Paper 28
Paper 28
Paper 28
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Table 1
Introduction
Students and young chemical engineers who rely on powerful
process simulation programs for coursework or job performance
often dont have the proper background in applied phase
equilibrium thermodynamics. This lack of experience becomes
obvious when either a poor choice is made in selecting a physical
property package, or the selection process itself is completely
overlooked. The heuristics presented in this paper are designed to
assist in selecting thermodynamic packages for process simulation
with a minimum of time and effort.
Table 2
Table 3
Background
Proper selection of thermodynamic models is absolutely necessary
as a starting point for accurate process simulation. A process that
is otherwise fully optimized in terms of equipment selection,
configuration, and operation can be rendered essentially worthless
if the simulation is based on inaccurate thermodynamic models.
Because of this, good heuristics and appropriate priority should be
placed both on selecting thermodynamic models, and in reporting
the selections in process reports.
Simulation generally differs from hand calculations in two ways: (1)
the simulator allows use of more sophisticated models without
significantly expending more of the engineers time and (2)
simulations in chemical engineering typically involve VLE (vaporliquid equilibrium) where the ideal gas EOS (equation of state) is
inaccurate. Selecting rigorous thermodynamic models, as
compared to models made for easy calculations, rarely diminishes
productivity. So, criteria for selecting thermodynamic models during
simulation are based primarily on accuracy, not the optimal
combination of accuracy and effort. And, acquiring accurate binary
interaction coefficients or data still fall within the realm of increasing
accuracy at the expense of increased effort.
During process simulation, thermodynamic model selection should
be performed in at least two steps. Firstly, as with initial process
configurations, the thermodynamic model should be chosen based
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on heuristics that provide for a good base case, but may or may not
provide the desired level of accuracy. Secondly, based on the
results of the base case simulation (complete with cost estimate),
improving the accuracy of the thermodynamic models should be
prioritized relative to optimizing other design parameters, such as
the configuration of unit operations, optimization of specific unit
operations, heat integration, and other degrees of freedom.
Optimization includes both economic and simulation accuracy
aspects. Thermodynamic model definition should be revisited as
often as necessary during process optimization.
This paper summarizes heuristics for selecting thermodynamic
models for base case simulation, and provides guidelines to help
identify the priority that should be placed on any efforts to improve
thermodynamic models after completing the base case. The
approaches described herein are largely a simplified version of
those described by Stanley M. Walas in his text Phase Equilibrium
in Chemical Engineering. The format of this paper provides a
transitory approach for those engineers who have not studied
applied phase equilibrium modeling beyond undergraduate
material. It should be sufficient to perform process simulation with
confidence, without being overwhelmed with the detail provided by
Walas. Walas provides a good source of explanation, theory, and
examples beyond those detailed here.
Modeling Phase Equilibrium
Thermodynamic property package selection is, appropriately, one
of the first necessary steps in process simulation. These packages
typically include EOSs, activity (solution) models, and other more
specialized models that take into account non-idealities in vapor
and liquid mixtures. Table 1 summarizes the parameters calculated
in these approaches. Vapor pressure models (e.g., Extended
Antoine equation) are generally accurate provided the parameters
are not specific to a range outside that of interest. Corresponding
states methods for pure component fugacity coefficients (e.g.,Chao
Seader Model) are typically only called upon for pure component
calculations when alternatives are not available. Selection of either
vapor pressure model, pure component fugacity models, or other
methods, such as interpolation of available data, are typically
performed automatically by simulation packages as needed, and
without operator interaction.
The present discussion is limited to the selection of EOS and
solution models, since these are used to solve the vast majority of
organic chemical processes.
VLE Model Selection
As summarized by the EOS and solution model equations of Table
1, both EOS and solution models can be used for VLE calculations.
Due to the complexity of the EOS calculations, this approach to the
solution of mixture VLE problems is typically not covered in the
undergraduate curriculum to the extent that students are prepared
to perform VLE calculations using common equations of state like
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also based on the ability of the model to go beyond fitting data, and
specifically, to the ability of the solution model to accurately
account for the impact of temperature. Based on the ability to
accurately account for changes in temperature, the Wilson
equation was selected over the Margules equation, even though
the Margules may provide a slightly better fit to the data.
The heuristics described above are designed to provide a starting
point for selection of thermodynamic packages to use for base
case process simulation. Depending upon the process and
availability of data, the best choices of thermodynamic packages
will vary.
It is interesting to note that even though the development of the
UNIQUAC solution model, in combination with the UNIFAC group
contribution, was groundbreaking work, the UNIQUAC model does
not consistently fit experimental data well. When using UNIFAC or
other group contribution methods, different binary coefficients will
be estimated based on LLE versus VLE options. The applicable
options or options should be chosen during process simulation.
Model Selection for Gas Solubility in Liquids
The equilibrium of a gas with a liquid can, and should, be divided
into two types of separation problems: a) the separation of a
volatile organic from a gas, like nitrogen, and b) the separation of
the gas from a liquid.
Separating volatile organic compounds from purge gases is
common practice in industry. For this system, the gas is typically
sparingly soluble in the liquid, so solution models, such as the
Wilson equation, accurately estimate the partial pressure of the
volatile organics.
In contrast, accurate modeling of a sparingly soluble gas in a liquid
is typically achieved only if experimental values are available to
specify binary interaction coefficients at low gas concentrations. As
seen in Table 3 (Walas), gas solubility can vary considerably,
depending upon the liquid. Furthermore, when comparing
estimates of the SRK EOS to the Wilson equation, the estimated
solubility can easily vary by greater than an order of magnitude.
Resolving this second type of gas-liquid solubility problem requires
further discussion.
By far, the best resolution of uncertainty issues related to the
solubility of gases in liquids is to do a sensitivity study. This could
be a formal simulation sensitivity study, or just a thought process.
In many instances, equipment sizes and configurations, as well as
bottom-line economics, are not substantially impacted, even if gas
solubility in a liquid is varied by two orders of magnitude. In such
instances, even if the thermodynamic model is off by a factor of 10,
the soundness of the design is not affected. When the gas solubility
does impact equipment design or economics, data should be
pursued. Walas does provide a listing of many gas solubilities that
can be converted to Henrys constants or solubility parameters for
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