Sustainable Process Synthesis-Intensification - 2015

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Computers and Chemical Engineering xxx (2015) xxxxxx
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Computers and Chemical Engineering

journal homepage: www.elsevier.com/locate/compchemeng
Sustainable process synthesisintensication

Deenesh K. Babi a , Johannes Holtbruegge b , Philip Lutze b , Andrzej Gorak b ,
John M. Woodley a , Raqul Gani a,
a
CAPEC-PROCESS Research Center, Department of Chemical and Bio-chemical Engineering, Technical University of Denmark, Sltofts Plads, Building 229,
DK-2800 Kgs. Lyngby, Denmark
b
FVT, Department of Chemical and Biochemical Engineering, Technical University of Dortmund (TU Dortmund), Emil-Figge-Str. 70, D-44227 Dortmund,
Germany
a r t i c l e
i n f o
Article history:
Received 16 December 2014
Received in revised form 9 April 2015
Accepted 23 April 2015
Available online xxx
Keywords:
Process synthesis
Process design
Sustainable design
Sustainability
Process intensication
Systematic framework
a b s t r a c t
Chemical industry is facing global challenges such as the need to nd sustainable production processes.
Process intensication as part of process synthesis has the potential to nd truly innovative and more
sustainable solutions. In this paper, a computer-aided, multi-level, multi-scale framework for synthesis,
design and intensication of processes, for identifying more sustainable alternatives is presented. Within
the framework, a three stage work-ow has been implemented where, in the rst synthesis stage an
optimal processing route is synthesized through a network superstructure optimization approach and
related synthesis tools. In the second, design stage, the processing route from the rst stage is further
developed and a base case design is established and analyzed. In the third, innovation stage, more
sustainable innovative solutions are determined. The application of the framework is illustrated through
a case study related to the production of di-methyl carbonate, which is an important bulk chemical due
to its multiplicity of uses.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
In the chemical industry improvements related to the use of
sustainable technologies and efcient use of resources are needed
in order to achieve reductions in energy consumption, waste generation, environmental impact and cost. Process improvements
are typically achieved through an evolutionary approach, where
knowledge gained from process understanding together with
expert knowledge on process engineering is applied. The limitation
with this approach, however, is that new, innovative and more sustainable process designs may not be found because the search space
employed is limited in size in the trial and error, experiment-based
approaches. The same is true for model-based solution approaches
where the models employed have limited application range.
The objective of process synthesis should be to nd the best
processing route, from among numerous alternatives, to convert
given raw materials to specic (desired) products, subject to predened performance criteria. Hence, process synthesis involves
analysis of the problem to be solved, and, generation, evaluation
and screening of process alternatives so that the best process option
can be identied. Process synthesis is usually performed through
Corresponding author. Tel.: +45 45 25 28 82; fax: +45 45 93 29 06.

E-mail address: rag@kt.dtu.dk (R. Gani).
the following three classes of methods: (1) Rule based heuristic

methods, which are dened from process insights and know-how;
(2) Mathematical programming based methods, where the best
owsheet alternative is determined from network superstructure
optimization. This class of method is useful when the system is
well dened and many combination of alternatives are to be considered; (3) Hybrid methods that uses process insights, know-how,
rules and mathematical programming. That is, models are used
to obtain good physical insights that aid in reducing the search
space of alternatives so that the synthesis problem to be solved
will involve less alternatives.
Process intensication (PI) has been dened as the improvement
of a process through the targeted enhancement of performancelimiting phenomena (Lutze et al., 2013) at different scales. At the
plant/process scale the entire process is considered. At the unit
operations scale the individual unit operations that comprise the
process are considered. At the task scale the functions performed by
the unit operations are considered. A task is dened as the function
performed by a unit operation, for example, a ash vessel or a distillation column represent separation tasks. At the phase/phenomena
scale the phenomena building blocks (see Section 2.3.1) that satisfy and thereby, make a task feasible are considered, while, at
the molecular scale (Freund, Sundmacher, Ullman, Lutze et al.,
2010) which is mainly considered for reactive systems, the molecular behavior of the molecules that affect the phenomena are
http://dx.doi.org/10.1016/j.compchemeng.2015.04.030
0098-1354/ 2015 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Babi DK, et al. Sustainable process synthesisintensication. Computers and Chemical Engineering
(2015), http://dx.doi.org/10.1016/j.compchemeng.2015.04.030
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D.K. Babi et al. / Computers and Chemical Engineering xxx (2015) xxxxxx
considered. According to Van Gerven and Stankiewicz (2009),

this enhancement can be achieved within four domains: process
structure, energy, synergy and time. One example of PI at the process/plant level is a hybrid distillation scheme which is an external
integration of two or more different unit operations that include at
least one operation, that is, a conventional distillation column, in
order to satisfy a separation task (Babi and Gani, 2014). Here, the
integration of membrane separations with distillation to overcome
thermodynamic boundaries such as azeotropes (Lutze and Gorak,
2013) could be considered. Divided wall columns are examples of PI
at the unit operation, task or functional scales (Asprion and Kaibel,
2010; Halvorsen and Skogestad, 2011; Madenoor Ramapriya et al.,
2014) while, membrane reactors (Assabumrungrat et al., 2003;
Van Baelen et al., 2005; Inoue et al., 2007) or reactive distillation
columns (Agreda et al., 1990; Shah et al., 2013; Holtbruegge et al.,
2014) are examples of PI that improve the conversion in a reaction
through the in situ removal of a product.
Similar to process synthesis, in principle, PI could also be
performed using the same three classes of methods. However, rulebased heuristic methods and the mathematical programing based
methods have not been developed for the intensication of entire
processes. For the design of specic hybrid/intensied unit operations within a process several methods (Bessling et al., 1997;
Amte, 2011; Caballero and Grossmann, 2004) have been reported.
For hybrid methods, a scheme for systematically achieving process
intensication has been proposed by Lutze et al. (2013). Also, other
hybrid schemes have been developed for intensifying specic parts
of a process, for example, at the phenomena and molecular level
(Peschel et al., 2012; Rong et al., 2008). Therefore, since process
intensication aims at increasing the efciency of processes, performing process synthesis and intensication together, should lead
to improved and more sustainable process deigns/operations. Sustainable process synthesisintensication, employed in this paper,
is dened (Babi et al., 2014a) as the generation of alternative
processing routes that show improvements related to economic
factors, sustainability metrics and LCA factors.
Sustainable process synthesis-design can be achieved through
the use of different methods (Halim et al., 2011; Smith et al., 2014;
Tieri et al., 2014) that operate at the unit operations scale. However, three limitations exist. First, the use of hybrid/intensied unit
operations is not considered. Second, the opportunity to innovate
through the potential generation of novel unit operations is not
provided because of the scale at which the methods operate. This
opportunity is possible at the task scale (Siirola, 1996; Agreda et al.,
1990) and phenomena scale (Lutze et al., 2013; Babi et al., 2014b,
2014c). Third, a comprehensive analysis, that is, an economic, sustainability and LCA analysis, are not used together for identifying
design targets through the identication of process hot-spots. A
process hot-spot are limitations/bottlenecks associated with tasks
that may be targeted for overall process improvement. Therefore,
by performing process synthesisintensication, these three limitations can be overcome in a systematic manner.
In this paper a systematic, computer-aided, multi-stage, multiscale framework for sustainable process synthesisintensication
that leads to the identication of more sustainable process design
alternatives is presented. The framework is summarized in Fig. 1.
In stage 1, that is, the synthesis stage, the problem is dened in
terms of an objective function, subject to process constraints and
performance criteria. A processing route is either found from a literature survey or generated from the application of the means-ends
analysis (Siirola, 1996), thermodynamic insights (Jaksland et al.,
1995) or superstructure network optimization (Zondervan et al.,
2011; Grossmann, 2012). In stage 2, that is, the design stage, a
base case design is rst established and then analyzed in terms
of economic factors, sustainability metrics and LCA factors for
identication of process hot-spots. These process hot-spots are
then translated into design targets that are to be satised if more

sustainable alternatives are to be determined. In stage 3, that is, the
innovation stage, desired tasks, phenomena, and the phenomena
search space are identied (dened as design targets) and those
desirable tasks and phenomena that may assist in overcoming the
process hot-spots are identied. Process synthesis is applied using
an integrated task-phenomena based approach in order to generate
alternatives that achieve the design targets. Mutli-scale synthesis
is possible because the base case design, in principle, can be decomposed from the unit operations scale to the task scale (Siirola, 1996)
and phenomena scale (Lutze et al., 2013; Babi et al., 2014b). In
the integrated task-phenomena based approach for process synthesis, phenomena are combined (rule-based) in such a manner
that they perform a task or a set of tasks. These combinations of
phenomena and/or tasks are then translated into unit operations
using a knowledge-based, thereby leading more sustainable process designs or owsheet alternatives. These designs are analyzed
and compared to the base case design with respect to preselected
performance criteria in order to determine the best, more sustainable process design.
Therefore multi-level synthesis is performed in the following
manner. In stage 1, synthesis and design is performed in order to
identify a feasible processing route that can be used as a base case in
stages 2 and 3. In stage 2, task based synthesis is performed where,
a task or set of tasks representing the function of a unit operation
are identied and analyzed for generation of intensied owsheet
alternatives (task based). In stage 3, phenomena based synthesis
is performed where, process phenomena are identied, analyzed
and combined to generate owsheet alternatives that are more
sustainable and constitute of hybrid/intensied unit operations.
In this paper, the detailed architecture of the framework
together with the main actions needed for successful application
of each step of the work-ow is presented. An overview of the
algorithms used in each step and the necessary methods and tools
embedded within the framework are presented. The framework is
applied to a case study of industrial importance, that is, the production of dimethyl-carbonate, where important features of the
method of solution are highlighted.
2. Process synthesisintensication: solution approach and
denitions
The process synthesisintensication problem is dened as follows (Babi et al., 2014b): For the production of a specied product,
generate more sustainable process designs. These alternatives may
include well-known, existing and novel hybrid/intensied unit
operations that provide improvements in terms of efcient use of
raw materials, sustainability metrics (impacts) as well as LCA factors compared to a reference (base case) design. The mathematical
description is given in Section 2.1, the solution approach in Section
2.2, the concept of performing process intensication at different
scales in Section 2.3 and the criteria for sustainability and LCA are
explained in Section 2.4.
2.1. Mathematical formulation of the process
synthesisintensication problem
The problem denition for process synthesisintensication is
translated into a mathematical form:
o
o
min/max fobj
= fobj
(X- , Y- , d- , z- , - )
(1)
subject to:
g(X- , z- , - )
(2)
f (X- , Y- , d- , z- , - ) = 0
(3)
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Stage 3
Innovation
Design
Sustainable design
Flowsheet:
Well-known + Hybrid/
Intensified + Innovative unit
operations
More Sustainable Designs
Stage 1 + Stage 2 + Stage 3
Stage 2
Design
(& Analysis)
Feasible design
Flowsheet:
Well-known + Hybrid/
Intensified unit operations
Process Synthesis-Design
Stage 1 + Stage 2
Search Space of Unit Operations
Stage 1
Synthesis
Knowledge-base
Computer-aided
Tools
Methods
Models
Unit operations scale

