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Computers and Chemical Engineering 94 (2016) 287–311

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Computers and Chemical Engineering
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A modeling strategy for integrated batch process development based
on mixed-logic dynamic optimization
Marta Moreno-Benito a,∗ , Kathrin Frankl b , Antonio Espuna
˜ c , Wolfgang Marquardt b
Centre for Process Systems Engineering, University College London, Torrington Place, London WC1E 7JE, UK
Process Systems Engineering, RWTH Aachen, Turmstraße 46, D-52056 Aachen, Germany
Department of Chemical Engineering, Universitat Politècnica de Catalunya, ETSEIB, Av. Diagonal 647, E-08028 Barcelona, Spain

a r t i c l e i n f o a b s t r a c t

Article history: This paper introduces an optimization-based approach for the simultaneous solution of batch process
Received 3 January 2016 synthesis and plant allocation, with decisions like the selection of chemicals, process stages, task-unit
Received in revised form 10 June 2016 assignments, operating modes, and optimal control profiles, among others. The modeling strategy is based
Accepted 31 July 2016
on the representation of structural alternatives in a state-equipment network (SEN) and its formulation as
Available online 6 August 2016
a mixed-logic dynamic optimization (MLDO) problem. Particularly, the disjunctive multistage modeling
strategy by Oldenburg and Marquardt (2008) is extended to combine and organize single-stage and mul-
tistage models for representing the sequence of continuous and batch units in each structural alternative
Batch process synthesis
Plant allocation
and for synchronizing dynamic profiles in input and output operations with material transference. Two
Dynamic optimization numerical examples illustrate the application of the proposed methodology, showing the enhancement
Generalized disjunctive programming of the adaptability potential of batch plants and the improvement of global process performance thanks
Synchronization to the quantification of interactions between process synthesis and plant allocation decisions.
Multistage modeling © 2016 Elsevier Ltd. All rights reserved.

1. Introduction Stephanopoulos and Reklaitis, 2011). Both sub-problems have sev-
eral degrees of freedom closely interrelated, which ultimately
Specialty chemical industries are meant to assimilate and define the process and the required equipment investment in new
execute many different processes along their lifecycle, as many or previously existing manufacturing facilities in grassroots or
specialty goods are subject to quickly changing markets or may retrofit scenarios, respectively. For instance, the development of
be displaced by rapidly advancing technologies. The fast introduc- a batch process stage includes decisions like the operating mode for
tion of new products and processes into manufacturing facilities determining the process structure – i.e. parallel, series or single unit
is crucial to be first in the marketplace. However, such processes operation – that best suits the process requirements in the batch
should be also sustainable to ensure a long-term economic via- system. This decision is closely related to the task-unit assignment
bility and maintain their competitiveness in front of stockholders. and equipment selection, especially in the case of existing plants
The investment of time and resources to design, construct, and vali- with a given set of units and connecting pipelines, and is crucial to
date a new plant each time that a different product is approved for exploit the adaptability potential of batch systems. Simultaneously,
commercialization is not a viable strategy in most cases. This way, each equipment unit has to accommodate the assigned tasks using a
batch systems are highly appropriate for specialty chemical sec- batch or semi-continuous procedure, which involves either a chain
tor because their inherent flexibility allows their adaptation and of batch operations or an intermittent use of continuously oper-
reconfiguration to incorporate new production lines with none or ated plant elements, respectively. Notably, batch operations are
only partial plant modifications. defined by their duration and dynamic feed-forward trajectories of
After the discovery of a new product and acknowledgment control variables, and their feasibility depends on physical con-
of its market opportunity, the integrated batch process devel- straints like the capacity of the selected units. Additionally, it is
opment problem addresses the synthesis of processing schemes necessary to determine the batch size and the number of batches,
and the allocation of manufacturing facilities (Rippin, 1983; as they are responsible for the total demand satisfaction and inter-
relate with the equipment capacity and process conversion. Other
degrees of freedom for full process development include the selec-
∗ Corresponding author. tion of process stages, the recirculation of intermediate flows, the
E-mail address: (M. Moreno-Benito). installation of buffer tanks for working with different cycle times or
0098-1354/© 2016 Elsevier Ltd. All rights reserved.

288 M. Moreno-Benito et al. / Computers and Chemical Engineering 94 (2016) 287–311

Problem sets and indices
Acronyms  set of technological specifications indexed by 
AIBN azobisisobutyronitrile j ⊆  technological specification of unit j ∈ U, |j | = 1, ∀ j ∈
AN acrylonitrile U indexed by 
B&B branch-and-bound i set of operating modes in task i ∈ PS indexed by
CHR convex-hull relaxation C set of chemical compounds involved into the pro-
CNF conjunctive normal form cess indexed by c
DMF dimethylformamide Cjs ⊆ C subset of potential reactants, solvents, or catalysts
DO dynamic optimization in unit j ∈ U indexed by c
EPC end-point constraints Di, ⊆ Ui subset of batch units Ui in task i ∈ PS whose input
GBD generalized Benders decomposition flow rate is a control variable in configuration ∈
GDP generalized disjunctive programming i . It is defined such that |Di, | = DOFi, − |Ui |, where
IFS initial feasible solutions |Ui | represents the degrees of freedom removed by
KPI key performance indicators output flow rates indexed by j
MIDO mixed-integer dynamic optimization Ij ⊆ Kj subset of input stages for unit j ∈ U at Level 1
MILP mixed-integer linear programming indexed by k
MINLP mixed-integer non-linear programming J set of all existing and potential equipment pieces,
MLDO mixed-logic dynamic optimization J = U ∪ T ∪ Sp ∪ Mx indexed by j
MP mathematical programming Ji ⊆ J subset of equipment pieces within potential task i ∈
NCO necessary conditions of optimality PS indexed by j
NLP non-linear programming Kj set of stages for unit j ∈ U at Level 1 indexed by k
OA outer approximation L set of potential stages at Level 0, L = {1, . . ., Lmax }
PC path constraints indexed by k and l
PWC piecewise constant La ⊆ L subset of active stages at Level 0 indexed by l
RTN resource-task network Lj0 ⊆ L subset of stages at Level 0 where unit j ∈ U can start
SEN state-equipment network
its operation, Lj0 = {1, |Kj | − |Oj | + 1 | j =
/ j, j ∈ U}
STN state-task network
indexed by l
VA vinyl acetate
Mj set of pipelines for unit j ∈ U at Level 1 indexed by
General variables
Mjin ⊆ Mj subset of input pipelines to unit j ∈ U at Level 1
z(t) derivatives of differential process variables
z(t) differential process variables indexed by m
y(t) algebraic process variables Mjout ⊆ Mj subset of output pipelines from unit j ∈ U at Level
udyn (t) dynamic control variables 1 indexed by m
ustat time-invariant or static continuous control variables Mx set of existing and potential mixers indexed by j
uint integer control variables N set of pipelines at Level 0 indexed by n
uBool logical or Booleans decisions Ni ⊆ N subset of pipelines at Level 0 for task i ∈ PS indexed
ubin binary decisions by n
 algebraic time-invariant variables Niin ⊆ Ni subset of input pipelines to process stage i ∈ PS
p process parameters indexed by n
Niout ⊆ Ni subset of output pipelines to process stage i ∈ PS
General functions indexed by n
f DAE system Ni,0 ⊆ N subset of pipelines at Level 0 whose flow rate is
g path constraints restricted to zero in configuration ∈ i of task i ∈
ge end-point constraints PS indexed by n
h algebraic equations evaluated at the final time f
Ni ⊆ N subset of pipelines at Level 0 for task i ∈ PS whose
l set of relations that define initial conditions f
flow rate is fixed by the preceding task, |Ni | = 1
m stage-to-stage continuity between consecutive
except for process stages preceded by a buffer j ∈ T
mathematical stages
indexed by n
fd DAE system in disjunctive equations
Nib ⊆ Ni bypass pipeline for process stage i ∈ PS, |Nib | = 1
gd path constraints in disjunctive equations
indexed by n and b
gd,e end-point constraints in disjunctive equations
Nr ⊆ N subset of pipelines at Level 0 for recirculation
hd algebraic equations evaluated at the final time in
indexed by n
disjunctive equations
Njin ⊂ N subset of input pipelines to unit j ∈ J at Level 0
ld set of relations that define initial conditions in dis-
junctive equations indexed by n
md stage-to-stage continuity between consecutive Njout ⊂ N subset of output pipelines from unit j ∈ J at Level 0
mathematical stages in disjunctive equations indexed by n
Bd equations system to define bypass stages in disjunc- Oj ⊆ Kj subset of output stages for unit j ∈ U at Level 1
tive equations indexed by k
 objective function P⊂C subset of desired products indexed by p

This way. sequencing and splitting. 2001. 2005. laboratory procedures used during the X i (*) configuration Boolean for alternative ∈ i in pro.l (t) flow rate of connection n ∈ N in stage l ∈ L at Level Given the complexity described above. the selection from a set of U set of existing and potential batch units indexed by alternative technologies. / Computers and Chemical Engineering 94 (2016) 287–311 289 PS set of potential process stages or tasks indexed by i xc. 1 and stage k ∈ L of unit j ∈ J\U at Level 0 Barbosa-Póvoa. 2003).k (t) composition of compound c ∈ C in input or output However. First.g. Mosat et al. 1995.. 1999..q (*) assignment Boolean for processing order q ∈ Q in els – to simplify the process stage representation (Robinson and unit j ∈ U Loonkar. thus . Finally. divide and conquer strategies jeopardize the efficiency connection m ∈ Mjin ∪ Mjout and stage k ∈ Kj of unit of the resulting process for several reasons. Besides.end final time of unit j ∈ U at Level 1 (DO). like the chemicals. Additionally. Other works focus on the optimal operation of individual Tf total time at Level 0 units through the application of tools like dynamic optimization tj. This way. j The mathematical formulation and the solution procedure Ui ⊆ U subset of existing and potential batch units in pro. batch integrity has to be guaranteed selected for every structural processing alternative by synchronizing the material transference between batch and semi-continuous plant Problem variables (* Control variables) elements as a function of the selected processing scheme and the Batchp production size associated with each batch of prod. In this case.. duration of batch operations (Vassiliadis et al. 1989.f total time of unit j ∈ U model at Level 1 last decades that addresses operating decisions like the dynamic tl (*) duration of stage l ∈ L at Level 0 profiles of control variables (Binder et al. the transition of 0 = qth element of the ascend- Boolean Wj.. degrees of freedom with regard to the flow rates process stage. Oldenburg et al. and j tk duration of stage k ∈ Kj of unit j ∈ U at Level 1 structural decisions that determine the configuration of processing ts starting time at Level 0 units (Jain et al. Srinivasan et al.q is true. The batch nature of the process involves not only a combinatorial assessment for linking Problem parameters the equipment and task networks (Gani and Papaeconomou. qual- Lmax maximum number of stages at Level 0 itative information has to be included regarding decisions like tasks pj.s starting time of unit j ∈ U at Level 1 2003).. 1994.q starting stage of unit j ∈ U when the task-unit the problem (Srinivasan et al. xc. Linninger et al. lj.. while some contributions include allocation Shortfallp unaccomplished demand of product p ∈ P decisions through sequential decision-making procedures (Cavin Sizej (*) discrete capacity of unit j ∈ U ∪ T et al.l (t) composition of compound c ∈ C in connection n ∈ N Q set of ordered positions that can be assumed by unit and stage l ∈ L at Level 0 procedures of j ∈ U indexed by q Yj (*) equipment Boolean for processing or storage unit Sp set of existing and potential splitters indexed by j j ∈ U∪T T set of existing and potential storage tanks indexed Zi (*) process stage Boolean for task i ∈ PS by j Tnr ⊆ T buffer tank for potential recirculation of flow n ∈ N r . In batch systems. product development phase are scaled-up to pre-specify the infor- mation related to the batch process synthesis. DO or optimal control is a well-received research field in the Tj. The design of jk (t) material volume in stage k ∈ Kj of unit j ∈ U t Level batch plants is a further area of extensive research (Reklaitis. 2003).q batch operations in batch process stages entails the mathematical ing sort of Lj0 of unit j ∈ U representation of discrete events (Barton et al. according to each senting the process performance and dynamic profiles of control configuration ∈ i 0 variables are necessary to fully explore the attainable region of lj.c values for the set of process parameters pj in unit selection.... the problem of batch 0 process development is usually decomposed in sub-problems and j int k (t)(*) internal control variable in stage k ∈ Kj of unit j ∈ U solved independently.. Most of the literature follows the nat- at Level 1 and stage k ∈ L of unit j ∈ J\U at Level 0 ural decomposition into process synthesis and plant allocation NBp (*) number of batches of product p ∈ P sequence for simplifying the problem. 2005) Demp demand of product p ∈ P but also the adjustment of processing conditions along time in each DOFi. 2000). 1999. j Sc (*) compound Boolean for reactant. solvent.. and j ∈ U when potential chemical alternative c ∈ Cjs is chemicals selection. 1972). 1985. M. tj. Iribarren. |Tnr | = 1. 2007) where the allocation of manufacturing facil- j ities and plant sizing are usually solved using predefined recipes V (*) technology Boolean for specification  ∈ j in processing unit j ∈ U or approximated models – e.. dynamic models are required for repre- at Level 0 at process stage i ∈ PS.n. 1998). Iribarren et al. for addressing this problem are challenging and computationally cess stage i ∈ PS indexed by j demanding activities for several reasons. cess stage i ∈ PS j operating conditions or processing times involved in the process. 2004. and the selection of chemicals. or catalyst Barton et al. the fixed time and size factor mod- Wj.m. tend final time at Level 0 2008). some studies Rn (*) recirculation Boolean for intermediate flow recycle address the synthesis of batch processes by disregarding the sub- n ∈ Nr sequent assignment of equipment items (Ahmad. 1994). Fn. c ∈ Cjs in unit j ∈ U Sharif et al. Ali. Moreno-Benito et al. the sequential j ∈ U at Level 1 solution of batch process development involves losing a signifi- cant part of the interaction among the degrees of freedom..k (t)(*) flow rate of input or output connection m ∈ Mjin ∪ input and output flows and the duration of the operations with Mjout in stage k ∈ Kj of unit j ∈ U at Level 1 material transference that occur at the same time. 2013. ∀n ∈ N r indexed by j batch sizes in successive process stages. equipment assignment. the synchronization uct p ∈ P of the material transference between consecutive processing units j requires establishing a link between the dynamic profiles of the Fm. Papaeconomou. task performance achieved. 1997.

