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Abstract
Interest in discovering multiple steady-state solutions for reaction and separation processes grew exponentially in the 1990s.
Process simulators like ASPEN PLUS, CHEMCAD, HYSYS, and PRO/II are designed to obtain at best one solution. Simulation
programs can find multiple solutions only by the expenditure of much effort. Here, a bifurcation technique using arclength
continuation is presented that can be incorporated as an add-in subroutine to a simulation program to automatically trace a
solution path, including turning points, to obtain multiple solutions with respect to a user-selected parameter. The technique is
illustrated with applications to the ASPEN PLUS process simulator. The algorithms are based on a predictor corrector
implementation where the predictors reside in add-in FORTRAN routines and the existing nonlinear equation solvers in ASPEN
PLUS equipment models serve as the correctors. Furthermore, the existing physical property packages in ASPEN PLUS are also
utilized. The method was tested successfully on an adiabatic CSTR example using the ASPEN RCSTR model, and homogeneous
azeotropic, heterogeneous azeotropic, and reactive distillation examples using the ASPEN RADFRAC model. Two of these
examples are presented here. In all four examples, the range of the selected bifurcation parameter covers a region that produces
three multiple solutions. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Multiple solutions; Bifurcation; Continuation
1. Introduction
Design of chemical processing systems that satisfy
economical and environmental requirements calls for
development of new design tools and instrumentation
for identifying the fundamental features of the processes. One of these features is the phenomenon of
multiple steady states, which is the characteristic of
numerous physiochemical processes such as chemical
reactions (catalytic and autocatalytic), mass-transfer
operations (distillation, extraction, absorption), and reactive mass-transfer processes. Multiple steady states
can take place at the levels of a single apparatus, a
group of functioning apparatuses, or even an entire
chemical process system.
Gani and Jrgensen (1994) define three types of
multiplicities. Output multiplicity, the most common
* Corresponding author. Tel.: +1-801-5816915; fax: + 1-8015859291.
E-mail address: j.seader@m.cc.utah.edu (J.D. Seader).
0098-1354/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S0098-1354(01)00624-X
446
2. Motivation
Chemical engineers use systems of equations to
model reactors and separation equipment. Frequently,
these equations, whether they be algebraic, transcendental and/or differential, are nonlinear in nature. Although linear algebraic equations have only one root
(or none if the coefficient matrix is singular), nonlinear
algebraic and/or transcendental equations can have
multiple roots. Except for a small number of special
cases (e.g. quadratic, cubic and quartic equations), a
direct analytical solution is not possible and one must
resort to an iterative numerical solution. The most
commonly applied numerical algorithms for systems of
nonlinear equations, as incorporated into steady-state
process simulators seek, at best, one solution. Additional steady-state solutions can sometimes be found by
making case studies, performing a sensitivity study on
one or more parameters, or varying initial guesses of
the solution. However, this procedure is not likely to
produce a smooth continuation or bifurcation curve
that includes turning points and all multiple solutions.
Simulator algorithms either require the user to provide
the initial guesses for the set of unknowns or provide a
built-in initialization procedure. In either case, an attempt is made to provide an initial guess that is within
the domain of a practical answer. This works in many
cases and fortunately, the solution obtained is often the
only practical solution. However, when multiple solutions exist in the practical domain, i.e. where the mole
fractions are between zero and one and flow rates and
absolute temperatures and pressures are positive and
real, it is desirable to have methods that find all
solutions.
In addition to iterative numerical methods, investigators have considered other mathematical tools that can
help detect multiple solutions. Some of the steady-state
process simulators (e.g. ASPEN PLUS, CHEMCAD,
HYSYS, and PRO/II) have algorithms that simultaneously adjust the recycle tear variables and the design
variables to satisfy the stationarity conditions. Unfortunately, they are of limited utility for the design of
processes that operate near or within regimes characterized by hysteresis and periodic or chaotic behavior.