Task scale
Phenomena scale
Fig. 1. Framework for more sustainable design through process intensication.
bL b1 X- + b2 Y- bU
(4)
2.2. Solution approach: decomposition based solution strategy
hL h(X- , Y- , d- , - ) hU
(5)
vL v(X- , Y- , d- , - ) vU
(6)
wL w(X- , Y- , d- , - ) wU
(7)
0
Y- = , X- 0
1
(8)
In order to manage the complexity related to the solution of

the MINLP synthesis-intensication problem, an efcient and systematic solution approach is needed. One approach (Karunanithi
et al., 2005), decomposes the problem into a set of sub-problems
that are solved according to a pre-dened calculation order. Most
of the sub-problems require bounded solution of a sub-set of equations and the nal sub-problem is solved as a set of NLP or MILP.
Therefore owsheet alternatives are generated by simultaneously
solving the process model equations, Eqs. (2) and (3), subject to the
constraints dened in Eqs. (4) and (5).
The objective function dened by Eq. (1) is calculated and
ordered for the remaining feasible owsheet alternatives. The generated alternatives are then assessed using a set of PI performance
criteria specied in Eq. (7). The performance criteria are related to
the performance and improvement in economic, sustainability and
LCA factors, of the whole or part of the process through the application of hybrid/intensied unit operations (Lutze et al., 2012; Babi
et al., 2014b). The owsheet alternative(s) that give the best objective function value are selected as the more sustainable process
designs. Note that a direct solution of the MINLP problem is also
possible (Zondervan et al., 2011; Quaglia et al., 2014).
The objective function (Eq. (1)) can be linear or non-linear, is

dependent on a set of, design/optimization variables X- , binary
(0,1) decision integer variables Y- , equipment (unit operations)
parameters d- , thermodynamic variables z- , and process and product specications - . Eq. (1) represents the objective function
to be minimized or maximized subject to a set of linear and
non-linear constraints (Eqs. (2)(8)). Eqs. (2) and (3) represent a
system of linear and non-linear equations (constraints), representing the process models. Here, the process models are considered
at steady state conditions only, consisting of the phenomena
as well as mass and energy balances. Eqs. (4) and (5) represent the owsheet physical constraints and equipment design
specications, for example, the process owsheet structure and
equipment boundaries, respectively. Eqs. (6) and (7) represents PI
constraints, that is, intensication design specications and performance criteria that the feasible owsheet alternatives must satisfy,
for example, the inclusion of intensied (mature/novel) equipment within the search space of available unit operations and
the improvement of sustainability/LCA factors, respectively. The
process synthesisintensication problem to be solved becomes a
mixed integer non-linear programming (MINLP) problem because,
as seen from Eqs. (1)(7), the objective function and constraints
can be linear and non-linear and binary decisions must be made
in selection between different phenomena/tasks/equipment for
the generation of feasible owsheet alternatives (Papoulias and
Grossmann, 1983; Quaglia et al., 2012; Lutze et al., 2013).
2.3. Phenomena-based synthesis and a comparison to CAMD

Phenomena-based synthesis is dened as the generation of
more sustainable designs from the combination of phenomena
building blocks (PBBs) at the lowest scale (phenomena) that perform a task at the higher scale (task). Therefore, in performing
phenomena-based synthesis, PBBs are combined to form simultaneous phenomena building blocks (SPBs), that are combined to
form basic structures that perform a task or set of tasks, using
pre-dened rules. These basic structures are then translated into
unit operations (highest scale) that constitute the nal owsheet
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Fig. 2. A comparison of phenomena-based synthesis to CAMD.
alternatives. The combination of PBBs to generate basic structures

is rule based and analogous to CAMD (Harper and Gani, 2000)
where atoms are combined to generate functional groups that are
combined to form molecules with a set of desired properties (performance criteria). The comparison of phenomena-based synthesis
to CAMD is shown in Fig. 2.
2.3.1. Phenomena building blocks and simultaneous phenomena
building blocks
A phenomena building block (PBB) is considered in this work
as the smallest unit that performs a task in a process. For example,
a mixing PBB performs a mixing task. A simultaneous phenomena
building block (SPB) is dened as the combination of one or more
phenomena building blocks using predened combination rules.
Most chemical processes can be represented by different combinations of mass, energy and momentum transfer phenomena
(Lutze et al., 2013) such as mixing (M), two-phase mixing (2phM),
heating (H), cooling (C), reaction (R), phase contact (PC), phase
transition (PT) phase separation (PS) and dividing (D). A dividing phenomena divides a stream into one or more streams. Each
PBB contributes to mass and energy balances that are solved for
the system boundary of the SPB. The inlet/outlet stream states
of the PBBs are liquid (L), vapor (V), solid(S) and/or their combinations, for example, vapor and liquid (VL), liquidliquid (LL),
vaporliquidliquid (VLL), and solidliquid (SL).
It should be noted that all possible combinations of SPBs are
obtained from the combinations of the 9 PPBs listed above. The 9
individual phenomena building blocks are used in the generation
of feasible SPBs using the following rules:
M If separation or reaction is occurring, mixing of the compounds in the separating mixture and/or mixing of the reactants
occur therefore, a M PBB is required;
R If a reaction is occurring, raw materials are converted to products, therefore, a R PBB is required;
2phM If separation or reaction is occurring in a two phase system, mixing of the two phases occur therefore, a 2phM PBB is
required;
PC If two phases are present then, contact of between the two

phases occur therefore, a PC PBB is required;
PT If two phases are present then transition from one phase
to the other occur, for example, consider a vapor-liquid system
where liquid transitions into vapor due to heating and vapor
transitions into liquid due to cooling. When this occurs a PT
PBB is required;
PS If two phases are present then separation of the two phases
occur therefore, a PS PBB is required;
H/C If a single phase or multiple phases are present and there
are changes in enthalpy due to internal and/or external energy
sources then a H or C PBB is required;
D If the dividing of streams is needed then a D PBB is required.
Fig. 3(a)(c) highlights the representation of three different unit
operations in terms of SPBs that are formed by combination of PBBs.
This is explained as follows:
Flash vessel (phases: vapor and liquid) In the ash vessel the
following are occurring simultaneously, mixing plus two phase
mixing, phase contact between vapor and liquid, transition from
one phase into another and the separation of two phases. Therefore, the following PBBs are required in order to generate feasible
SPBs that represent the ash vessel, M, 2phM, PC(VL), PT(VL),
PS(VL) as highlighted in Fig. 3(a);
Distillation column (phases: vapor and liquid) In the distillation column, the same PBBs as the ash vessel are selected plus
heating and cooling PBBs for properly representing the condenser
and reboiler. The following PBBs are required in order to generate feasible SPBs that represent the distillation column, M, 2phM,
PC(VL), PT(VL), PS(VL), H, C as highlighted in Fig. 3(b);
Reactive distillation (phases: vapor and liquid) In the reactive distillation column, the same PBBs as the distillation column
are selected plus reaction because reaction and separation are
also occurring simultaneously. The following PBBs are required
in order to generate feasible SPBs that represent the reactive
distillation column, M, 2phM, PC(VL), PT(VL), PS(VL), H, C, R as
highlighted in Fig. 3(c).
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Fig. 3. Basic structures representing three unit operations (a) a ash column, (b) distillation and (c) a single feed reactive distillation column with reaction only.
2.3.2. Basic structures

A basic structure is dened as the combination of multiple SPBs
using predened combination rules (Babi et al., 2014b). A basic
structure performs a targeted or set of targeted tasks and are represented by SPBs, which are classied as initiator, intermediate and
terminator (for more details, see Table S1 in the supplementary
material). An initiator SPB is one that fullls the main objective of
a task but may not fulll the entire task. A terminator SPB represents the nal task to be performed in an operation. An initiator
SPB, when repeated more than once to represent an operation is
classied as an intermediate SPB. These intermediate SPBs can be
repeated multiple times to complete the tasks of an operation.
A basic structure can then be expanded in order to fulll a task.
When a basic structure is expanded and fullls a task, it is referred
to as the completion of the desired (needed) operation which is
then translated into a unit operation (see Fig. 3). The number of
times an intermediate SPBs can be repeated is determined by using
the extended Kremser method (Lutze et al., 2013), for example,
the number of trays of a distillation column is equivalent to the
number of repeated intermediate SPBs. For a ash vessel the basic
structure is also an operation and as it performs (see Fig. 3(a)) the
desired separation task. However, for the distillation column and
reactive distillation column, intermediate SPBs must be added until
the process specications (such as product purity, recovery, etc.)

are matched (see Fig. 3(a)(c)).
2.4. Criteria for evaluation
In order to evaluate a more sustainable design compared to the
base case design for identifying non-tradeoff designs, different performance criteria related to economic, sustainability/LCA factors
are applied (Eq. (7)). These are categorized as follows:
1. Economic Cost related, for example:
a. Utility cost
b. Operational cost
c. Total annualized cost
d. Prot
2. Sustainability metrics/LCA factors Environmental related, for
example
a. Carbon footprint
b. Environmental impacts (Kalakul et al., 2014):
i. HTPI Human Toxicity Potential by Ingestion
ii. HTPE Human Toxicity Potential by Exposure
iii. GWP Global Warming Potential
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iv. HTC Human toxicity (carcinogenic impacts)

v. HTNC Human toxicity (non-carcinogenic impacts)
3. Sustainable process synthesisintensication framework
The detailed workow for the systematic, computer-aided,
multi-stage, multi-scale framework for sustainable process
synthesisintensication together with the different computeraided tools utilized by the framework is shown in Fig. 4.
The framework is based on the proposal of Lutze et al. (2013)
where the concept of phenomena based synthesis was proposed for
intensication of an entire process. The ideas of Lutze et al. (2013)
have been extended and briey described by Babi et al. (2014a,
2014b, 2014c). In this paper, a detailed and full version of the multiscale framework is presented.
The framework consists of 8 steps that operate at the unit
operation-task scales and, 4 integrated task-phenomena-based
synthesis (IT-PBS) steps that operate at the task-phenomena scales.
According to the work-ow (see Fig. 4), in each step an objective
must be accomplished in order to proceed to the next step. The
information from a previous step is used as the input to the next
step. Note, however, additional data/information may be needed as
input to a step. To achieve the objective of each step, the user must
perform a series of actions. Each step of the work-ow is presented
together with a list of associated methods and tools.
3.1. Step 1 problem denition
Objective: To obtain production and cost information about the
raw materials and products.
Action 1.1 Perform a literature/online search to nd the main
uses of the product (or products) to be produced.
Action 1.2 Perform a literature/online search in order to, estimate the annual production of the product.
Note The main uses of the product provide the information
needed to establish the motivation for determining more sustainable owsheet designs for production of this product.
3.2. Step 2 problem (and Fobj ) denition
Objective: To dene the mathematical problem in terms of objective function and constraints.
Action 2.1 Dene the problem, that is, whether a new process
or an existing process retrot is to be investigated.
Action 2.2 Dene the objective function (Eq. (1)) to be maximized or minimized, for example, prot, utility cost, operational
cost or total annualized cost.
Action 2.3 Dene the constraints. The constraints are of four
types, logical constraints (1 ), structural constraints (2 ), operational constraints (3 ) and performance criteria (). An example of
each constraint is as follows:
The objective function is one of the means by which the generated

