.
Basic Calculations
An energy balance taken around a steady-state single-phase fluid
flow system results in a pressure drop equation of the form:
(2)
(3)
(4)
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
ρ = fluid density
v = fluid velocity
= acceleration due to standard earth gravity
g = acceleration due to gravity
φ = angle of inclination
= total pressure gradient
= friction pressure gradient
= elevation pressure gradient
= acceleration pressure gradient
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,
(5)
where:
= superficial liquid velocity = volumetric liquid flowrate/cross
sectional area of pipe
= superficial gas velocity = volumetric gas flowrate/cross sec-
tional area of pipe
Equations (2), (3), and (4) are therefore rewritten to account for
these phase property differences:
(6)
(7)
(8)
where:
= fluid density =
= liquid and gas holdup terms subscript tp refers to the
two-phases.
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:
(9)
The exponent s is given by:
(10)
(12)
where:
= friction factor obtained from the Moody diagram for a
smooth pipe
= no-slip liquid holdup = vsl/ (vsl + vsg)
= superficial liquid velocity
= superficial gas velocity
The liquid holdup term, HL, is computed using the following corre-
lations:
(13)
where:
(14)
where:
= Froude number
= liquid velocity 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).
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 corection factors given below are used to cal-
culate the liquid holdup.
(16)
(17)
(18)
where:
= Reynolds number
The liquid holdup, HL, used in calculating the mixture density, ρ, in
the friction term is computed using the Eaton correlation. In this
correlation, the holdup is defined as a function of several dimen-
sionless numbers.
The elevation term is calculated using equation (3). The mixed den-
sity, ρ, however, is calculated not by using the Eaton holdup, but by
using the liquid holdup calculated by the Flanigan correlation:
(19)
The acceleration term is calculated using the Eaton correlation:
(20)
where:
W = mass flow rate
v = fluid velocity
Mukherjee-Brill (MB)
(5)
For bubble or slug flows:
(6)
For mist flows:
(7)
where:
= 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.
(8)
where:
= slip velocity
The density, , 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:
(9)
(10)
(11)
(12)
(13)
(14)
where:
= liquid viscosity number
Gray
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, φ = ≥ 70 degrees
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
where:
σ = surface tension
= in situ oil volumetric flowrate
= in situ water volumetric flowrate
= mixture volumetric flowrate
= diameter number
(23)
(24)
(25)
(26)
where:
G = mass flux
= no-slip liquid holdup
= Oliemens density
= effective diameter
A = pipe cross sectional area
L and g refer to the liquid and gas phases respectively
The acceleration term is set equal to zero, while the elevation pres-
sure drop term is computed using:
(27)
(28)
where:
φ = angle of inclination
subscripts L and g refer to the liquid and gas phases respectively
Hagedorn-Brown (HB)
(29)
where:
Reference
Pumps
General Information
The PUMP unit operation in PRO/II contains methods to calculate
the pressure and temperature changes resulting from pumping an
incompressible fluid.
Basic Calculations
The GPSA pump equation is used to relate the horsepower required
by the pump to the fluid pressure increase:
(1)
where:
HP = required pump power, hp
q = volumetric flow rate, gal/min.
∆P = pressure increase, psi
e = percent efficiency
The factor 1714.3 converts the pump work to units of horsepower.
The work done on the fluid calculated from (1) above is added to
the inlet enthalpy. The temperature of the outlet fluid is then
obtained by performing an adiabatic flash.
Note: The PUMP unit should only be used for incompressible flu-
ids. Compressible fluids may be handled using the COMPRES-
SOR unit operation.
Reference
GPSA Engineering Data Book, 9th Ed., 5-9
Side draws may be either liquid or vapor, and the location and phase
of each must be specified. Solid side draws are not allowed. There
may be an unlimited number of products from each stage.
Feed tray locations are given as the tray number upon which the
feed is introduced. A feed may be liquid, vapor or mixed phase.
PRO/II also allows for different conventions for mixed phase
(vapor/liquid) feeds. The default convention NOTSEPARATE
introduces both the liquid and the vapor to the same stage. SEPA-
RATE places the liquid portion of the feed on the designated feed
tray and the vapor portion of the feed on the tray above the desig-
nated feed tray.
A pumparound is defined as a liquid or vapor stream from one tray
to another. The return tray can be either above or below the pumpa-
round draw tray. The pumparound flowrate can be specified or cal-
culated to satisfy a process requirement. If a heater/cooler is used
with the pumparound, it must be located on the pumparound return
tray. The pumparound return temperature, pressure, liquid fraction,
and temperature drop will be computed if it is not specified.
Heater/coolers may be located on any tray in the column. A heater/
cooler is treated only as a heat source or sink. Rigorous models of
external heat exchangers are available via the attached heat
exchanger option.
Feed rates, side draw rates and heater/cooler duties may be either
fixed or computed. For each varied rate or duty, a corresponding
design specification must be made.
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
(1)
where:
Sj = the Stripping Factor for stage j
V = the net vapor leaving the stage
L = the net liquid leaving the stage
(2)
and SPK is a design specification equation.
This system of equations is solved using the Newton-Raphson
method. The first Jacobian matrix is obtained by finite difference
approximation. This Jacobian is then inverted, and at subsequent
iterations the inverse Jacobian is updated using Broyden's method.
To evaluate the errors in the enthalpy and specification equations
for a given set of stripping factors, the component flows and stage
temperatures must be computed for the given stripping factors and
simple model parameters. Figure 5-2 shows a schematic diagram of
a simple stage.
(6)
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:
(7)
where K is the vapor liquid equilibrium fugacity ratio. Now the
component mass balance can be written as:
(9)
where B and C are given by:
(10)
(11)
Sidestream withdrawal factors are defined as:
(12)
The vapor equilibrium K-value simple model is given by:
(13)
(14)
In equation (12) Tref is a reference temperature. Using this defini-
tion of the simple K-value model and the sidestream withdrawal
factors, the material balance (4) can be rewritten as:
(15)
The set of equations defined by (13) still form a tridiagonal matrix
so that equation (7) still applies. Bij and Cij from (8) and (9) now
become:
(16)
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
VLE K-values from the new compositions resulting from the inner
loop calculations.
The simple model used for VLE K-values is given by equations
(11) and (12). The initial value of Kb on each stage j is computed
by:
(18)
and substituting equation (11) into the bubble point equation:
(19)
(20)
Once Kb has been determined, equation (12) can be arranged so
that the bubble point temperature can be solved for directly. The
bubble point expression is:
(21)
The simple enthalpy models are of the form:
where:
(23)
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 solu-
tion. Estimate should be used to debug a non-converged column.
Estimate 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.
With Partial intermediate printout, the following information is pro-
vided at each iteration:
ITER 1 E(K)= 1.0717E-01 E(ENTH+SPEC)=1.392E-03 E(SUM)=
3.159E-01
INNER 0 : E(ENTH+SPEC) = 1.104E-02
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.
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
vapor-liquid-liquid equilibrium problems as well as chemical reac-
tions.
Basic Algorithm
Figure 5-3 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:
(1)
Energy Balance:
(2)
Vapor-Liquid Equilibrium:
(3)
(4)
(5)
where:
Fi =total feed flow to tray i
Li =total liquid flow from tray i
Vi = total vapor flow from tray i
Qi = heat added to tray i
Ti = temperatures of tray i
Xi,j = ln(xi,j) natural log of the liquid mole fractions
Yi,j = ln(yi,j) natural log of the vapor mole fractions
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
L =refers to a liquid property
V = refers to a vapor property
other:
^ refers to properties on a molar basis
lower case letters refer to component flows
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
(6)
(7)
and:
= total liquid flows of the first and second liquid phases,
respectively.
= 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
. The resulting tray temperatures and com-
position of the bulk liquid phases are used in performing liquid-liq-
uid equilibrium flash calculations. If a single liquid phase exists, the
calculations proceed as in the basic algorithm. If a second liquid
phase is detected, the liquid compositions of the two liquid phases
are used to calculate the K-values and the derivatives with respect
to each liquid phase. Using the chain rule and the definition of a
total derivative, these composition derivatives are used to calculate
the derivative of the VLE equations with respect to the bulk liquid
phase. A new Jacobian matrix is calculated and the Newton-Raph-
Reference:
Basic Algorithm
Figure 5-4 shows a schematic of an equilibrium stage for the case of
twophase 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
The mass balance equations are the only equations which must have
consumption and production terms added. The new equation is:
(6)
The kinetic rates of reaction are given by:
(8)
such that:
(10)
In equation (32), t is varied from zero to 1. The first challenge is
choosing the proper homotopy, the second is determining the
sequence of t that allows you to move from the simple equations to
the difficult equations.
The methods for tracking the homotopy path from 0 to 1 are classi-
fied as either "simplicial", discrete methods, or "continuation", dif-
ferential methods based on the integration of an initial value
method. Currently, the reactive distillation algorithm in PRO/II uses
a "classical" homotopy with a set of predefined steps. In most cases
involving reaction, this approach is sufficient.
The reactive distillation algorithm uses a physical homotopy with
the reaction volume being linked directly to the homotopy parame-
ter. That is, initially, the reaction volume is zero and the "simple" set
of equations corresponds to the basic distillation problem. At the
final point, the reactive volume is equal to the specified volume and
the equations are the full set describing reactive distillation. This
homotopy is only used for those systems using a reaction volume.
These are the most difficult systems to solve.
The actual function used to increase the reaction volume is a combi-
nation of functions. Initially, there may not be any products present
in the tower and the reaction may proceed very quickly. Therefore,
the volume is initially increased on a log fraction basis which very
gradually introduces the reaction. After the products begin to accu-
mulate on the trays, the reaction volume is increased linearly. The
transition between the two modes is at 25%.
Summarizing, if the reaction homotopy is used, the initial problem
is solved with no chemical reaction on the trays. After the solution
is reached, the reaction volume is increased by a small amount and
the problem is resolved using the no reaction solution as a starting
point. After the solution is reached, the reaction volume is again
increased and the problem is resolved. This continues until the reac-
Reference
Initial Estimates
As previously mentioned, initial column profiles are needed for
solution of the column heat, mass, equilibrium, and performance
specification balances. These may either be provided by the user,
or generated internally by PRO/II using an initial estimate genera-
tor.
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, flowrates, 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-
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.
For complex fractionators, the product draw temperatures are usu-
ally known or can be estimated from the product ASTM distilla-
tions.
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 5-2 with the column algorithm.
Electrolyte Default*
Recommendations
Provide reasonable estimates with the product information.
ELDIST Algorithm
The ELDIST algorithm in PRO/II is a combination of a Newton-
based method which is used in Chemdist for solving MESH equa-
tions and the solution of liquid phase speciation equations described
in Section - Electrolyte Mathematical Model.
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 5-5.
(1)
(2)
(3)
where:
γ =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:
(4)
(5)
Carbon Balance:
(6)
H+ Balance:
(7)
Electroneutrality Equation:
(8)
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 , and the recon-
stituted mole fractions .
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.
(9)
(10)
(11)
Summation x: (1)
(12)
Summation y: (1)
(13)
Reference:
Equations
Vapor Phase Component Material Balances
The vapor and liquid phase equations are written in terms of total
component molar flow rates. Total flow rates are chosen as inde-
pendent variables instead of net flow rates to allow for total pumpa-
rounds and total draws from stages. The original paper by
Krishnamurthy and Taylor [ref 1] used net liquid and vapor compo-
nent rates as independent variables.