They have no bifurcation algorithms that can trace
steady-state solution paths, perform a stability analysis
(evaluation of the eigenvalues of the Jacobian), and
locate the global optimum.
One method for finding multiple solutions, described
by Morgan (1987), but restricted to sets of polynomial
equations, takes the starting system of equations or a
partial reduction of it, and applies differential arclength
continuation using a special homotopy that establishes
parallel continuation paths that lead robustly to all
possible roots, real and complex. This method is widely
available in two software packages, CONSOL (Morgan, 1987) and POLSYS1H in HOMPACK90 (Watson,
Sosonkina, Melville, Morgan, & Walker, 1997). Alternatively the interval-Newton method in conjunction
with generalized bisection, as implemented in the public
domain software program INTBIS of Kearfott and
Novoa (1990) can locate multiple solutions of general
sets of nonlinear equations. This method has the advantage that the user restricts the search domain and then
INTBIS finds all of the roots within that domain. A
third method involves the use of bifurcation analysis
and singularity theory to locate higher-order singular
points in addition to limit points, such as real bifurcation points and Hopf bifurcation points, which homotopy algorithms fail to detect. AUTO ( Doedel, Wang,
& Fairgrieve, 1994) is one such package that can perform a bifurcation analysis. Doedel, Keller, & Kernevez
(1991) present an exhaustive discussion on the numerical analysis and control of bifurcation problems in
finite dimensions with several illustrative examples.
Bekiaris, Meski, Radu, and Morari (1993) used bifurcation analysis to compute the solution diagram for the
special case of homogeneous azeotropic distillation with
an infinite number of trays and infinite reflux ratio.
This method has come to be known as the infinity/infinity analysis. Results obtained from this limiting case
are then applied to the actual finite column case.
For all the above methods, investigators have written
specialized programs that include model equations,
thermodynamic routines, and in some cases, corresponding equation solvers to carry out the necessary
calculations. Also, simplifying assumptions have sometimes been made to successfully solve specific cases.
Often, these assumptions have been unsuitable for
other case studies. The aim here is to utilize existing
process models already present in simulators like ASPEN PLUS, thus saving the user the time of writing
and debugging separate and specialized codes to perform a bifurcation analysis. ASPEN PLUS was chosen
to illustrate the bifurcation methods developed here
because it is widely used and its architecture is well
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suited for adding user-supplied subroutines. Before presenting the details of the bifurcation methods, it is of
interest to discuss the use of the sensitivity analysis tool
of ASPEN PLUS and its shortcomings when attempting to use it for locating multiple solutions.
(1)
where the rate of the exothermic reaction is second-order with respect to propylene oxide, and the rate constant, k, can be expressed in Arrhenius form:
k= A e-E/RT = 9.15
1022 exp (18,700/Tr) m3/ kmol-s
(2)
where Tr, is the temperature in the reactor in K. The
problem specification is shown in Fig. 1. The feed
consists of a mixture of 1.3202 m3/h propylene oxide,
1.3202 m3/h methanol (M) and water. Methanol is
added in order to increase the bubble-point temperature
of the mixture. Varying the flow rate of water from 5.4
to 8.2 m3/h varies the total volumetric flow rate, while
448
(4)
RNET
=0
QCA0
(5)
Eq. (3) and Eq. (5) were solved by AUTO with initial
values of Q=8.0 m3/h, CA = 0.081 kmol/m3, CB =
34.76 kmol/m3, CC = 2.26 kmol/m3, and Tr =78C.
Since methanol does not participate in the reaction
mechanism, its mass balance equation was not included
with the rest of the mass balance equations. The four
nonlinear algebraic equations (3 mass balance and 1
energy balance) were solved to obtain the solution
vector u, which is made up of elements, CA, CB, CC and
T. The total volumetric flow rate, Q was the selected
bifurcation parameter.