owsheet alternatives are quantitatively compared.
3.3. Step 3 reaction identication/selection
Objective: (1) To select the reaction pathway, raw materials
state and catalyst; and (2) To determine the reaction type, that is,
exothermic or endothermic.
Action 3.1 Perform a literature-search to nd a feasible reaction pathway for producing the desired product. If more than one
reaction pathway is found then a reaction pathway analysis is recommended, for example, that proposed by Kongpanna et al. (2014).
If available, retrieve reaction equilibrium data (for example, equilibrium data), catalyst information (homogenous or heterogeneous,
selectivity, deactivation, etc.) and reaction kinetics, for the selected
reaction pathway. If no reaction information can be obtained then
reaction path synthesis for identication of a feasible set of reaction
paths, of which, one must be selected, can be performed (Voll and
Marquardt, 2012).
Action 3.2 Identify the phase(s) of the reaction, that is, the
phase(s) in which the reaction takes place. Determine the heat of
reaction, identify if the reaction is reversible or irreversible, and,
identify the reaction type, that is, exothermic or endothermic. The
heat of reaction is determined from the reaction data and the heats
of formation HFi , of the reactants and products.
Note The reaction information also provides important additional information number of phases and phase types as well
as information about the catalyst(s) that are used. These data are
needed for rigorous simulation and modeling in steps 78 and ITPBS.3, respectively.
3.4. Step 4 check for availability of the base case design
Objective: To select a base case design (process route) based on
a literature survey or on the process information on stored in a PI
knowledge-base. Note, if a base case design has been user-specied,
proceed to step 5.
Action 4.1 Perform a literature-search to check if an available
design uses the reaction pathway selected in step 3. If yes, then it is
pre-selected as a base case design and one proceeds to step 5, else,
proceed to step 6.
Note If a base case design is available then the design needs
to be veried (see step 5). However, if a base case design is not
available then synthesis, design and innovation design is performed
to generate one (see steps 67).
3.5. Step 5 check for base case feasibility
Objective: To verify the feasibility of the base case design
obtained in step 4.
Action 5.1 Apply the process synthesis method of Douglas
(1985). If the base case design does not pass the verication test,
then generate a new design (go to step 6).
Note To pass the verication test, the pre-selected design
must satisfy the rules given in process synthesis method of Douglas
(1985) with respect to the inputs/outputs of the process, the separation tasks structure and the energy structure. If the design passes
the verication test, it is listed as the base case (reference) design.
1. 1 The product (and by-product) purity;

2. 2 PBBs are connected to form SPBs based on combination
rules;
3. 3 Raw materials are assumed to be in their pure state except
if otherwise dened;
4. Sustainability and LCA factors must be the same or better.
-
3.6. Step 6 generate a base case design
The full list of the constraints mentioned above is given as supplementary material in Table S2.
Note The problem statement provides the scope of the synthesis, design and more sustainable design problem, related to the
design of a new process or the retrotting of an existing process.
Objective: To generate a processing route to be used as a reference (base case) design for the production of the product from the
raw materials.
Action 6.1 Generate a processing route using one of the
following three methods (or a combination of them): network
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Framework Work-flow &

Architecture
Part II-Innovative Design

Stage 3
Part I-Synthesis and Design

Stage 1 and Stage 2
C
o
m
p
l
e
x
i
t
y
Computer-Aided Tools
ASPEN/
PROII
Database
Integrated Task-Phenomena based Synthesis

Step 7
Perform
Rigourous
simulation
IT-PBS.1
Step 6
Generate a base
case design
No
Step 5
Base Case
Feasibility?
No
Step 2
Problem Definition
MoT
Process Analysis
ECON
SustainPro
LCSoft
IT-PBS.3
Step 8
IT-PBS.2
Economic,
Sustainability &
LCA Analysis
Identification of
desirable tasks &
phenomena
Generation of
feasible flowsheet
alternatives
IT-PBS.4
ECON
LCSoft
Perform
EconomicSustainability
analysis
Selection of best
flowsheet
Y es
Step 3
Step 4
Reaction
identification/
selection
Availability-Base
Case?
Final flowsheet
inclusive of PI
Step 1
Need Identification
Data/Information
Fig. 4. Framework workow and architecture for sustainable process synthesisintensication.
superstructure optimization (Grossmann, 2012; Quaglia et al.,

2014), the means-ends analysis (Siirola, 1996) and thermodynamic
insights (Jaksland et al., 1995). Identify feasible tasks for reaction
and separation based on pure compound and mixture property
analyses (thermodynamic insights). From these results, unit operations that fulll the identied tasks are identied (Jaksland et al.,
1995).
Note The base case (processing route) generated from this step
does not include the use of hybrid/intensied unit operations, but
only well-known unit operations.
3.7. Step 7 perform rigorous simulation
Objective: To rigorously simulate the base case (reference)
design.
Note The rigorous simulation of the base case (reference)
process design provides the data (properties of all streams in
the owsheet obtained from mass and energy balance) needed
to perform the economic, sustainability and LCA analyses. The
data needed to set-up a rigorous simulation are, number of unit
operations, number of streams, stream properties, number of compounds, number of reactions, and unit operations specic data, for
example, the number of trays, reux ratio and product recovery.
Action 8.3 Perform a LCA analysis. A LCA analysis based on

an indicator based method using a cradle to the gate concept and
implemented in a computer-aided tool, LCSoft (Kalakul et al., 2014),
is recommended. Retrieve the carbon footprint (CO2 footprint) and
environmental impact for each unit operation.
Action 8.4 Translate the indicator values from the analyses into
targets process hot-spots elimination using Table 1.
Action 8.5 Translate the process hot-spots into design targets
using Table 2.
Note The economic analysis provides an indicator related to the
distribution of utility costs and operating costs. The sustainability
analysis provides information on where in the process economic
value is being lost, for example, raw material loss in a waste
stream. The LCA analysis provides environmental indicators related
to how sustainable the process is with respect to the environment,
for example, through the calculation of the carbon footprint. The
method and tools used for these analyses are explained in Section
4. The results from the economic, sustainability and LCA analyses
are translated into process hot-spots, from which the most sensitive
are selected as design targets. Matching of these design targets minimizes/eliminates the process hot-spots and therefore, generates
non-tradeoff process designs.
3.9. IT-PBS.1 process analysis
3.8. Step 8 economic, sustainability and LCA analysis

Objective: To identify process hot-spots as targets for sustainable
design through rigorous; economic, sustainability and LCA analyses.
Action 8.1 Preform an economic analysis. Models available
in Peters et al. (2003) were used (supplemented by Biegler et al.,
1997). The software, ECON (Kalakul et al., 2014), which has these
models has been used. Retrieve the utility costs and the capital costs
for each unit operation.
Action 8.2 Perform a sustainability analysis (see Section 4.2). A
sustainability analysis based on the method of Carvalho et al. (2009)
and implemented in a computer-aided tool, SustianPro (Carvalho
et al., 2013), is recommended.
Objective: Translate the base case owsheet into tasks, PBBs and
the PBBs associated with each hot-spot.
Action IT-PBS.1.1 Translate the base case owsheet into a taskbased owsheet by applying Algorithm I.1 (see Section 4.1.1).
Action IT-PBS.1.2 Translate the task-based owsheet into
phenomena based owsheet using Algorithm I.2 (see Section 4.1.1)
and store the identied PBBs.
Action IT-PBS.1.3 Retrieve pure compound data (see Table 14)
from any appropriate properties database, for example the CAPEC
database (Gani et al., 1997) and perform a mixture analysis
(Jaksland et al., 1995): (1) analysis of pure compound properties
using a binary ratio matrix, (2) azeotropic analysis including its
pressure dependency and (3) miscibility analysis.
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Table 1
List of established relations between indicator values and the process hot-spots.
Indicator values
Base case property
Cause
Identied process
hot-spot
1 , raw material recycle/cost

1 -MVA
Un-reacted raw
materials
Equilibrium reaction
2 -utility cost
2 -EWC
1 -CO2 equivalent
2 -utility cost
2 -EWC
1 -CO2 equivalent
2 -utility cost
3 -capital cost
Hrxn < 0 reactor

cooling
Exothermic reaction
-Activation problems
-Limiting
equilibrium/raw
material loss
-Contact problems of
raw materials/limited
mass transfer
-Limited heat transfer
-Highly exothermic
reaction
Hrxn < 0 reactor

heating
Endothermic reaction
-Highly endothermic
reaction
Reactor operating
conditions
4 -product sale
2 -PEI
Formation of
by-product(s)
-Explosive mixture
-Product degradation
by temperature
-Formation of
undesired
side-products
2 -utility cost
1 -MVA
2 -EWC
1 -CO2 equivalent
2 -PEI
Un-reacted raw
materials and products
recovery
Temperature and
pressure operating
window for the reactor
NOP, number of
desired products plus
number of undesired
products
-Presence of
azeotrope(s)
-High energy
usage-heating/cooling
-Azeotrope
-Difcult separation
due to low driving
force
-High energy
consumption/demand
Note: Economic (
) and LCA ( ) analysis, MVA mass value added, EWC Energy to waste cost, CO2 equivalent carbon footprint, PEI potential
- ), sustainability (
environmental impact, NOP number of products.
The binary ratio matrix (Jaksland et al., 1995) is calculated as

the ratio between pure compound properties for all binary pairs
formed by the mixture compounds. The number of binary pairs,
NB, is given by NB = NC(NC 1)/2, where NC is the number of compounds in the mixture. The binary ratio, rij , for a binary pair is
calculated as, rij = pAi /pBj , where pkij is the pure compound property
i of compound k in mixture j; A and B indicate the compounds in
the binary pair.
The azeotrope analysis is performed by investigating the effect
of pressure on the change in the azeotropic composition and temperature.
A miscibility analysis is performed through liquid miscibility
(stability of the liquid phase) calculations. This would indicate the
presence of more than one liquid phase as well as mutual solubilities of the mixture compounds.
Note The base case owsheet is transformed from higher scales
(unit operations scale) to lower scale (task and phenomena scale).
Through analysis of the stream (mixture) and unit operation, a set
of feasible tasks and phenomena are identied.
3.10. IT-PBS.2 identication of desirable tasks and phenomena