NOC equations per segment; where NOC is the number of compo-
nents.
i=1.NOC, j=1..NT
Where
i is the component
j is the segment
Pump around
PA
NF Number of feeds
li , j − N i , j = li , j −1 (1 − rl j −1 ) + ∑ liF, j + ∑ liPA
,j
NF NPA
(2)
i=1..NOC, j=1..NT
Where
(3)
Where
v v v I
q j = htcj (T j − T j )
(4)
v Vapor Temperature
Tj
I Interface Temperature
Tj
TotalEnthalphy = nT H j
∂(nT H j )
Partial molar enthalpy H i, j = , k = 1..c, k ≠ i (5)
∂ni, j
T , P, nk
∂( H j )
H j + nT k = 1,2...c, k ≠ i
∂ni , j T , P ,nk
(6)
( 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 )
(7)
(8)
Where
L L I L
q j = htcj (T j − T j )
(9)
I Interface Temperature
Tj
L Liquid Temperature
Tj
PA
∑(l
NOC
i, j − Ni, j )hi, j = ∑(li, j−1 −sli, j−1)hi, j−1 +qL j +∑ ∑lFi, j hF j + ∑ ∑lPAi, j h i, j
NOC NF NOC NPANOC
−∑QL j +∑QLPAj
Equilibrium
NQ E Relationships
(10)
In general,
The KValues are functions of the interface temperature, vapor phase
mole fractions and the liquid phase mole fractions
K I i , j = f (T I i , j , y I i , j , x I i , j ) (12)
Ni, j = N v i, j
Component index
k
∑N
NOC
ij H ij + q v j = ∑N
NOC
ij hi j + q L j
(14)
∑N ij
j
H ij + h v tcj (T v j − TI ) = ∑N ij h ij + h L tcj (T I j − T L j )
NOC NOC (15)
Ni, j = N Li, j
Component Index
k
∑x
NOC
I
i, j = 1.0 i = 1,2...., NOC. (17)
∑y
NOC
I
i, j = 1 .0
i = 1,2...., NOC (18)
N v i , j = J v i , j + y bulk i , j N Tj i = 1,2....NOC
(19)
Where :
( Jv) j = B v [ ] [Φ ] [exp[Φ ]− [I ]] (y
−1
j
v
j
v −1
j
bulk
− yI ) j
(20)
[B ]v −1
j
Matrix of multicomponent mass transfer
coefficients on segment j.
[Φ ] [exp[Φ ]− [I ]]
v v −1 Correction factors for finite mass trans-
j
fer fluxes. Elements of the matrix Φ v [ ]
are given by equations (24 & 25)
1 1 i = 1,2....., ( NOC − 1)
Bin = − y bulk ij −
kin , j kic , j i≠n
(22)
Diagonal element
Bij
Off-diagonal element
Bin
1 1 i = 1,2....., ( NOC − 1)
Φ in = − N i , j −
kin , j kiC , j i≠n
(24)
Where:
Diagonal element
Φ ij
Off-diagonal element
Φ in
N i , j = J v i , j + y ave i , j N Tj
(25)
Where:
y bulk i , j + y I i , j
Y ave i , j =
2 (26)
The diffusion flux of any component i is proportional to only its
own concentration gradient. Thus:
Liquid phase
N L i , j = J L i , j + x I i , j N Tj i = 1,2....., ( NOC − 1)
(28)
Where
x I i, j C x I n, j i = 1,2...( NOC − 1)
Bij = +∑
kiC n =1 kin , j (29)
n ≠i
(30)
1 1
Bin = − x I i , j − i = 1,2...( NOC − 1)
k in , j k ic , j i≠n
Where
Diagonal element
Bij
Off-diagonal element
Bin
(32)
Ni, j NOC N n, j i = 1,2...( NOC − 1)
Φij = +∑
k ic , j n =1 k in , j
n≠i
(33)
1 1 i = 1,2...( NOC − 1)
Φ in = − N i , j −
k in , j k ic , j i≠n
Where
Diagonal element
Φij
Off-diagonal element
Φ in
N L i , j = J L i , j + x ave i , j N Tj
Where
x ave i , j x I i , j + x bulk i , j
2
(∂ ln yi ) j
J L i , j = k L ieff 1 + xi
∂xi j
−1
( ) (
(Θieff ) eΘieff − 1 j x I i , j − x bulk i , j )
Where
Θ ieff
Θ ieff (1 + xi
(∂inyi )−1
∂xi (34)
−1
NT ∂ ln Γi
1 + xi
k L ieff ∂xi
(e − 1) (x I i , j − x bulk i , j )
Θieff Θieff
J L i , j = k L ieff φieff e
−1
(35)
k ieff
Effective diffusivity procedure to compute
Vapor phase
For any segment j
v
Vapor phase binary mass transfer coefficient
k ic , j 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
ReL L
apµL
PrL a ρ L2
gρ L2
WeL L2
a pσ ρ L
Liquid Viscosity
µL
Acceleration due to gravity
g
Liquid Density
ρL
Surface tension
σ
L (l L ) 13 (L )
2
k in
gµ L
= 0.0051
aw µ L
3
(Sc ) (a ρ d ρ )
L
in
−1
2 1 0. 4
(38)
Where
ScinL µ L / (ρ L Din )
Liquid Viscosity
µL
k av (Sc )
2
3 = (htc ) ( ρr ) 3
2 (39)
Cρ mix
Schmidt number
Sc
Mixture density
ρ mix
Average diffusivity
Dav
ρr Prandtl number
ρr cρ µ mix / ktmix
mix
Where
P Pressure
Molecular weights
M A, M B
M AB [
2 M1 +
A MB
]
1 −1
T Temperature
C 15.9
H 2.31
O 6.11
N 4.54
F 14.7
Cl 21.0
Br 21.9
I 29.8
φB M B T (41)
o
D AB = 7.4 X 10 −8
µ BV A0.6
T Temperature
Viscosity of solvents B
µ
( )(
o
D A, B = D AB
1+ xB − xi ) / 2
(D )(
o 1+ xi − x j )/ 2
BA
(42)
Reference
1. R. Krishnamurthy, R. Taylor, "A non equilibrium stage model
of multicomponent 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).
3. Fuller, E.N., P.D. Schettler and J.C. Giddings, Ind. Eng. Chem.
Vol 58, No. 5, May 1966 pages 19-27.
4. Fuller, E.N., N.K. Ensley and J. C. Giddings, Journal of Physi-
cal Chemistry, Vol 75, No. 11, Nov 1969, pages 3679-3685.
5. Wilke, C.R. and P. Chang, AIChE J, Vol 1, pg 264, 1955.
6. Reid, Robert C, Prausnitz, John M and Poling, Bruce E., The
Properties of Gases and Liquids, Fourth Edition, McGraw-Hill,
Inc, ISBN 0-07-051799-1.
7. Taylor, Ross and R. Krishna, Multicomponent Mass Transfer,
1993, John Wiley & Sons, ISBN 0-471-57417-1.
8. Krishna, R. and G.L. Standart, AIChE Journal, 22, 1976, pg 383
9. Krishna, R. and G.L. Standart, Chem Eng Comm, 3, 1979, pg
201
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.
(1)
where:
Vload = vapor load capacity
ACFS = actual vapor volumetric flow rate
(2)
where:
∆P = total pressure drop, inches liquid
∆Pdry = dry tray pressure drop, inches liquid
∆Pl = pressure drop through the liquid on the trays, inches liquid
The dry tray pressure drop is obtained from nomographs relating
the pressure drop to the weight of the valves at low vapor flow
rates, and to the square of the vapor velocity at high vapor flow
rates.
For sieve trays, the method of Fair is used to calculate the dry tray
pressure drop, which is given by:
(3)
where:
= discharge coefficient
= superficial vapor velocity
For bubble cap trays, the dry tray pressure drop is calculated by the
method of Bolles:
(4)
where:
=bubble cap slot height
The dry cap coefficient, , in equation (4) is a function of the
ratio of the annular to riser areas.
(5)
where:
L =total liquid flow rate, gpm
= weir length, inches
= weir height, inches
The pressure drop through the liquid on the sieve or bubble cap tray
is given by:
(6)
For sieve trays,
(7)
For bubble cap trays,
(8)
where:
= calculated height of clear liquid over trays (dynamic seal)
= weir height
= static slot seal (weir height minus height of top slot above
plate floor)
= height of crest over weir
= hydraulic gradient across plate
The dimensionless aeration factor, β, in equation (6) is a function of
the superficial gas velocity.
Table 5-8: Random Packing Types, Sizes, and Built-in Packing Factors (ft2/
ft3)
T Random (mm 6. 9.5 12. 15. 19 25. 31. 38 50 76 88
Y Packing ) 3 0.37 7 9 0.7 4 7 .1 .8 .2 .9
P Type (in) 0. 5 0.5 0.6 5 1.0 1.2 1. 2. 3. 3.
E (size 25 25 #25 5 5 0 0 5
) #15 #4 #5 #7
0 0 0
1 IMTPR 51 41 24 18 12
(Metal)
2 Hy-Pak TM 45 29 26 16
(Metal)
3 Super Intalox 60 30
R
Saddles
(Ceram)
4 Super Intalox 40 28 18
Saddles
(Ceram)
5 Pall Rings 95 55 40 26 17
(Plastic)
6 Pall Rings 81 56 40 27 18
(Metal)
7 Intalox 725 1000 580 145 92 52 40 22
Saddles
(Ceramic)
8 Raschig Rings 1600 1000 580 380 255 179 125 93 65 37
(Ceramic)
9 Raschig Rings 700 390 300 170 155 115
(1/32" Metal)
1 Raschig Rings 410 300 220 144 110 83 57 32
0 (1/16" Metal)
1 Berl Saddles 900 240 170 110 65 45
1 (Ceramic)
IMTP and Intalox are registered marks of Norton Company. Hy-Pak is a trademark of Norton
Company.
(9)
where:
= superficial vapor velocity at flood
Fp = packing factor
ϕ = ρw/ρL
ρw = density of water
ρG = density of vapor
ρL = density of liquid
gc = gravitational constant
µL = liquid viscosity
= liquid mass flux
= vapor mass flux
Alternately, the flood point may be supplied by the user.
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:
(10)
where:
(11)
where:
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.
If Norton IMTP packing is used, an alternate method may be used
to compute the HETP values. In this method, more rigorous calcula-
tions are made based on the size of the packing and the total vapor
and total liquid leaving a packed stage. The height of a vapor phase
transfer unit is given by:
(12)
where:
HG = height of vapor phase transfer unit, m
ϕ = packing parameter
= lesser of column diameter or 0.6096 m (2 ft)
zp = height of packed bed, m
ScG = gas phase Schmidt number =
(13)
where:
φ = packing parameter
Cfl = function of Fr
Fr = vG/vGf at constant L/V
vG = superficial vapor velocity, m/s
vGf = superficial vapor velocity at flood, m/s
ScL = liquid phase Schmidt number =
DL = liquid diffusion coefficient, m2/s
The HETP is then computed from:
(14)
where:
λ = ratio of slope of equilibrium line to operating line = mV/L
Packing factors for the various random packing types are given in
Table 5-8.
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 20 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:
(15)
where:
VG = superficial vapor velocity, m/s
ρG = vapor density, kg/m3
ρL = liquid density, kg/m3
Capacity correlations are obtained by plotting the experimental
capacity data on a so-called Souder diagram. On this diagram, the
capacity factor is plotted versus the flow parameter, ϕ, which is
defined as:
(16)
where:
L = liquid flow, kg/s
(17)
where:
VL = superficial liquid velocity, m/s
cL is related to the vapor capacity factor by:
(18)
where:
m and n are constants.
The straight line correlations given in (17) were obtained for two
separate hydraulic regimes:
Low liquid loads, (cL)1/2 < 0.07 (m/s)1/2
High liquid loads, (cL)1/2 > 0.07 (m/s)1/2
The capacity correlations have been shown to predict the column
capacity within an accuracy of 6%.
Pressure Drop
The pressure drop model used in PRO/II for structured packings is a
sum of three separate correlations as shown in Figure 5-6.
(6)
Region I is for columns operating below 50% capacity. In this
region the wetted wall column model is used to obtain a straight-
line relationship between the logarithm of the pressure drop and the
logarithm of the F-factor. At the end of region II (and the beginning
of region III), where the capacity limit is reached, the pressure drop
is obtained from the capacity correlation. Finally, the correlation in
region II is modeled by using a quadratic polynomial to join regions
I and III. At the juncture of regions I and II, the polynomial approx-
imation has the same slope as the wetted wall correlation in region
I. It should be noted that the pressure drop correlations for all Sulzer
packing types were developed without considering the liquid vis-
cosity.