However.290 M. 1996. the combination of hybrid discrete/continuous modeling and the task-unit assignment. the combination of these modeling equipment. In consequence. however. equipment capacities may represent either model con- cation should be solved simultaneously. albeit using an iterative evaluation of struc. of short-term scheduling (Bhatia and Biegler.... ing and combination of the coexisting single-stage and multistage cess performance using dynamic models in allocation problems has dynamic models that represent the multiple processing units that received a strong impulse in the last two decades in the context compose alternative processing schemes. Finally. For instance. In par- and allocation decisions like the selection of the operating mode ticular. In other chronization of process stages for linking operations with material works. series. addressed the problem solved in this work. bearing in mind that the sequence of et al. or adaptation of chemical processes in rapidly changing and the targets in bench-scale experiments – e. 2004). This way. Addi. process synthesis and plant allo. competitive markets. physical constraints of existing equipment units are not transference in consecutive processing units is addressed in the considered. and procedure. The principal objective batch operation instead of a chain of operations (e. Charalambides 2008. the syn. like the input/output flow rates – over the duration of the hensive mixed-logic dynamic optimization (MLDO) model that operations with material transference. 2008). Halim et al. 2011. straints in existing processing items or further decisions on plant Significant efforts have been made for combining synthesis and investments. Besides. not restrict the operation of the selected tasks (e. design.g. the representation of the pro. and intermediate flow recycles.g.g. Additionally. the definition of the operating mize the processes and guarantee the best utilization of available mode in single. time without simplifications. Chu and You. or each batch process stage is composed of a single processing units is not known beforehand. 2012. 1995). operations of the different batch units that happen at the same tural and performance decisions instead of a simultaneous solution time. reaction yield – fre. selection. Simultaneously.. 2004).. 1999). Moreno-Benito et al.. Furman et al. equipment and new investments. et al.g.. the whole process is sistent allocation solutions.. among others. other works opt for constant set-points (iii) The synchronization of the flow rates and compositions over for defining the processing conditions while solving the syn. which characterize single-stage and multistage models. between equipment units (e. improve- objectives are taken into account in the decision-making. modeling stage with each task.g. Our goal is the systematic optimization industrial-scale objectives (Moreno-Benito et al. or equipment sizing. the selection of technologies and chemicals. Other approaches simplify the prob. Finally. 1995) and its they involve the pre-specification of the sequence of process stages mathematical formulation as a MLDO problem (Section 4). variables. In contrast. ment. some studies address this prob. The combination of all these degrees of freedom in an allocation sub-problems with different degrees of integration over integrated optimization problem is solved in this paper for the first the last fifteen years.. 2007). the into account the physical restrictions of the given plant to ensure problem includes plant allocation decisions.g. Ferrer-Nadal et al.. the task-unit assignment.. instead of considering the dynamic profiles of the are eliminated by addressing the synchronization of coexisting input and output flows over a time interval. the named screening models (Allgor et al. some 2012). material and energy balances represented by a unique multistage model by associating one are evaluated in a unique time point in each operation with mate. For instance. Capón-García Previous contributions on process optimization have not et al. Frankl et al. Overall. lem using DO and mixed-integer dynamic optimization (MIDO) Essentially. these contributions do not cover other synthesis authors only study one single process stage (e. the dynamic feed-forward trajectories of control variables (Allgor (ii) The definition of multiple representation levels to link the and Barton. and the batch sizing. perform such a synchronization is the need of linking dynamic This paper presents a novel modeling strategy to optimize the profiles of the input and output flows – some of them being control integrated batch process development problem using a compre. which problem studied here (Section 2) comprises process synthesis deci- are usually global objectives that include all the different parts of sions like the determination of process stages or tasks and their the process – e. Bumann et al. Linninger and Chakraborty. 2009. and generalized disjunctive programming proposed by Oldenburg lem through the approximation of the batch process behavior and Marquardt (2008) is extended herein to incorporate: using algebraic models – e. 2014). and the synchroniza- conditions (Grossmann et al. the major novelty of this work is the order- 2011. Nie et al. Sharif et al.. tionally. of batch processes according to global objectives that embrace the tial of decisions like temperature profiles or task durations for process as a whole. 1999) and posynomial functions (Iribarren et al. 2002. while they use heuristic approaches based on path elements to handle simultaneously all the decisions previously dis- flow decomposition and indicator-based assessment (Banimostafa cussed has not hitherto been applied in the context of batch process et al. time and the duration of operations with material transfer- thesis and allocation problems simultaneously (Chakraborty and ence. Oldenburg et al. Besides. 2003) or do not use dynamic variables in the material transference chemicals. splitting into subtasks. The poten. Carvalho et al. duration of batch equipment may force its operation in extreme and even infeasible operations.. Simon et al. or parallel operation. and design decisions such as the selection of process technologies. These (i) The combination of single-stage and multistage models to rep- approaches have been complemented with the optimization of resent continuous and batch processing elements.. namely the equipment the feasible execution of the new processes.. The integrated batch process development quently differ from those of industrial-scale manufacture. to fully opti. the modeling strategy (Section 3) relies on the formulations to optimize the reference trajectories of control vari. tasks sequences is only relevant if production-scale restrictions and This way. 1987). all these assumptions rial transference. 2014. 1999). several authors seek the sustainable design of processing schemes in retrofit scenarios taking into account the previously existing To the authors’ knowledge. the direct implementation of fixed recipes in existing the definition of feed-forward control trajectories. it is crucial to take tion of operations with material transference.g. / Computers and Chemical Engineering 94 (2016) 287–311 restricting the evaluation of the system trade-offs according to decisions simultaneously. and previously existing equipment in grassroots and retrofit scenarios. 2012. With this last simplification. The technical difficulty to batch processes. processing conditions. performance.. we provide a tool for the agile development.. by taking the maximum advantage of new and improving global processing times. In our work. representation of processing alternatives in a state-equipment net- ables (Charalambides et al. whose ordering is not known beforehand. the total cost and environmental impact.. what implies that particular equipment constraints do context of scheduling and design of batch plants (Ferrer-Nadal et al. Corsano of the synchronization in these works is to elude physically incon.. 1999). 1995. although work (SEN) superstructure (Smith and Pantelides. 2008).. 2013. as a function of the selected process structure and tasks Linninger. This is opposite to linking a evaluates all the interactions between synthesis and allocation single time point and requires the definition of the corresponding .

the sequence of processing units is not known and multipurpose campaigns. Superstructure representation Batch design and scheduling problems require superstruc- • Planning data: set of products. In the formalized as generalized disjunctive programming (GDP) (Raman second case. icals involved in each process stage – i.e. • Process dynamics: DAE systems to represent the process behav. batch order... sentation of equipment items and states of transferred material. stage models. Floudas and Grossmann. 1995). alternative chem. solvents. ture representations that combine plant. M. the modeling approach is a key issue for the successful solution of the problem. 2010). beforehand. and possible reuse of interme. as it depends on structural decisions like the task selection or the operating mode. allowed technologies.. In pre- defined sequences of process stages. technological specification. and (iii) general hybrid discrete/continuous impact indicators. among others. and Pantelides. 2012. or catalysts –. Hybrid discrete/continuous models ior in each unit procedure.1. intermediate flows to be used in the next batch. 1991.g. chemi. Among them. and rapidly became an alternative to mixed-integer modeling for representing structural decisions (Grossmann. programming. or This representation enables the direct formulation of equipment catalysts –. (ii) multistage models. qualitative information. These kinds of problems were later problem can be solved in grassroots and retrofit scenarios. 1994). they are classified as: (i) single- final product. which is later formulated into Denbigh competitive reaction system (Section 6) and an acrylic a mathematical model. solvents. (STN) (Kondili et al. states. and Grossmann. Frankl et al. 2013... Depending on the type parameters to evaluate the objective function – e. Modeling strategy overall approach can be solved through several solution methods. dynamic control trajectories • Synthesis of processing schemes: selection of process stages have also been optimized in the field of batch process synthesis and splitting into subtasks. 2012). and raw materials. 3. other contributions in the operations within each unit procedure. synchronization of 3. The solution of optimization problems with structural decisions The benefits associated with the proposed optimization-based is usually addressed through the representation of all processing strategy are illustrated with two numerical examples.. Srinivasan et al. The use of logics in optimization problems single. (Allgor and Barton. operating mode – i. the SEN entails the repre- • Task network: potential and mandatory tasks. The incorporation of logical variables and equations into math- • Allocation of manufacturing facilities: selection of processing ematical models allows the combination of quantitative and and storage units. operating expenses in processing units. Nie. The entire problem is defined as follows. 1999. e. or parallel operation –. duration of 2007). Mixed-logic formulations with . a direct-simultaneous methodology is used in this work (Section 5). 2003).g. to be finally optimized (Grossmann and fiber production process (Section 7).e. Corsano et al. 1985.. trajectories of the feed-forward control variables. models. Charalambides et al. 1995. cals involved – i.2. the resource-task network (RTN) tially installed equipment units for each process stage or task.1. while enhancing the process efficiency and plant flexibility compared to the use of 3. For itative decisions are mathematically represented using Booleans the sake of completeness. with tion rates. ment in new or existing manufacturing facilities.1.. Background fixed recipes. namely the alternatives in a superstructure. environmental explicit discontinuities. recirculation of and You.3. Given: 3. initial conditions. process. and set of process These are dynamic models that represent batch process per- variables and dynamic or time-invariant controls. and set of limiting processing conditions of problems with process dynamics (Nie et al. compositions. formance and batch events by combining discrete and continuous • Data related to performance evaluation: decision criteria and variables (Barton and Pantelides. 2012. each equipment unit. reference 1999). In this procedure. and starting and final times. 1994). and material expected demand for final products. series. where qual- fined size value unless their capacity expansion is considered.. Precisely. batch of preceding process stages. mulation as a MLDO problem. The background of mathematical in order to define the process and the required equipment invest- tools for understanding such a strategy is presented next. without discrete events. the already existing equipment units have a prede. amortiza. of material flows on selected processing paths and conversion • Batch process operation: allowed task-unit assignments. Problem statement degrees of freedom and interactions that characterize the inte- grated batch process development in a holistic optimization model. reactants. The resulting MLDO model of our 3. such that the adopted performance metrics are optimized. intermediates. Nie et al. This work solves the batch process synthesis and the plant allo- The approach is based on a bi-level SEN representation and its for- cation sub-problems simultaneously in single-product campaigns. 2014. as it is the case of decisions associated with multiproduct Additionally.e. 2001. operation to operation literature have applied SEN superstructures to solve scheduling switching conditions. study. and batch sizes. 2014). This Duran and Grossmann.e. Moreno-Benito et al. The most popular proposals are the state-task network • Plant diagram: the SEN superstructure of available and poten. and the state-equipment network (SEN) (Smith pipelines and connection nodes like mixers and splitters. Sharif et al.1. and material transfer synchronization between tasks – i. 1994).. 1993). selling price of of discontinuities represented. 1996. (Pantelides. and maximum time horizon. / Computers and Chemical Engineering 94 (2016) 287–311 291 time interval in the time axis of the semi-continuous elements. and short-term scheduling (Capón-García et al. 1986). Hybrid dis- crete/continuous models have been widely used in DO problems for the goal is to determine: determining the optimal control profiles of individual processing units over time (Binder et al. capital costs. Guillén-Gosálbez. was initially proposed by Balas (1985) in the so-called disjunctive • Plant design: equipment sizing. task-unit assignment. equations and clearly illustrates the dependence of the profiles diates in following batches.1. batch plant design (Bhatia and Biegler. direct cost of raw materials. reactants. Logic-based modeling flow rates. it is worth noting that there are other and available process knowledge and heuristic rules are formu- process development decisions which are out of the scope of this lated through logical propositions. with implicit and explicit discontinuities. This work presents a novel modeling strategy for representing all the 2. Chu batch operations composing each process stage.