Objective: To identify desirable tasks and PBBs for overcoming
the identied process hot-spots.
Action IT-PBS.2.1 Identify the tasks and their corresponding
PBBs needed to overcome the hot-spots by applying Algorithm I.3.
Add to this list, the PBBs identied in IT-PBS.I.2 (see Section 4.1.1),
dening thereby, the PBB-based search space before screening of
alternatives.
Action IT-PBS.2.2 Reduce the identied PBB based search space
using the structural constraints 2 and performance criteria
dened in step 2. For example, if the use of a mass separating agent
to minimize waste is not to be considered, then 2 is adjusted to
reect this constraint. That is, PBBs that require the use/addition of
a mass separating agent (for example PT(LL)) is removed.
Action IT-PBS.2.3 Identify the operating window of each identied PBB using the relationships given in Table 3. Through analysis
of the properties (for example, boiling point, melting point, reaction pressure, etc.), the feasible range of the operating variables (for
example, temperature, pressure) are established.
Note The identied desirable tasks are translated into PBBs
and added to the initial list of PBBs from IT-PBS.1. A desirable task
is dened as a task that if performed has the potential to minimize/eliminate a process hot-spot. New PBBs may now be included.
The properties involved with each PBB helps to dene the operational boundary for each PBB with respect to temperature and/or
pressure. Properties such as pH, viscosities, etc. are not considered
at this point.
3.11. IT-PBS.3 generation of feasible owsheet alternatives
Objective: To generate feasible intensied owsheet alternatives
using an integrated, task-phenomena-based approach.
Action IT-PBS.3.1 Generate feasible SPBs by applying Algorithm
II.1 (see Section 4.1.2).
Action IT-PBS.3.2 Generate a task-based superstructure of
alternatives by applying Algorithm II.2 (see Section 4.1.2).
Action IT-PBS.3.3 Identify and verify feasible tasks from the
task-based superstructure that must be performed by applying
Algorithm II.3 (see Section 4.1.2).
Action IT-PBS.3.4 Identify the basic structures that perform
a desired task by applying Algorithm II.4 (see Section 4.1.2). An
excerpt of the generated basic structures is given as supplementary
material (see Table S3).
Action IT-PBS.3.5 Identify the task-based owsheets from the
basic structures by applying Algorithm II.5.
Action IT-PBS.3.6 Translate the task-based owsheets into process owsheet alternatives at the unit operations scale by applying
Algorithm II.6.
Action IT-PBS.3.7 Perform a model based analysis of the generated owsheet alternatives to analyze/understand the performance
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Design (Intensication)
targets
Activation
problems
Limiting
equilibrium
Contact
problems of
raw materials/limited
mass
transfer
Limited heat
transfer
*
*
*
*
*
*
*
*
*
*
*
*
Highly
exothermic
reaction
Highly
endothermic
reaction
Explosive
mixture
Degradation
by
temperature
*
*
*
*
Formation of
undesired
sideproducts
Azeotrope
Difcult
separation due
to low driving
force
High energy
consumption/
demand
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
Note: * represents the corresponding design target for a given process hot-spot.
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Increase raw material

conversion
Reaction-change in catalyst
Reaction-use of a solvent
Reaction-new
Reaction-mixing
Reduce raw material loss
Reduce product loss
Reduce energy
consumption
Reduce utility cost
Improvements in
LCA/Sustainability
indicators
Unit operations reduction
Product purity
Production target
Reduce operational cost
Waste minimization
Process hot-spots
Table 2
Translation of process hot-spots into design targets.
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Table 3
List of relationships between tasks, PBB, operating variables and properties.
Task
PBB
Operating variables
Properties to be checked
Example
Reaction (single phase)

Concentrations below the
dew point line
T, P
TB , TM , Tazeotrope
Single phase is liquid-P-Reaction pressure (reported in

literature)
T lowest boiling compound or azeotrope
T lowest highest melting compound
Reaction (two phase)
T, P
Mixing (single phase)

Concentrations below the
dew point line
T, P
Phases: vapor/liquid
P reaction pressure
T highest boiling compound in the liquid phase
T lowest melting compound
Ideal mixing: T lowest melting compound
Ideal mixing: T highest boiling compound

Vapour mixing: T lowest boiling compound or minimum
boiling azeotrope
Two-phase mixing
Concentrations in VL
equilibrium regions are
between the dew and
bubble point line
2phM
T, P
T lowest melting compound
T 2nd highest boiling compound or minimum boiling

azeotrope
Heating/cooling
H/C
Phase contact
PC
Phase transition
Concentrations in VL
equilibrium regions are
between the dew and
bubble point line
PT
TST , TTD
NA
VL: NA
LL: NA
SL: NA
T, P
TB , Tazeotrope
T lowest boiling compound or minimum boiling

azeotrope
T highest boiling compound or maximum boiling

azeotrope
Phase Separation
PS
VL: NA
LL: NA
SL: NA
Note: NA not applicable, T temperature, P pressure, TB boiling point, TM melting point, TST thermal stability and TTD thermal decomposition.
of hybrid/intensied unit operations that may constitute the owsheet alternatives investigated in IT-PBS.4. First, retrieve models
from a model library incorporated in ICAS-MOT (Heitzig et al.,
2011) for hybrid/intensied unit operations, for example, reactive
distillation and membrane reactor. Second, perform model-based
studies, for example, conversion and product purity achieved for
reaction plus separation occurring simultaneously. Third, screen
the owsheet alternatives using the dened logical constraints (1 ),
structural constraints (2 ), operational constraints (3 ) for further
investigation in IT-PBS.4.
Note Multiple basic structures may perform the same task,
thereby, expanding the search space for unit operations inclusive
of hybrid/intensied unit operations. Also, the same basic structure
may perform multiple tasks, thereby, reducing the number of unit
operations in a generated owsheet alternative. Basic structures
are used to identify feasible task-based owsheet alternatives from
a task-based superstructure. The basic structures are translated
into unit operations that includes well-known plus novel/mature
hybrid/intensied unit operations (where applicable).
3.12. IT-PBS.4 comparison and selection of the best owsheet
alternatives
Objective: To perform economic, sustainability and LCA analyses and calculate the objective function for selection of the best
owsheet alternative.
Action IT-PBS.4.1 Calculate the economic, sustainability and

LCA indicators by applying actions 13 from step 8.
Action IT-PBS.4.2 Calculate the objective function value for each
feasible owsheet alternative and select the best owsheet alternative by ordering them according to objective function values.
Each feasible owsheet alternative must also satisfy the following
constraints: logical (1 ), structural (2 ), operational (3 ), performance criteria (, step 2) and design targets (see step 8). The
improvements related to sustainability/LCA factors are part of the
performance criteria and are simultaneously checked and compared to the base case design. In non-tradeoff solutions, the selected
alternatives must show improvements (or no change) with respect
to all considered performance criteria.
4. Process synthesisintensication: algorithms,
supporting methods and tools
4.1. Process synthesisintensication algorithms
Application of the process synthesisintensication framework
requires the use of different algorithms, as highlighted above. The
algorithms are grouped into two sets: set-I correspond to algorithms that are needed to decompose the problem from the largest
scale (unit operation) to the smallest scale (phenomena); set-II correspond to those that are needed to aggregate from the smallest
scale to the largest scale. Set-I consists of three sub-algorithms
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Table 4
List of objectives and outcomes of each sub-algorithm employed in the process
synthesisintensication framework.
Sub-algorithm
Objective
Algorithm I.1
To transform a base case owsheet into a

task-based owsheet
Identication of the PBBs in the base case
owsheet
To transform that task-based, base case
owsheet, to a phenomena-based owsheet
Identication of desirable task and PBBs for
overcoming the identied process hot-spots
Identication of the PBB search space
Generation of feasible SPBs using combination
rules
Generation of a task-based superstructure for
identifying feasible task-based owsheets
Identication of feasible tasks to be performed
Generation of basic structures
Generation of task-based owsheets
Translation of basic structures into unit
operations
Algorithm I.2
Algorithm I.3
Algorithm II.1
Algorithm II.2
Algorithm II.3
Algorithm II.4
Algorithm II.5
Algorithm II.6
Table 5
Generation of feasible SPBs using SPB building blocks.
Inlet
Rule
SPB building block

M=C
1 . . . n(L, V, VL)
M = 2phM
1 . . . n(L, V, LL, VL)
M=R
1 . . . n(L, V, VL)
PC = PT
1 . . . n(VL, LL)
PC = PT = PS
1 . . . n(VL, LL)
Performs cooling of a
stream
Mixing of a stream
with two phases
Preforms a reaction
without an external
energy source
Performs the contact of
two phases
Preforms the
separation of two
phases
SPB (feasible)
M = 2phM = PC = PT
1 . . . n(LL,VL)
M=R=C
1 . . . n(L,V,VL)
M = R = 2phM = PC = PT = PS
1 . . . n(LL,VL)
while set-II consists of six sub-algorithms. A summary of the objective of each sub-algorithm is given in Table 4.
4.1.1. Set-I algorithms
For the application of set-I algorithms, the following problem
denition is used: Given: a base case design and identied process
hot-spots that have been translated into design targets; Identify: a
set of desirable tasks and the PBBs representing these tasks.
Algorithm I.1. Identify each unit operation; nd their corresponding tasks (from a database of unit operation versus tasks);
replace each unit operation by a single or multiple tasks to obtain
a task-based owsheet.
Algorithm I.2. For each task, nd the corresponding PBBs (from a
database of tasks versus PBBs); replace each task with their corresponding PBBs to obtain a PBB-based owsheet. The database used
for the identication of PBBs based on tasks and unit operations
is given as supplementary material in Table S4. An example of the
application of Algorithm I.1 and Algorithm I.2 is shown in Fig. 5.
Algorithm I.3. Identify alternative tasks and their corresponding
PBBs from the identied hot-spots (from a database of known hotspots, tasks and PBBs linked to property ratio matrices of binary
mixtures); add these PBBs to the original list of PBBs. The database
used for the identication of PBBs based on tasks and unit operations is given as supplementary material in Table S5.
4.1.2. Set-II algorithms
For the application of set-II algorithms, the following problem
denition is used: Given: a set of phenomena building blocks and
design targets; Identify: generate feasible sustainable designs that
minimizes/eliminates process hot-spots and satises the design
targets.
Algorithm II.1.
Calculate the number of possible SPBs using Eq. (9) (Lutze et al.,
2013) where nPBBE , nPBBM and nPBBD are the number (n) of
energy (E, that is, heating and cooling), mixing (M) and dividing
(D) PBBs, respectively.

nPBB,max
NSPBmax =
k=1
(nPBB 1)!
+1
(nPBB k 1)!k!
nPBB,Max = nPBB (nPBBE 1) (nPBBM 1) nPBBD
(9)
11
Performs the mixing of

two phases
Preforms a reaction
with external energy
source-cooling
Performs a reaction,
phase creation and
phase separation
From the total number of possible SPBs, identify the feasible SPBs
using pre-dened SPB building blocks and combination rules. An
example is given in Table 5. An SPB building block is a pre-dened
feasible SPB as is or it can further be combined with other SPB
building blocks for generating more SPBs
Algorithm II.2.
Generate the task-based superstructure: Identify the minimum
number of separation tasks that need to be performed and
sequence the tasks starting from all possible reaction tasks to
separation tasks (level 1)
Consider merging of adjacent reaction-separation tasks and
update the task-based superstructure (level 2)
Algorithm II.3. Check the feasibility of the identied tasks
through mixture property analyses (Lutze et al., 2013; Babi et al.,
2014b).
Algorithm II.4. Identify the basic structures that are able to perform a task; list this task as a feasible task with a corresponding
basic (SPB) structures.
Algorithm II.5. Generate task-based owsheets consisting of
basic (SPB) structures.
As an example, consider the reaction (exothermic, single liquid
phase) where A and B react to produce C. The order of the boiling
points of the compounds A, B and C are as follows: A < B < C. The
following scenarios are considered: An azeotrope exist between B
and C. Applying Algorithm II.3 and Algorithm II.4, the task-based
superstructure and feasible basic structures are given in Fig. 6 and
Table 6, respectively.
Applying Algorithm II.5, the feasible task-based owsheet is
shown in Fig. 7. It should be noted that one task based owsheet is
feasible from the task-based superstructure, however, by using the
concept of basic structures, two feasible basic structures are feasible with respect to performing separation task 2. Therefore, at the
unit operations scale this will lead to the generation of 2 owsheet
alternatives compared to 1, if one operated at the task scale.
Algorithm II.6. Use a database to translate the basic structures to
tasks and then to unit operations. An example of a database used
for the translation of basic structures into unit operations is given
as supplementary material in Table S6. If the basic structure and
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Fig. 5. Moving toward lower scales, that is, unit operations scale to phenomena scale.
Fig. 6. Task-based superstructure considering task merging (shaded). R task-reaction task, S task-separation task.
Fig. 7. Task-based owsheet (shaded) from the task based superstructure presented in Fig. 6. R task-reaction task, S task-separation task.
its corresponding unit operation do not exist, then in principle, a