Efficiency
The column efficiency or separation performance for Sulzer pack-
ing is measured by the number of theoretical stages per meter
(NTSM). The NTSM is therefore the inverse of the height equiva-
lent of a theoretical plate (HETP). The NTSM is defined as:
(7)
where:
ShG = Sherwood number of the vapor phase =
DG = diffusion coefficient of the vapor phase
= interfacial area per unit volume of packing, m2/m3
dh = hydraulic diameter of packing, m
kG = vapor phase mass transfer coefficient
The mass transfer in Sulzer packings has been modeled by neglect-
ing the liquid phase mass transfer coefficient, kL. This was done
because the value of the vapor phase mass transfer coefficient, kG,
is most often much less numerically than kL. Experimental data
were used to obtain the following relationship for the Sherwood
number:
(8)
The relationship for the interfacial area is given by:
Reference:
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.:
(10)
where:
y = mole fraction in the vapor phase
x = mole fraction in the liquid phase
subscripts i, j refer to components i and j respectively
superscript N refers to tray N
For small variations in volatility throughout the column, an average
volatility, may be defined. This is taken as the geometric average of
the values for the overhead and bottoms products:
(12)
where:
subscripts B,D refer to the bottoms and distillate respective.
Underwood Method
The values of the relative volatilities of the feed components deter-
mine which components are the light and heavy key components.
The light key component for a feed of equivalent component con-
centrations is usually the most volatile component. For a feed where
some components are found in very small concentrations, the light
key component is the most volatile one found at important concen-
trations. The heavy key component is similarly found to be the least
volatile component, or the least volatile component found at signifi-
cant concentrations.
The relative volatility of each component can therefore be
expressed in terms of the volatility of the heavy key, i.e.,
(13)
where:
J refers to any component, and hk refers to the heavy key compo-
nent
For components lighter that the heavy key, αJ > 1, and for compo-
nents heavier than the heavy key, αJ < 1. for the heavy key compo-
nent itself, αJ = 1.
The Underwood method is used to determine the reflux ratio requir-
ing an infinite number of trays to separate the key components. For
a column with infinite trays, the distillate will exclude all compo-
nents heavier than the heavy key component. Similarly, the bottoms
product will exclude all components lighter than the light key.
Components whose volatilities lie between the heavy and light keys
will distribute between the distillate and bottoms products. An
(14)
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:
(15)
(16)
where:
q = thermal condition of feed
= heat to convert to saturated vapor/heat of vaporization
HG = molar enthalpy of feed as a saturated vapor
HF = molar enthalpy of feed
Hv = molar latent heat of vaporization
xJ,F = mole fraction of component J in feed
φ = a value between the relative volatilities of the light and heavy
keys, i.e., αhk (=1) < φ < αlk
The second equation to be solved is:
(6)
where:
m = number of theoretical stages above the feed tray
p = number of theoretical stages below the feed tray
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 5-8 shows
Distillation Models
There are two shortcut distillation models available in PRO/II, as
shown in Figure 5-9. 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
series of one feed, two product columns, starting with the bottom
section. In this model, there is no reflux between the sections.
Simple Columns
Simple columns are defined a columns in which a single feed loca-
tion may be defined, located somewhere between the reboiler and
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
define rates for all products (either directly or indirectly). For illus-
tration, consider the following example shown in Figure 5-10:
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 cal-
culation 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.
* Standard cuts
Reference
Basic Algorithm
Figure 5-13 shows a schematic of an equilibrium stage with a
lighter liquid (denoted as liquid-1) and a heavier liquid (liquid-2) in
equilibrium.
(6)
(7)
(8)
(9)
(10)
where:
Fi =total feed flow to tray i
=total liquid-1 flow from tray i
=total liquid-2 flow from tray i
Qi =heat added to tray i
Ti =temperatures of tray i
=natural log of the liquid-1 mole fractions
=natural log of the liquid-2 mole fractions
Ki,j =liquid-liquid equilibrium constant for component j, on tray i
NC =number of components
NT =number of trays
subscripts:
For highly non-linear systems which may oscillate, the user can
restrict the step size by specifying a damping factor which reduces
the changes in the composition variables. A cutoff value is used by
the algorithm so that when the value of the sum of the errors drops
below the given level, the full Newton correction is used. This
serves to speed the final convergence.
Reference
(1)
where:
δq = heat transferred in elemental length of exchanger dz
Uo = overall heat transfer coefficient
∆T = overall bulk temperature difference between the two
streams
δA = element of surface area in exchanger length dz
Once an appropriate mean heat-transfer coefficient, and tempera-
ture difference is defined, equation (1) may be re-written for the
entire exchanger as follows:
(2)
where:
Q = total exchanger heat duty
Uom = overall mean heat-transfer coefficient
Ao = total exchanger area
∆Tm = mean temperature difference
(7)
For cocurrent flows,
(9)
where:
h = sensible heat transfer coefficient
H = enthalpy of utility stream
Zones Analysis
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 (3) and (4) in the previ-
ous section - Simple Heat Exchangers). Optionally, PRO/II can
compute a duty-averaged LMTD. This option becomes increasingly
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 characteristics of the stream
changing phase. Zone analysis may therefore be extremely useful
for locating internal temperature pinches.
(1)
For a total of n zones, LMTDzones is calculated from the individual
zones values as a weighted LMTD:
(2)
where:
Q = total exchanger duty
Qi = heat duty in zone i
LMTDi = logarithmic mean temperature difference for zone i
The LMTD values for the individual zones are computed using the
temperatures of the streams entering and leaving each zone.
For countercurrent flows in zone i,
(3)
For cocurrent flows in zone i,
Example
An example of a zones analysis of a countercurrent heat exchanger
is given next, and shown in Figure 6-2.
Reference
Bowman, R. A., Mueller, and Nagle, 1940, Trans. ASME, 62, 283.
Shellside
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:
0.8
0.037 N Re G N Pr
N Nu (tur ) =
− 0. 1
2
1 + 2.443 N Re G Pr − 1
N 3 (1)
(2)
(3)
(4)
where:
where:
h = average shellside heat transfer coefficient
hideal = shellside heat transfer coefficient for an ideal tube bank
Jc = correction factor for baffle cut and spacing
Jl = correction factor for baffle-leakage effects
Jb = correction factor for bundle bypass flow effects
Js = correction factor for inlet and outlet baffle spacing
Jr = correction factor for adverse temperature-gradient build-up
Tubeside
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 tubeside heat transfer coef-
ficient is obtained from the Sieder-Tate equation:
(6)
where:
µw = fluid viscosity at the wall temperature
The above relationship holds for the following flow regimes:
(7)
where:
NNu = Nusselt number
NRe = Reynolds number =
NPr = Prandlt number
L = tube length
D = effective tube diameter
W = total mass flow rate in tubeside
At = cross sectional tube area
(8)
For NGz < 100, a relationship first developed by Hausen is used:
(9)
For NGz > 100, the Sieder-Tate relationship is used:
(10)
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:
(11)
where:
htrans = heat transfer film coefficient for the transition regime
hturb = heat transfer film coefficient for the turbulent flow regime
hlam = heat transfer film coefficient for the laminar flow regime
The user may also supply the film coefficients directly.
(12)
For NRe > 100,
2
W ( 2 + 0.6N cw )
∆P wi = ---------------------------------------
-
2g c S m S w ρ
(13)
The pressure drop for an ideal crossflow section is then calculated:
(14)
where:
∆Pwi= pressure drop for an ideal window section
∆Pbi= pressure drop for an ideal crossflow section
µb= viscosity of shell side stream at fluid temperature
µw= viscosity of shell side stream at wall temperature
W=shell side stream flow rate
lb=central baffle spacing
(15)
where:
∆Ps = actual shellside pressure drop
Nb = number of segmental baffles
Rb = bundle bypass flow correction factor
Rl = baffle leakage effects correction factor
Rs = correction factor for unequal baffle spacing effects
The stream analysis method, proposed in 1984 by Willis and
Johnson, is an iterative, analytical method. At each iteration the
crossflow resistance, Rc, the window flow resistance, Rw, the tube
to baffle resistance, Rt-b, the shell to baffle resistance, Rs-b, the
leakage resistance, Rl, the flowrate through the windowed area,
Ww, the crossflow pressure drop, ∆Pc, the window pressure drop,
∆Pw, and the crossflow fraction, Fc are calculated as follows:
(17)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
where:
Sc = crossflow area
Dc = crossflow equivalent diameter
Iterations are stopped once the value of Fc meets the following cri-
terion:
The shellside end space pressure drops at the inlet and outlet of the
exchanger, ∆Ps,in, and ∆Ps,out, and the actual shellside pressure
drop, ∆Pss, are then calculated using the equations:
(26)
(27)
(28)
(29)
(30)
where:
∆Ps,in = mean shellside end space pressure drop at
exchanger inlet
∆Ps,out = mean shellside end space pressure drop at
exchanger outlet
Rs,in = end space resistance at exchanger inlet
Rs,out = end space resistance at exchanger outlet
¯¯¯¯¯= denotes an average
Tubeside
The tubeside pressure drop may be determined by one of two meth-
ods; BBM (Beggs-Brill-Moody) method (newly added), or HEX5
method (existing method).The BBM method is the default method
used by PRO/II. Please refer Section "Pipes" for further details of
BBM.
HEX5 method is supported for the backward compatibility and the
following equations used in the HEX5 method.
(31)
(32)
(33)
where:
∆Pt = pressure drop in tubes
∆Pr = pressure drop in return tubes
∆Pts = total pressure drop in the tubeside
µc = fluid viscosity factor
F = friction factor
Gt = mass flux
L = tube length
n = number of tube passes
Di = tube inner diameter
Sp = specific gravity of fluid
The friction factor, F, and viscosity factor, µc are computed using
different correlations for each flow regime:
For turbulent flows, NRe > 2800,
(34)
(35)
(36)
For transition flow regimes, 2100 < NRe < 2800, F and c are
obtained by interpolation between the laminar and turbulent values:
(37)
(38)
Bundle weight
AS = AT ⁄ NS ⁄ NP
(39)
0.537
A = [ ( ( 12 L ) ⁄ ( Di ) ) + 2.5 ]
(42)
1.611
B = ( Di )
2
V S = ΠL ( ( Di ) ⁄ 2 ) ⁄ 144.0
(47)
For kettle reboilers, the shell weight with water is calculated assum-
ing that the tube bundle diameter is 60 percent of the shell diameter.
The Volume of shell (VS) is calculated as follows:
(48)
2
Y 1 = 0.5 C 1 [ ( Di ) ⁄ 2 ]
(49)
3
Y 2 = 0.192 [ ( Di ) ⁄ 2 ]
(50)
2
Y 3 = Π [ ( Di ) ⁄ 2 ] – Y 1 + Y 2
(51)
V S = L ( ( Y 3 ) ⁄ 144.0 )
(52)
2 2
V T = ( ΠLN [ d o – d i ] ) ⁄ ( 4 × 144.0 )
(53)
WW = DW ( VS – VT )
(54)
W SW = W B + W S + W W
(55)
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 tubeside and shell-
side, the user may input separate factors to account for thermal and
pressure drop resistances due to exchanger fouling. Thermal fouling
resistances cannot be calculated analytically. Tables for thermal
heat transfer coefficients (the inverse of thermal resistances) for a
number of common industrial applications may be obtained from
standard references on heat exchangers such as Perry's handbook,
or the book by Kern.
Reference
Calculation Methods
The LNG exchanger is divided into hot or cold "cells" representing
the individual cross-flow elements. Cold cells represent areas where
streams are cooled, while hot cells represent areas where streams
are heated. The following assumptions apply to the LNG heat
exchanger:
■ Each LNG exchanger must have at least one hot and one cold
cell.
■ The exchanger configuration is ignored.
■ At least one cell does not have a product specification and all
unspecified cells leave at the same temperature.