1a. which determine their usage and their order.. and synchronize the multi. is represented by either a single-stage or a multistage model asso. This is either because the physical constraints of exist.g. and scheduling of continuous processes with grade transitions (Prata et al. Oldenburg and Marquardt (2008) and Oldenburg et al. sequencing.292 M. this modular bi-level repre- sentation allows the ordering of processing elements as a function The proposed modeling strategy is based on the combination of of decisions like the task-unit assignment because. stage models are replicated for every possible new stage. the formulation only considered individual units rather than task sequences. in order to perform the coordination and timing of con- elements with dynamic profiles have not addressed the order. with connection nodes. 2a. this way..1. Transformation of single-stage models at Level 0 into mul- as well as hybrid discrete/continuous models – referred to as tistage models. The connection between the models of the multistage models in this paper –. so the ordering and synchronization of processing units were not approached. This formulation is inspired by models at Level 0 into multistage models that include all the the approach by Oldenburg and Marquardt (2008) for solving possible batch operations at Level 1. 2b. A basic SEN superstructure illustrates the inter. ing equipment units were not considered (Charalambides et al. the processing alternatives in a SEN superstructure. elements as well as the definition of the profiles of material flows Additionally. However. 1. In the context of batch process development.. processing units. currently.2. respectively. This superstructure representation enables the formu. However. and their process stages of the different models using standard optimization tools. these kinds of models have to be synchronized in operations with material transference as a function of the selected sequence of processing units. containing batch units. which is divided time coordinates of batch units within the integrated optimiza- into two representation levels and formulated mathematically as a tion problem can be moved in relation to the time horizon of other MLDO problem. configuration. (2003) presented a MLDO formulation that combined hybrid discrete/continuous models and GDP for solving the optimal control profiles. Since the several ciated with a semi-continuous or batch procedure. simultaneous design and control (Bansal et al. different processing units requires the conversion of single-stage cess performance in each unit. With this purpose. Here. 1. as illustrated in Fig. respectively. there are neither modeling frameworks nor software tools which can handle coexisting multistage and single-stage Therein. each unit stage-to-stage relations. This synchronization involves establishing a link Fig. 2008). batch units.4. the plant elements and their mod- 1995). 2004). Overall. conversion. Coexisting single-stage and multistage models for synchronization purposes Single-stage and multistage models can be used to repre- sent batch and semi-continuous procedures in the superstructure. Moreno-Benito et al. Normalization of mathematical stages. Since it is necessary to guarantee the lot integrity. organize. / Computers and Chemical Engineering 94 (2016) 287–311 dynamic equations have contributed to the solution of several problems such as model predictive control (Bemporad and Morari. and opera- tion of batch equipment items with structural decisions. Fig. all the models are 3. or because batch process stages were simplified as a single els are distributed into two representation levels by dividing the batch operation and the whole process could be represented by a SEN superstructure into Level 1. Independently of their representation level. 2. duration of the operations with material transference. and the ple equipment units in the SEN superstructure according to the continuity of process variables is guaranteed by incorporating processing alternative that is selected. but simplifying the problem through approximated process per- formance models. 3. each mathematical stage corresponds to a batch operation. models.e. the equations that compose the optimization problem are refor- The mathematical formulation of the superstructure and all the mulated as following detailed: associated decisions into a MLDO model comprises disjunctions and logical propositions. 1b for the previous exam- ple. processing elements at Levels 0 and 1 may be composed of a . their order. storage tanks. the optimization of individual units. Bi-level SEN representation and MLDO modeling strategy optimized at the same time. Previous works on optimization of sequences of processing Moreover. secutive units. The novel coexistence and connection between the existing and potential equipment units synchronization of single-stage and multistage models are illus- and the states of material flows according to the plant diagram. For visualizing this concept.. Linninger and Chakraborty (1999) and Chakraborty and Linninger (2002) addressed the problem of batch process synthesis and plant allo- cation including logical rules in the superstructure formulation. which determine the pro. the MLDO formulation With this purpose. the sets of equations of the original single- is extended to combine. 2002). trated in Fig. In contrast. which define the structural decisions. The time links across the different models are e. these multistage and single-stage models are nested ing and combination of several multistage models associated with in their entirety inside specific terms of the disjunctive equations. and Level unique multistage model – i. as represented in Fig. Basic SEN superstructure (a) and bi-level superstructure (b) of the motivating between the dynamic profiles of the input and output flows and the example 1. established through disjunctive equations and logical propositions lation of physical plant restrictions and procedures of processing in the formulation. by associating one modeling stage 0. and semi-continuous with each task (Corsano et al. batch units and the complete process. 1999). for enabling the relations across the mathematical as a function of the selected units.

Multistage and single-stage models of the motivating example 1 to represent batch and semi-continuous plant elements respectively. The key sets. / Computers and Chemical Engineering 94 (2016) 287–311 293 Fig. as shown in Fig.1. Notation stages of synchronized operations. Except for the actual first stage. whereas two additional stages would be required in series operation to complete the hold and unload operations of a sec- The variables and equations that compose the optimization ond batch unit U2 . Synchronization of batch stages and flow rates at Levels 0 and 1 for configu- of stage-to-stage continuity equations. it is possible to match the timespans of the mathematical 4. the iden.1. 2. stages l ∈ L at Level 0 to synchronize the duration of batch oper- tity of each mathematical stage at Levels 0 and 1 is preserved ations in units j ∈ U. For instance. 2b) which should be solved simultaneously. 1 could involve the three operations load. hold. the selected tasks i ∈ PS and operating modes ∈ i . The normalization of the time intervals defined in the previous step has a collateral advan- tage of expressing the stage durations as explicit variables. The maximum number of stages Lmax concerning this section according to the modeling strategy mentioned above all processing alternatives is determined by the structural system (Section 3). the number of total mathematical because it is a key issue for the synchronization of the selected divisions that are necessary at Level 0 for this purpose depends on processing units. M. This way. 4. This way. 3a (configuration ˛) and d model for integrated batch process development are detailed in (configuration ). rations ˛. and unload of 4. 2c. Out of . with |Kj | = 3. it is nec- essary to normalize their time axis. 3. ˇ. the utilization of a single batch unit U1 in the superstructure of Fig.1. Mathematical formulation unit U1 . . the initial conditions of all other stages should be treated as degrees of freedom whose values are subject to the fulfillment Fig. The normalization of time intervals is carried out by multiplying the differential equations by the stage duration and redefining their derivation interval from 0 to 1. diverse number of mathematical stages with different duration (see Fig. Mathematical stages Mathematical stages k ∈ Kj at Level 1 should be linked with Beyond these reformulations of the model equations. Moreno-Benito et al. as illustrated in Fig. 0 is then divided into Lmax intervals with different durations. U2 }. all the stages of every model can be solved at the same time. The total time Tf at Level understand the formulation are first presented. However. 3. parameters and variables required to composed of all the batch units in series. ∀ j ∈ {U1 . Explicit definition of stage durations. and of the motivating example 1.

uint . t j. Boolean decision variables uBool : selection of tasks Zi . the inflows j tk equal to zero and a set of equations that override the dynamic and outflows of batch units should be restricted to zero in those model of the batch process. the resulting set of stages L = {1. j . ⎢ Bd (z˙ j. u . . algebraic yj.k ⎥ j pounds Sc . 5. zj. where no process takes place. by removing the extra degrees of freedom. and md are the DAE system. uj.|Kj | (1).k (zj. yj. 1].k (t).m. ⎣ ⎦ j. processing and storage units Yj . Moreno-Benito et al. these variables refer specifically to equipment units or mathemat- ical stages. 2c): 4. d ⎥ batch operations tl represented by mathematical stages l at Level ⎢ ⎥ ⎢ ⎥ 0.k (t). these are termed input and output stages and the superstructure. j ∈ U ∪ T. hdj is the set of equations to calculate time-invariant variables in operations with material transference. ∀ k ∈ Kj .k improve the efficiency of the search procedure and reduce con.2.k (t). ∀ k ∈ {1.k (zj. yj.k (1).end = 0. ⎥ intermediate flows Rn . 1]. u . zj. c ∈ C of processing units j ∈ U. When stages k ∈ Kj . u stat . time-invariant or static variables . pj ). and stage-to-stage continuity in vergence issues. ∀ k ∈ Kj .f = 4.k (t). Static or time-invariant decision variables ustat : duration of ⎢ ⎥ ⎢ zj. zj.kd (z˙ j. and c ∈ C chemicals. Other variables and parameters dyn j trol uj. udyn (t). yj. stages. Let us consider discontinuous units j ∈ U located at Level 1 of ference. udyn (t).k (t). taking into account that the time interval has been normalized (see Fig. only the subset La com. t ∈ [0. technological specifications V .s T j.k (1)) = 0. namely differ- j j ˙ ential variables z(t) and their derivatives z(t). 4. Batch procedures at Level 1 posed by the so-called active stages is in force in each structural alternative. ustat . t j.k+1 (0) − mj.1.e . 4. ⎢ j tk = 0. ustat . represented by a |Kj |-stage model. ljd are the relations to determine the ini- are mostly connected with logical decisions and dynamic control tial conditions. ∀ j ∈ U. . |Kj | − 1}. it is possible to j. operating modes ⎡ ⎤ ¬Yj X i . The reduction variables  j evaluated at the final time (t = 1) of the last stage of the number of control variables is analyzed at the end of this |Kj |. tj = 0 The consideration of all these decisions may lead to over- d . Petri net representing process and bypass stages k ∈ Kj in the model of batch unit j ∈ U at Level 1. yj. 4.2.1. m ∈ Mjin ∪ Mjout and internal control ⎢ gj. which stage k ∈ Kj of unit j ∈ U. They are characterized by stage durations as input and output variables. and the |Kj |-stage Additionally.k (t) variables – including input/output flow rates Fm.e stat int ⎥ 2. stages that are not input Kj \Ij or output Kj \Oj stages respectively. 5.k (t). ⎥ ⎢ j j. if Yj is false. a two-term dis- junction controlled by Boolean Yj is introduced. ⎢  j ⎥ (1) ⎣ j tk .k (t). Their operation and process performance are are denoted by Ij ⊆ Kj and Oj ⊆ Kj respectively.k (zj.k (t). If Yj is true. Bypass stages are represented j j flow rates Fm.k (t). uj. pj ). .end = t j. udyn (t).k j j ⎥ j variables int k (t) over operations k ∈ Kj in batch units j ∈ U. Fig. the disjunctive equation for batch unit j ∈ U is defined to guarantee the absence of material transmission.2. end-point constraints (EPC). t ∈ [0.k (t) and The problem comprises other types of variables. which are referred to in the Petri net of Fig. ∈  in process stages i ∈ PS.k (t) and internal control variables int k (t) – in y(t). Integer decision variables uint : number of batches NBp of prod.k (t).4. ⎥ 3. and chemical com.k j. pj ) = 0. ⎢ ljd (z˙ j. Input and output flows processing item is selected to allocate one task.k j. g d.k (t) and compositions xc.k (1). Particularly.|K | (1). ⎥ ⎢ j. ⎥ ⎢ j. n ∈ Nr . ⎢ ⎥ ⎢ dyn gj.1. Essentially.q . For each unit.k (t) and differential zj.k (1).k specified problems in some cases.m. ustat . .k (t). and con- 4.k (t). Overall. ⎥ j ⎢ d ⎥ put connections Fm. 2008) is applied in order to define (denoted by m ∈ Mjin ∪ Mjout ) and are linked between the two lev- an equivalent number of |Kj | mathematical stages. Input/output variables and stages of batch unit j ∈ U models. ∀ k ∈ K . Batch units relevant to stages that represent operations with material trans.294 M. (PC).. Control variables ⎡ Yj ⎤ There are four types of decision or control variables: ⎢ fj. It is also characterized by process parameters pj and . processing orders Wj. g d . path constraints where fj. uint . input and output flows of batch units are repre. As illustrated in Fig. q ∈ ⎢ ⎥ j Q.k ⎥ ⎢ ⎥ 1. considering min ∈ Mjin input and mout ∈ Mjout output flows.1 (0)). yj. algebraic variables compositions xc. i ∈ k ∈ Kj PS. the unit is not selected and a bypass strat- egy (Oldenburg and Marquardt. d..s + T j. / Computers and Chemical Engineering 94 (2016) 287–311 Fig. t ∈ [0. uint .1.  ∈ . p ) ≤ 0. this 4. Circles symbolize stages and bars represent stage-to-stage transitions. and parameters p. The dynamic model of unit j ∈ U comprises time-dependent derivatives z˙ j. termed bypass els in the formulation. T j.3. ∀ k ∈ Kj . Lmax }. Dynamic control variables udyn (t): flow rates in input and out. by the following form. these flows are characterized by stages. On the sented at both Level 0 (denoted by n ∈ Njin ∪ Njout ) and Level 1 contrary. they may be written with subindices j or k respectively. model in the corresponding disjunctive term is activated. pj ) ≤ 0. 1]. .1 (0). and recirculation of ⎢ ⎥.f = 0. uint .f ⎦ uct p ∈ P and discrete sizing Sizej of equipment units j ∈ U. Therefore. The connection between Levels 0 and 1 is especially 4. and Bjd are the equations that define the system in bypass section based on the optimization model. ⎢ dyn j = hdj (zj.|Kj | (1). .

