Non-Linear Programming Distillation Model For Simultaneous Process Optimization
Non-Linear Programming Distillation Model For Simultaneous Process Optimization
A publication of
Guest Editors: Petar S. Varbanov, Qiuwang Wang, Min Zeng, Panos Seferlis, Ting Ma, Jiří J. Klemeš
Copyright © 2020, AIDIC Servizi S.r.l.
DOI: 10.3303/CET2081096
ISBN 978-88-95608-79-2; ISSN 2283-9216
Distillation columns are prevalent process units used to purify chemicals. However, they consume significant
amounts of energy for heating and cooling. A rigorous non-linear programming (NLP) distillation model where
mass, equilibrium, summation and heat (MESH) equations are applied to each stage is proposed to be used in
conjunction with existing Heat Integration models for simultaneous process optimisation to reduce energy
consumption. In the NLP model, a continuous variable is used for each stage to determine whether a stage is
active or inactive. This variable controls whether there are any changes in stream properties as a stream passes
through a stage. It also enforces the equilibrium constraint for streams exiting active stages. The continuous
variable mimics a binary variable as it only takes on values of 0 or 1 in an optimal solution.
The distillation model and a Heat Integration model for a multi-stream heat exchanger (MHEX) were
implemented in GAMS with a case study on the separation of air consisting of N2, O2 and Ar. Analysis of the
model performance showed that it achieved convergence in a short time (6 min for a model with 2,161 variables
and 25,260 equations) even with crude initialisation methods. Results of the case study showed that the energy
requirement per unit mass of oxygen product is not minimized at 100 % oxygen recovery. The average oxygen
recovery was around 96 %. Optimisation of the case study on an air separation unit (ASU) reduced energy
requirement by 5.4 % for some cases.
1. Introduction
Distillation columns are energy-consuming process units used to purify products. Heat integration may be the
key to reducing the energy consumption of distillation systems. More energy savings may be realized if an entire
distillation system, including the heat recovery unit, is optimised simultaneously in an equation-oriented (EO)
environment, as opposed to using sequential modular methods. Pinch Analysis is one method of Heat
Integration which may be used to maximise the potential of heat recovery in distillation systems. In Pinch
Analysis, the minimum cooling and heating utility requirements are identified given a minimum temperature
approach in a heat recovery system comprised of selected process streams. However, Pinch Analysis is usually
applied after a process has been designed. This sequential method of Heat Integration may result in wasted
potential to reduce energy consumption. Duran and Grossmann (1986) pioneered an EO method for Pinch
Analysis which can be applied to simultaneous optimisation. The method involved the use of a max operator,
which proved to be challenging to commercial solvers due to its non-smooth nature. Subsequently, different
methods of replacing the max operator were developed, including a smoothing approximation used in the same
work by Duran and Grossmann, and the use of binary variables in a mixed integer non-linear programming
(MINLP) formulation as well as an NLP model using the concept of pseudo temperatures by Hui (2014).
With the development of equation-oriented Heat Integration models, it then became possible to simultaneously
optimise an entire distillation system comprised of distillation columns and a heat recovery network or MHEXs.
However, simultaneous optimisation of distillation columns with Heat Integration results in large model sizes
with many infeasibilities, which may lead to premature termination of the solver. The modelling of distillation
columns may require discrete variables to represent the number of stages when the number of stages is not
fixed, leading to further difficulties in solving the model as an MINLP formulation such as the one by Farkas et
al. (2008). Other works have utilized shortcut distillation models (Yeoh et al., 2019) or developed rigorous NLP
distillation models (Kraemer et al., 2009) to circumvent the need to use an MINLP formulation. However, shortcut
models may not be able to accurately capture the behaviour of distillation columns. Another rigorous NLP
distillation model developed by Dowling and Biegler (2015) appears to be robust and effective in conducting
flowsheet optimisation with Heat Integration and complex thermodynamic methods, showing the benefits of
using a rigorous NLP model to represent the distillation process when used with Heat Integration.
In this work, an alternative formulation for an NLP-based distillation model is proposed that may be used with
Heat Integration methods in simultaneous process optimisation. The novel NLP model may be more robust than
previous ones as it has less variables. A case study on the optimisation of an ASU consisting of two distillation
columns and a MHEX was conducted to test the robustness and effectiveness of the novel NLP distillation
model in flowsheet optimisation.