(1)
where:
Note: The last three specifications listed above (outlet phase, tempera-
ture 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
N R N EU FR ρWF2
∆pS =
1.2 × 1011
(1)
F2
µ
N EU = N EUI W
µ
(2)
N EUI = N EUK AK 1
(3)
(4)
WF DOT
N Re =
12 µ K
(5)
W
WF =
ρZXC
(6)
π
C = 1 −
4 p t / DOT
(7)
DOT = DO + 2t f 1
(8)
if N Re > 2 .9 and N Re ≤ 2 × 10 3
3
0 .102 × 10 3 − 0 .286 × 10
N Re
3
0 .207 × 10 +
N Re
E1 = 0 .272 +
N Re
(9)
(10)
(11)
(12)
A2 = 1.007 F30.655
(14)
A3 = 1.004 F30.539
(15)
0.297 − 0.0265
F
A4 = 1.218 − 3
F3
(16)
(17)
NR
1 2 3 4 5 6 7 8 9 10
FR1 3.3405 2.4903 2.0068 1.7551 1.6041 1.5034 1.4315 1.3775 1.3356 1.3021
FR2 1.2497 1.1897 1.1397 1.1048 1.0838 1.0698 1.0598 1.0524 1.0466 1.0419
FR3a 1.895 1.1575 1.02 1.025 1.02 1.0167 1.0143 1.0125 1.0111 1.01
FR4a 2.6543 1.8216 1.5325 1.1480 0.9139 0.3704 0.4603 0.5278 0.5803 0.6222
(18)
(19)
(21)
(23)
(24)
pt
F3 =
pl
(27)
A1 = 0 . 93 F 30 . 48 if F 3 > 1 .6
= F 3− 0 . 048 if F 3 ≤ 1 .6
(28)
(29)
0.113
− 0.708 + 0.55 −
F3
A3 = 1.28 + if F3 > 1.6
F3
= 2.016 + F3 (−1.675 + F3 (0.948 + F3 (−0.234 + 0.021F3 ))) if F3 ≤ 1.6
(30)
(31)
NR
1 2 3 4 5 6 7 8 9 10
FR1 0.8089 0.8841 0.9227 0.9421 0.9536 0.9614 0.9669 0.9710 0.9742 0.9768
FR2 0.2595 0.4946 0.6562 0.7422 0.7937 0.8281 0.8527 0.8711 0.8854 0.8969
FR3 0.450 0.6701 0.780 0.8351 0.8680 0.890 0.9057 0.9175 0.9267 0.9340
FR4 1.1593 1.1044 1.0696 1.0522 1.0418 1.0348 1.0298 1.0261 1.0232 1.0209
FR5 1.50 1.335 1.230 1.1725 1.1380 1.115 1.0986 1.0863 1.0767 1.069
(33)
B1 = 1.25
(34)
B2 = 1.5
(35)
B3 = 2.0
(36)
E1′ = E1
(37)
E 2′ = E 2
(38)
E3′ = E3
(39)
(40)
Inline arrangement
B1 = 1. 5
(41)
B2 = 2.0
(42)
B3 = 2.5
(43)
E1′ = E 2
(44)
E 2′ = E3
(45)
(46)
N EUK = E3′ if p tc ≥ B3
( E3′ − E 2′ )( p tc − E 2′ )
= E3′ + if p tc > B2 and p tc < B3
( E3′ − E 2′ )
( E 2′ − E1′ )( p tc − E1′ )
= E3′ + if p tc > B1 and p tc ≤ B2
( E 2′ − E1′ )
= E1′ if p tc ≤ B1
(47)
2) Finned tubes
∆ps = ∆ps′ K1
(48)
K f G s2 YC 1 C 2
∆ p s′ =
5 . 22 × 10 10 sD v
(49)
0.075
K 1 = 0.42 N Re 1 Inline arrangemen t
= 1 .0 Staggered arrangemen t
(50)
0 .00806
Kf = 0 .1321
N Re 1
(51)
W
Gs =
AF
(52)
(53)
0 .6
Yl
C2 =
pt
(54)
4 ( XYZ − N T T L T V )
Dv =
ABX
(55)
ABX = TL N T DO F
(56)
πD ′ 2 ′ + 2 H F ) 2 − DOT
π (( DOT 2
)TF N F
OT
+
4.0 4 .0
TV =
144 . 0
(57)
ρ
s =
62.5
(58)
WF DV
N Re 1 =
µK
(59)
W
WF =
ρAF
(60)
′
N T TL ( D OT + 2 N F H F TF )
AF = XZ −
12 N R
(61)
(62)
Where
H air = H C + H R AT + H W AW AT
(64)
Calculation of HC
1) Bare tubes:
12 N Nu(cal) K air
HC =
DOT
(67)
N Nu(cal) = N Nu(row) F1 F2
(68)
2 2
NNu(row) = 0.3 + (NNu(lam) )0.5
+ NNu(tur)
(69)
0.5 0.33
N Nu(lam) = 0.664 N Re N Pr
(70)
0 .8
0 .037 N Re N Pr
N Nu(tur) = − 0 .1 0 .667
1 + 2 .443 N Re ( N Pr − 1)
(71)
W F D OT
N Re =
12 µ k
(72)
(73)
π
C = 1 −
4 pt / DOT
(74)
DOT = Do + 2tfl
(75)
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)
(76)
1 + ( N R − 1) F3
F2 =
NR
(77)
0.667
F3 = 1 + Staggered arrangemen t
pl′
p′
0.7 l − 0.3
= 1 + p ′t Inline arrangement
2
1 .5 p′
C l + 0.7
′
pt
(78)
pl
p l′ =
D OT
(79)
(80)
2Y ( X + Z )
AW =
π N T D O TL
(81)
AT = 1.0
(82)
2) Finned tubes:
12 N Nu(cal) K air
HC =
′
DOT
(83)
N Nu(cal) = N Nu(row) F2
(84)
( N R − 1)
F 2= 0 .5 +
NR
(86)
(87)
pt
p ′t =
′
D OT
(88)
′
D OT = D OR + 2t fl
(89)
W F D OT
N Re =
12 µ k
(90)
W
WF =
ρ AF
(91)
′
N T TL ( D OT + 2 N F H F TF )
AF = XZ −
12 N R
(92)
A1
FF =
A2
(93)
A1 = A3 + A 4
(94)
A2 = 0 . 2618 D o
(95)
A5 = N FTF
(96)
π {DOR (1 − A5 ) + ( DOR + 2 H F ) A5 }
A3 =
12
(97)
(98)
2Y ( X + Z )
AW =
πN T D OR TL
(99)
D OR
AT =
Di FF′
(100)
A1
FF′ =
A6
(101)
A6 = 0 .2618 D i
(102)
Where:
(1)
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.
7-2 Reactors
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 (1).
The heat balance will be printed in the reactor summary if the
PRINT PATH statement is input.
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:
(2)
where:
Hf = heat of formation of each component at 25 C
Heat of formation data are available in the component databank for
library components and can be estimated for petroleum components
using internal correlations. For NONLIBRARY components this
data must be furnished.
Conversion Reactor
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
by the corresponding stoichiometric ratios. Conversions may be
specified as a function of temperature, as follows:
(1)
(2)
7-4 Reactors
but both the methanation and shift reactions take place simulta-
neously.
(3)
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.
A single reaction is considered for the stoichiometric and simulta-
neous equilibria of two reactions are computed for the methanator
model.
For chemical equilibrium calculations in PRO/II, ideal behavior is
assumed for reaction in either the liquid or vapor phase.
For a reaction,
(1)
The equilibrium constant is:
for vapor phase:
(2)
for liquid phase:
(3)
Note: Keq is dimensionless for liquid phase reactions and has the
dimension of (pressure unit) with = c + d - a - b for vapor phase reac-
tions.
(4)
where:
Keq = reaction equilibrium constant
A-H = Arrhenius coefficients
T = absolute temperature
When no approach data are given, all reactions go to equilibrium by
default. The approach to equilibrium can be given either on a frac-
tional conversion basis or by a temperature approach. The conver-
sion itself can be specified as a function of temperature.
When the temperature approach is given, Keq is computed at T,
where:
T = Treaction - T(endothermic reactions)
T = Treaction + T(exothermic reactions)
Based on the value of Keq, conversion of base component and
product compositions can be calculated.
If the approach to equilibrium is specified on a fractional conver-
sion basis, the conversion of the base component B, is given by:
(5)
where:
7-6 Reactors
BR = moles of component B in the product
BF = moles of component B in the feed
BE = moles of component B at equilibrium
= specified approach to equilibrium
=
The coefficients C0, C1, and C2 may appear in any combination,
and missing values default to zero. For a fixed approach, C1 and C2
are zero. When no approach data are given, reactions attain equilib-
rium, and C0=1.0, C1=0.0, and C2=0.0.
The equilibrium reactor can also be used with specialized reactor
models for shift and methanation reactions.
(6)
Just as in the Stoichiometric Reactor, the desired conversion is
determined from an equilibrium model for the shift reaction. PRO/
II has incorporated the National Bureau of Standards data for equi-
librium constants. This can be represented by:
(7)
where:
A and B are functions of temperature
T = absolute temperature, R
and
(8)
where:
p = partial pressure in any units
(9)
Just as for the shift reaction, the National Bureau of Standards data
are available for methanation reaction. The methanation equilib-
rium is given by:
(10)
where:
p = partial pressure in psia
7-8 Reactors
5 If the calculated and assumed temperatures do not agree,
repeat the calculations with the new temperature.Only one
approach to equilibrium, i.e., either a temperature approach
or a fractional conversion approach, is allowed.
Gibbs Reactor
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
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 sto-
ichiometry from the user except when the reaction extent or a tem-
perature approach is to be specified for the individual reaction.
(1)
where:
NS = number of solid components
NP = number of fluid phases
NC = number of fluid components
(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 (3)).
The standard state Gibbs free energy is defined as at reactor temper-
ature, 1 atm, and ideal gas state for all fluid components, and at
reactor temperature, 1 atm, and solid state for all solid components
(3)
where:
NR = number of reactions
Gj = change of Gibbs free energy of formation at modified temper-
ature T'
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 flowrate has to be equal to the feed flowrate, i.e.:
(4)
where:
7-10 Reactors
bk = feed quantity of element group k
NE = number of element groups
mjk = number of element group k contained in component j
If the product rate of a component is fixed, either by the constraint
of fixed product rate or by the fixed percentage of feed amount
reacted, the additional mass balance constraint can be written as:
(5)
(6)
where:
dj = specified or derived fixed product rate
NSFIX = number of solid components with fixed product rate
NCFIX = number of fluid components with fixed product rate
If a reaction has a specified reaction extent, the additional mass bal-
ance contraint is:
(7)
where:
r = fixed reaction extent arj = matrix element derived from the
inverse of stoichiometric coefficient matrix
From equations (1), (4), (5), and (6), the overall objective function
for the minimization of Gibbs free energy can be expressed as equa-
tion (7):
j=1,..., NS (9)
k=1,..., NE
r=1,..., NR
j=1,..., NSFIX
j=1,..., NCFIX
Note that since these are the necessary, but not the sufficient, condi-
tions for Gibbs free energy minimization, a local minimum Gibbs
7-12 Reactors
free energy can be obtained. Multiple solutions may be found when
multiple fluid phases coexist in the mixture. Providing different
initial 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.
(10)
where:
n = the solution point from previous iteration
N' = the new solution point from equation (8)
= step size parameter
The parameter is adjusted to ensure the new solution point, N' will
further minimize Gibbs free energy. A Fibonacci search procedure
is applied when is close to zero. When a Fibonacci search is per-
formed, the thermophysical properties of the reactor mixture can be
either based on the same properties from the final result of the pre-
vious iteration or updated at each searching step of a new .
The convergence criterion is based on the relative or absolute
change of Gibbs free energy and the relative change of component
product rate between two consecutive iterations:
(11)
or
(12)
and
(13)
and
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
7-14 Reactors
Continuous Stirred Tank Reactor (CSTR)
The Continuous flow Stirred Tank Reactor (CSTR) is a commonly
used model for many industrial reactors. The CSTR assumes that
the feed is instantaneously mixed as it enters the reactor vessel.