lj. To complete batch unit models at Level 1. each batch unit model is synchronized equipment capacity Sizej in any stage k ∈ Kj . ∀ k ∈ Kj \Oj (Eqs.B respectively.s of unit j ∈ U (Level 1) is calculated from the U1. For instance. Once a unit is selected. This constraint Wj.k ⎦ The time axis for the models of batch units j ∈ U that are selected j Fmout . the following equation is defined: ⎡ ⎤ 4. j ∈ U. / Computers and Chemical Engineering 94 (2016) 287–311 295 Fig. Assignment Booleans it is a fixed variable associated with an existing item. ∀ j ∈ U. .3. the rela- and its operation should start in stage lj. With this purpose.3.A and U1..k (t). this should be assigned one and only one processing order jk (t) ≤ Sizej . ∀ j ∈ U.2. Fig. which indicates (Level 0) by: j whether such specification is selected (V j = true) or not (V = false) ⎡ ⎤ Wj. time-invariant variables  j . ∀ mout ∈ Mjout . 6 shows a SEN with two technological alternatives A and B in equipment units • The starting time tj. like product selectivity or j Sc . Hence. ⎥ .q ∀ j ∈ U. ∀m ∈ Mjin ∪ Mjout – have this case. or catalysts equal to the duration tl of the corresponding stage l ∈ L (Level 0) c ∈ Cjs that are involved in the process of unit j ∈ U is represented by by: j ⎡ ⎤ Boolean Sc .q j equipment unit j ∈ U is represented by Boolean V . Chemical compound alternatives • The duration t j of stage k ∈ Kj of unit j ∈ U (Level 1) has to be k The selection of chemicals like reactants.q in the same unitary operation. the variables of models at Levels 0 and 1 are connected as processing item j ⊆ .q j j (Sc = true) or not (Sc = false). The selection between alternative j technologies requires the representation of different equipment tion between stage k ∈ Kj at Level 1 and its corresponding stage l ∈ L arrangements that determine the particular physicochemical equa. The SEN of Fig.k (t) and xc. by restricting their value j to zero. every alternative has to be associated with a specific basis.c stages respectively. either Sizej is a free with the models of other plant elements by relating the set of stages decision variable to design a newly installed unit or an expansion or Kj at Level 1 to specific stages l ∈ L at Level 0. different processing technologies  can be used 0 ∈ L0 . Moreno-Benito et al. (7) j q∈Q t j. ∀c ∈ C.3.q 0 .q and is related to the equipment Boolean Yj as follows:  ⎣ 0 −1 ⎦ .q . . as illustrated in Fig.2. and batch operations sequences for each case. 1]. This constraint is defined as follows: process conversion in j ∈ U.m. ∀ j ∈ U. t ∈ [0.k (t) = 0. . In 1) – i. 3. 6. Processing order of batch units ⎣ m . (1) and (2) with Yj = true) should be moved over the time axis of the entire process at Level 0 according to their processing order. Then. ∀ j ∈ U. Technological specifications q∈Q In some cases.e. Synchronization Yj ⎢ j ⎥ ⎢ F in (t) = 0.2. parameters. the volume k (t) at unit j ∈ U cannot surpass the as illustrated in Fig.q are defined to lead the synchronization by indicating the order is formulated by: q ∈ Q of unit j ∈ U with reference to other batch units. This way. The technology  ∈ j associated with 0 general starting time ts and duration tl of stages that precede lj. solvents. ∀ j ∈ U. (2) 4.c associated to be equal to the profiles of the analogous variables at Level .s = t s + tl Yj ⇔ V . On this q ∈ Q of unit j ∈ U through the function l = k + lj. ∀ k ∈ Kj \Ij . j Additionally. (5) c ∈ Cs pj = pj. 4. M. ∀  ∈ j . (4) l=1 4. |K | + l0 − 1} j l−l0 +1 j.q j. (1)) but only the set of parameters pj . which indicates whether a chemical compound is used Wj. (1). Fm. input/output variables j Sc should be dismissed in those stages which are not input/output  . 6 illustrates an example  ⎣ j ⎦ . Basic SEN superstructure of the motivating example 2. (6) 4. at Level 0 can be expressed as a function of the processing order 0 − 1 ∈ L.q alternative technologies  ∈ j . Unlike the case of q∈Q tl = t . (8) with two possible compounds c1s and c2s in unit U2 . in order to characterize follows: its DAE system through Eq. (3) q ∈ Q: Yj ⇔  Wj.q tions. ∀ k ∈ Kj . ∀ min ∈ Mjin . such parameters are defined by the values pj. the choice of a chemical compound c ∈ Cjs does not necessarily affect the complete set of equations in • The profiles of input and output variables of unit j ∈ U (Level j j the model of unit j ∈ U (Eq. ∀ j ∈ U. |j | = 1. ∀ l ∈ {lj. necessary for the objective function and with alternative c ∈ Cjs according to the chemical selection Boolean other key performance indicators (KPIs).1.

ends at final time tend .l (t) (10) 4. . The two exclusive alternatives are defined through the following disjunction: are not required at Level 0 are overridden by forcing stage durations tl to zero and withdrawing dynamic equations and constraints of Zi ¬Zi Level 0 elements. nin ∈ N in j Xi ⇔ WU1 . 1]. previously applied to batch units j ∈ U (see 4.nout . the stage duration is zero in extra stages l ∈ L\La . ∀ l ∈ L j ⎢  ⎣ Fn. 1]. . and (18) bypass stages:tl = 0. distributions with each operating mode. Fn. 5). xc. ∀c ∈ C. Lmax } for semi-continuous elements at Level 0. according to: ∀ c ∈ C.l (t) = Fnout . |Njin | > 1.0 in each configuration ∈ i is restricted to zero.l (t) = Fn. 1]. ∀ n ∈ Niin . ∀ l ∈ {|La | + 1. The resulting equation for every pair of equivalent flows at Levels 0 and 1 (n. are characterized by several input connections nin ∈ Njin .l (t) = 0. with the corresponding Boolean where Tf is the total batch processing time which starts at initial variables X i . ∀ b ∈ Nib .e.  . (19) X i ⇔ WU1 .n. and are described by: X˛i ⇔ WU1 . To do so. 1. . A logical proposition is used to define each configuration. represented by variable Wj. con- Additionally. Semi-continuous elements The time variables at Level 0 are related as follows: ∀ l ∈ L. t ∈ [0. ˇ. Following the bypass strategy.2 .1. c ∈ C of connec- in U1 .q 0 − 1} Xi  ⎣ ⎦. .l (t). ⎥ ⎥ ⎣ Fn. . Process stages The bypass strategy.296 M. 1].n..4.q j. ⎥  ⎢ ⎢ j.l (t).1 ∧ ¬YU2 . single operation in U2 . Gray elements ⎢ Fn. the flow rate of nin ∈ N in j a specific set of connections n ∈ Ni.l (t)xc. Additionally. ⎦ ∀ j ∈ U.l (t). that should be dis- therefore. L\La . is also used at Level 0 to define the set of extra stages Logical variable Zi represents the selection of task i ∈ PS and. and is divided in Lmax intervals with following proposition: duration tl .l (t) = x c. Mjin ) ∪ (Njout .q .1 ∧ WU2 .l (t) = 0 Fb. .5. (14) ∀ nout ∈ Njout . .5. This is defined through the time ts . ∀ l ∈ {1. ∀ l ∈ L 4.q l ∈ L\La = {|La | + 1. ∀ j ∈ Mx.l (t) = Fnout .0 . . t ∈ [0.q . ∀ j ∈ Mx.2.q ⎥ q∈Q ⎢ ∀ l ∈ {lj. (11) ∈ i upper tU bounds in active ones l ∈ La : The principal purpose of configuration Booleans is to govern the t L ≤ tl ≤ t U .n.4. Mjout ) reads as: ⎡ ⎤ Fig.l (t) = 0. . (20) . . t ∈ [0. . as well as in the case that unit j ∈ U is not selected. Moreno-Benito et al.q 0 0 − 1}. . t ∈ [0. Petri net representing active stages l ∈ La = {1. Fb. ∀ l ∈ L. mixers j ∈ Mx are series operation in U1 followed by U2 in the example of Fig.1 ∧ WU2 .l (t) = 0. . xc. this decision is related configuration X i . . 1]. ⎡ ¬Y ⎤ ∈ i Fn. Lmax }. (9) ∀ i ∈ PS. (13) Fnin . material balances in connecting nodes at Level 0 figurations i = {˛. ∀ n ∈ Ni.l−l0 +1 (t). and tions n ∈ N in every stage l ∈ L. 6. t ∈ [0. |Kj | + lj.1 ∧ ¬YU1 .  Tf = tl .l (t) = 0. |Kj | + lj. (12)  Xˇi ⇔ WU2 . ∀ i ∈ PS. whereas it is confined between lower tL and Zi ⇔  Xi .. Process stages Fig. . configuration Booleans X i enforce specific flow Fnin . . As shown in Fig. ∀ nout ∈ Njout ..nin .1 .. ⎦ ⎡ ⎤ ∀ l ∈ L\{lj. In particular. the latter ones have to be fixed to zero in the remaining non- synchronized stages.l (t) = 0. controls whether the input flow n ∈ Niin is processed or regarded in each structural alternative.l (t). 1].l (t) = F j j ⎥ represent feasible paths for other locations of stage |La |.n. |Njout | = 1. their processing order q ∈ Q. t ∈ [0. represented by variable Yj . (15)  Additionally.l−l0 +1 (t). |La |}.1. The reason is that the set of active stages La representing the sequence of batch operations whether it is bypassed through pipeline b ∈ Nib to the following in the complete process depend on the selected tasks Zi and their task.l (t) and xc. t ∈ [0. ⎢ m. 1]. and defined by: a single output nout ∈ Njout . parallel operation in U1 and U2 . 7. l∈L (17) 4. |La |} and bypass stages Wj. m) ∈ (Njin . ∀n ∈ Njin ∪ Njout . only one can be selected. ∈ i in a process stage i ∈ PS. . the set of stages l ∈ L\La that to splitter Sp3 . 7. .q 0 . } which correspond to single operation relate flow rates Fn.. Plant elements at Level 0 4.n.m.l (t) and compositions xc.. ∀ l ∈ L.4. ⎥. Operating mode Out of the set of allowed operating modes or configurations t end = t s + T f .l (t)xc. out of the total number of stages Lmax . / Computers and Chemical Engineering 94 (2016) 287–311 0 – i. For example. . (16) xc. In the problem superstructure of Fig. selection of equipment items j ∈ U.

∀ l ∈ L 4. In particular. ∀ n ∈ Nr .l (t).l (zj. (9).l (t = 0) in the gj.1 (0) = zj. (26) Since storage tanks operate continuously.2.l = ∈ gj. t ∈ [0. Batching ⎢ d fj.l j proposition reads as: and mdj.l (t). uj. . ustat .|La | (1).. the bypass method is required to differentiate active Rn La and bypass L\La stages according to Fig. and are described by: lowing batch is represented by connection n ∈ Nr . t ∈ [0.l (t).l+1 d.|La | (1). ∀ l ∈ {1. ustat . pj ) ≤ 0.l (1). the simultaneous solu- ⎢ ⎥ ⎢ ⎥ (23) tion of batch process development incorporates the optimization ⎢ dyn j = hdj (zj. ustat . . .e gj. The logical d . . t ∈ [0. what reads as: its complete model is deactivated like in the case of batch units j ∈ U. uint . t ∈ [0. ∀ j ∈ Sp. and uj. ∀ nin ∈ Njin . uint . ⎦ . .g.l+1 (0) − mdj.|La | (1). / Computers and Chemical Engineering 94 (2016) 287–311 297 whereas splitters j ∈ Sp are characterized by a single input connec.l (t) = xc. zj. |Njout | > The recirculation of an intermediate material to be used in a fol- 1. gj. pj ).l d = gd . pj ). |La |}. ∀ l ∈ L. and Shortfallp is the unaccomplished demand. ⎦ NBp Batchp + Shortfallp ≥ Demandp . |L |}.6.e usage of intermediate material. |La |}. . |La | − 1}. 1]. uj. yj. Second. j . ∀ l ∈ L It is not necessary to remove these equations in bypass stages The recirculation of intermediate flows additionally requires the because all flow rates would be forced to zero through previous installation of buffer tanks j ∈ Tnr in the superstructure – e. pj ) = 0.nin . ustat . Number of batches ⎢ ⎥ ⎢ ljd (z˙ j. and control variables in .l+1 j. yj. uj. t ∈ [0. The resulting formulation of storage tanks j ∈ T reads as: ⎡ Yj ⎤ 4. ∀l {1.l (t). Such models comprise the general functions fj. ∀ j ∈ T.  ⎣ Bjd (z˙ j. Fnin .1 (0). (21) Rn  FnL ≤ Fn. tank Eqs.l (t).l (t). Following. ⎥ task sequencing sub-problems. Objective function and degrees of freedom dyn The optimization problem presented above is solved to mini- where z˙ j.l (t).. uj. r in the example of Fig. uj. ∀ n ∈ N r ... As a result. pj ) ≤ 0. and ⎢ ⎥ ⎢ zj. ⎥ The batching problem consists in the division of the total prod- ⎢ ⎥ ⎢ ⎥ uct demand into a number of batches of a specific production size. Lmax } where Demandp is the total demand of product p ∈ P.l (t) ≤ FnU .6.. algebraic.l+1 . the bypass strategy is first stage l = 1 of unit Tnr are set to be equal to the final conditions applied to two situations: First. and several outputs nout ∈ Njout . ∀ l ∈ {1. . t ∈ [0.e . yj. zj.l (t). yj.l for storage tanks j ∈ T and mathematical stages l ∈ La . uint .l (t).l dyn (zj. hd . ∀ l ∈ L xc. 1].l (t). provided that this unit .1 (0)).1.l (t).l (t) = 0.l (t). which indicates if the inter-  mediate flow is recirculated (Rn = true) or not (Rn = false).l j j.|Lmax | (1). ∀ l ∈ {1. (22) . 1]. ustat . if storage unit j ∈ T is not selected.l j.l (1)) = 0. this decision is controlled by Boolean Rn . j . uint . . timing. ∀ nout ∈ Njout . t ∈ [0. (28) ∀ l ∈ {|La | + 1. . 1]. ⎥ the batching activity and following solve the allocation. NBp repre- ⎡ ¬Yj ⎤ sents the number of batches. 7. ∀ n ∈ Nr . the flow rate can either acquire a value between the lower FnL and nout ∈ N out upper FnU bounds or be canceled: j ∀n in ∈ Njin .l (t). |La | − 1}. yj. In this work. all the equations are d = fd repeated in active stages as defined by fj. ∀ j ∈ Sp.e d. yj.l (t). . uint .7.l (zj. ⎥ ⎢ ⎥ of the number of batches by means of the following equation: ⎢ bypass stages: ⎥ ⎣ dyn Bjd (z˙ j. 6 – in order to store the intermediate T11 Storage units j ∈ T are also defined at Level 0 by |L|-stage mod. els. 1].l (1). ∀ j ∈ Tnr . zj. (27) zj. (19) and (21). 1]. . ∀ p ∈ P. a ⎥ 4. initial conditions zj.l (t). |Njin | = 1. . ∀ l ∈ {1. 4.l (t). ustat . 1].l dyn (z˙ j.l (t). ∀ j ∈ Tnr is selected. zj. zj. . ⎢ ⎥ dyn d gj. (25) Fn. t ∈ [0. ⎢ ⎥ Common approaches for solving scheduling problems first address ⎢ d.l . . . 1].l (t = 1) in the last stage l = Lmax . Moreno-Benito et al. . M. pj ) = 0.l (t). . zj. g d. . ld .l (t).l (t) = Fnout . Recirculation of intermediate flows tion nin ∈ Njin . yj.5. material that is later supplied in a subsequent batch. Batchp stands for the batch production size.l (1). udyn j. uint . ∀ l ∈ L. and In order to define mathematically the sequence of storage and j. Rn ⇔ Yj .l (t).l (t) are the time dependent mize the objective function : derivatives and differential.nout . g d .. ¬Rn ∀ c ∈ C.