The bifurcation package of AUTO generates an output file that contains parameter values (the volumetric
flow rate of water) and state variables (temperature and
concentrations), along with indicators for turning
points and algebraic bifurcation points. The sign next
to the step number determines the stability of a particular solution. Stable points are indicated with the ()
sign and unstable points by the (+ ) sign. In the
following example, turning points were found at entering water rates of 7.79 and 6.04 m3/h, with the absence
of any real bifurcation points. The bifurcation diagram
from AUTO for this problem is presented in Figs. 2
and 3 as solid lines. One observes a decrease in the
propylene oxide conversion from 96 to 65% as the
water flow rate increases from a starting point of 5.4
m3/h to the first turning point at 7.79 m3/h. Thereafter,
an unstable steady state is calculated and the conversion continues to fall at decreasing flow rates until the
second turning point is reached at 6.04 m3/h with a
conversion of 15%. Beyond the second turning point,
the flow rate again increases with a marginal drop in
conversion (15 4%) corresponding to a second stable
steady-state region. Calculations are terminated arbitrarily at a water flow rate of 8.2 m3/h. Thus, two stable
steady states and one unstable steady state exist for
total volumetric flows between the two limit points of
7.79 and 6.04 m3/h, which defines the region of multiplicity. Unique steady states exist outside the region of
multiplicity.
A sensitivity analysis run using ASPEN PLUS with
the RCSTR model was carried out for each of the two
options provided in ASPEN PLUS. In the first option,
current results are used as initial estimates for the next
step, which involved a new value of the volumetric
water flow rate. In the second option, results are reinitialized at each step, with ASPEN PLUS supplying a
new set of initial estimates to begin each step. In Fig. 2,
where no reinitialization was done at each step, the
initial water rate is 5.4 m3/h and is incremented by 0.1
m3/h for each sensitivity step. Open square markers
show the ASPEN PLUS results. Conversion decreases
gradually until the first turning point is approached at
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Fig. 3. Comparison of ASPEN PLUS (with reinitialization at each step) and AUTO results.
ASPEN PLUS sensitivity analysis finds only one solution in the region of multiplicity and is not a reliable
tool to accurately predict turning points. In Fig. 3, the
results obtained from the second sensitivity option are
compared to the AUTO results. It can be seen that
ASPEN PLUS calculates the unstable solution sporadically at a few water flow rates. Therefore, with neither
sensitivity option is it possible to obtain a smooth
bifurcation curve with all the steady-state solution
branches in the region of multiplicity.
450
(6)
where s denotes some parameterization. From the starting point, the branch is traced out in a stepwise manner
(7a)
(7b)
where Ds is the step size along the branch and superscript T is the transpose. The advantage of using the
inflated system of Eq. (7) is its capability of computing
past limit points on a branch, because the Jacobian for
Eq. (7),
fu
u
f&0xFFFD;
, is not only nonsingular at a
&0xFFFD;
regular solution point of Eq. (6) where fu is nonsingular, but also at a simple turning point. Points where the
variable l% changes sign are located by a secant iteration scheme and are treated as potential turning points.
Once a turning point is detected, the solution branch is
continued in the new direction using pseudo-arclength
continuation. In order to implement this scheme into
ASPEN PLUS, it would be necessary to access the
derivative information fu and fl, where fu is the Jacobian matrix of all functions with respect to state variables u, and fl are the function derivatives with respect
to parameter l. Alternatively, the derivatives can be
calculated using a finite differencing scheme by directly
accessing the functions. Unfortunately, neither was possible with ASPEN PLUS and, therefore, an alternative
method was developed. The detection of a turning
point is treated the same for both algorithms as explained next in some detail. Branch switching is handled differently for the RCSTR and RADFRAC
models because the latter deals with equilibrium-stage
operations, whose temperature and composition profiles can be suitably exploited to enable the algorithm to
successfully negotiate around turning points.