Heating and cooling duty may be supplied at user's discretion. A
schematic of a CSTR is given in Figure 7-2
Design Principles
The steady-state conservation equations for an ideal CSTR with M
independent chemical reactions and N components (species) can be
derived as:
Mass balance:
(1)
(2)
where:
Cj = exit concentration of jth component
Fj = mole rate of component j in product
Fjf = mole rate of component j in feed
P = reactor pressure
αij = stoichiometric coefficient of jth species for ith reaction
V = volume of the reacting phase
= rate of ith reaction
H(T) = molar enthalpy of product
H(Tf) = molar enthalpy of feed
Tf = feed temperature
T = reactor temperature
∆Hi = molar heat of reaction for the ith reaction
Q* = heat removed from the reactor
In PRO/II, only power law models for kinetics are provided. How-
ever, any kinetic model can be introduced through the user-added
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:
(3)
where:
Ai = Arrhenius frequency factor
Ei = activation energy, energy/mol
7-16 Reactors
R = gas constant
T = temperature
α = temperature exponent
Cj = concentration of jth species
N = total number of reacting components
γj = exponents of concentration
= reaction rate for reaction i.
For multiple, simultaneous reactions, the overall reaction rate for
each reacting component is:
(4)
where:
7-18 Reactors
In the PRO/II CSTR unit operation, either solution is possible and
there is no built-in logic to ascertain that the correct solution is
found. The final solution can be influenced by the addition of an
initial estimate on the OPERATIONS statement. Generally, the
CSTR will find the high temperature solution if the initial estimate
is above the ignition temperature and the low temperature solution
for initial estimates below the ignition temperature.
For some exothermic reactions and for all endothermic reactions
there may be only one intersection between the heat generation and
heat removal curves, indicating only one steady state. PRO/II
readily finds this solution.
Total = 2N + 3
Reaction rate, equation (3)
Energy balance, equation (2)
The degrees of freedom or the number of variables to be fixed is 2.
The rest of the variables or unknowns are then calculated by solving
the model equations. Since the pressure P is fixed by the CSTR
input, the user can choose to fix one of the other variables T, Q, or
V. This leads us to the discussion on the possible operational modes
of the CSTR.
Design Principles
The steady state mass and energy balance for the one-dimensional
PFR for M simultaneous reactions can be derived as follows:
Mass balance:
(1)
7-20 Reactors
Energy balance:
(2)
where:
G = mass flow per unit area through the reactor
ξ = extent of reaction per unit mass
= rate or reaction for the ith reaction
= total reaction rate of whole system
z = axial distance from the inlet of the reactor
T = temperature at a distance z from the inlet
(3)
Q* = heat transferred to or from the reactor per unit area
P = pressure
J = heat transfer ratio,
(4)
(5)
or
(6)
where:
7-22 Reactors
■ countercurrent flow (the outlet temperature of the cooling
stream is required).
The thermal mode of operation is the default.
There are two methods of numerical integration available in PRO/
II. The Runge-Kutta method is the default method, and is preferred
in most cases. When sharply varying gradients are expected within
the reactor, the Gear method, which has a variable integration step
size, may be preferred.
For exothermic reactions, two valid solutions (the low conversion
and the high conversion) are possible. The plug flow reactor model
in PRO/II is not equipped to find the hot spot or ignition tempera-
ture. The user can manipulate the exit cooling temperature for coun-
tercurrent reactors or stream product temperature for autothermal
reactors to get either the low conversion or the high conversion
solution.
Reference
Smith, J.M., 1970, 2nd Ed., Chemical Engineering Kinetics,
McGraw-Hill, NY.
Available Methods
A.Packed bed model of plug flow reactor
The pressure drop through packed beds will be calculated using the
ERGUN equation. User supplied data includes the particle size,
shape factor (alternately supplied by designating the packing as
spherical or cylindrical) and void fraction. These parameters will
be made available to the Procedure section.
150(1 − Φ )µ
)( )
(
DP / DL = G / lg c D p (1 − Φ ) / Φ 3
Dp
+ 1.75G
(8)
where:
P = pressure, lb/ft2
(10)
vo To 1 P
ρ = ρ o = ρ o
v T 1 + εA Po
From equation 1 and 3 we have
7-24 Reactors
(11)
dP − G 1 − Φ 150(1 − Φ)µ PT
= 3 + 1.75G o (1 + ε A X A )
dL ρ o g c D p Φ Dp To P
Where ,
ε A = Fractional change in volume of the system between no con-
version to Complete conversion.
xA = Fractional conversion of A
Equation 11 can be used to calculate pressure along the length of
the reactor using the Runga-Kutta , Gear or LSoda integration
methods.
Dryer
General Information
PRO/II has the capability of simulating a simple continuous solids
dryer in which the drying gas and solid streams flow countercurrent
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:
Calculation Methods
As a solid-liquid mixture is filtered, a layer of solid material, known
as the filter cake, builds up on the filter surface. Vacuum filtration is
used to drain liquid through the filter cake. An important character-
istic of the filter cake is its permeability. The permeability is
defined as the proportionality constant in the flow equation for lam-
inar flow due to gravity through the bed. The permeability is a func-
tion of the characteristics of the cake, such as the sphericity and size
of the cake particles and the average porosity of the cake, and is
given by:
(1)
where:
K = permeability of filter cake
gc = acceleration due to gravity
dp = diameter of cake particle
ε = average porosity of filter cake
A,B are constants
(2)
(3)
The pressure drop across the filter cake is then given by:
(4)
where:
L = liquid volumetric flowrate through the cake
µL = liquid viscosity
S = rate of dry solids in the feed
kc = cake resistance
θ = angle of filtration
D = diameter of filter drum
W = width of filter drum
ϖ = drum rotational speed in rad/s =
RPM = rotational speed of drum in revolutions/min
Atot = total filter area =
The actual pressure drop across the drum filter is then given by:
(6)
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:
(7)
where:
ρL = liquid density
The residual cake saturation, s0 is calculated based on the value of
the capillary number:
For 0.002 < Nc < 0.03,
(8)
For Nc > 0.03,
(9)
For Nc < 0.002,
(11)
(12)
where:
(13)
For design calculations, an iterative method solution method is
used, in combination with the equations given above, to calculate
the filter diameter and width required to produce a specified pres-
sure drop.
Reference
Filtering Centrifuge
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 8-1.
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:
(1)
where:
(2)
where:
= mass of solids remaining in the basket
= radius of inner surface of filter cake
h = height of basket
= solid density
= average filter cake porosity
The thickness of the filter cake is given by:
(3)
The surface area of the filter basket, and the log-mean and arith-
metic mean area of the filter cake are given by:
(4)
where:
= log-mean surface area of filter cake
(5)
where:
K = permeability of filter cake
= diameter of cake particle
A,B are constants
(6)
For φ < 1.5,
(7)
The residual cake saturation, a result of small amounts of liquid
held between the cake particles by surface tension forces, is a func-
tion of a dimensionless group known as the capillary number, Nc.
The capillary number is given by:
(8)
(9)
For Nc > 0.03,
(10)
For Nc < 0.002,
(11)
The cake drain number and height are calculated from the cake per-
meability, centrifugal force, and the liquid density and surface ten-
sion:
(12)
The average cake saturation is then given by:
(13)
where:
= average filter cake saturation
The corresponding moisture content of the filter cake, Xcake, is cal-
culated using:
(15)
where:
= rate of filtrate
= total mass rate of feed to centrifuge
= weight fraction of liquid in feed
= weight fraction of solid in feed
= total mass rate of inert components in feed
For design calculations, an iterative method solution method is
used, in combination with the equations given above, to calculate
the filter diameter required to produce a specified filtrate flow.
Reference
Countercurrent Decanter
General Information
Mixtures of solids and liquids may be separated by countercurrent
decantation (CCD). This unit operation consists of several settling
tanks in series. If the purpose of the CCD unit is to obtain a thick-
ened underflow, then the tank is referred to as a thickener. The
solid-liquid mixture is flowed countercurrently to a dilute liquid
wash stream. In each tank, the solids from the slurry feed settles
under gravity to the bottom of the tank. The clarified overflow is
transferred to the previous tank to be used as the wash liquid, while
the underflow from the tank is transferred to the next tank in the
Calculation Methods
A typical stage of the countercurrent decantation system is shown in
Figure 8-1.
Component Balance:
(2)
where:
= composition of underflow from a stage
= composition of overflow from a stage
The mixing efficiency for each stage, EN, is given by:
(3)
The mixing efficiency is generally a function of temperature and
composition. However, in PRO/II, it is assumed that the mixing
efficiency is constant for each stage. This assumption, along with
the fixing of the ratio of the overflow solids concentration to the
underflow solids concentration, decouples the solution of equations
(1-4), and enables the equations to be solved simultaneously. Equa-
tions (1-4) may be re-written as:
(4)
(5)
(6)
where:
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
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.
(18)
The remaining overflow rates are then calculated from the last stage
backwards to the first stage using equation (2).
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 triagonal equations (5-7) avoids matrix inversion, buildup of
truncation errors, and avoids negative values of xi,N being pro-
duced. The triagonal equations can be reduced to:
(19)
where:
(20)
(21)
(23)
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.,
(24)
The compositions on other stages are then obtained by backward
substitution:
(25)
For the design mode calculations, the number of stages is not given,
but a recovery specification is made on either the overhead or
underflow product. In this case, PRO/II will begin the calculations
described above by assuming a minimum number of stages present.
If the design specification is not met, the number of stages will be
increased, and the design equations re-solved until the specification
is met.
Reference
Scandrett, H.E., Equations for Calculating Recovery of Soluble Values
in a Countercurrent Decantation Washing System, 1962, Extractive Metal-
lurgy of Aluminum, 1, 83
Dissolver
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.
(1)
where:
ρp = density of solid particle, kg/m3
Vp = volume of particle, m3
Ap = surface area of particle, m2
kL = liquid phase mass transfer coefficient, kg/m2-sec
ρL = liquid density, kg/m3
S = solubility, kg solute/kg liquid
C = liquid phase concentration of solute, kg/m3
t = time, sec
As , equation (1) becomes:
(2)
(3)
where:
r = radius of solid particle, m and
(4)
Equation (4) describes the mass transfer rate per unit area as depen-
dent on two factors; the mass transfer coefficient and concentration
difference. The mass transfer coefficient is the liquid phase coeffi-
cient, since diffusion of the solute from the particle surface through
the liquid film to the bulk of the liquid solution is the dominant or
rate-controlling step. The concentration difference is the difference
(5)
represents the change in particle size due to the dissolution process.
The following simplifying assumptions are used in the development
of the dissolver model:
■ The solid particles are spherical in shape.
■ There is no settling, breakage, or agglomeration of solid parti-
cles.
■ The liquid in the dissolver follows a continuous stirred tank
type flow, whereas the solid particles are in plug flow. As a
result, the temperature and liquid phase concentration in the
dissolver are uniform, and all the solid particles have the same
residence time.
■ The dissolution of a single solid component only is modeled,
and the presence of "inert" components has no effect on the dis-
solution process.
(9)
(10)
where:
(11)
where:
a,b are mass transfer coefficient parameters
dcut = solid particle cut-off diameter, m
When the mass transfer coefficient is a function of particle size,
equation (4) can be integrated as:
(12)
using numerical quadrature.
Note: Both r (radius) and dp (diameter) are used for particle size here,
but interconversion between r and dp is done in the program.
(14)
Overall,
(15)
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,
(16)
solvent,
(18)
where:
solute refers to the solute component
solvent refers to the solvent component
i refers to the inert component
(19)
(20)
where:
= mass rate of solute component in feed liquid, kg/sec
PF = mass rate of solid in feed, kg/sec
(21)
where:
MWsolute = molecular weight of solute component kg/kgmol
MWvapor = molecular weight of overhead product, kg/kgmol
E = mass rate of overhead product, kg/sec
Y = mole fraction in overhead product
(22)
Solid-liquid Equilibrium,
(23)
Vapor-liquid Equilibrium,
(24)
Residence Time,
(25)
where:
τ = residence time in the dissolver, sec
Concentration,
(26)
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.
Reference
Crystallizer
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 nonequilibrium considerations.Solid-liquid equilibrium is
defined in terms of solubility, which is the equilibrium composition
of the solute in a liquid solution containing the solvent component.