and  j are time-invariant uint . This parameter determines time or batch size for different parts of the process. In the . ˙ defined by derivatives z(t). 1]. Wj. Rn }. differential variables z(t). mathematical stage l ∈ L. ustat . a constraint to limit the max. j j according to the control variables udyn (t) = {Fm. ustat age tank size. uBool variables which may contribute to the evaluation of the objective function or KPIs in unit j ∈ T. udyn (t). uint . (24) j ustat = {tl }. which reads as: variables y(t). pj are process parameters.q . Finally. int k (t)}. uBool . time-invariant variables  and parameters p. the number of practical control variables in the reality. Sizej } and uBool = {Zi . Sizej is the maximum capacity of the tank. p . t ∈ [0. The decision on the selec. algebraic imum volume should be also formulated. Yj . z(t). V . ustat are time-invariant control variables. where jl (t) is the inventory volume of unit j ∈ T in stage l ∈ L and j Sc . X i . (29) namely stage durations. The degrees of freedom of the optimization model are the num- tion of intermediate tanks is crucial for allowing the recirculation ber of decision variables remaining after subtracting the number of intermediate flows as well as for defining more than one cycle of equations and predefined values. . ∀ j ∈ T. uint = {NBp . udyn (t). y(t). jl (t) ≤ Sizej .k (t). uint are integer decisions such as the stor. ˙ minimize  z(t). ∀ l ∈ L.

detailed in the next subsections. ∀ i ∈ PS. v . In ematical programming (MP) problem. able contributions. Sc . each variable on the reformulation of the mixed-logic problem into a mixed. t ∈ [0. and Sahinidis. After their decomposition. the system over-specification deteriorates the performance of methods. x are the (DP) based on Hamilton–Jacobi–Bellman formulation to trans. There exist different direct fact. (2015). (2). Wj. and obligatory variable con- defined in preceding tasks. 1975). the variables that are decomposed are of the fol- solutions under fairly general assumptions. depending on what parts of the problem are discretized. Wj.k (t) ⊆ udyn (t). provide a math- chronized cannot behave as decision variables simultaneously. and (26)). (11). ∀k ∈ Ij . X i . Yj . This is because the Ad problem reformulation allows exploiting the advantages of mixed. 1} . | = DOFi. u) ≤ 0 and rules about the process and their direct conversion into mathe- matical equations – as well as using well established MIDO solution strategies. like the big-M (Raman and Grossmann. (19) and Notably. tion presented in the previous section. This technique is based on the decomposition of all problem (Oldenburg and Marquardt.q . u ∈ R. whose 0 and 1 values cor- Xi respond to prior false and true values respectively. / Computers and Chemical Engineering 94 (2016) 287–311 j j equations (Luus. ∀j ∈ Di. Sc . 1978).298 M. To address the relaxation of the original MLDO model ∀ mout ∈ Mjout . 1]. ⎢ j ⎥  ⎢ F in (t) ∈ udyn (t). ustat . and (iii) direct methods which j convert the time-continuous optimization problem into a finite- flow rates in batch units Fm. as both process and control variable profiles i ∈ PS because they depend on the total number of flow rates are approximated by a series of finite points along the time horizon. In particular. the vector of logical decision variables uBool = corresponds to the degrees of freedom assigned to the output flows j j {Zi . these equations are Eqs. Tsang et al. 1990. rn }. Through sub- form the original problem into a system of partial differential stituting the Booleans Ad ∈ {true. For instance. conditions of optimality (NCO) derived from Pontryagin’s for- (9). and mum and most advanced algorithms are also able to provide global uint . 1996). The set Di. 1998). 2004). after the discretization of the input and output flow rates of different units j ∈ U that are syn- time-dependent variables of the original problem. (4).k (t) ∈ udyn (t). where |Ui | 0. except for control variables udyn (t). we use binary the integrated batch process development formulated as a MLDO multiplication. The the variables that are contained in the disjunctive terms into vari- majority of deterministic methods guarantee to find a local opti. Ad ∈ {true. ∀ k ∈ Oj . the parameter DOFi. the number of equations in splitters and mixers The resulting problem is a mixed-integer non-linear programming |Spi ∪ Mxi |. and the number of predefined flow rates. e. 2008. In particular. ∀ j ∈ Ui . (12)–(15).k ⎦ transformed into mixed-integer equations.. However. X i .g. let us or the problem solution with logic-based solution techniques. Moreno-Benito et al. the advantage of the direct approaches is that they do not (21)). (25). these profiles are interre- dimensional nonlinear programming problem by discretization. First. (ii) indirect methods through necessary case of Booleans uBool = {Zi . ⎥ . Rn } is transformed into a vector of binary in Eq. (5). The resulting equation reads as: j j ⎡ ⎤ variables ubin = {zi . term and its corresponding Boolean variable. Thus. the natural inference of previous knowledge d∈D Fd (x. x ∈ R. 1990). Overall. MLDO solution eral alternatives for performing this transformation. disjunctive equations that enclose other constraints are (32) ∈ i ⎣ m .  . the evaluation of degrees of freedom of dynamic require an explicit derivation of the necessary conditions of opti- profiles between consecutive units is especially relevant because mality and the adjoined equations and. dependent variables. (33) logic modeling – e.g. 1 . (30) This work employs the classical direct-simultaneous strategy f = |Ni | − |Spi ∪ Mxi | − |Ni. the solution search procedure. false} by the binaries ad ∈ {0. Ad are the Among the classical methods for solving MIDO problems. deterministic approaches are based time-invariant  variables. V .0 | in configuration ∈ i and input flows |Ni | second order derivatives computation. V . false are replaced by binaries ubin ∈   i ∈ PS.1. = No. ⊆ Ui are formations are  required in  the formulation. (16). flow restrictions |Ni. Yj . and differ for each configuration ∈ i and process stage the dynamic model. (31) into MIDO one in classical solution methods. is defined such as |Di.q . There are sev- 5.˙ differential z(t). there is a full discretization of DOFi. at Level 0 |Ni |. equations − No. In the specific case of the direct-simultaneous strategy (Neuman The degrees of freedom related to flow rates are denoted by and Sen. Boolean defined as control variables in configuration ∈ i of process stage variables uBool ∈ true. As for the dynamic control profiles of mulation (Bryson and Ho. the reformulation of Booleans as continuous variables. their disadvantage is that the model size DOF i. Second.0 | − |Ni |. lated through global balances in mixers and splitters (Eqs. outflows of batch units are always considered as free-decision variables: 5. the number of degrees of freedom is limited by logical propositions (Eqs. and u are the decision variables. Rn }. (31). The reader interested in alter- native stochastic and hybrid solution strategies is addressed to To adjust the number of control variables according to the Moreno-Benito et al. sc . where D is the set of disjunctive terms in the equation. In this work. namely the f (MINLP) model that can be solved without requiring sensitivities. (6). is com. false}. several trans- while only the inflows of the subset of batch units Di. tinuity. 1973. lowing types: derivatives z(t). t ∈ [0. contribution is associated with the constraints inside a disjunctive integer one. − |Ui |. degrees of freedom of each structural alternative. Fd find three different groups. wj. (Beaumont. as opposed to direct-sequential approaches (Sargent and puted as follows: Sullivan. 1975).. Stein et al. In the MLDO formula- ∀min ∈ Mjin . (23). 1991) and the convex-hull reformulation Different kinds of solution strategies can be used to tackle (CHR) (Türkay and Grossmann. we Boolean variables that control each of disjunctive terms d ∈ D. (27) and (32). The consider the following disjunctive equation: methods of the first group are also known as classical solution approaches and are the most extended ones. variables − No. MLDO reformulation j Fmout .q . ∀ i ∈ PS. fixed variables can increase exponentially in the discretization step. xi . Therefore. (1). 1]. (7)–(10). yj . namely: (i) Dynamic Programming are the functions nested in each disjunctive term d ∈ D. algebraic y(t).

. Ne } – and sub-problems (Nemhauser and Wolsey. N} are the clauses that must be true in the prob. Diamonds represent the approximations of z(t). u ∈ R. Finite elements discretization for differential z(t). M. and-bound (B&B) methods with non-linear programming (NLP) eral intervals – referred to as finite elements e ∈ {1. are expressed as linear constraints. d∈D (34) Overall. and accuracy properties (Cuthrell and Biegler. the full discretization approach application of a series of pure logical operations. (11)–(15) and defines the order of the resulting polynomials. In fact. . a good approximation of the discretized variables and small enough junctive normal form (CNF) of the original logical equations. it is possible to obtain an expression like C1 ∧ C2 ∧ . MIDO solution of the batch times. Cuthrell and Biegler (1989) to solve optimal control problems The originated MINLP problem can be solved through sev- with discontinuous control profiles. algebraic y(t). where continuity is only enforced for the first ones. This technique was originally introduced by possible to reduce the model size. The number of collocation points is a critical parameter because it Finally. 2002). which were first is applied to each of the mathematical stages k ∈ Kj . namely Eqs. 1996) can nomial. As illustrated in integer combinations and have to address a NLP problem for each Fig. . x ∈ R. with high-order polynomials. .2. linear global optimization solver BARON (Sahinidis. guarantee an accurate discretization. this factor can be adjusted according to the length of the time inter- lem. such as Lagrange polynomials. where Cn . and approximating the state and control variable profiles in these 1986) or generalized Benders decomposition (GBD) (Geoffrion. an adaptive strategy could be implemented. 1}. It is usually selected (26) of the formulation. In this work. M. the resulting true-clauses Cn can be transformed into duration of the batch operations is a decision variable. . compared into variable contributions xd and Eq. and udyn (t) and triangles represent the estimates of the derivatives z(t) ˙ in the finite elements e ∈ {1. symmetry. these approaches Further details about the calculation of the collocation points also have the disadvantage of rendering costlier computational and the construction of the orthogonal polynomials used in the loads because they operate through the systematic enumeration of numerical examples are provided in Appendix B. (4). and renders attractive stabil. by adjusting the number of finite elements for the The solution of the resulting MIDO problem is addressed discretization of each mathematical stage of the formulation iter- through the full discretization of the model using the orthogonal atively according to their specific duration. The strategy consists of dividing the time axis into sev. the length algebraic equality or inequality equations using a number of equiv.1). u) ≤ 0. . . M} – tion. such as branch- Section 3. a large number of finite ele- ments is selected in this work. since the problem previous element e − 1 in time te with the symmetry properties of is iteratively solved through mixed-integer linear programming the method. contrast. boundary conditions are defined for differential variables integer solution.. it could be collocation method. . . ad ∈ {0. This for limiting the increase in the computational demand associated way. 1989. Since the A. M + 1}. 1988). eral search algorithms available in literature (Grossmann. availability of finite lower and upper bounds on the variables and mial basis representations. . / Computers and Chemical Engineering 94 (2016) 287–311 299 and applying binary multiplication. is determined by the number of collocation points M and finite ele- d∈D ments Ne . However. This way. On the one hand. Next. . Ne } and boundary and collocation points m ∈ {0. 8. . expressions in the MINLP to be solved.. control variables are approximated to a piecewise constant (PWC) function.3) in Appendix B). (B. locations. or on decomposi- specific time points – termed collocation points m ∈ {1. j ∈ U and k ∈ L formalized by Clocksin and Mellish (1981). which are summarized in Table 5 of Appendix A. For this. 1991). the variables x are decomposed in the polynomials that define the differential variables. it is necessary to establish a larger order Mth (MILP) master problems with linearized equations and NLP primal Fig. Alternatively. enumeration strategies like the B&B non- points is determined by computing the roots of an orthogonal poly. related by “and” operators (∧). On the other hand. like the shifted Legendre polynomial of order M. (6). Such a considering the trade-off between being large enough for securing transformation can be done systematically by formulating the con.. the advantage of decomposition z(t) in each finite element e to enforce their continuity from the approaches is precisely their higher efficiency. ity. . 8. for algebraic and control variables.. . n ∈ {1. such as outer approximation (OA) (Duran and Grossmann. as represented in Fig. and so is the complexity of the resulting MINLP problem. continuity across neighboring elements is not necessary  x= xd ad . As for the number of finite elements. 1. The operations are detailed in Appendix defined number of finite elements and collocation points. with order (M − 1)th (see Eqs. Then. 8. taking into account the upper bounds 5. . (33) is reformulated as: to the polynomials of algebraic y(t) and control variables udyn (t). ∧ CN . the quality of the approximation of the dynamic model ad = 1. . of the finite elements can vary after scaling the time intervals of alences between logical and algebraic expressions (Raman and the optimal solution according to their final values. y(t). the guarantee global solutions under general assumptions like the state and control variable profiles are approximated using mono. . .2) and (B. This procedure involves the val to be discretized. logical propositions. as reported by Raman that compose the multistage models of the formulation using a pre- and Grossmann (1991). and control udyn (t) variable profiles. The position of the collocation 1972). Their strategies are either based on enumeration. Moreno-Benito et al. In Fd (xd . In order to Grossmann.