The methods used for detecting turning points and
for performing branch switching are explained with the
help of Fig. 4, which is a schematic of a typical
bifurcation curve with more than one steady state,
where, u i is a component of the vector of state variables
u, and l is the bifurcation parameter. The variable u i
represents a state variable like temperature or component mole fraction, and l represents an input or equipment variable that is being varied over a range of
values. The S-shaped curve consists of three steadystate solution branches that change directions at the
two turning points, and hence between the turning
points there are three sets of state variables that satisfy
the process model. The first is between points S and A,
the second between A and D, and the third between D
and B. Solutions on branches SA and DA cease to exist
to the right of point A. Similarly, solutions on branches
AD and BD cease to exist to left of point D. For
451
Du 0
(8)
(9)
(10)
452
453
1. All three steady-state profiles are distinct. The maximum differences in temperature and composition
for profiles III and I is found for the last few stages
at the bottom.
2. The temperature and composition values for the
first few stages from the top are nearly identical for
all three profiles.
3. The unstable profile II is characterized by temperatures that are close to the stable profile III for stages
above the feed stage. Stage temperatures for profile
III are lower than for the other two profiles for the
entire column. For stages below the feed stage [22],
stage temperatures of profile II increase suddenly
and approach those of profile I. Since the temperature transition seemed to occur close to the feed
stage, a study of the effect of feed stage location on
the unstable state profile was carried out for feedstage (f.s.) locations of 6, 11, 15, 22 and 28. Results
obtained from this study are presented in Fig. 8,
which shows a strong dependency of the unstable
profile on the feed stage location. This characteristic
behavior is exploited and used in the pseudoarclength algorithm to enable branch switching. A
similar behavior was also found for heterogeneous
azeotropic and reactive distillation examples.
The continuation method presented here also makes
use of the two most recent converged solutions. The
difference in the two state variable vectors uprevious and
ucurrent and in the corresponding parameter values is
454
(11)
(12)
dl/ds = (lcurrent-lprevious)/Ds
(13)
(14)
Fig. 6. Temperature profiles of all three steady-states of the homogeneous azeotropic distillation column at a distillate flow rate of 1.58 kg/h.
Fig. 7. Methanol composition profiles of all three steady-states of the homogeneous azeotropic distillation column at a distillate flow rate of 1.58
kg/h.
455
Fig. 8. The unstable temperature profile for different feed stage locations of the homogeneous azeotropic distillation column.
(15)
(16)
It is important to note that since an adaptive stepsize strategy is implemented to achieve this, Ds is not
equal to Dsnext, which is managed independently in the
algorithm with a maximum value supplied by the user
at the start of the run.
The RADFRAC model in ASPEN PLUS allows the
user to supply estimates of temperature and component
mole fractions for each stage as computed in step 3
above. The program variables for temperature estimates are called T-EST and those for liquid and vapor
mole fraction estimates are X-EST and Y-EST, respectively. In the region of multiplicity, where more than
one steady-state exists, it is possible to converge to a
specific steady-state solution by specifying both temperature and mole fraction estimates for some or all stages.
However, for a given set of initial estimates that are
close an actual solution:
1. The inside-out method with the default option may
converge to a solution different from the one originally sought, usually on the stable steady-state
branch.
2. The NEWTON option of the inside-out model is
more predictable and converges usually to the
456
457
458
Fig. 10. Bifurcation diagram of exit reactor temperature for the adiabatic CSTR.
Fig. 11. Bifurcation diagram of the exit propylene oxide concentration for the adiabatic CSTR.
spondingly, the concentrations of both water and propylene oxide are the lowest when temperature is the
highest. All the diagrams presented in this section were
constructed from data points obtained from a single
run. In all there were 34 ASPEN PLUS simulations
carried out to solve this problem. The conversion plot
similar to Figs. 2 and 3 is shown in Fig. 14. In the
region of multiplicity, three operating points are possible. The maximum amount of propylene glycol is produced if the reactor is operated on branch I. It is best
to operate the reactor with an inlet water flow rate of
459
Fig. 12. Bifurcation diagram of the exit water concentration for the adiabatic CSTR.