new unit operation is generated. As an example, consider the identied basic structures for separation task 1 and separation task 2
in Table 6. The list of unit operations are then screened based on
the phase identity of the feed stream, use of a mass separating
agent (MSA) and the presence of azeotropes with the data given
in Table 7. The selected feasible unit operations are highlighted in
bold in Table 7.
4.2. Supporting methods and tools
Table 8 gives a list of different methods and tools that have been
available for use through the process synthesisintensication
framework.
The supporting methods used in the framework for owsheet generation and pure compound and mixture analyses are
the means-ends analysis (step 6 and IT-PBS.3) and method of
thermodynamic insights (step 6 and IT-PBS.3). The means-ends

analysis is based on identifying transformation operators, that is,
tasks, for eliminating property differences in moving from an initial
state to a goal state (objective) (Siirola, 1996).
The method of thermodynamic indicators consists of two levels. In level 1, the binary ratio is calculated and, pure compound
analysis and mixtures analysis are performed in order to, identify
all feasible tasks for reaction and separation. Feasible separation
techniques, for example extractive distillation, are then identied
using the compound analyses and identied tasks. In level 2, redundant tasks identied in level 1 are removed and the need for the
use of external agents, for example, mass separating agents (for
example, solvents) is identied. The remaining tasks in level 2
are screened using model-based calculation and/or graphical techniques for dening a feasible task search space. These tasks that are
associated with the identied unit operations (in level 1) are then
combined to generate owsheet alternatives (Jaksland et al., 1995).
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Table 6
Identied basic structures that perform a task.
Note: * identied from Algorithm II.3.
Table 7
List of identied unit operations based on identied basic structures for three cases: phase identity of feed stream; MSA and the presence of azeotropes.
SPB initiator in the basic structure
Task
Reaction/separation
operation
Screening 1:
feed phase
Screening 2:
MSA-Y/N
Screening 3:
azeotrope
=2phM = PC(VL) = PT(VL) = PS(VL)
Separation
Separation
Separation
N
N
N
Y/N
Separation
Extractive distillation
Y/N
Separation
Reboiled absorption

Separation
Separation
Y
Y
N
N

Separation
Separation
Separation
Stripping
Reuxed stripping (steam
distillation)
Reboiled stripping
Evaporation
Divided Wall Column
N
N
N
N
N
N

=PC(VL) = PT(PVL) = PS(VL)
=PC(VL) = PT(VV) = PS(VV)
Separation
Separation
Separation
Vapor and/or
liquid
Liquid
Vapor and/or
liquid
Vapor and/or
liquid
Vapor and/or
liquid
Liquid
Vapor and/or
liquid
Liquid
Liquid
Vapor and/or
liquid
Liquid
Vapor
Vapor

Partial condensation or
vaporization
Flash vaporization
Distillation
Y
N
N
N
Y
Y
Supercritical Extraction
Membrane-pervaporation
Membrane-vaporpermeation
The sustainability analysis uses an indicator-based methodology where a set of calculated closed- and open-path indicators
for identifying the most critical paths that are used to identify the
process hot-spots within any process owsheet. The method calculates and ranks a set of mass and energy indicators, from data
obtained from steady-state process simulation or plant real-time
data (Carvalho et al., 2009). A brief explanation of the sustainability indicators and what should be done in order to improve the
process are presented:
Material value added (MVA) The indicator provides an estimate

of the value added between the entrance and exit (open path) of a
given compound in a given process stream (path). Negative values
of this indicator show that the component has lost its value in this
open-path and therefore, point to potential for improvements.
Energy and waste cost (EWC) The indicator is applied to both
open- and closed-paths (recycle streams). It takes into account
the energy (EC) and compound treatment costs (WC). The indicator represents the maximum theoretical, amount of energy that
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Table 8
Methods and supporting information for performing synthesis, design and sustainable design.
Synthesis
Design
Innovative design
Methods
Superstructure
Optimization
Simulation and analysis
Input data
Result
-Compounds
-Reactions
-Conversion
-Separation factors
-Unit operations
-Processing route
-Compounds
-Reactions
-Conversion/kinetics
-Thermodynamic model
-Unit operations
-Final design
-Process hot-spots
-Design targets
Model
-Balance models (mass and energy)
Model complexity
Simple but qualitatively correct
-Thermodynaimc models
-Process models
-Control models
More complex but qualitatively as well
as quantitatively correct
-Process intensication
-Generation of more sustainble
designs
-Compounds
-Mass balance
-Energy balance
-Unit operations (inclusive of
hybrid/intensied)
-Sustainable design
-Improvement in economic factors
-Improvement in
LCA/environmental factors
Design and sustainabilty share the
same common tools
Model solution stragety
Complex because of the number of

alternatives to evaluate
Complex because of the type of

models-rigorous
Tools
-GAMS
-Excel + GAMS
-EOLO + GAMS
-ICAS
-PROII+
-ASPEN
-HYSYS
-MoT
-gPROMS
-SuatinPro
-LCSoft
-SimaPro
can be saved in a path. High values of this indicator show high

consumption of energy and waste costs. Therefore, these paths
should be considered in order to reduce the indicator value.
Total value added (TVA) The indicator describes the economic
impact of a compound in a path. It is the difference between MVA
and EWC. Therefore, negative values of this indicator show high
potential for improvements related to the decrease in the variable
costs.
The tools used in the framework for performing various calculations associated with synthesis, design and innovation design are
presented in Table 9.
5. Application of process synthesisintensication: case
study
Application of each step of the framework is highlighted through
a case study involving the production of di-methyl carbonate (DMC)
from propylene carbonate (PC) and methanol (MeOH) with, propylene glycol (PG) as a by-product.
5.1. Step 1 need identication
Action 1 Di-methyl carbonate (DMC) is an important, environmentally friendly, bulk chemical that is used as a fuel additive
compared to methyl tert-butyl ether (MTBE) (Bilde et al., 1997),
among other uses. The by-product of the reaction considered in
this case study is also a valuable product, that is, propylene glycol (PG). Propylene glycol can be used for making plastics and heat
transfer uids, among others (CEFIC, 2008).
Action 2 The total production per year of DMC based on
three of the main producers, Henan Zhongyuan Dahua Group
located in China and, UBE and HighChem located in Japan, is
Simple but qualitatively correct

(design tagets identication)
Complex but qualitatively as well
as quantitatively correct
(evaluation of alternatives)
Qualitatively correct (design tagets
identication)
Complex because of the type of
models-rigorous (evaluation of
alternatives)
Design and sustainability share the
same common tools
100 103 tons/year (World of Chemicals, 2012). Therefore, the

specied production target is 1700 kg/h (Holtbruegge et al., 2013a).
The purity of the product and by-product are set to be greater than
or equal to 99.9 wt% and 99 wt%, for DMC and PG, respectively.
5.2. Step 2 problem denition
Action 1 Problem statement: The identication of more sustainable process designs for the production of DMC.
Action 2 The objective function is dened in terms of minimizing the total annualized cost, Eq. (10) subject to constraints and
performance criteria. In Eq. 10, C, m, E and t represent cost, mass and
energy ows, and the project lifetime set at 10 years, respectively:
Max Fobj =
Ei CUt,i + (CEquip /tproj )

mprod
(10)
Action 3 The considered constraints are given in Table 10.

5.3. Step 3 reaction identication/selection
Action 1 The raw materials for the selected reaction are
MeOH and PC. The Gibbs free energy, G0 = 4.76 kJ/mol at standard
conditions (T = 298 K and P = 1 bar) and the equilibrium constant,
Keq = 0.247, is obtained by tting experimental data to a model
(Williams et al., 2009). The operating temperature of the reaction is
set at 313 K based on data reported by Holtbruegge et al. (2013b):
2CH4 O + C4 H6 O3 C3 H6 O3 + C3 H8 O2
(11)
Action 2 The products and by-products from Eq. (11) are in the
liquid phase. The heat of reaction is calculated to be 41.67 kJ/mol
using standard heat of formation data, with an equilibrium conversion of approximately 54%. The reaction is an equilibrium reaction,
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Table 9
Tools applied in each step of the sustainable process synthesisintensication framework. IT-PBS integrated task-phenomena based synthesis, S step.
Step
Method/database
Objective
Tool
ICAS/ICAS databasea
Database
Azeotrope databasea
Knowledge-baseb
Database
Database
Phase diagram
generation/compound
data
Azeotrope data
Hybrid/intensied
unit operations
Property
Prediction
Binary ratio
Process
simulation
Economic
analysis
Sustainability
analysis
LCA analysis
Model
evaluation
ProPred
Model based
CAPSSa
ASPEN/PROII
Model based
Model based
ECONa
Model based
a
SuatainPro
Model based
LCSOfta
MoTa
Model based
Equation
oriented
problem
solution
CAMD/Database
SolventProc
S1
S2
S3
*
S4
S5
S6
S7
S8
IT-PBS.1
IT-PBS.2
IT-PBS.3
IT-PBS.4
*
*
*
*
*
*
*
*
*
*
Solvent
selection
Part of ICAS (Gani et al., 1997).

The knowledge base tool consists of a list of hybrid/intensied unit operations (Lutze et al., 2013; Babi et al., 2014b) and the information specied in algorithm I and
algorithm II.
c
The corresponding tool for a given process step in the framework.
b
that is, it is reversible. The heat of reaction, Hrxn < 0, therefore the
reaction is exothermic.
5.4. Step 4 check for availability of the base case design
Action 1 From a literature survey, a known base case design
(Schlosberg et al., 2002) is available and was pre-selected. It
Table 10
Logical, structural and operational constraints and, performance criteria for achieving sustainable process synthesisintensication of DMC production.
Objective
Constraint
1
Flowsheet structure: reaction + separation
Reaction occurs in the rst unit operation
The product purity of DMC and Propylene
glycol is dened is 99 wt%
PBBs are connected to form SPBs based on
combination rules
SPBs are connected to form Basic Structures
based on combination rules
Do not use mass separating agents for
reaction/separation
Recycle un-reacted raw materials
Do not use recycle streams if not necessary
Raw materials, methanol and acetic acid are
assumed to be in their pure state
The equilibrium conversion is dened as 54%
(is to possibly be increased)
Production target of DMC is set at
122 102 tons/year
PI screening criteria for basic structures to unit
operations: Novel equipment feasible
Increase MeOH conversion is explored
Minimization/reduction in energy
consumption
Inclusion of intensied equipment
Reduction in the number of unit operations
Waste minimization
Sustainability and LCA factors must be the
same or better
2
Performance
criteria ()
-
3
*
*
*
*
*
*
*
*
is shown in Fig. 8. The pre-selected base case design consists

of 5 unit operations: 1 reactor (R1) and 4 distillation columns
(T1T6).
A brief description about the process is as follows. The raw materials, MeOH and PC, are fed at a mole ratio of 5:1, with MeOH in
excess, to the reactor. In the reactor a trans-esterication reaction
occurs to produce DMC and PG. The reactor outlet (efuent) consists of a multi-component mixture of MeOH, PC, DMC and PG. A
minimum boiling azeotrope exists between MeOH/DMC. The rst
distillation column (T1) separates PC and PG (bottom of T1) from
the reactor efuent. The top of T1 contains MeOH and DMC. The top
stream of T1 is separated using pressure swing distillation, that is,
the use of two distillation columns, (T2 and T3). The feed composition of MeOH and DMC entering T2 at the column pressure of 10 bar
is to the left hand side of the azeotrope, therefore, high purity DMC
is obtained as the bottom product of T2 and the top product of T2
is the MeOH/DMC azeotrope. The feed composition of MeOH and
DMC entering T3 at the column pressure of 1 bar is to the right hand
side of the azeotrope, therefore, MeOH is obtained as the bottom
product. The recovered MeOH is recycled to the reactor and the top
product is the MeOH/DMC azeotrope. In T4, PG is separated from
PC. The recovered PC is recycled to the reactor.
5.5. Step 5 check for base case feasibility