Solubility is a function of temperature, and is calculated from either
the van't Hoff equation or user-supplied solubility data. The solubil-
ity 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 concen-
tration exceeds the equilibrium solubility at the crystallizer temper-
ature. Supersaturation is generally created by cooling the liquid
and/or evaporation of the solvent. Additionally, for crystallization
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
force for both nucleation and crystal growth is the degree of super-
saturation. In addition, nucleation is also influenced by mechanical
disturbances such as agitation, and the concentrations and growth of
solids in the slurry. These rate relationships are normally expressed
as power law expressions, which are similar to equations for power
law kinetics used for chemical reactions. The constants in the two
rate equations are the nucleation rate constant and growth rate con-
stant.
The heat effect associated with the crystallization process is
obtained from the input value of the heat of fusion of the solute
component. This, along with the enthalpies of the feed and product
streams, will determine the heating/cooling duty required for the
crystallizer. This duty is generally provided by an external heat
exchanger across which a ∆T is maintained. The feed consisting of
the fresh feed and recycled product slurry is circulated through the
(1)
where:
G = growth rate of crystals, m/sec
kG = growth rate constant, m/sec
S = supersaturation ratio
Nucleation Rate:
(2)
where:
Bo = crystal nucleation rate, number/sec.m3
kB = nucleation rate constant
= magma density, i.e., concentration of crystals in slurry, kg
crystals/m3 slurry
RPM = impeller speed, revolutions/min
BEXP1, BEXP2, BEXP3, BEXP4 = exponents
(3)
where:
no = nucleii number density, number/m/m3 slurry
ε = liquid volume fraction in slurry, m3 liquid/m3 slurry
(9)
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
Residence time is defined as:
(10)
(11)
Using the initial condition: n(ro) = no at ro = 0,
(12)
(13)
For any k, the generalized expression is:
(14)
For feed containing no solids, equation (9) simplifies to:
(15)
The magma density, MT (the weight concentration of crystals in
slurry) is calculated from the third moment of the particle size dis-
tribution,
(16)
where:
ρc = density of crystals, kg crystal/m3 crystal
(17)
Overall,
(18)
where:
F = feed rate, kg/sec
E = overhead product rate, kg/sec
B = bottom product rate, kg/sec
Component,
(19)
(20)
(21)
where:
subscripts solute, solvent, and i refer to the solute, solvent and inert
components respectively
(22)
(23)
where:
(24)
where:
Ysolute = vapor phase mole fraction of solute
MWvapor = molecular weight of overhead product, kg/kgmol
MWsolute = molecular weight of solute, kg/kgmol
(25)
Solid-liquid Equilibrium,
(26)
where:
= equilibrium mole fraction of solute in crystallizer liquid
at crystallizer temperature
Vapor-liquid Equilibrium,
(27)
where:
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-
tions, along with material balances. The algorithm used is shown in
Figure 8-5.
Reference
Treybal, R.E., 1980, Mass Transfer Operations, 3rd Ed., McGraw
Hill, N.Y.
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.
The calculation scheme for this unit operation is shown in Figure 8-
6.
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 simulta-
neously. 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.
Note: The XPROD splitting factors specify only the relative composi-
tion of components in the synthesized product. This means they do not
and cannot be used as a basis for calculating the rate of the synthe-
sized product; some splitting factor that establishes 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.
Phase Envelope
General Information
The PHASE ENVELOPE module generates a phase envelope or
constant liquid fraction curve (in tablular or plot form) for streams
using the Soave-Redlich-Kwong or Peng-Robinson equation of
state methods.
Reference
Michelsen, M.L., 1980, Calculations of Phase Envelopes and Criti-
cal Points for Multicomponent Mixtures, Fluid Phase Equil., 4, pp.
1-10.
The Phase Envelope calculations are always performed after the
flowsheet 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.
10-2 Utilities
Heating / Cooling Curves
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-
10-4 Utilities
Figure 10-2: Phenomenon of Retrograde Condensation
10-6 Utilities
Table 10-1: GAMMA and KPRINT
Report Information
Component name X
Component gamma (activity coefficient) X
Component vapor pressure X
Pure component fugacity coefficient X
Component Poynting correction X
Component vapor fugacity coefficient X
Availability of Results
Heating/Cooling units always perform their calculations during the
output pass of the flowsheet 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
flowsheet. 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 flowsheet calculations,
■ HCURVE data are not accessible through the SPECIFICA-
TION feature
■ HCURVE data cannot be used to affect flowsheet 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-
cations (see the PRO/II Data Transfer System User's Guide). Also,
a small subset of the HCURVE data is included in the export file
created by using the DBASE option.
10-8 Utilities
The subsequent lines of information in Table 10-3 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
listing. Table 10-3 interprets the data for a typical point of the
curve.
All the data are expressed in the dimensional units used to supply
input data in the original problem definition. For example, Table
10-3 indicates temperature is presented in degrees Celsius. Alterni-
tively, if the dimensional unit of temperature in the original input
file had been, for example, Rankine, then the temperatures pre-
sented in Table 10-2 and Table 10-3 would represent Rankine tem-
peratures. This reasoning also applies to the enthalpy and rate data.
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 flowsheet convergence. It
is always executed during the output calculations phase of simulator
execution, after the flowsheet 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.
10-10 Utilities
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.
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 represents 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 second liquid
phase columns are distinguished by asterisks. For example, X(1)*
represents mole fractions of component 1 in the first liquid phase
while X(1)** is used for fractions of component 1 in the second liq-
uid 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 fugac-
ity coefficients, an additional column appears labeled Distribution
Coefficient. The distribution coefficients are liquid-liquid equilib-
rium analogs of vapor-liquid equilibrium K-values. Therefore, the
distribution coefficient of component i would be defined as:
(1)
where:
10-12 Utilities
Hydrates
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. Their characteristics
are given in Table 10-4. Table 10-5 lists the gas molecules which
may occupy the cavities of these hydrates.
Cavity diameter
Small 7.95 7.82
Large 8.60 9.46
The hydrates formed are stabilized by forces between the host water
and guest gas molecules.
10-14 Utilities
(1)
where:
= difference in chemical potential between the filled
gas-hydrate lattice and the empty hydrate lattice
vi = number of cavities of type i in the hydrate
Yki = probability of cavity i being occupied by a hydrate-forming
molecule of type k
The probability, Yki, may be described by a Langmuir-type adsorp-
tion expression:
(2)
where:
fk= fugacity of hydrate-forming component k
Cki = adsorption constant
Using equation (2), equation (1) then becomes:
(3)
The adsorption constant Cki is related to the spherical-core cell
potential by:
(4)
where:
k = Boltmann's constant = 1.38 x 10-16 erg/K
T = temperature, K
(5)
(6)
where:
Γ = Kihara potential, ergs
ε = characteristic energy, ergs
α = core radius,
σ + 2α = collision diameter,
Summing the gas-water interactions over the entire lattice yields:
(7)
and,
(8)
where:
z = coordination number of cavity
Rc = cell radius
10-16 Utilities
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:
(9)
where:
= chemical potential difference between water in the liquid
phase and the empty hydrate
xw = mole fraction of water in the liquid phase
For gas mixtures, a binary interaction parameter, aj, representing
the interaction between the most volatile hydrate-forming gas mole-
cule and all other molecules is introduced into equation (8).
(10)
where:
αk = binary interaction parameter between the most volatile
component and component k
yk = mole fraction of component k in the vapor phase
The method used for determining the temperature and pressure con-
ditions under which hydrates form is given in Figure 10-4.
10-18 Utilities
Reference
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, flowsheet convergence. Exergy results
appear after the Stream Summary reports in the PRO/II output
report.The availability function, B, is defined as:
(1)
where:
H = enthalpy
T = temperature
S = entropy
10-20 Utilities
Table 10-6: Availability Functions
B(EVS) The exergy (availability) at the EnVironmental State
(i.e., the reference or "zero" state at Tzero and
Pzero). B(EVS) TOTAL is calculated rigorously
assuming the stream is actually at Tzero, Pzero
conditions, and no assumptions are made about
the phase state. B(EVS) VAPOR also is calculated
at Tzero and Pzero, but an a priori assumption is
made that the stream is exclusively in a vapor
state. This is provided as a convenience to users
who make this simplifying assumption when
performing manual calculations.
B(MES) This represents stream exergy (availability) at
Modified Environmental State, computed as
follows:
where:
H = total stream enthalpy
Si = entropy of component i
xi = mole fraction of component i in the stream
(2)
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
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
different approach: Every unit in the flowsheet is solved using the
most efficient algorithms developed for each case. For example,
one can choose different methods for multiple distillation columns,
ranging from shortcut to a variety of rigorous models and, for each
case, PRO/II will use the corresponding specialized column algo-
rithms. Should an error occur in any unit, due, for example, to
incorrect column initialization or poorly chosen design parameters,
it can be easily identified, confined and corrected.To calculate a
flowsheet of interconnected units, a sequence of unit calculations is
determined automatically (or optionally provided by the user). If
recycles are present, an iterative scheme is set up where recycle
streams are "torn" and a succession of convergent "guesses" is cre-
ated. These guesses are obtained by directly substituting the values
calculated in the previous pass through the flowsheet (the Direct
Substitution technique) or by applying special recycle acceleration
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.
Single variable controllers which affect units within loops will be
included in the loops. In turn, multivariable controllers and optimiz-
ers which affect units within loops will not be included in the loops.
If any of these options is not desired a user-defined calculation
sequence should be used.
Convergence Criteria
Convergence is defined as being met when the following
three requirements are achieved for two successive determi-
nations of the recycle streams: Component molar flow con-
vergence test:
(1)
where:
= current and last values of the flow of component i
in the recycle streams
Only components with mole fractions greater than a threshold value
(default is 0.01) are considered for the above test. The component
tolerance and threshold value may be set by the user using the TOL-
ERANCE statement in the General Data category of input. Values
of these tolerances may also be provided on the LOOP statements.
Care should be exercised that inside loop tolerances are set always
as tight or tighter than those for outside loops.
Temperature convergence test:
(3)
Default component molar flow, temperature and pressure toler-
ances of = 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.
Acceleration Techniques
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 represent the estimated rate of a
component or a temperature of a recycle stream at the beginning of
trial k and the calculated rate or temperature after trial k. The
estimated rate for trial k + 1, , will be computed using these
values as follows:
(1)
In equation (1), q is the so-called acceleration factor and is deter-
mined by the following formula
(3)
Figure 11-4: shows how values of q affect convergence.
The more negative the value of q, the faster the acceleration. How-
ever, if the value of q thus determined is used without restraint,
oscillation or divergence often results. It is therefore always neces-
sary to set upper and lower limits on the value of q. These limits
should be set based on the stability of the recycle stream. Normally,
the upper limit should be at 0.0. A conservative value for the lower
limit may be set at, -20.0 or -50.0 to speed up the convergence.
The Wegstein acceleration can be applied only after one or more tri-
als with direct replacement have been made. If the initial estimate
of the recycle stream composition is far different from the expected
solution, e.g., zero total rate, a number of trials should first be made
with direct replacement. Once started, Wegstein acceleration may
be applied every trial or at frequencies specified by the user.
Reference
Wegstein, J. H., 1958, Comm. ACM, 1, No. 6, 9.
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:
(4)
where:
=a damping factor
In equation (4), is given by:
(5)
The update of Hk is performed using the following formula:
(6)
where:
(7)
The algorithm starts with , 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
Reference
Broyden, C.G., 1965, Math Comp., 19, pp 577-593.
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 feedrates, 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
flowrates, 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).
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.
(1)
where n is the number of variables, m1 is the number of specifica-
tions and m2 is the number of constraints.
Typical Application
depicts a typical optimization application:
(2)
The feed tray location is the optimization variable. The flowsheet
has two additional degrees of freedom, the heat duties of the
reboiler and the condenser. These are used as flowsheet variables
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 basecase, 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 basecase 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, flowrates
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
as the vector of the optimization variables which define the state of
the system.
(4)
where:
= the relative accuracy with which the functions are evaluated.
For simple functions this is on the order of machine precision (~
10E-6); for complex flowsheets with sufficiently tight tolerances
the relative accuracy is on the order of 10E-3 to 10E-4.