Fig. 13. Bifurcation diagram of the exit propylene glycol concentration for the adiabatic CSTR.
460
Fig. 14. Bifurcation diagram of the exit propylene oxide conversion for the adiabatic CSTR.
461
another. The large temperature increase can be explained by the material balance relationship between
internal vapor, reflux, and distillate flow rates. The
reflux flow rate is kept constant for the entire parameter
range and, by material balance, the vapor flow rate is
equal to the sum of the distillate and reflux flow rates.
Hence, the increased distillate demand can only be met
by an increase in internal vapor flow rate. This is
possible only by supplying more steam to the reboiler,
which in turn causes the bottoms temperature to rise.
Fig. 15. Bifurcation diagram of the methyl-butyrate bottoms composition for the homogeneous azeotropic distillation column.
Fig. 16. Bifurcation diagram of the methyl-butyrate bottoms composition for the homogeneous azeotropic distillation column (in terms of mass
fractions).
462
Fig. 17. Bifurcation diagram of the methanol distillate composition for the homogeneous azeotropic distillation column.
Fig. 18. Bifurcation diagram of the bottoms temperature for the homogeneous azeotropic distillation column.
463
6. Conclusions
FORTRAN programs based on algorithm pseudocodes were linked with the different modules of
ASPEN PLUS via in-line FORTRAN, which can be
used to write FORTRAN statements and expressions in
design specifications, FORTRAN blocks, optimization
problems, sensitivity blocks and scaling reports. In-line
FORTRAN statements invoke most FORTRAN features, such as subroutine calls, I/O statements, array
variables, and labeled COMMONs. ASPEN PLUS
checks the FORTRAN code interactively as it is entered. Most syntax errors are detected before actually
running the simulation. ASPEN PLUS interprets most
Fig. 19. Bifurcation diagram of the reboiler duty for the homogeneous azeotropic distillation column.
464
in-line FORTRAN statements. FORTRAN that cannot be interpreted is compiled and dynamically linked
to the ASPEN PLUS module. Thus, the overhead for
in-line FORTRAN requiring compilation is small. In
addition to all the features mentioned above, in-line
FORTRAN also allows access to all stream and block
results. Program diagnostics like convergence results
that are not available from inline-FORTRAN are accessed using the Summary File Toolkit routines of
ASPEN PLUS.
To help run the continuation algorithms, three FORTRAN blocks named F-1, F-2, and F-3 were written.
Initially, the user does not use these blocks with either
the RCSTR or RADFRAC programs. As shown in
Fig. 9(a), the problem is specified in the standard
ASPEN PLUS format. After running the initial simulation, the bifurcation parameter and a set of observable
variables for the particular problem are chosen. The
appropriate interface needed to run the algorithms with
RCSTR and RADFRAC programs is created using
F-3. The interface consists of a set of files that carry the
guess values for the current step, the converged values
of the previous step and values of the program parameters like ISF, IBR, ISTEP, etc. This step is shown in
Fig. 9(b). After obtaining these files, F-3 is hidden from
the RCSTR/RADFRAC program using the Hide option for FORTRAN blocks. Next, blocks F-1 and F-2
are revealed to run as part of an overall flowsheet with
the ASPEN PLUS programs. As shown in Fig. 9(c)
block F-1 runs before the program and F-2 after. The
results of block F-2 are written into a set of output files.
These files are later copied into a set of input data files,
using a UNIX shell script. While the main job of F-1 is
to enter guess and parameter values for the next iteration, the arclength algorithms reside in block F-2. The
UNIX shell script calls ASPEN PLUS a number of
times until the entire bifurcation diagram is calculated.
Each iteration of the shell script represents one pass
through the flowsheet sequence F-1 (RCSTR or
RADFRAC) F-2. The parameter and initial estimate
values in the input file are replaced at each pass
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