2012) and solved through the decomposition-based OA solver DICOPT 6. 1986). it is desirable to repeat the optimiza. As seen in Table 1. .1. / Computers and Chemical Engineering 94 (2016) 287–311 problems with fixed integer variables. Numerical example 1: Denbigh reaction system (Duran and Grossmann. Moreno-Benito et al. ustat is the duration tl of mathematical stages l. the reduced problem is solved in a price pˆ S of product S. the operating modes that can be selected are: oper- output flow rates (7. a penalty is applied to the product shortfall. Results and discussion (35) The optimal solution of the integrated problem is compared with a fixed recipe that has a predefined production size of whose kinetic and thermodynamic data are available in Table 300 kg/batch of product S and requires 70 batches and a batch S1 (see Supplementary Material). the Denbigh the prior IFSs and with no IFS. 2. U2 } and fixing the configura- optimal solution is compared to a standard predefined recipe to tion Booleans X 1 = true for each of the four possible configurations quantify the potential of the proposed approach. . Additionally. functions in mixers.1 (Rosenthal. The SEN superstructure of the cycle time of 2. and The production target is to fulfill a demand of 21 t of product j S minimizing the raw material expenses within a time horizon of k (t).k (t). Next.3 (t). Since the configuration ˇ. which are the number of batches NBS . the OA solver DICOPT has been selected as the most j j where udyn (t) comprise input F1. 2. with a value of 43. setting Boolean decisions Xˇ1 . j of the already existing equipment items. e. compounds Sc . (36) udyn (t). The limitation.6 to handle the NLP and MILP sub-problems respectively.1 cD /kg (see Eqs. comprising within the time horizon of 144 h. according to the direct-simultaneous strategy explained in tions. and uBool represent the Booleans for possibly local but already improve the results of non-integrated equipment units Yj . and recirculation flows Rn . technologies V . given that the starting point for the solver does not regulate the optimal con- The MLDO problem is reformulated into a MINLP one using 32 figuration obtained with the full-space MINLP search. which are incorporated j into the optimization problem as operating constraints. Unit U2 is defined to operate with maximum input and contemplated. maximum reaction temperature (110 ◦ C) to guarantee that the total parallel in-phase operation in U1 and U2 (configuration ). YU2 .300 M. Many of the MINLP solution algorithms have been implemented minimize  = Cost A + Penalty. 1. Optimization problem • Structurally optimal recipe: optimization of structural decisions j j with constant profiles of control variables F1. equipment units Yj . the ∈ {˛.24. which summarizes reaction system (Denbigh. The operating mode is fixed to two batch reactors U1 and U2 with a capacity of 1 m3 . and unload operations structural and the performance decisions: and the control variables are the input and output flow rates and the reaction temperature. The j principal disadvantage met using global enumeration solvers is the and reaction temperature k (t) in stages k ∈ {1. ˇ. 1958): the features of the resulting MINLP model implemented in GAMS.k (t) and output F2. In this The numerical example presented in this section addresses the example. and WU2 . 3}. in this case. 3} of batch units difficulty to find feasible solutions after more than 50 h of compu.17A and CPLEX 12. The complete MLDO model for solving this example is pro- ables.2. k ∈ {1. Specifically. j ∈ {U1 . constant profiles of the control variables can be used. 2.q . Problem solution sible structural decisions in the IFSs is chosen randomly. (S23)).06 h/batch to fulfill the demand of 21 t in its entirety example corresponds to the reactor network of Fig.g. and configurations X 1 . the best solution is obtained by solving the full MINLP problem initialized with IFS 4. the complete MINLP problem is solved with process consists of a competitive reaction mechanism.k (t) flow rates suitable alternative to be used in this study due to its efficiency. (S17) and preliminary step by fixing feasible combinations of structural vari.7. • Dynamically optimal recipe: optimization of dynamic control profiles with fixed configuration ˇ. Section 5. This is implemented in GAMS v. in front of the attainment of optimal solutions.1 (t). or series demand is satisfied. ustat .3. The problems. uint is tation. four IFSs are first generated using constant profiles for the j j j introduction of a new chemical into an already existing plant by control variables F1. unit ordering Wj.8 cD /kg (for further details. is 144 h. including the specifications operating modes X i . The combination of fea- 6. the optimization problem is defined by: the nonlinear objective function and constraints are convex. U2 }.q . F2. in not more than 3 h with DICOPT. and k (t) within each mathematical addressing the integrated batch process development problem.7 m3 /h) during load and unload operations and ation in one single unit U1 (configuration ˛) or U2 (configuration ˇ). j ∈ {U1 . uBool different solvers for optimizing the numerical examples of Sec- tions 6 and 7. finite elements and three collocation points in normalized Legendre the objective is to start the search from different search space loca- roots. calculated considering twice the selling order to generate IFSs effectively. vided in the Supplementary Material. U2 }. F2. with rial). The stage k ∈ {1. (S16) and (S21) in Section S1 of the Supplementary Mate- tion procedure using different initial feasible solutions (IFSs). Hence. Batch procedures cases with different degrees of freedom to track the effect of the in the reactors are composed of load. whereas the Penalty term represents the economic charge of the intention of identifying accidental local optima.1 with investment in new equipment units and pipelines is initially not a true value. hold.k (t). see Eqs. using CONOPT 3. 6. task-unit assignments Wj. 2012). in commercial software and operate through modeling interfaces like GAMS (Rosenthal. In this work. bilinear in base of a raw material price pˆ A of 4. in unaccomplished demand. 3} of units j ∈ {U1 . namely the selection of process stages Zi . Additionally. Ultimately. first term of the objective function CostA stands for raw material Global optimality cannot be guaranteed with the OA algorithm expenses of the complete production campaign and is computed due to the existence of non-convex terms in the model. 6. that decomposition approaches only guarantee local optima unless This way. The optimization problem is solved for three operation in U1 followed by U2 (configuration ). }. After comparing the performance of uint .

Improvement extent expenses does not affect the optimal temperature profiles in this The incentives to improve the process performance through the example.578 4294 optimizing the dynamic profiles with a predefined configuration ˇ. } and complete MINLP problem initialized with IFS 4. b4–c4) shows process variables operations. At the same time. feed-forward profile of reaction temperature is also kept constant rial transference is illustrated through the equivalence between the in operations with material transference (Fig. show a 12% reduction in the consumption of A by mic. processing costs associated with heat con- proposed modeling strategy are assessed by comparing the raw sumption also diminish (see Table 2) thanks to the reduction in material savings obtained with the fixed recipe.2 = 2580 kcal/kmol). Additionally. 10c4) than in the fixed one (Fig. Regardless. obtained using 32 finite elements and three collocation points in the discretization step: IFS solutions with fixed configurations X 1 = true. 10(b2–c2)). Such an increase is reflected in a molar fraction of product S at the final time which is higher in the optimal solution (Fig. sum. 9.1. 6.4 = 1210 kcal/kmol) to improve the selectivity of the desired In all cases.633 98. No. whereas the generation of byproducts like T is considerably lower. 3}. ∈ {˛. favoring reaction 3 (Ea. Optimal solution in the Denbigh example: operating mode and synchroniza. The trajectories feed-forward trajectories of flow rates in the optimal recipe are j j j of dynamic control variables F1. in Fig. k ∈ {1. b2–c2). Since heating costs are not included in the objective function. M. series configuration favors the pro- This configuration activates and synchronizes the 3-stage models cess performance by increasing the reaction volume. as shown in Fig.5. Trade-offs among KPIs (Fig. Going a step further. the consumption of intermediate R rises significantly in the optimal recipe. In con- output flow rate F3. In the unit procedure of U2 . production is restricted 6. the interaction between the selectivity of product S and the processing 6. 0.2. the temperature profile in the optimal recipe starts at the lower bound 50 ◦ C in the unit procedure of U1 (Fig. The synchronization of operations with mate. which illustrates the mathematical stages at tions with material transference barely affects the solution.639 159. the improvement of product selectivity is due to the optimization of the dynamic temperature profile and the arrange- ment of the two reaction units in series (configuration ). Fig. continuous variables No. .3. The Levels 1 and 0 for the production of one batch. U2 } are presented in Fig. like the reaction volume and molar compositions. Dynamic controls in operations with material transference of the optimal recipe i. The reduction of raw material expenses is related to the increase in the product selectivity. For the case 6. from 0. and k (t). The • Optimal recipe i: simultaneous optimization of dynamic profiles profile gradually increases to the upper bound of 80 ◦ C in U1 . equations No. in this example.597 in the three optimal solutions (see Table 2). 2. On the other hand. The dynamic and upper bounds.4. see Table S1 in the Supplemen- tary Material) with respect to reaction 2 (Ea. 10(b1–c1)).1 unit U2 . ture profile rises even more (Fig. order to enhance the selectivity of R with respect to T by favoring tion of unit procedures. lead to their upper bound most of the load/unload time intervals j ∈ {U1 . whereas the expenditure decreases as far as a 24% when qualitative decisions are considered as degrees of freedom with constant pro- files. All of them are compared to the trajectories of the fixed recipe in batch unit U2 6. load and unload operations evolution of the control variable profiles range between their lower tend to be as rapid as the pumping capacity permits. 9b. Therefore. 10(b1–c1. 10b1). and 0. reaching the upper bound of 110 ◦ C in this unit.3.209 98. Key decision variables Essentially.3. The results.2 U1 from unit U and the input flow rate F U2 to trast.1 = 1000 kcal/kmol.339 6 346. 10(b3–c3. 10a4). ˇ. of units U1 and U2 . this improvement becomes a 25% when all decisions are optimized simultaneously in the optimal recipe i. 9a.448 in the fixed recipe to 0. F2. thus and structural decisions according to the problem statement.3 = 1800 kcal/kmol) with respect to reaction 4 (Ea. Results in all recipes by the maximum time horizon of 144 h (see Table 2) The optimal operating mode for both optimizations that include and by the available equipment capacities of 1 m3 in U1 and U2 structural decisions is series configuration .3 (t). energy consumption in side reactions 2 and 4. On the one hand.3. showing the (Fig.593. the use of dynamic control variables in opera- detailed in Fig.791 159.321 10 345.1 (t). Thus. (Fig.3.507. 10(a1–a4)). / Computers and Chemical Engineering 94 (2016) 287–311 301 Table 1 Features of the MINLP models implemented in GAMS in the Denbigh example. which are endother- marized in Table 2. 10(a3–c3)). reaction 1 (Ea. discrete variables Non-zero elements Non-linear terms Solution time (s) IFS 1 (fixed ˛) 259 IFS 2 (fixed ˇ) 226 103. such that the unload operation of the first unit corresponds to the load operation of the second one. the synchronization of batch operations is In contrast. the dynamic control profiles are exploited in other batch 1 1. 10c1). Moreno-Benito et al. the number of batches and the duration of batch product S instead of U. The rise of S selectivity also goes hand in hand with a reduction . the tempera- operations are free decision variables.578 IFS 3 (fixed ) 581 IFS 4 (fixed ) 276 MINLP with IFS 4 102.3.

10. the heat results reflect the duplication of labor costs. Control and process variable profiles in the fixed and optimal recipe i in the Denbigh example. / Computers and Chemical Engineering 94 (2016) 287–311 Fig.302 M.5% compared the profit (case ii) and profitability (case iii) maximization. optimal recipe benefits from a collateral reduction of heating costs of a 15%. Consequently. improvements of the 11. namely mode . Moreno-Benito et al. since new investments are not considered. Besides. In order to evaluate the potential of the proposed strategy the total profit is higher in the dynamically optimal solution with to enhance the batch plant flexibility and adaptability. null 6. the opti- fixed configuration ˇ than in the optimal recipe i with operating mal recipe is solved according to other decision criteria. due to a significant increase in occupation costs by using two reactors. This way. Adaptability potential amortization values are computed in all recipes. These reaction mixture required in the system. These . Moreover.9% and 6.4. of reactant consumption and to a decrease in the total amount of to the profit of the fixed recipe are obtained. such as unit cleaning needed for achieving the reaction temperature is smaller and the and rental. respectively.

by including occupation costs into the objective upper bound in unit U2 . In this last case.595 0. (iii) profitability maximization. Temperature profiles in batch units in the Denbigh example for the fixed the original 1 m3 volume become degrees of freedom and have and optimal recipes in cases: (i) raw material cost minimization.a ) of unit j.596 Total energy consumption [kWh] 38.98 6.08 Batch cycle time [h/batch] 2. mization. structurally optimal recipe with constant control profiles.046 9.159 two objectives additionally include product revenue (RevenueS ).49 144.841 4. and (iv) profit maximization with capacity The resulting KPIs in these cases are presented in Table 2.046 9.989 1.065 825 1. uint .096 5.699 1. the higher processing capacity in opti- in optimal recipes ii and iii (see Table 2 and Eqs. hence. single operation of U1 . processing cost (Costj. and amor- tization cost (Costj. and simultaneous optimal recipes for all degrees of freedom in the problem statement in cases: (i) raw material cost minimization. the profit maximization ber of lots. KPI Fixed Dynamically Structurally Optimal Optimal Optimal Optimal recipe optimal optimal recipe i recipe ii recipe iii recipe iv Equipment configuration ˇ ˇ   ˛ No. Finally.212 29. the optimal recipe with equipment capacity a compromise in U2 . (iii) profitability maximization. case ii instead of 47 in case i. the because the simultaneous operation of U1 and U2 in configura.448 0.14 11.00 5.03 Batch processing time [h/batch] 2. This way.593 0.26 2. In contrast. j ∈ {U1 . Moreno-Benito et al. Overall.06 2. expansion. in optimal recipe ii compared to the use of the fixed recipe. and (iv) profit maximization with capacity expansion. Regarding the temperature profiles. udyn (t).046 9. are reduced significantly maximization alone.03 66.696 2.p + Cost j.897 31. an improvement of the 23% in the total profit is noted processes. profitability maximization reaches the 3. the profit maximization problem is solved allowing the re-sizing of batch reactors to evaluate the additional process improvement that can be obtained with plant modifica- tions (case iv). and temperature profiles.06 2.5 m3 .558 38. 11. batches 70 54 47 47 23 31 13 Batch size [kg/batch] 300 389 447 447 913 677 1615 Total processing time [h] 144. and are defined by the minimization problems: minimize  = −Profit.046 9.a ). (ii) profit maximization.333 5. the num. batch processing times.03 144.441 0. operating at 94 ◦ C rather than at the upper expansion involves the re-sizing of unit U1 with a new volume of bound of 110 ◦ C. uBool = −RevenueS + Penalty + Cost A (37)  + (Cost j.67 3. the last ones illustrated in (case i) leads to the maximum temperature of 80 ◦ C in unit U1 and Fig.440 1. The most relevant variations between optimal recipes i–iv are the selected operating modes. (38) uint . / Computers and Chemical Engineering 94 (2016) 287–311 303 Table 2 KPIs and individual economic weights in the Denbigh example: fixed recipe.o ).08 Total profit [D ] 4.06 3.692 35. M.861 5.956 33.p ). Additionally. dynamically optimal recipe in U2 . optimal solution takes into account the compromise between the tion  involves a that fewer batches are needed – e.26 2.965 Total revenue 9.046 Raw material cost 2.o + Cost j.597 0. occupational expenses (Costj. Items in bold correspond to the objective function. uBool considering the economic data detailed in Table S2 (see Supplemen- tary Material). 11.507 0.088 32. (S2) and (S19) mal recipe iv permits the functioning at the minimum temperature in the Supplementary Material).67 6. ustat . (ii) profit maxi- associated amortization cost.764 5.03 144. since the processing time reduction is con- function. the optimal configuration is ˛ with the Table 2). which have a term almost three times less – compared to optimal recipe ii with profit that depends on the number of start-ups.080 5. the sum of start-ups in the processing time in optimal recipe iii achieves a lower value – each unit decreases and the occupation costs. This .03 144. making the smaller unit U2 available to other Essentially. ustat .14 11.692 Processing cost in U 967 899 827 822 789 955 729 Occupation cost in U 1. equipment capacities larger than Fig. As for the processing mode with in recipes with a much longer processing time and batch size (see capacity expansion of U1 .g. Moreover. As a result. the series configuration is replaced by parallel one  templated indirectly in the objective function (case iii).440 720 944 535 Amortization in U 0 0 0 0 0 0 125 Penalty 0 0 0 0 0 0 0 Profit per batch [D /batch] 68 99 108 108 254 157 459 Profitability [D /h] 33 37 35 35 41 73 41 Selectivity of S [kmol S/kmol total] 0.046 9.06 6.687 1.286 1.03 144. udyn (t). 23 lots in economic gain and the reduction of the processing time.250 1.U2 } and minimize  = −Profitability = −Profit/T total .046 9.