2. Methodology
This section provides details on the formulation of the NLP distillation model and supporting models such as the
Heat Integration model. Other information, such as the thermodynamic module and the flowsheet of the case
study are also mentioned here. Assumptions and where to find parameters are also included in this section.
2.1 NLP distillation model formulation
Traditionally, distillation columns are modelled as a series of stages where flash operations occur. The inlet and
outlet streams and relevant properties of a typical stage in a distillation column are shown in Figure 1. Liquid
streams are saturated liquid at the bubble point, while vapour streams are saturated vapour at the dew point.
Figure 1: Representation of streams and relevant stream properties of a typical stage in a distillation column
In Figure 1, f represents the molar flowrates, x and y represent the liquid and vapour composition of component
i, T and P represent the temperature and pressure of the stream, while H represents the enthalpy of the stream.
L and V show whether the streams are liquid or vapour and n represents the stage where the stream exits from.
An active stage is a stage where the outlet stream properties differ from those of the inlet. The liquid and vapour
outlet streams of an active stage are in equilibrium with each other. Inactive stages are stages where the outlet
stream properties are the same as those of the inlet. The constraint where the liquid and vapour outlet streams
are in equilibrium with each other does not apply to inactive stages and needs to be relaxed. Since the number
of active stages is an optimisation variable and is not known a priori, a surplus of stages will first be defined. A
continuous variable is used to activate or deactivate the stages.
MESH equations such as the ones shown below are applicable to both active and inactive stages.
𝑓𝐿,𝑛−1 + 𝑓𝑉,𝑛+1 = 𝑓𝐿,𝑛 + 𝑓𝑉,𝑛 ∀ 𝐿 ∈ 𝐿𝑖𝑞; 𝑉 ∈ 𝑉𝑎𝑝; 𝑛 ∈ 𝑁 (1)
𝑓𝐿,𝑛−1 𝑥𝑖,𝑛−1 + 𝑓𝑉,𝑛+1 𝑦𝑖,𝑛+1 = 𝑓𝐿,𝑛 𝑥𝑖,𝑛 + 𝑓𝑉,𝑛 𝑦𝑖,𝑛 ∀ 𝐿 ∈ 𝐿𝑖𝑞; 𝑉 ∈ 𝑉𝑎𝑝; 𝑛 ∈ 𝑁; 𝑖 ∈ 𝐼 (2)
Zn is a continuous variable with a value between 0 and 1. It is used to activate or deactivate a stage as necessary.
𝜀 is a slack variable with a lower limit of 0. The summation of 𝜀𝑛 is added to the objective function to be minimized
and it’ll take on a value of 0 in optimal solutions. From Eq(4) to Eq(6), whenever any one of the stream properties
change, Zn must take on a value of 1 in order to force the left-hand side of the equations to be 0 to satisfy the
equality constraint. In this way, stages where Zn = 1 are active stages where the stream properties change.
Conversely, whenever the stream properties do not change, Z n could take on any value, as the left-hand side
of the equation will always be equal to 0. However, as the following constraints also apply, it is not physically
possible for Zn to take on a value of 1 for an inactive stage.
This formulation where zero-flowrates do not occur circumvents a problem highlighted in Grossmann et al.
(2005), where MESH equations are reduced when inlet and outlet flows are non-existent, leading to
convergence failure. Addition of the slack variable was also done to avoid this problem, as 0 x 0 values are
possible within the complementarity constraints in Eq(4) to Eq(6). Many of these characteristics to avoid singular
equations are found in (Dowling and Biegler, 2015) but it can be observed that the novel model has less
variables, as bypass streams do not need to be defined for each stage.
Eq(4) to Eq(6) are not required for the vapour streams, as the vapour stream properties will be determined by
the MESH equations. The change in H, enthalpy, is not included because it is calculated from other properties.
Change in pressure is not considered either as the outlet stream pressures will be controlled by other equations.
As mentioned before, the liquid and vapour outlets are in equilibrium for an active stage but not for an inactive
one. The following set of equations are used to enforce the equilibrium constraint whenever a stage is active.