*
The pre-selected base design in step 4 is veried using the process synthesis method of Douglas (1985). Based on the analysis
the pre-selected base case design satised the synthesis method.
Therefore, step 6 is by-passed.
*
*
*
*
*
*
*
*
*
5.6. Step 7 perform rigorous simulation

Action 1 The base case design is rigorously simulated using
equilibrium based models for the reactor and separators using
Aspen Custom Modeler (Holtbruegge et al., 2013b). MeOH is fed in
excess in order to achieve the equilibrium conversion. An overview
of the simulation results is given in Table 11.
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Fig. 8. Selected and simulated base case design. The closed path (CP) from the sustainability analysis is also highlighted.
Table 11
Base case design simulation results.
Value
Feed mole ratio (MeOH:PC)
DMC product (kg/h)
Energy usage (MJ/h)
Utility cost ($/year)
5:1
1700
133,563
4393,537
Improvements in LCA/sustainability indicators

Unit operations reduction
Product purity (kept as the base case)
Production target (kept as the base case)
Reduce operational cost
Waste minimization
Table 12
Closed Path (CP6, see Fig. 8) that has the highest potential for improvement.
Path
Compound
Flowrate
(kg/h)
MVA
(103 $/year)
TVA
(103 $/year)
EWC
(103 $/year)
CP6
MeOH
761.83
10253
Action 2 The following data are extracted from the simulation

of the base case design, detailed mass and energy balance data,
number of streams and unit operations that constitute the base
case design. This data is used for the analyses in step 8.
5.7. Step 8 economic, sustainability and LCA analysis
Action 13: An economic, sustainability and LCA analysis are performed. The sustainability analysis is shown in Fig. 8 where the
most critical stream (path) are highlighted and listed in Table 12.
The LCA analysis and utility cost distribution (obtained from the
economic analysis) are shown in Fig. 9(a) and (b) respectively.
From Table 12, CP6 which follows the raw material MeOH, has a
high EWC. This translates into a high ow of MeOH being recycled
within this path, resulting in high loads of energy and waste/use of
utilities. From Fig. 8, the unit operations belonging to this closedpath are T2 and T3. From Fig. 9, T2 and T3 also have high carbon
footprints, that is, the reboiler of these two columns account for
30% and 15% of the utility costs.
Action 4 The identied process hot-spots are given in Table 13.
Action 5 Using Table 2, the design targets to be set/met are:
Reduce energy consumption
Reduce utility cost
Fig. 9. (a) LCA analysis; (b) utility cost distribution. Cond-condenser; Reb-reboiler.
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Table 13
Identied process hot-spots for the base case design.
Indicator values
Base case property
Cause
Identied process
hot-spot
1 -raw material cost

1 -MVA
Un-reacted raw
materials
Equilibrium reaction
2 -utility cost
1 -MVA
2 -EWC
1 -CO2 eq
2 -PEI
Un-reacted raw
materials and
products recovery
-Presence of
azeotrope(s)
-High energy
usage-heating/cooling
-Limiting
equilibrium/raw
material loss
-Azeotrope
-Difcult separation
due to low driving
force
-High energy
consumption/demand
MeOH
Reaction Task
MeOH+PC
PC
Separation Task
MeOH+DMC/PC+PG
Separation Task
MeOH/DMC
Separation Task
MeOH/DMC
MeOH
DMC
Separation Task
PC/PG
PG
PC
Fig. 10. Task based owsheet of the base case design.
Table 14
Binary ratio matrix for a set of selected properties.
rij (Binary pair)
MeOH/PC
MeOH/DMC
MeOH/PDO
PC/DMC
PC/PDO
DMC/PDO
Property Binary Ratio

Mw
Tm
Tb
RG
SolPar
VdW
VM
VP
3.19
2.81
2.37
1.13
1.34
1.18
1.28
1.56
1.21
1.22
1.05
1.28
1.52
1.08
1.36
1.42
1.12
1.27
2.20
2.09
2.03
1.05
1.08
1.03
1.13
1.46
1.00
1.30
1.12
1.46
2.08
2.13
2.15
1.02
1.03
1.01
2.10
2.09
1.82
1.01
1.16
1.15
2736.13
2.28
980.63
1198.69
2.79
429.61
MW molecular weight (g), Tb normal boiling point (K), RG radius of gyration

(), Tm normal melting point (K), VM molar volume (m3 /mol), SolPar (Hansen)
solubility parameter, VDW (m3 /mol) Van der Waal volume, VP (kPa) vapor
pressure.
5.8. IT-PBS.1 process analysis

Action 1 The task based owsheet of the base case design is
shown in Fig. 10.
Action 2 The phenomena based owsheet of the base case
design is generated and shown in Fig. 11. The identied PBBs in
the base case design are:
Reaction task: M, R, C
Separation task:
VL-M, 2phM, C/H, PC(VL), PT(VL), PS(VL)
Action 3 The binary ratio matrix and the azeotrope analysis are
presented in Table 14 and Fig. 12.
From Fig. 12 a minimum boiling binary azeotrope is found

between MeOH/DMC. This is can also be pre-conceived from the
boiling point binary ratio matrix value because it is also the only
binary pair that has a value close to unity. The azeotrope is further analyzed for pressure dependence and from Fig. 12, it can be
seen that the azeotrope is pressure dependent. At low pressures
the MeOH/DMC azeotrope reaches a MeOH purity of approximately
80 mol% and at high pressure the azeotrope disappears.
5.9. IT-PBS.2 identication of desirable tasks and phenomena
Action 1 The additional PBBs selected are PT(PVL), PT(VV), and
PS(VV). These are selected as follows. From step 7 one of the identied process hot-spots is the presence of an azeotrope, which may
need to be broken in order to obtain the compounds that are associated with the azeotrope. Therefore, using Table S5.1, the process
hot-spot azeotrope is identied (in column 1). Then, the properties listed in column 3 of Table S5.1 are retrieved from the ICAS
database (Gani et al., 1997) and from these the binary ratios are
calculated (see Table 14). The rule for selection is that if the binary
ratios are greater than 1.2, the corresponding PBBs are selected.
For binary ratios close to unity or less than 1.2, the separation promoted by the PBBs is not feasible. For example, the boiling point
binary ratio of the binary pair MeOH/DMC is 1.08 which is close
to unity, therefore, a PBB PT(VL) will most likely not separate a
stream of these two compounds into two high purity products. The
selected PBBs are PT(PVL), PT(VV), and PS(VV). Therefore, the total
list of PBBs are: R, M, 2phM, C, H, PT(VL), PT(PVL), PT(VV), PC(VL),
PS(VL), PS(VV), D.
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MeOH
PC
M, 2phM, C/H, PC(VL),

PT(VL), PS(VL)

PT(VL), PS(VL)
M, C, R

PT(VL), PS(VL)
MeOH
DMC

PT(VL), PS(VL)
PG
PC
Fig. 11. Phenomena based owsheet of the base case design.
1
0.9
0.8
0.7
x1
0.6
DMC/MeOH
0.5
MeOH/DMC
0.4
0.3
0.2
0.1
0
0
10
15
20
25
30
35
P/bar
Fig. 12. Pressure dependence analysis of the minimum boiling azeotrope between MeOH and DMC.
Action 2 The remaining PBBs from applying the constraints

dened in step 2 are R, M (assuming four types: ideal liquid,
ow, rectangular, ideal vapor), 2phM, C, H, PT(VL), PT(PVL), PT(VV),
PC(VL), PS(VL), PS(VV), D.
Action 3 The operating window for each PBB is given in
Table 15.
5.10. IT-PBS.3 generation of feasible owsheet alternatives
Action 1 The maximum number of phenomena that can be
combined to form an SPB, nPBB,Max , is calculated to be 11. The total
number of SPBs that can be generated, having a maximum of 11
PBBs is calculated to be16278. A list of feasible SPBs assuming three
types of mixing, that is, that is ideal liquid, ow and rectangular,
are presented in Table 16.
Action 2-3 The generated task based superstructure is shown
in Fig. 13.
Action 4 Table 17 gives the identied basic structures that
perform reaction and separation tasks.
Action 4 The identied task based owsheets that are highlighted in level 1 (no task-merging) and level 2 (considering
Table 15
List of operating windows of the identied PBBs in the base case design. All concentrations are below the dew point line and above the bubble point line. Subscript: Id
ideal, V vapor.
Phenomena
Operating window
Tlow = 337.70 K (lowest boiler)