tion and suspension copolymerization reactors j ∈ {R11 . i. Operating mode in the polymer wash and filtration (stage 7). processing costs. uint . I to environmental impact of organic and aqueous solvents depends initiator azobisisobutyronitrile (AIBN). sions are achieved (Bajaj et al. R12 }. Fout. quantifies the interaction between process synthesis and plant allo- cation decisions like the selection of process stages. Solution or suspension copolymerization in the reaction (stage objective with respect to the fixed recipe. the plant modification the copolymerization reaction (stage 1). Optimization problem technology. udyn (t). The reason is that the original two-reactor to the copolymerization reaction (stage 1) in a subsequent batch. Process stages in acrylic fiber production system: general processing scheme (solid lines) and potential processing alternatives (dashed lines). 12. 2011). dropping all the costs except for 7. 1). a maximum – for example.k (t)) supplied to the evaporator j ∈ {E2 }. 2.k (t)) and cooling temperature ( cool.. hold. Selection of washing and filtration (stage 3). Particularly.1. the following objective function: there exist trade-offs between polymerization and downstream minimize  = Cost M1 + Cost M2 + Cost I + Cost S tasks. which comprises . following the gen. among oth- ers. i. batch copolymerization process to produce an acrylic fiber with a specific composition and quality in a grassroots scenario. 3} load. 8. which determine (Qheat. equipment 7. the Supplementary Material for further details). 12 (see Section S2 of which follow three operations k ∈ {1. Selection of separation (stage 2). plant was already equipped with the necessary capacity to ful. the magnitude of the where M1 refers to AN monomer. the following qualitative decisions can be made: sumption. process stages and structural alternatives for acrylic fiber produc- structing the integrated optimization model that simultaneously tion is presented in Fig. j the control profiles of input and output flow rates (Fin1. due to a higher S selectivity. 13. 4..e. Operating mode in the solvent recovery (stage 8). the consideration of expand. uBool +Cost a + Cost p + Cost waste .k (t). 1). Numerical example 2: acrylic fiber production system 9. chemicals. aqueous solvent sodium thiocyanate and cleaning technologies influence the polymerization processes (NaSCN(aq)). Multiple operating respectively. 1996). ing the capacity of processing units in case iv hardly improves 3. and horizon of 144 h. Recirculation of the washing water of the filtration (stage 3) to units are properly arranged.e. the choice of processing conditions. eral process stages of the block diagram of Fig. single unit F71 or series F71 followed by F72 .k (t). occupation. A single-product campaign polymer quality. the auto-acceleration and the Trommsdorf effect deviation of the 0. lower energy con. tion exhibits the highest total cost and the lowest selectivity of 2. provided that the processing 6.304 M. Moreover. 5. M2 to VA monomer.025 in the composition should be fulfilled to – which determine the compromise between productivity and guarantee polymer quality constraints. Besides. / Computers and Chemical Engineering 94 (2016) 287–311 Fig. increase is related to a reduction of raw material. Moreover. Recirculation of the solvent recovered in the separation (stage 2) ment modifications. which also contribute to the achievements of the over. and unload. polymer-solvent separation can be omitted when high conver. Recirculation of the solvent recovered in the separation (stage 8) to the copolymerization reaction (stage 1) or the repulping This case study addresses the development of an industrial-size (stage 4). such is assumed to produce the total amount of final product in a time as reactor temperature and monomer feed rate trajectories. and reduction in the number of unit start-ups. dimethylformamide (DMF). The goal is to produce 5 t of acrylic fiber composed of 85% of The study of the integrated problem solution is motivated by the acrylonitrile (AN) and 15% of vinyl acetate (VA) in bulk format min- complex reaction mechanisms and physicochemical phenomena imizing the total operational and capital cost. and S to organic solvent on their molecular composition (Gol’dfein and Zyubin. even though this solu. the problem tackles the optimization processing times is crucial to determine the resulting polymer of the batch production process and the batch plant according to properties and production yield (Giudici. optimal recipe iii involves a rise of the 121% in the profitability 1. Organic or aqueous solvent in solution copolymerization (stage all the optimal solutions. fill the requested product demand. or suspension medium water. udyn (t) represents (Capón-García et al. Nevertheless. and solvent recovery and reuse. Also. the amortization. Moreno-Benito et al. affects the expense distribution. With The resulting SEN superstructure representing all the possible this purpose. single unit C81 or series C81 followed by C82 . and the required processing units and their synchronization. the total profit compared to the optimal solution without equip. Additionally. 7. The process for acrylic fiber production comprises a primary j j j stage for bulk copolymer production and a secondary stage for Fin2. Particularly. ustat (39) all economic and environmental production targets. 2000). the presented modeling strategy is applied for con.k (t)) in the solu- transforming the copolymer into spun format. Then. It also represents the control profiles of the heat j modes can be considered for each particular task. 1990).

e. E2 } and the tion S2 of the Supplementary Material. washing and filtering units F3 . Cost I . Specifically. i. ated by fixing the Boolean variables that define specific structural mining the selectivity and production yield – and the separation alternatives of the process. spinneret S6 . Therefore. the multiple terms of the objective func. NaSCN(aq)}. Regarding the logical decisions uBool . Moreno-Benito et al. Moreover. Equipment elements in gray represent the secondary part of the process for spun production. initiator I. Problem solution of separation stage (Zi .8. 2}) and the duration of batch operations (tl . R12 . 3} in reactors j ∈ {R11 . (ii) equipment amortization (Costa ). j ∈ {R11 }). Their process performance is rep- of both fractions. c ∈ {M1 .  ∈ {solu. M. such as polymerization reac.1 ). In particular. Cost M2 . Cost S ). and (iv) waste disposal costs non-convex terms. 3. and suspension medium. (Eq. evaporator E2 . R12 }). strategy. unload of distillate. even if it is moderate in size. and buffer tanks T2 . T4 . (S39) and Table S11). separation unit j ∈ {E2 }. i ∈ {2}). as it can be (Costwaste ). namely stages k ∈ {1. The MLDO problem is solved through a direct-simultaneous organic or aqueous solvent in solution copolymerization reac. respectively. in example 1. solver DICOPT in GAMS v. F5 . repulping unit R4 .2 (Rosenthal. using CONOPT mentary Material. the dynamic models are approximated in load and tion  refer to: (i) the expenses of raw material. files of control variables. I}. 2.in1. and solvent recovery and elements and three collocation points in normalized Legendre reuse after the separation (R2. The definition of these terms and the corresponding observed in Table 3. three operations k ∈ {1. composed of: solution and suspension polymerization reactors R11 and R12 . Superstructure of the acrylic fiber example. and logical propositions to relate the mentioned qualitative Several IFSs are used to initiate the search procedure from dif- alternatives. 13.k . monomers unload operations. These decisions are related to roots. The model and process parameters are available in Sec- for the capacity (Sizej ) of processing units j ∈ {R11 . the process stages that have a critical impact to several subsystems of the integrated problem and are gener- on the cost function are the copolymerization reaction – deter.15D and CPLEX 12. the starting points correspond units. given the low influence of tors j ∈ {R11 . susp}. Finally. The resulting MINLP model is com- (Cost M1 . Equipment elements in black represent the addressed primary polymerization process for bulk polymer production.23. following combinations of technologies and solvent: . R12 }. c ∈ {DMF. M2 . and recirculation buffer dynamic profiles in operations with material transference observed tank j ∈ {T2 }. The subsystems are determined by the stage – governing the potential recovery of unreacted monomer. and solvent or suspension medium S R12 } and evaporator j ∈ {E2 }.2. ∀ l) and uint stands operations. solution or suspension technologies j in copolymerization reactors (V . F71 and F72 . / Computers and Chemical Engineering 94 (2016) 287–311 305 Fig. The dynamic model is fully discretized using eight finite j tor (Sc . 2012). as well as multistage models representing potential ferent initial points. M1 and M2 . j ∈ {R11 . putational intense for global optimizers due to the presence of (iii) total processing cost (Costp ). T81 and T84 . k ∈ by dynamic feed-forward control trajectories and duration of batch {1. and unload solvent.4 optimizers in the NLP and MILP sub-problems The MLDO model additionally includes disjunctive equations respectively. number of batches NB. Piece-wise constant functions are used to define the pro- the selection of procesing units (Yj ). 3} load. distillation columns C81 and C82 . these include the selection 7. T3 . ustat denotes the composition of raw resented by dynamic models with discrete events and is controlled j materials in the reactors’ input stages (cc. the problem is solved with the OA economic parameters can be found in Section S2 of the Supple.

equations No. 18. 7.1 = false in sub. 3b). The KPIs and cost contributions of the subsystem solutions and In the specific case of solution polymerization with organic sol. R2. with plant allocation decisions.1 = true. the model to provide favorable solutions by evaluating the deci- the selection of separation stage depends on decisions made in sions trade-offs.996 85 IFS 5 (subsystem 2b) IFS 7 (subsystem 3b) MINLP with IFS 3 16. The computa.e. this similarity does not rep- 3a).. 2a. Vsolu the solvent selected.3. No. R2. illustrated in Fig. there exists the possibility of not having separation stage too the most significant weights are equipment amortization and raw (Z2 = false in subsystem 3c). whereas solution polymerization with an organic solvent is resent homogeneous optimal solutions but the adaptability of the best alternative otherwise (subsystem 1b). Therefore. Overall. Trade-off among process stages investment for the evaporator E2 and the recirculation storage T2 .3.860 8285 4 66. vent. 14.3. S R11 Vsolu = true.860 8285 14 66. / Computers and Chemical Engineering 94 (2016) 287–311 Table 3 Features of the MINLP models implemented in GAMS in the acrylic fiber example. like dynamic control pro- files.608 15. Vsusp simultaneous evaluation of the trade-offs between process stages to obtain the optimal solution. thanks to the consideration of the number of batches chosen when there is no recirculation of the distillate (subsystem as a degree of freedom.e. these alternatives are evaluated without the recirculation of distillate from the evaporator E2 (R2. 15. approach integrates all these degrees of freedom and permits the NaSCN(aq) R12 = true. At the same time. The optimal solution among Comparing these results with preliminary calculations with the three polymerization and solvent alternatives 1. the integrated problem are summarized in Table 4. However. Cost balance systems 1a. Notably. in Table 3. the optimal solution gives pri- ority to the total cost minimization by eliminating the equipment 7. This solution is compared to an equivalent optimization with halved unitary amortization costs. 2b. i. followed by organic and aqueous solvent costs in R11 . i.4. 7. and 3b. Total cost for each subsystem and the integrated problem with and without recirculation and avoiding separation stage (i. Z2 = false) in the economic scenario. 16. 3a) and with recirculation (R2.4 h) the process generates slight excess of monomers and fulfills the minimum monomer conversion of the 75% required for this processing structure. 2014) enhanced the batch plant flexibility by dosage. seven sets water costs in the reaction and the heating costs in the separation. Additionally. since the raw material savings are prioritized in front of amortization costs. Essentially. it was observed how the results presented here reaction stage depends on decisions associated with other process have closer values of the objective function for the different sub- stages like the recirculation choice. which determine the achieved monomer conversion. VsuspR12 = true. continuous variables No. aration is to utilize solution polymerization with DMF achieving (2) Solution polymerization and aqueous solvent. The optimal temperature trajectory in the polymerization reactor follows a monotonically increasing func- tion. i. illustrated in Fig. System adaptability grated MINLP problem for comparison. In black. 17. and is characterized by the control and processing variable profiles rep- resented in Fig. are characterized by a reduction of the . The proposed modeling R11 .e. System response The optimal processing scheme corresponds to solution poly- merization without separation.306 M. The only possibility for disregarding the sep- DMF true.1 = true in 1b. obtained using eight finite elements and three collocation points in the discretization step: IFS solutions with problem subsystems 1a. 1c. of fixed logical variables are used to generate IFSs. 2b. the optimal solu- tion is suspension polymerization with recirculation (i.2. S R11 = (1) Solution polymerization and organic solvent. which are larger than in the original Fig.3. acrylic fiber example. Moreno-Benito et al. a minimum conversion (subsystem 1c). previous research on flexible plant design the reaction. 14 presents the optimal objective function of each subsystem in front of the optimal solution of the inte. Results and discussion savings obtained with recirculation. Suspension polymerization is systems. discrete variables Non-zero elements Non-linear terms Solution time (s) IFS 1 (subsystem 1a) IFS 3 (subsystem 1c) 16. The diagram of Fig. The combined expenditure of monomers M1 and M2 is the most tional performance to calculate some of these IFSs is summarized relevant one. and combining process synthesis decisions. The control and processing variable profiles.1 = false.3. 2.996 338 R11 . the possibility of recirculating solvent in subsystems 1b and 2b encompasses important raw material savings without loss of the reaction effectiveness.608 15. In this case. Thanks to the dosage profile and the long task duration (i.1. 7. like the polymerization temperature and monomer (Moreno-Benito et al. like batch sizing. which are considerably higher than the cooling through the logical propositions of the problem.e. The remaining Booleans are computed material expenses. whereas the M1 dosage features a local maximum in the second half of the process that guarantees the desired polymer composition of 85% of M1 . Nevertheless.1 = true).3. (3) Suspension polymerization.e. and whole MINLP problem initialized with IFS 3.e. or 3 in the fixed batch size. despite the raw material 7. R2. integrated solution.