𝑦𝑖,𝑛 ≥ 𝐾𝑒𝑞,𝑖,𝑛 𝑥𝑖,𝑛 − (1 − 𝑍𝑛 )𝑀 ∀ 𝑛 ∈ 𝑁; 𝑖 ∈ 𝐼 (7)
𝑃𝑠𝑎𝑡,𝐿,𝑖,𝑛
𝐾𝑒𝑞,𝑖,𝑛 = ∀ 𝐿 ∈ 𝐿𝑖𝑞; 𝑉 ∈ 𝑉𝑎𝑝; 𝑛 ∈ 𝑁; 𝑖 ∈ 𝐼 (9)
𝑃𝑉,𝑛
Where 𝐾𝑒𝑞,𝑖,𝑛 is the equilibrium constant. In this work, it is calculated from the saturated pressure of the liquid
and the vapour pressure following Raoult’s Law in Eq(9). M is a sufficiently large scalar.
Whenever Zn = 1, indicating an active stage, Eq(7) and Eq(8) are effectively equal to Eq(10).
𝑦𝑖,𝑛 = 𝐾𝑒𝑞,𝑖,𝑛 𝑥𝑖,𝑛 ∀ 𝑛 ∈ 𝑁; 𝑖 ∈ 𝐼 (10)
As mentioned before, it is not possible for Z n to take on a value of 1 for an inactive stage. This is because
fulfilling Eq(10) without any changes in stream properties would require the inlet liquid and vapour streams to
already be in equilibrium prior to entering the stage. Such a point is known as a Pinch point, and according to
Westerberg and Wahnschafft (1996), an infinite number of stages is needed to go through the Pinch Point.
Since the liquid and vapour outlets of an inactive stage cannot be in equilibrium, (1-Zn) cannot take on the value
of 0, and (1-Zn) multiplied by M is used to relax the equilibrium constraint for inactive stages.
Other than being in equilibrium with each other, another constraint where the temperature of the liquid and
vapour outlet are equal applies to active stages. The constraint is implemented via Eq(11) and Eq(12).
𝑇𝐿,𝑛 ≥ 𝑇𝑉,𝑛 − (1 − 𝑍𝑛 )𝑀 ∀ 𝐿 ∈ 𝐿𝑖𝑞; 𝑉 ∈ 𝑉𝑎𝑝; 𝑛 ∈ 𝑁 (11)
Ω(𝑥) = 0 (18)
The equations are modified in this way because there are no hot or cold utilities. Eq(18) enforces energy balance
for the streams entering and exiting the MHEX.
2.3 Thermodynamic module
An ideal thermodynamic module was employed to calculate stream properties such as enthalpy and vapour-
liquid equilibrium. The ideal thermodynamic module utilizes equations and parameters from the IDEAL method
available in Aspen Plus V11. For example, Eq(19) is used to calculate the ideal gas specific heat capacity.
2 2
𝐶𝑜3,𝑖 /𝑇 𝐶𝑜5,𝑖 /𝑇
𝐶𝑃,𝑖 = 𝐶𝑜1,𝑖 + 𝐶𝑜2,𝑖 ( ) + 𝐶𝑜4,𝑖 ( ) ∀𝑖 ∈𝐼 (19)
sinh(𝐶𝑜3,𝑖 /𝑇) cosh(𝐶𝑜5,𝑖 /𝑇)
Where Co1 to Co4 are component-specific parameters. In this work, 𝐶𝑃,𝑖 is assumed to be constant and equal to
Co1,i due to the complexity of the sinh and cosh operators in Eq(19). This simplification does not greatly affect
the calculation of CP,i, as the contributions of the second and third terms of Eq(19) are negligible compared to
the first term within this study.
2.4 Details of the case study and models of the auxiliary equipment
Figure 2 shows the flowsheet used in the case study. The ASU shown here uses the double-column
configuration, found to be the best in (Dowling and Biegler, 2015). Optimisation of the flowsheet is conducted at
different oxygen product purities with the objective of minimizing energy consumption per kg of oxygen product.
LPVD
LPEXP
LP
EXPANDER LPREF
LPFEED
LPBV
AIR LPEXP01 THVALVE2
LPBL THVALVE1
COMPR MHEX HP
CWCOOLER SPLITTER LPEXP0
HPD
COMPAIR
HPFEED0
COMPOUT HPB
LPVDOUT HPFEED
O2PROD LPBLOUT
MIXER LPBVOUT
Table 1 shows the specifications that were fixed in the optimisation. All feeds to the columns enter at a pressure
ΔP higher than the feed stage. Results of the case study were verified in Aspen Plus.