To aid the user in selecting appropriate stepsizes, 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 11-4 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-
Termination Criteria
The following conditions are tested at every optimizer cycle:
1 Is the relative change in the objective function at consecu-
tive 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
variable)?
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:
(5)
where:
= a vector which contains the first derivatives of the objective
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
determined 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).
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.
■ For a liquid-phase feed, then the initial vapor composition in
the vessel will be set equal to the vapor in equilibrium with the
feed liquid at its bubble point temperature.
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:
(1)
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
(2)
where:
12-2 Depressuring
r = radius of vessel
L = tangent to tangent vessel length
Vfac = volume factor which corrects for pipes and fittings
Vend = end cap volume, which is given by:
(3)
The optional user-supplied volume correction factor, Vfac, defaults
to a value of 1.0, if not supplied.
(4)
where:
r = radius of vessel
h = tangent to tangent vessel height
The end cap volume, Vend, is again given by equation (4) above.
Spherical Vessel
(5)
(6)
where:
Cf = critical flow factor, dimensionless
(7)
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:
(8)
where:
MW = molecular weight of discharge stream
MWair = molecular weight of air
T = temperature of stream, oR
The stream molecular weight is given by:
(9)
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 supersonic
flow conditions:
12-4 Depressuring
(10)
where:
(11)
For subsonic flow, the pressure drop across the valve must satisfy:
(12)
The valve rate for subsonic flow is given by:
(13)
Again, substituting equations (9) and (10) into (13), the valve rate
for subsonic flow becomes:
(14)
where:
(15)
The constant C1 has units of :
(weight/time) / (pressure.weight / volume)0.5.
Alternatively, the user can specify a constant discharge rate:
(16)
The user may also specify a more general valve rate formula:
(17)
where:
A = a constant with units of (weight.volume/pressure.time2)1/2.
(18)
and,
(19)
If Y > 1.5, Yf is not calculated by equation (17), but is instead set
equal to 1.0.
The control valve coefficient, Cv, is defined as "the number of gal-
lons per minute of water which will pass through a given flow
restriction with a pressure drop of 1 psi.". This means that the value
of Cv is independent of the problem input units.
User-defined Model
This heat model is given by:
(20)
where:
Q = heat duty in millions of heat units/time
12-6 Depressuring
C1, C2, C3, C4, C5 = constants in units of millions of heat units/
time
Ttv= 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.
(21)
where:
C1, C2, = constants whose values are given in Table 12-2
At = current vessel wetted area = Ai
Ai = initial wetted area, ft2
APISCALE Model
This heat model is similar to the API 2000 heat model, except the
heat duty is scaled and is given by:
(23)
Again, an area scaling factor may or may not be specified. If Afac is
used, At is given by equation (17). If Afac isn't specified, At is set
equal to the initial wetted area.
(24)
Again, an area scaling factor may or may not be specified. If Afac is
used, At is given by equation (17). If Afac isn't specified, At is set
equal to the initial wetted area.
(25)
Again, an area scaling factor may or may not be specified. If Afac is
used, At is given by equation (21). If Afac isn't specified, At is set
equal to the initial wetted area.
12-8 Depressuring
(26)
where:
C1, C2, C3 = user-supplied constants
(27)
The heat transfer to the fluid inside the vessel is computed using:
(28)
(29)
where:
hv = heat transfer coefficient between the vessel and the vapor
phase of the fluid
Avap = area of vapor phase in vessel
Tfluid = temperature of fluid in the vessel at time t
hl = heat transfer coefficient between the vessel and the liquid
phase of the fluid
Aliq = area of liquid phase in vessel
The gas is depressured isentropically using either a user-defined
isentropic efficiency value or the default value is 0.0. For each time
interval, the heat transfer from the vessel is calculated by using the
Nusselt heat transfer correlations. The heat transfer coefficient
between the vessel and the vapor phase of the fluid, hv, is deter-
mined using:
(31)
(32)
where:
= volumetric coefficient of thermal expansion, 1/oF
gc = acceleration due to gravity
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.
(33)
where:
kl = thermal conductivity of liquid phase
12-10 Depressuring
The Grashof and Prandtl numbers are given by the following rela-
tionships:
(34)
(35)
where:
l = viscosity of liquid
cpl = heat capacity of liquid
The change in the wall temperature, Twall, is determined from the
isentropic enthalpy change and the heat transferred to the gas from
the wall, i.e.,
(36)
where:
qfluid = change in specific enthalpy of the fluid, BTU/lb-mole
qisen = isentropic specific enthalpy change as the gas expands
Mt = moles of gas depressured in time period t, lb-mole
Wvess = weight of depressuring vessel, lb
cpvess = heat capacity of depressuring vessel, BTU/lb-F
Reference
Condenser
dH1
V2 − (1 + R ) D = − F1
dt
(1)
n n n n
dH J
Vn +1 − Ln − D = ∑ − ∑ F j + ∑ WL j + ∑ Wv j
j =1 dt j =1 j =2 j =2
(2)
Reboiler
dH n
LN −1 − VN = − Fn + B + Wvn
dt
(3)
n N −1
dHn N N
−D=∑ − ∑ F j + ∑ WL j + ∑ Wv j
n =1 dt j =1 j =2 j =2
(4)
Reboiler
−
dH n X iN
Ln −1 X in −1 − ( K in v + B) X iN = − f i1
n dt
(7)
Where i = 1, …, n (n – no. of components)
−
L n = Ln + WLn
(8)
(9)
Where
B Bottom residual
D Distillate
Hi Holdup of tray i
R Reflux ratio
Condenser
dH1hL1
V2 hv 2 − (1 + R ) DhL1 − Qc = − F1hF 1
dt
(10)
(11)
Reboiler
dH n hL N
QR + LN −1hLN −1 − VN hVN = − FN hFN + BhLN + Wvn H vn
dt
(12)
Overall
N −1
N
dH n hL N N N
QR − Qc − DhL1 = ∑ − ∑ F j H Fj + ∑ WLJ H LJ + ∑ WVJ hVJ
n =1 dt j =1 j =2 j =2
(13)
Where
Qc Condenser duty
QR Reboiler duty
Equilibrium relation
∑ (Ki
in − 1) X in = 0
(14)
Y
K ij = ij
X ij
comp
∑Y i =1
ij =1
(15)
VLE
yin = K in X in
(16)
State
Gn ρ n
Hn =
Mn
(17)
Where
ρn Density
Mn Molecular wt
Mn
ρn =
XM
∑i ρ i(T i)
i n
(18)
M n = ∑ X in M i
i
(19)
hLn = hLn Tn , ρ n , xn
−
(20)
hvn = hvn Tn , ρ n , yn
−
(21)
kin = kin Tn , ρ n , xn yn
− −
(22)
dHρ
= D − Wρ
dt
(23)
(24)
(or)
dX iρ
Hρ = D( X i1 − X iρ )
dt
(25)
2 Index
CALCULATOR , 11-13, 11-18, 11-23, 11-24, 11-26 Compressibility , 3-5, 3-8, 3-10, 8-2, 12-3
Caprolactam , 5-65 Compression , 3-2, 3-3, 3-4
Carbon Balance , 5-28 Compressor , 3-2, 3-3, 3-5, 3-6, 3-9, 4-12
CASESTUDY , 10-2, 10-10 Compressor work , 3-6
Cat Fractionators , 5-81, 5-84 CONREACTOR , 7-3
Caustic Regenerator , 5-58 Constraints , 11-22, 11-26, 11-27
Caustic Wash , 5-58 Contents , 1-1, 2-11, 8-1, 8-2, 8-6, 8-15, 8-24, 10-3, 12-1,
CCD , 8-10, 8-11, 8-12 12-2
Table , 1-1
Ceram , 5-60
Continuation Method , 5-24
CG , 5-66
Functional Equations , 5-19
Chao-Seader , 2-9
Continuous Stirred Tank Crystallizer , 8-24
Chao-Seader-Erbar , 2-9
Continuous Stirred Tank Dissolver , 8-18
Characteristics , 5-6, 8-2, 8-5, 12-1
Continuous stirred tank reactor , 7-15
function , 8-2, 8-3, 8-4, 8-5
Continuous Stirred Tank Reactor (CSTR) , 7-15, 7-17, 7-
Chemdist , 1-1, 5-1, 5-2, 5-14, 5-19, 5-24, 5-28 19
Simple Stage , 5-14
CONTROLLER , 5-1, 10-2, 10-7, 10-10, 11-13, 11-14, 11-
Chemical Engineer s Handbook , 5-65 15, 11-16, 11-17
Chemical Engineering Handbook , 2-9, 6-21, 12-11 sequence , 11-14
Chemical Engineering Kinetics , 7-23 Controllers , 11-1
Chemical Engineers , 8-22, 10-21 CONVENTIONAL , 5-26, 5-27, 5-79
Chemical Reaction Equilibrium Analysis , 7-9 Convergence Criteria , 2-3, 11-7
Chilton , 5-69, 6-22 Convergence Region , 11-9
Chlorine Balance , 5-28 Conversion Reaction , 5-5
Clarified Oil , 5-84 Conversion Reactor , 7-3, 7-4
Clathrates , 10-13 Cooler/heater , 5-28
CO , 7-4, 7-8 Cooling Curves , 10-3
CO2 , 5-29 Correlations , 5-65, 5-66, 5-67, 5-68, 5-69
CO2 Absorber , 5-58 Countercurrent Decantation Washing System , 8-15
CO2 Regenerator , 5-58 Countercurrent Decanter , 8-10, 8-11, 8-14
Cocurrent , 6-2, 6-3, 6-5, 7-20, 7-22 Cpv , 12-6
Cold Box , 6-23 Cpvess , 12-11
COLUMN , 11-23, 11-24, 11-25, 11-26, 11-27 Cricondenbar , 10-2
Column Hydraulics , 5-57, 5-60, 5-65 Cricondentherm , 10-2
column specifications , 5-76 Critical Point and Retrograde Region Calculations , 10-4
Complex Columns , 5-79, 5-86 Critical Points , 10-4
Complex Distillation Column , 5-2, 5-3 Multicomponent Mixtures , 10-2
Component Balance , 5-28, 8-11 Critical pressure , 10-4
COMPONENT ERROR , 5-6 Crossflow , 6-12, 6-14
number , 6-14
Component Libraries , 7-5
Component library databank , 7-4, 7-5 Cross-references , 1-1
Crude Unit Yields Incremental Yields , 5-87
Component Mass Balance , 2-2, 5-14
Crude-distillation , 5-14