530 1.0 89. coming from raw ous process stages within the complete process.9 18.614 44.83 0.309 3.3 18.981 E2 Amortization 8.2 18.824 732 236 99 129 2. Additionally. alternatives according to diverse processing.267 1.405 4. or sustain- merization time is shorter in this case.567 42.750 9. Consequently.187 38.0) (1.412 16.750 8. 2a–b.432 42.233 10. to allow the reduction of the cycle time and increase the production ology is the holistic evaluation of the decision criteria.309 3.083 12.919 41.980 2.154 Initator I cost 3.151 8.234 14. with a cycle time of 9. This excess dom. able production drivers.234 12. Subsystems Integrated 1a 1b 1c 2a 2b 3a 3b Polymerization type Solution Solution Suspension Solution Solvent type DMF NaSCN(aq) – DMF Process structure (Z2 .448 2.114 1.571 – T2 Amortization – 3. so it could be than the separation.368 8.234 12.262 1.083 15.1 h.2 144.5 2 2.4 Batch cycle time [h/batch] 16. The in a limited time horizon.234 14. and the whole MINLP problem.37 0. economic.309 3.5 1.56 0.013 2.418 13.368 – 10.44 0. it could expedite the analysis of processing is recovered in the distillate fraction in E2 .1) (0.368 – Energy cost 202 257 – 268 452 655 977 – Waste disposal cost 1. batches 8 9 6 6 9 17 22 6 Batch size [kg/batch] 625 556 833 833 556 294 227 833 Total processing time [h] 119.9 89.192 692 2.057 38.4 Total cost [D ] 46.083 Water consumption cost 113 114 113 106 104 372 369 113 Monomer M1 cost 12.562 6. time [h/batch] 18.445 1.0 18.355 2. Moreno-Benito et al.620 R11 or R12 Amortization 12. .6 8.309 3.145 7.5 2 No.633 8.716 14.309 3.368 8.309 Cost per batch [D /batch] 5. There is also a higher excess interactions between synthesis and allocation degrees of free- of monomer M1 to guarantee the desired composition.653 2. the consideration of more poly.9 134.637 2.130 – 1.258 1.0) (1. tors and their arrangement in parallel out-of-phase configuration To conclude. The primary copolymerization stage for the solution exhibits a polymerization reaction significantly longer acrylic fiber production has been solved successfully.309 – T4 Amortization 3. Items in bold correspond to the total cost minimization objective.9 11.0 144.048 13. further degrees of freedom would be challenging to reduce the cycle time in case of desiring could be incorporated into the model.1 ) (1. 3a–b. monomer dosage along the second stage of R12 .683 Monomer M2 cost 5.918 6.3 19.568 8. like the use of several reac- larger production rates.526 1.5 1.0) (1. Additionally.6 10.9 86.016 1.R2.2 18.904 41.4 7.1) (0.436 7. Even though the poly.296 Solvent/suspension S cost 1.865 4.309 3.9 11. due to a higher optimization model considers the trade-offs between the vari- input of monomer in the first load operation.082 6. 15.0) Equipment size [m3 ] 1.1) (1.7 16.9 Batch proc. Optimal structure and logical variables in the acrylic fiber example.309 – 3.309 – – 3.309 3.9 89.437 Monomer conversion 0.5 10.767 2. the major strength of the proposed method. M.75 0.876 7.449 2.5 2 1. as well as the material and recirculation flow rates.619 8.0) (1.75 Fig.71 0. challenging to consider the secondary polymerization process to merization reactors with a parallel out-of-phase configuration exploit the methodology.4 18. / Computers and Chemical Engineering 94 (2016) 287–311 307 Table 4 KPIs and individual economic weights in the acrylic fiber example considering: subsystem alternatives 1a–c.29 0.

The promising results of the numerical example show improvements between the 23% and the 121% in the objective function compared to the use of fixed recipes in all the optimization scenarios i–iv of the Denbigh example. dynamic opti- mization. (b1) vapor flow. in economic scenarios or decision criteria. Conclusions and future directions This work introduces a modeling strategy to tackle batch process development and improvement at production scale. / Computers and Chemical Engineering 94 (2016) 287–311 8. multiple degrees of freedom associated with process synthesis and plant allocation sub-problems are solved simulta- neously. while taking into account the plant design and retrofit. as they could be changes the optimal solution in the acrylic fiber example: (1) flow rates/dosage and temper. pursuing opti- mal solutions that enhance process efficiency and guarantee the best utilization of available equipment and new investments. significant progress has been made to coor- dinate coexisting multistage and single-stage models through the combination of hybrid discrete/continuous models. Fig.308 M. the rapid evaluation of diverse objec- tive functions proves the potential of the proposed strategy to adapt Fig. the resulting MLDO model manages the problem complexity using mixed-logic equa- tions. The notable improvement of plant adaptability gained through the presented approach justifies and stimulates the research in this direction. Moreno-Benito et al. 17. The complex mathematical implications and the risk of obtaining mathematically intractable problems can be addressed with appropriated solution strategies like the use of initial fea- sible solutions and the definition of proper variable bounds. Also. while its reformulation into a MINLP problem enables its optimization through well-established search algorithms. in a formulation that can be handled by current optimization tools. and (a2–b2) molar compositions and volumes. Control and process variable profiles of the polymerization reactor R11 for master recipes according to in-time needs. Control and process variable profiles of the polymerization reactor R12 and the separator E2 for the optimal solution with reduced amortization costs in the acrylic fiber example: (a1) flow rates/dosage and temperature. and to analyze the sys- ature and (2) molar compositions and reaction volume. . and mixed-logic modeling. Overall. The principal novelty of this strategy is the synchronization of unit procedures with dynamic profiles as a function of alternative processing schemes in an integrated optimization problem. With this purpose. tem response in front of uncertain parameters. 16. From a modeling perspective.

In particular. with the Appendix B.5000. a2 − a1 ≤ 0 cases tested. Like. The large advantage of the presented integrated Table 5 summarizes the relation between logical and algebraic strategy is its potential to assess all processing alternatives simul. the consideration of dynamic Disjunction “or” (∨) A1 ∨ A2 ∨ · · · ∨ AN a1 + a2 + · · · + aN ≥ 1 “exclusive or” () A1  A2  · · ·  AN a1 + a2 + · · · + aN = 1 flow rate profiles in the operations with material transference has a Implication (→) A1 →A2 1 − a1 + a2 ≥ 1 minor impact. ation and multi-product/multi-purpose production campaigns. . since most of the corresponding stages are character. is identified in the Denbigh example in comparison to the opti- Logical operator Logical expression Algebraic equation mization of dynamic profiles with fixed equipment configuration. . (A. . 0. . d ∈ {1. Both cases render improvements over the fixed recipe of the 24% Conjunction “and” (∧) A1 ∧ A2 ∧ · · · ∧ AN a1 ≥ 1. . M. . expressions. The collocation points used in the numerical egy should allow the direct extension of the formulation to achieve examples are calculated with a shifted Legendre polynomial P( ) of this purpose. or(¬A1 ∨ A2 ) ∧ (¬A2 ∨ A1 ) or a1 = a2 Finally. taneously and avoid methodologies based on the identification of challenging solutions and their independent solution. . P( ) = 20 3 − 30 2 + 12 − 1. Therein. .. the refinement of solution strategies is highly order M = 3. or ¬A1 ∨ A2 or a1 − a2 ≤ 0 ized by constant profiles in the optimal solutions of the numerical Equivalence (⇔) (A1 → A2 ) ∧ (A2 → A1 ) a1 − a2 ≤ 0. In this regard. the influence of the distillate recirculation on reaction decisions like the selection 3.8873} of the collocation points m ∈ {1. . of this problem using hybrid approaches that combine determinis. raw monomer concentration. Lagrange polynomials are used for the approxima- of research. . / Computers and Chemical Engineering 94 (2016) 287–311 309 This strategy also enables the quantification of interactions Table 5 Basic logical operators expressed using logical and algebraic equations (Raman and between synthesis and allocation sub-problems. algebraic y(t). 1991). recursively by using the following equivalence: wise. in addition to the boundary points located at 0 = 0 and tic solvers with evolutionary algorithms is another promising area M+1 = 1. In contrast. . elements Future work can be focused on the incorporation of additional degrees of freedom in the problem. The 1989) is used to perform the full discretization of the time- modular representation of unit procedures in the presented strat- continuous model. The roots of the above polynomial provide the normalized loca- els according to the selected batch times is suggested. Moreno-Benito et al. reaction decisions like the temperature and dosage profiles. The solution tions m = {0. like out-of-phase parallel oper- Orthogonal collocation on finite elements (Cuthrell and Biegler.1) ucts. the acrylic fiber example shows the trade-offs among decisions in neighboring process stages. and derivatives z(t)˙ have the following form: Acknowledgements  M  M The authors would like to thank the financial support received z(t) = ze.1127.m .. Equally. a2 ≥ 1. 0. which is defined as: relevant to propitiate the use of global optimization solvers and to face problems with a larger number of process stages and prod..4) possibility of omitting separation stage if high monomer conver- sions are achieved. A larger influ- Grossmann. aN ≥ 1 and the 12% respectively. the polynomials of the differential z(t). and processing times determine the (A1 ∧ A2 ) ∨ A3 ⇔ (A1 ∨ A3 ) ∧ (A2 ∨ A3 ). according to Raman and Grossmann (1991).. tion of the state and control variables. (B. M}. d ∈ {1. Distributing the “or” operator (∨) over the “and” operator (∧) of the polymerization technology and solvent is illustrated. where Ad . N} are Boolean variables and ad . Then. ence on structural decisions with constant set-points optimization N} are the equivalent binaries. Application of orthogonal collocation on finite probability of missing optimal solutions. the study of adaptive approaches that adjust the number of finite elements in the discretization of the dynamic mod. and control udyn (t) variables. .

m .m (t). ˙ z(t) = ze.

Appendix A. linear constraints M = 3 with normalized locations m = {0. . udyn (t) = ue. from the Spanish Ministry of Economy and Competitiveness and m=0 m=0 the European Regional Development Fund (research project SIG. 0. Reformulation of logical propositions into . (B.. 0. Marta y(t) = ye.m . Ne } and collocation or boundary points m ∈ {0. . . dyn where ze. M.. 1.m m (t). M + 1}.˙ m (t). Luis Puigjaner for the fruitful m=1 m=1 discussions held during the development of this work. 1}.m represent the approximations of the dif- ferential. ye.1127.5000. . 0.m . and control variables in finite elements e ∈ {1. .2) M  M dyn ERA DPI2012-37154-C02-01 and FPU Research Fellowship).8873. Moreno would also like to thank Prof. algebraic.m m (t). and ue. .

m ) (t − te. 3}. these (t − te. Considering Boolean variables Ad .m ) . d ∈ {1. 2.m (t) and m (t) represent the basis functions defined by: The operations for formulating the conjunctive normal form (CNF) of a logical proposition were formalized by Clocksin and  M  M Mellish (1981).

m = 1. m (t)= .m (t)= . accurate initial conditions ¬(A1 ∨ A2 ) ⇔ ¬A1 ∧ ¬A2 . The purpose is to define 2. (A. (A.m ) m = 0. This is necessary to enforce their continuity from previous element e − 1 in time te .m ) (te.1) higher Mth than the polynomials of algebraic y(t) and control variables udyn (t). Moving the negation inward by applying DeMorgan’s Theorem: boundary conditions of the approximation of differential variables ze. thanks to the symmetry properties ¬(A1 ∧ A2 ) ⇔ ¬A1 ∨ ¬A2 .3) ze.2) of the method.0 = z(te−1 ) = ze−1.3) operations are: (te. with order (M − 1)th.m − te. (A. Thus.M+1 can be calculated through the evaluation of . (B.m − te. Replacing the implication by its equivalent disjunction: The polynomials of differential variables z(t) are one order A1 ⇒ A2 ⇔ ¬A1 ∨ A2 .0 in each finite element e. m = / m m = / m 1.

Mellish. 5024–5029. Integrated scheduling and dynamic optimization of network finite element: batch processes. 2014.2014.. F.0 = ze−1. / Computers and Chemical Engineering 94 (2016) 287–311 the first polynomial in Eq. Programming in Prolog. C.6858593.F. Moreno-Benito et al. You.2) at the final point M+1 = 1 of each Chu.m . ISSN 0743-1619.  M Clocksin. Springer-Verlag. 1981.doi. http://dx. pp.S. New ze.310 M. In: American Control Conference (ACC). (B. W.

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