575
Compressor work and work produced by the expander are calculated using the following formula:
𝛾−1
𝑓𝑉 . 𝑅. 𝑇𝑖𝑛 . 𝛾 𝑃𝑉 ,𝑜𝑢𝑡 𝛾
𝑊= . (( ) − 1) ∀ 𝑉 ∈ 𝑉𝑎𝑝 (20)
𝛾−1 𝑃𝑉 ,𝑖𝑛
𝑐𝑝
Where 𝛾 is the ratio of specific heat capacities, , R is the ideal gas constant and 𝜂 is the efficiency. W is
𝑐𝑣
multiplied by 𝜂 for the expander and divided by 𝜂 for the compressor. Expander work will be negative.
The flowsheet optimisation is shown below, with the objective function to minimize energy consumption per unit
mass of O2 product. MW is the molecular weight while f(x) and g(x) are the equality and inequality constraints.
𝑊𝐶𝑂𝑀𝑃𝑅+𝑊𝐸𝑋𝑃𝐴𝑁𝐷𝐸𝑅
𝑚𝑖𝑛 𝑂𝑏𝑗 = ∑ + ∑𝑛 𝜀𝑛 s.t. 𝑓(𝑥) = 0, 𝑔(𝑥) ≤ 0 (21)
𝑖 𝑓𝑂2𝑃𝑅𝑂𝐷 𝑦𝑖,𝑂2𝑃𝑅𝑂𝐷 𝑀𝑊𝑖
The NLP model generates solutions quickly as seen in Table 2, which makes it suited for multi-start initialisation
to obtain multiple local optimal solutions or to provide good initial values and bounds to a global solver.
Initialisation of stream properties was done by fixing parameters such as the reflux ratio and feed temperature
of the HP column, before solving the model by minimizing the sum of the slack variable. These fixed values
were subsequently allowed to vary. Constraints such as condenser and reboiler coupling were added prior to
optimising the system with the objective function in Eq(21) without pressure drop before the final optimisation
was performed with pressure drop considered. Results from the system without pressure drop tends to activate
excess stages. When pressure drop is considered, the NLP model reduced the number of stages, showing that
it can optimise the number of stages to an extent. However, the solutions presented here were achieved by
optimising the system again with addition or removal of stages to compare the values of the objective function.
Better solutions were found but the values only differed by around 1 %. The model may benefit from using
aggregate distillation models with pressure drop considerations for initialisation, as pressure drop has an impact
on the solution. Even with the crude initialisation procedure used here where the final values differed greatly
from the initial values, the NLP model converged most of the time.
576
In certain cases, the optimisation procedure reduced the energy consumption by 5.4 % from an initially feasible
solution (e.g. 754) to the final value (e.g. 713), showing that the model can identify potential energy savings. A
transition in a process parameter is seen in Table 3, where liquid product is preferred at 94 mol % purity, but
vapour is preferred above 95 mol %. Higher reboiler and condenser duty may be needed to achieve higher O 2
and N2 purities, leading to more vapour in the LP column. At lower purities, drawing liquid may be preferred as
the temperature of liquid is lower than vapour of the same O2 purity. A lower HP condenser pressure is then
needed to meet the ΔTmin, since the HP distillate temperature needed to heat the reboiler is lower. The minimum
energy requirement does not occur at maximum number of stages or 100 % O2 recovery, possibly because
more stages and higher recovery lead to higher pressure drop throughout the columns and higher compressor
power. The O2 recovery decreases for 98 % purity, which may be due to limitations of the ASU configuration
presented, as the ΔT in the MHEX is at the minimum for all streams for this purity.
4. Conclusions
A novel NLP distillation formulation was presented and implemented with a case study on an ASU. The NLP
formulation was found to be fast with good convergence qualities when combined with Heat Integration models,
even with crude initialisation methods. However, it tended to get stuck at local optimums and may benefit from
better initialisation methods. Results of the case study found that 5.4 % energy savings are attainable compared
to a feasible initial point. It was also intriguing that the minimum energy requirement and maximum product
recovery do not coincide, with an average optimal product recovery of around 96 % for the proposed system.
Acknowledgements
The authors thank the financial support from the Hong Kong Research Grants Council (RGC-GRF 16211117).
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