Component Mass Balance Equations , 5-89
Crude-preflash , 5-83
Composition Convergence , 2-5, 2-7
Compostion sensititve K-values , 5-6 Crystal Particle , 8-26
Crystallization , 6-21, 8-23, 8-30
4 Index
Energy Balance , 5-17, 5-28 Feed BlendingConsiderations , 9-1
Energy Balance Equation , 5-89 Feed Tray Location , 11-23, 11-26
Englewood Cliffs , 2-10 Feedback Controller , 6-24, 11-12, 11-13, 11-16, 11-18
Enthalpy , 2-1, 3-2, 3-5, 3-10, 4-12, 5-6, 5-19, 5-71, 5-89, Feedback controller-typical application , 11-14
6-2, 6-23, 7-1, 7-8, 7-15, 8-23, 10-3, 10-7, 10-20, 12-6 Feeds , 5-71, 9-3
Enthalpy-temperature characteristics , 6-4 flowsheet , 9-3, 9-4
Entropy , 2-11, 3-1, 3-2, 3-5, 3-10, 10-20 thermal condition , 5-72
Thermodynamic Generators , 3-1 Fenske , 5-24, 5-70, 5-76, 5-85
EnVironmental State , 10-20 calculate , 5-80
Equations of State , 2-2, 3-1, 10-1, 10-4, 10-10, 10-13 estimates , 5-79
number , 5-76
Equilibrium , 7-8
violate , 5-78
Equilibrium Constants , 5-89, 7-5, 7-8, 7-9
F-factors , 6-3
Equilibrium Flash , 2-1
Fibonacci , 7-13
equilibrium reactions , 5-2
Ficken , 5-24
Equilibrium Reactor , 7-5, 7-7, 7-8
Filtering Centrifuge , 8-6, 8-8
Equilibrium Stage , 5-19, 5-20
FINDEX , 5-84, 5-85
Equilibrium Unit Operations-flash drum , 2-11
Fire Relief Model , 12-6
Equilibrium Unit Operations-mixer , 2-13
First-order Derivatives , 11-28
Equilibrium Unit Operations-splitter , 2-13
Fixed Duty , 2-12
Equilibrium Unit Operations-valve , 2-12
Flanigan , 4-5, 4-11
Equlibrium , 5-89
FLASH , 7-2, 7-3
EQUREACTOR , 7-5
Flash Calculations , 2-1, 2-2, 2-5, 2-7, 2-8, 2-9, 2-10, 2-11,
ERRINC , 5-92 2-12, 2-13
Estimate Generator , 5-24, 5-26, 5-27, 5-28 Flash calculations-MESH equations , 2-1, 2-2
Estimates , 5-6, 5-76 Flash Drum , 2-11
Fenske , 5-76
Flash Unit Operation , 2-12
Estimating Separation Efficiency , 5-69
Fletcher , 11-33
Ethylbenzene , 5-65
Flow Distribution , 6-22
EVAL , 10-11
Flowrate , 4-9, 6-2, 6-15, 7-10, 7-14, 8-3, 9-2, 11-13, 11-
EVALUATE , 10-11 14, 11-16, 11-18
EVS , 10-20 utility , 6-2, 6-3, 6-4
Exergy , 10-20, 10-21 Flowrate/cross , 4-3
EXisting State , 10-20 Flowrates , 5-8, 5-24, 8-19, 9-3, 11-14, 11-16, 11-18, 11-27
Expander , 3-1, 3-9, 3-10, 3-11, 3-12 varying , 11-18
EXS , 10-20 Flowsheet , 5-19, 9-1, 9-2, 9-3, 9-4, 10-7, 10-10, 10-20, 11-
1, 11-3, 11-5, 11-12, 11-14, 11-18, 11-19, 11-22, 11-27
Extractive Metallurgy , 8-15
balance , 9-4
feeds , 9-4
number , 11-18
F results , 11-14
Solve , 11-20, 11-27, 11-28
Factors , 6-21
streams , 11-1
Fouling , 6-21
Flowsheet basecase , 11-22
Features Overview , 5-4
Each Algorithm , 5-4 Flowsheet Control , 11-12
Fugacity , 5-1, 5-6, 10-6, 10-10, 10-11, 10-13 Glitsch , 5-4, 5-57
6 Index
GSE , 2-11, 3-1 HEXAMER , 2-11, 3-2
HF , 5-71
Hfac , 12-6
H Hideal , 6-11
8 Index
model , 6-23 Methanators , 7-4, 7-8
set , 6-23 Michelsen , 10-2
solve , 6-23
MINI , 11-32
LNG Heat Exchanger , 6-23, 6-24
minimum number of trays , 5-70
LOOP , 11-7, 11-8
minimum reflux ratio , 5-70, 5-73
LS , 7-9 Minimum Tear Streams , 11-5
LS Components , 5-4
Missen , 7-14
LTMD , 6-6, 6-8
MITA , 6-23
Ludwig , 5-88 Mixer , 2-13
Mixer Unit , 2-13
10 Index
Performing , 5-18 Prediction , 10-19
LLE , 5-18 Hydrate Formation , 10-13
Perry R , 2-9 Pressure , 7-1
Petro , 4-1, 5-57, 7-1 Pressure Calculations , 4-1
Petrochemical Plants , 5-88 Pressure Drop , 4-3, 4-4, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 5-
PFR Operation Modes , 7-22 57, 5-59, 5-60, 5-62
Phase Equilibria , 8-20, 8-28 Pressure Gradients Occuring During Continuous Two-
Phase Flow , 4-3
Phase Equilibrium Equations , 8-22, 8-29
Pressure Losses Occurring During Continuous Two-
Phase Split , 7-14 Phase Flow , 4-3
Physical Continuation Approaches , 5-19 PRH , 2-11, 3-1
Solving Reactive Distillation Problems , 5-14
PRH MARGULES , 2-11
Pipe , 4-1, 4-2, 4-3, 4-4, 4-9, 4-10, 4-11
PRH VANLAAR , 2-11
Pipe Flow , 4-3 PRINT , 5-85
Friction Factors , 4-3
PRINT PATH , 7-3
Pipelines , 4-11, 4-12
PRM , 2-11, 3-1
Pipes , 4-1, 12-3
PRM UNFV , 2-11
Platteeuw , 10-14
PRM VANLAAR , 2-11
Plug flow reactor , 7-20, 7-22, 7-23
PRO/II Application Briefs Manual , 1-1
Plug Flow Reactor (PFR) , 7-20, 7-22
PRO/II Casebooks , 1-1
Polytropic , 3-5, 3-6, 3-7, 3-8, 3-9, 3-12
PRO/II CONTROLLER , 11-13
Polytropic compressor , 3-8
PRO/II CSTR , 7-19
Polytropic efficiency , 3-1, 3-2, 3-5, 3-7, 3-9
PRO/II Data Transfer System , 10-7
Polytropic Efficiency Given , 3-7, 3-9
PRO/II databanks , 2-10
Polytropic efficiency gp , 3-8, 3-10
PRO/II dissolver , 8-15
Polytropic efficiency n , 3-12
PRO/II Help , 1-1
Polytropic expander , 3-10
PRO/II Keyword Input Manual , 9-1, 10-3
Population Balance Equations , 8-24
PRO/II optimizer , 11-24
Possible Calculation Sequences , 11-6
PRO/II sequencer , 11-15
Postoptimality Analysis , 11-32
PRO/II Unit Operations Reference Help , 1-1
Poynting correction , 10-6, 10-10
PRO/II User-added Subroutines User s Manual , 7-15
PR , 3-1, 10-4
PRO/II utility , 10-8
PR Huron-Vidal , 3-1
Problems , 5-14
PR Modified , 3-1
Process Heat Transfer , 6-22
PR Panagiotopoulos-Reid , 3-1
Process Method , 11-5, 11-6, 11-7
PR1 UFT3 , 2-11
Process Simulation Program , 10-21
PR1 UNFV , 2-11
Process Unit Grouping , 11-3
Practical Methods , 11-27
Processes , 10-21
Optimization , 11-27, 11-28, 11-30, 11-31, 11-32, 11-
33 PROCHEM User s Manuals , 5-28
Practical Optimization , 11-27 PROPERTY , 10-6
Prandlt , 6-10, 6-12 Propylene-propane , 5-78
Prandtl , 12-10, 12-11 PROVISION Graphical User , 1-1
Prausnitz , 2-10, 10-19 PROVISION User s Guide , 10-3
12 Index
solve , 5-71 Sidestrippers , 11-3, 11-4
value , 5-72 Sieder-Tate , 6-12, 6-13
Robinson , 10-19 Silverblatt , 8-5, 8-6
Rotary Drum Filter , 8-2, 8-6 Simple Columns , 5-77, 5-78, 5-85
Rubin-Starling , 2-9 Simple Heat Exchangers , 6-2, 6-4
Rules-of-thumb , 5-60 Simple Stage , 5-7, 5-8, 5-15, 5-89
Runge-Kutta , 7-23 Chemdist , 5-14, 5-15, 5-17, 5-18
Russell , 5-6, 5-14 I/O , 5-6, 5-8, 5-12
LLEX , 5-89, 5-91, 5-92
Simple-rigorous , 11-3
S Simplicial , 5-19
SimSci Method , 11-5, 11-6
Sample HCURVE , 10-8
Simultaneous Modular Solution , 11-2
Scandrett , 8-15
Simultaneous Modular Solution Technique , 11-1
ScG , 5-63
Simultaneous Modular Techniques , 11-1
Schmidt , 5-63, 5-64, 8-19
Size Distribution , 8-24
Seader , 10-21
Sizing , 5-57, 5-58
Seider , 7-14
trayed , 5-57
Separation Columns
Skjold-Jorgensen , 10-19
Distillation , 5-69
Smith , 7-14
Sequence , 11-14, 11-19
Soave Redlich-Kwong , 3-1
CONTROLLER , 11-14
Sequencing-PROCESS , 11-5 Soave-Redlich , 2-9
Soave-Redlich-Kwong , 2-9, 3-1, 10-1, 10-4
Sequential Modular Solution Technique , 11-1, 11-2, 11-4
Sodium Balance , 5-28
Series-parallel , 7-4
Shadow Prices , 11-31, 11-32 Solid Phase , 8-23
Solid/Liquid Separation Equipment Scale Up , 8-5
Shadow prices-Optimizer , 11-27
Solid-liquid Equilibrium , 8-22, 8-29
Shell weight (dry) , 6-19
Shell weight (with water) , 6-20 Solid-liquid Solute Balance , 8-21, 8-28
Solids Handling , 8-1
Shellside , 6-11, 6-14, 6-15, 6-17, 6-21, 6-22
Solids Handling Unit Operations , 8-1
Shellside Pressure Drop , 6-22
Shellside Reynolds , 6-15 Solubility Data , 8-23
Soluble Values , 8-15
Shell-to-baffle , 6-12
Solute component kg/kgmol , 8-21
Sherwood , 5-68, 8-19
Shift Reactor Model , 7-4, 7-7 solute components , 8-20, 8-23, 8-28
Solute Vapor Balance , 8-21, 8-29
ShiftReactorModel , 7-7
Solute/kg , 8-16
Shiras , 5-72
SHORTCUT , 5-86, 5-88 Solutility , 8-20
Solution Algorithm , 2-3, 2-10, 11-26, 11-27
Shortcut Distillation , 5-1, 5-70, 5-71, 5-76, 5-77
Solution Procedure , 5-17, 5-91, 8-22, 8-30, 11-19
Shortcut Distillation Column Condenser Types , 5-76
Shortcut Distillation Column Models , 5-76 Solve , 2-8, 5-73, 6-24, 8-14, 11-19, 11-25, 11-27
basecase , 11-24, 11-25, 11-27
Should Use This On-line Manual , 1-1
flowsheet , 11-19, 11-27
Si , 10-20, 12-6 LNG , 6-23, 6-24
Sidestream , 5-6, 5-9, 5-10, 5-13 Rachford-Rice , 2-8
Sidestream withdrawl , 5-13 Rmin , 5-71
triagonal , 8-14
14 Index
Superset , 10-6 Thomas , 8-14
KVALUE , 10-6 Three-phase Flash Calculations , 2-10
Supplying , 10-20 Three-Phase Solid , 10-13
EXERGY , 10-20
Time-pressure-temperature , 12-1
Sure , 5-1, 5-2, 5-4, 5-26 determine , 12-1
Sure Algorithm , 5-13 TOLERANCE , 11-7
Surface Tension , 4-1 Top Section , 5-58
Switzerland , 5-65 Absorbing Type Demethanizer/Deethanizer , 5-57
Sulzer Brothers , 5-65 Topped Crude , 5-84, 5-85, 5-88
SYSTEM , 3-1 TORSION , 8-6
System Factors , 5-58 Total Mass Balance , 2-2, 8-11
TPSPEC , 2-12
Tracking , 5-23
T homotopy , 5-19
Tablular , 10-1 Transport Properties , 4-1
16 Index
Volume Based , 5-19
W
Wang , 10-21
WATER , 10-5, 10-6
Water and DryBasis Properties , 10-5
Water decant , 2-1, 2-9, 5-1
water partial pressure , 2-9
Water/hydrocarbon , 5-1
Wegstein , 11-1, 11-8
Recommended Uses , 11-8
Wegstein Acceleration , 11-8, 11-9
Weight.volume/pressure.time2 , 12-3
Weight/time , 12-3
Westerberg , 11-5, 11-7
White , 7-14
WIDE , 8-6
Wiley , 11-33
Willis , 6-15, 6-22
Wright , 11-33
X
XOVHD , 9-2
XPROD , 9-3
Y
Yadav , 8-22
Ysolute , 8-29
Z
Zones Analysis , 6-4, 6-6, 6-24
Zp , 5-63