Thigh = 313.15 K (set T for reactor according to base case)
Tlow = 337.70 K (lowest boiler)
Thigh = 514.70 (highest boiler)
Tlow = 175.15 K (lowest melter)
Thigh = 514.70 K (highest boiler)
Tlow = 336.66 K (lowest boiling azeotrope)
VL present
Tlow = 336.66 K (lowest boiling azeotrope)
Thigh = 514.70 K (highest boiler)
VL present
Component afnity
Component afnity
VV present (all compounds in the vapour phase)
MV
Mld
MV , 2phM
PC(VL)
PT(VL)
PS(VL)
PT(PVL)
PT(VV)
PS(VV)
H
C
D
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Table 16
Partial list of feasible SPBs. Mix. mixing, Cool. cooling, Heat. heating, React. reaction, Sep. separation, Ph. Cr. phase creation, Div. dividing.
SPB
Connected PBB
In
Out
Task they may perform
SPB.1
SPB.2
SPB.3
SPB.4
SPB.5
SPB.6
SPB.7
SPB.8
SPB.9
SPB.10
SPB.11
SPB.12
SPB.13
SPB.14
SPB.15
SPB.16
SPB.17
SPB.18
SPB.19
SPB.20
SPB.21
SPB.22
SPB.23
SPB. . .
SPB.70
M
M = 2phM
M=R
M=H
M=C
M=R=H
M=R=C
M = R = H = PC(VL) = PT(VL)
M = R = C = PC(VL) = PT(VL)
M = R = 2phM = PC(VL) = PT(VL)
M = R = 2phM = PC(VL) = PT(VL) = PS(VL)
M = R = 2phM = PC(VL) = PT(PVL) = PS(VL)
M = R = H = 2phM = PC(VL) = PT(PVL) = PS(VL)
M = R = C = 2phM = PC(VL) = PT(PVL) = PS(VL)
M = 2phM = PC(VL) = PT(VL)
M = 2phM = C = PC(VL) = PT(VL)
M = 2phM = H = PC(VL) = PT(VL)
M = 2phM = PC(VL) = PT(VL) = PS(VL)
M = C = 2phM = PC(VL) = PT(VL) = PS(VL)
M = H = 2phM = PC(VL) = PT(VL) = PS(VL)
M = 2phM = PC(VL) = PT(PVL) = PS(VL)
M = 2phM = PC(VL) = PT(VV) = PS(VV)
M = 2phM = PT(VV) = PS(VV)
...
D
1 . . . n(L,VL,V)
1 . . . n(L,VL,V)
1 . . . n(L,VL,V)
1 . . . n(L,VL,V)
1 . . . n(L,VL,V)
1 . . . n(L,VL,V)
1 . . . n(L,VL,V)
1 . . . n(L,VL,V)
1 . . . n(L,VL,V)
1 . . . n(L,VL)
1 . . . n(L,VL)
1 . . . n(L,VL)
1 . . . n(L,VL)
1 . . . n(L,VL)
1 . . . n(L,VL)
1 . . . n(L,VL)
1 . . . n(L,VL)
1 . . . n(L,VL)
1 . . . n(L,VL)
1 . . . n(VL)
1 . . . n(VL)
1 . . . n(L,VL,V)
1 . . . n(V)
...
1(L;VL,V)
1(L,VL,V)
1(L,VL,V)
1(L,VL,V)
1(L,VL,V)
1(L,VL,V)
1(L,VL,V)
1(L,VL,V)
1(L,VL,V)
1(L,VL,V)
2(V/L)
2(V;L)
2(V;L)
2(V;L)
2(V;L)
2(V;L)
2(V;L)
2(V;L)
2(V;L)
2(V;L)
2(V;L)
2(V;L)
2(V;V)
2(V;V)
...
1 . . . n(L;V; VL)
Mix.
Mix.
Mix. + React.
Mix. + Heat.
Mix. + Cool.
React. + Heat.
React. + Cool.
React. + Heat.
React. + Cool.
React. + Sep.
React. + Sep.
React. + Sep.
React. + Sep.
React. + Sep.
Mix. + Ph. Cr
Mix. + Ph. Cr.
Mix. + Ph. Cr.
Mix. + Sep.
Cool. + Sep.
Heat. + Sep.
Mix. + Sep.
Mix. + Sep.
Mix. + Sep.
...
Stream Div.
R-Task 1
S-Task 1
S-Task 2
S-Task 3
React.
Sep. A(BCD)
Sep. B(CD)
Sep. C(D)
React.
Sep. B(ACD)
Sep. C(BD)
Sep. C(D)
Sep. B(ACD)
Sep. D(BC)
Sep. B(D)
Sep. C(ABD)
Sep. A(CD)
Sep. B(C)
Sep. D(ABC)
Sep. C(AD)
Sep. A(D)
Sep. AB(CD)
Sep. D(AC)
Sep. A(C)
Sep. AC(BD)
Sep. A(BD)
Sep. A(B)
Sep. AD(BC)
Sep. B(AD)
Sep. A/C/D
React.+Sep.
AB(CD)
Sep. D(AB)
React.+Sep.
AC(BD)
Sep. A(BC)
React.+Sep.
AD(BC)
Sep. B(AC)
React.+Sep.
(CD)
Sep. C(AB)
React.+Sep.
(BD)
Sep. A(B)
React.+Sep.
(AD)
Sep. A(B)
Level 1
Level 2
(task merging)
Note: For each task an

example of all the
possible connections
(infeasible + feasible)
are shown in the
superstructure
Sep. A(C)
Sep. A(D)
Sep. B(C)
Fig. 13. Task-based superstructure, including task-merging. Flowsheet alternatives 3 (bold), Flowsheet alternatives 5 (italics), Flowsheet alternatives 9 (underlined). A-PC,
B-MeOH, C-DMC, D-PG. R task-reaction task, S task-separation task, React. reaction, Sep. Separation.
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Table 17
Identied basic structures that perform single or multiple tasks.
Note: * the SPB number corresponds to the SPB given in Table 16; for combined basic structures, only the SPBs present in the combined basic
structure are highlighted in this table; each binary pair that represents the inlet to a task is actually representing the two key compounds under
consideration.
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task-merging) of the task based superstructure shown in Fig. 13

are explained as follows:
Level 1: Flowsheet alternative 23 highlighted bold in Fig. 13:
Flowsheet alternative 23: A reactor feed, as in the base case
design, of a 5:1 mole ratio of MeOH to PG is used. The reaction is
reversible taking place in the liquid phase, therefore, the reactor
outlet contains a mixture of raw materials and products. Therefore, a basic structure containing a R(L) PBB is selected to perform
the reaction task.
From the mixture analysis, the minimum boiling, pressure
dependent azeotrope basic structures containing a PT(PVL) or
PT(VV) PBB is selected to separate MeOH from DMC.
The stream from S-Task 1, contains DMC, PG and PC. No
azeotropes are present in this mixture. From the basic structures
identied in Table 17, a basic structure containing a PT(VL) PBB
is feasible to perform the S-Task 1 and S-Task 2. At this point all
recovered unreacted raw materials are recycled thereby closing
the task based owsheet.
Level 2: Flowsheet alternative 45 highlighted in italics and
owsheet alternatives 69 underlined in Fig. 13:
Flowsheet alternative 45: In level 2 the task merging is considered and is feasible because the same basic structure performs
multiple tasks and this reduces the overall number of tasks that
must be performed in meeting a desired design target.
Therefore, the merging of the S-Task 1 and S-Task 2 is considered. The tasks are merged based on the system properties: (1)
Distinct boiling points between the compounds to be separated
DMC, PG and PC and (2) no azeotropes present. This is given in
Table 18.
Flowsheet alternative 69: The merging of reaction and separation tasks is considered and found to be feasible because SPBs that
perform simultaneous reaction and separation (see, for example,
Table 16, SPB.10) can be combined to form basic structures that
perform these two tasks simultaneously. Therefore, the merging
of R-Task, S-Task 1, S-Task 2 and S-Task 3 is considered. This is
possible based on the system properties: (1) esterication reaction (2) an azeotrope is present and (3) the reaction is in the liquid
phase. The basic structures are be combined to perform a R = S
Task together. This is given in Table 19, where the basic structures presented in Table 18 have been combined, therefore, the
corresponding tasks are merged.
Action 6 The basic structures that perform the different identied tasks are translated into unit operations. The nal owsheet
alternatives are presented in Fig. 14 using a superstructure representation. In Fig. 14(a), owsheet alternative 2 uses a pervaporation
membrane and owsheet alternative 3 uses a vapor permeation
membrane. In Fig. 14(b), owsheet alternative 4 uses a pervaporation membrane and owsheet alternative 5 uses a vapor
permeation membrane. In Fig. 14(c) owsheet alternative 6 is a
single feed RD column with reactive stages only, owsheet alternative 7 is a double feed RD column with reactive stages only,
owsheet alternative 8 is a single feed RD column with both
reactive and non-reactive stages and owsheet alternative 9 is
a double feed RD column with both reactive and non-reactive
stages.
Action 7 The owsheet alternatives are analyzed and screened
in order to select the feasible alternatives for IT-PBS.4.
1. The owsheet alternatives are analyzed using the following
models while satisfying the following logical (1 ) and operational constraints (3 ) (dened in step 2), 1 The product purity
of DMC is dened is 99 mol%, 3 Production target of DMC is
set at 1700 kg/hr:
Fig. 14. The generated owsheet alternatives for the production of DMC. (a) Flowsheet alternatives 23, (b) owsheet alternatives 45, (c) owsheet alternatives 69,
(d) owsheet alternative 9. VP vapor permeation membrane, PV pervaporation
membrane.
Flowsheet alternative 25: From the availability of data

(Holtbruegge et al., 2013c) and the system properties, a vapor
permeation membrane is selected. It should be noted that in
principle, since the reactor outlet is liquid, a pervaporation
membrane would be a better membrane candidate. However,
the limitation of availability of data for such a membrane
exists. For the investigation of the dividing wall column, the
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Table 18
Identied basic structures for owsheet alternatives 3. Note each binary pair that represent the inlet to a task represent the two key compounds under
consideration.
Note: * the SPB number corresponds to the SPB given in Table 16. For combined basic structures, only the SPBs present in the combined basic structure
are highlighted in this table.
method of Rangaiah et al. (2009) and the method of Halvorsen

and Skogestad (2011) was used.
Flowsheet alternative 69: Reactive distillation model. This
investigation was carried out by Holtbruegge et al. (2013a,
2014). Alternatively, the elemental-based method for reactive
distillation design by Daza et al. (2003), where the compounds
in the system are represented by elements and analyzed, can
be employed for analysis of the reactive distillation superstructure. It was found that the best conguration of the
reactive distillation column was a double feed RD column
with both reactive and non-reactive stages. The top composition of the column consists of the MeOH/DMC mixture
and the bottoms PG. The top product of the RD column is in
the vapor phase, therefore, it is fed to a vapor permeation
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Table 19
Identied basic structures for owsheet alternatives 69.
Note: * the SPB number corresponds to the SPB given in Table 16. For combined basic structures, only the SPBs present in the combined basic structure
are highlighted in this table.
membrane where MeOH is removed until the composition

is on the side of the azeotrope where DMC can be recovered by vapor-liquid separation. The basic structures for these
two separations, that is, the removal of MeOH and the separation of DMC/MeOH to recover DMC, are given in Table 18
(containing PT(VV) PBB) and Table 17 (containing PT(VL)
PBB), respectively. The nal owsheet alternative is given in
Fig. 14(d).
2. The screening of the owsheet alternatives is given in Fig. 15. The
total number of generated SPBs was 16,278 and using the combination rules (structural constraint), 64 were found to be feasible.
The 64 SPBs were then combined to fulll reaction, separation
and reaction-separation tasks and 9 owsheet alternatives were
generated. The 9 owsheet alternatives were screened based on
the availability of membrane data and, the logical and operational constraints dened in step 2. Of the 9 alternatives, 4 were
found to be feasible.
The 4 feasible owsheet alternatives selected for further analysis in IT-PBS 4 are ow-sheet alternative 1 (not shown), owsheet
alternative 3 (see Fig. 14(a), with vapor permeation membrane),
owsheet alternative 5 (see Fig. 14(b), with vapor permeation
membrane) and owsheet alternative 9 (Fig. 14(c), double feed RD
column with both reactive and non-reactive stages, the nal design
is shown in Fig. 14(d)).
5.11. IT-PBS.4 comparison and selection of the best owsheet
alternatives
The results of the economic factors, sustainability metrics and
LCA factors for the four feasible more sustainable process designs
are given in Table 20. The total operating time of each process is
assumed to be 300 days/year. The prices used for different utilities
are: cooling water at 0.35 $/GJ, LP Steam at 7.78 $/GJ and electricity
at 16.80 $/GJ (Peters et al., 2003).
The results of the objective function (Eq. (10)) are given in
Table 20. Flowsheet alternative 1 and owsheet alternative 5 show
the best values of the objective function and the lowest carbon footprint (see LCA results in Table 20). The four owsheet alternatives
are all better than the base case design with respect to economic
factors and sustainability metrics and LCA factors. The payback
periods of the equipment based on capital investment for the
different alternatives are given in Table 20. It can be seen that
alternative 1, alternative 5 and alternative 9 have the lowest payback period. Also, these alternatives earn higher prots per year
compared to the base case design. The prot is dened as the
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ARTICLE IN PRESS
Fig. 15. Screening of the 9 generated owsheet alternatives.
Table 20
Economic, sustainability and LCA analysis for the 4 feasible owsheet alternatives generated for the production of DMC.
Measures of comparison (units)
Base case
Alternative 1
Alternative 3
Alternative 5
Alternative 9
Feed mole ratio

Mole feed to reactor (kmol/h)
Mole feed Make-up (kmol/h)
PC conversion
Input-MeOH (kg/h)
Input-PC (kg/h)
Input-total (kg/h)
51
177:35
38:19
0.54
1215.65
1936.6
3152.25
21
70:35
38:19
0.535
1212.329
1937.97
3150.299
51
38:19
51
38:19
0.54
1211.614
1949.66
3161.274
0.54
1211.614
1953.859
3165.473
12.5
237:19
38:19
99.5
1214.45694
1934.69658
3149.15352
Outlet information
DMC product (kg/h)

Operating Days
Product purity (DMC,%)
By-product purity (PG,%)
Raw material loss-MeOH (kg/h)
Raw material loss-PC (kg/h)
Raw material loss-total (kg/h)
1698
300
99.9
99
4.86
7.74
12.59
1698
300
99.9
99.1
0.72
7.79
8.51
1702
300
99.92
98.6
0.00
0.19
0.19
1699
300
98.9
98.1
0.00
23.70
23.70
1698
300
99.9
99
6.24
9.95
16.19
Results summary
Energy usage (MJ/h)

Utility cost ($/year)
Raw material cost ($/year)
Operating cost ($/year)
133,563
4393,537
24,853,986
29,247,523
28,424
979,301
24,858,022
25,837,323
17,818
906,474
24,981,958
25,888,432
17,734
593,541
24,820,352
25,413,893
64,816
2,011,964
24,829,564
26,841,528
Primary performance
metrics
Raw material usage (kg raw material/kg DMC product)

Energy usage per kg of product (MJ/kg of DMC product)
Raw material cost per kg of product ($/kg of DMC product)
Equipment capital investment ($)
Utility cost per kg of product ($/kg of DMC product)
Operational cost ($/kg of DMC product)-min
Product Sale ($/year)
Product sale per kg of product ($/kg of DMC product)
Prot ($/year)-max
Prot ($/kg of DMC product)-max
Payback period-equipment (years)
Fobj -TAC ($/kg of DMC product)-min
1.86
78.65
2.03
667,541
0.36
2.39
32,580,433
2.66
3,332,909.93
0.27
0.2
0.36
1.85
16.74
2.03
284,523
0.08
2.11
32,415,861
2.65
6,578,537.92
0.54
0.02
0.08
1.86
10.47
2.04
1,640,804
0.07
2.11
32,672,416
2.67
6,783,984.39
0.55
0.24
0.09
1.86
10.44
2.03
1,780,088
0.05
2.08
32,538,792
2.66
7,124,898.39
0.58
0.15
0.06
1.85
38.17
2.03
1,801,222
0.16
2.20
32,550,111
2.66
5,708,583.86
0.47
0.15
0.18
LCA results
Total carbon footprint (kg CO2 /kg of DMC product)

HTPI (1/LD 50)
GWP (CO2 eq.)
HTC (kg benzen eq)
HTNC (kg toluen eq.)
2.08
2.83E04
6.15E+00
4.68E03
6.84E02
0.46
2.76E04
4.53E+00
4.01E03
6.68E02
0.31
2.75E04
4.37E+00
3.94E03
6.65E02
0.31
6.08E05
3.70E+00
3.80E03
6.63E02
0.98
2.78E04
5.05E+00
4.20E03
6.73E02
Inlet information
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ARTICLE IN PRESS
25
Operational Cost
0%
20%
GWP (CO2 Eq)
Utility Cost
40%
60%
80%
100%
HTPI (1/LD50)
Energy usuage
Carbon Footprint (CO2 Eq)
Base Case
Alternative 1
Profit
Alternative 3
Alternative 5
Alternative 9
Fig. 16. Economic and LCA improvements relative to the base case design per kilogram of DMC produced. HTPI Human Toxicity Potential by Ingestion, GWP Global
Warming Potential.
difference between the product sale and the operating cost (Babi
et al., 2014a, 2014b, 2014c). The operating cost in this case study
includes the raw material costs and the utility costs.
The results presented in Table 20 are represented in terms of
a radar plot (Babi et al., 2014b). From Fig. 16 it can be seen that
for all the considered criteria, the alternatives are better that the
base case design and therefore, non-tradeoff solutions have been
obtained because the values of the indicators all lie within the radar
plot.
From the results presented in Table 20 and the design targets
set in step 8, the following can be concluded for each alternative. Reductions in energy consumption and utility cost have been
achieved. The alternatives have a better value of the objective
function compared to that of the base case design while showing
improvements in the sustainability metrics and LCA factors. The
number of unit operations for each alternative have been reduced
for each alternative that is: 5 (base case), 4 (owsheet alternative 3),
4 (ow-sheet alternative 5) and 3 (owsheet alternative 9). For each
of the alternatives the product purity has been kept or improved
while maintaining the production target. The operational cost of
the alternatives showed improvement compared to the base case
design and raw material lost has been minimized.
6. Conclusion
A computer-aided, multi-level, multi-scale, synthesis, design
and intensication framework to achieve more sustainable process alternatives has been presented. The framework operates at
three different scales, the unit operations scale, task scale and
phenomena scale. The synthesis-intensication problem has been
formulated as an MINLP problem and in order to manage the
complexity in solving the problem, a decomposition based solution strategy method is applied. The framework is systematic with
a given hierarchal structure following a series of steps in order
to achieve sub-objectives dened by each step. The framework
is computer-aided because different computer-aided tools assist
in achieving the objectives of a particular step. The framework
is multi-level because it operates at different stages, that is, the
synthesis stage, design (and analysis) stage and innovation design
stage. The framework is multi-scale because it performs process

synthesisintensication at different scales, that is, the unit operations scale, the task scale and phenomena scale. The framework
has the exible ability to cover/handle a wider range of applications
and robust-reliable for its ability to solve a wide range of synthesisintensication problem using reliable numerical methods. It has
been shown that based on the application of the framework, more
sustainable process designs inclusive of hybrid/intensied unit
operations can be generated by simultaneously performing process
synthesis and intensication together.
To identify design targets that would lead to more sustainable
design alternatives, three analyses have been implemented within
the framework. These are, economic factors, sustainability metrics
and LCA factors that provide the relevant indicators. If all design
targets are met, process hot-spots are either minimized and/or
eliminated, thereby producing non-tradeoff solutions for process
designs that are therefore, more sustainable.
For the DMC process, 9 feasible owsheet alternatives have
been generated, including those containing hybrid/intensied
unit operations. These have been generated using a rule based
approach by rst combining PBBs to form SPBs. These SPBs
are then combined to form basic structures that satisfy a task
or set of tasks for reaction, separation and, simultaneous reaction and separation. The 9 alternatives are screened using the
dened structural and operational constraints and evaluated for
selection of the more sustainable owsheet designs (4 in total
were selected). The reduction in energy consumption (per kilogram of product) and utility cost, varies from 78% to 86% for
the 4 more sustainable designs which has a positive impact
on the carbon footprint showing an improvement of between
53% and 85%. The objective function related to the total annualized cost is the best for owsheet alternative 5, which employs
a divided wall column. The framework has also been successfully applied to a wide range of case studies employing further
chemical processes, that is, the production of isopropyl acetate
(Lutze et al., 2013) and methyl acetate (Babi et al., 2014b, 2014c),
as well as bio-processes, that is, the production of N-acetyl-dneuraminic acid (Lutze et al., 2012) and bio-diesel (Mansouri et al.,
2013).
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26
ARTICLE IN PRESS
The results indicate that the hybrid/intensied unit operations

play a major role in the design of new, more sustainable processes
because the owsheet alternatives that employ them show reductions/improvements in economic factors, sustainability metrics
and LCA factors, respectively. Therefore, in order to generate and
nd novel, innovative, more sustainable process designs, it is necessary to consider the use of hybrid/intensied unit operations when
performing process synthesis, design and intensication, for the
design of new processes.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.compchemeng.
2015.04.030
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CACE-5183; No. of Pages 27

Contents lists available at ScienceDirect

Computers and Chemical Engineering

Sustainable process synthesisintensication

Corresponding author. Tel.: +45 45 25 28 82; fax: +45 45 93 29 06.

the following three classes of methods: (1) Rule based heuristic

considered. According to Van Gerven and Stankiewicz (2009),

then translated into design targets that are to be satised if more

CACE-5183; No. of Pages 27

Search Space of Unit Operations

Unit operations scale

Fig. 1. Framework for more sustainable design through process intensication.

2.2. Solution approach: decomposition based solution strategy

In order to manage the complexity related to the solution of

The objective function (Eq. (1)) can be linear or non-linear, is

2.3. Phenomena-based synthesis and a comparison to CAMD

Fig. 2. A comparison of phenomena-based synthesis to CAMD.

alternatives. The combination of PBBs to generate basic structures

PC If two phases are present then, contact of between the two

2.3.2. Basic structures

the process specications (such as product purity, recovery, etc.)

CACE-5183; No. of Pages 27

iv. HTC Human toxicity (carcinogenic impacts)

The objective function is one of the means by which the generated

1. 1 The product (and by-product) purity;

3.6. Step 6 generate a base case design

CACE-5183; No. of Pages 27

Framework Work-flow &

Part II-Innovative Design

Part I-Synthesis and Design

Integrated Task-Phenomena based Synthesis

superstructure optimization (Grossmann, 2012; Quaglia et al.,

Action 8.3 Perform a LCA analysis. A LCA analysis based on

3.8. Step 8 economic, sustainability and LCA analysis

Base case property

1 , raw material recycle/cost

Hrxn < 0 reactor

Hrxn < 0 reactor

The binary ratio matrix (Jaksland et al., 1995) is calculated as

3.10. IT-PBS.2 identication of desirable tasks and phenomena

CACE-5183; No. of Pages 27

Increase raw material

CACE-5183; No. of Pages 27

Reaction (single phase)

Single phase is liquid-P-Reaction pressure (reported in

Reaction (two phase)

Mixing (single phase)

Ideal mixing: T highest boiling compound

T lowest melting compound

T 2nd highest boiling compound or minimum boiling

T lowest boiling compound or minimum boiling

T highest boiling compound or maximum boiling

Action IT-PBS.4.1 Calculate the economic, sustainability and

CACE-5183; No. of Pages 27

To transform a base case owsheet into a

SPB building block

1 . . . n(L, V, LL, VL)

nPBB,Max = nPBB (nPBBE 1) (nPBBM 1) nPBBD

Performs the mixing of

its corresponding unit operation do not exist, then in principle, a

thermodynamic insights (step 6 and IT-PBS.3). The means-ends

CACE-5183; No. of Pages 27

Hrxn < 0 reactor

Hrxn < 0 reactor