Chemical Engineering Science 203 (2019) 1–11

Contents lists available at ScienceDirect

Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

CO2 footprint reduction via the optimal design of Carbon-Hydrogen-

Oxygen SYmbiosis Networks (CHOSYNs)
Marc Panu a, Kevin Topolski a, Sarah Abrash a, Mahmoud M. El-Halwagi a,b,⇑
a
Department of Chemical Engineering, Texas A&M University, College Station, TX 77843, United States
b
Gas and Fuels Research Center, Texas A&M Engineering Experiment Station, College Station, TX 77843, United States

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The paper addresses the problem of

designing an industrial symbiosis
network.

Mass integration is used to create
opportunities for the conversion of
CO2 into value-added chemicals.

A multiscale targeting approach is
developed.

Optimization is used to aid process
synthesis with economic and
environmental objectives.

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

Article history: Carbon dioxide (CO2) has significant potential as a chemical feedstock as it is an abundant source of car-
Received 24 October 2018 bon atoms, entails zero or negative acquisition costs and utilization reduces environmental impact.
Received in revised form 21 March 2019 However, significant challenges remain as the use of this feedstock involves unfavorable thermodynamics
Accepted 26 March 2019
in reaction and separation, material transportation and end use application. Opportunities exist to over-
Available online 27 March 2019
come these limitations especially within eco-industrial parks which involve a group of facilities cooper-
ating by exchanging materials and energy. An important class of EIPs, Carbon-Hydrogen-Oxygen
Keywords:
SYmbiosis Networks (CHOSYN), has been recently introduced to integrate hydrocarbon streams from
Industrial symbiosis
Process integration
multiple plants while allowing for chemical conversion (in addition to the conventional exchange, sepa-
Synthesis ration, and allocation) through a multiscale targeting approach. The objective of this work is to address
CO2 the problem of designing a CHOSYN with the conversion of CO2 into value-added chemicals while reduc-
Mass integration ing the carbon footprint for the whole system. A multi-scale synthesis and optimization approach is pro-
posed. First, atomic-level information coupled with economic data are used to establish benchmarks for
the utilization of process streams, the purchase of external sources, and the discharge of CO2. A pre-
synthesis approach is adopted to develop optimal policies for the CO2-separation technologies.
Candidate CO2-utilization reactions are integrated with the existing plants to produce value-added chem-
icals while addressing economic and environmental objectives. Carbon-footprint constraints are added
based on life-cycle analysis of the used sources and energy associated with the various reaction and sep-
aration steps. This systematic procedure captures significant interactions between surrounding CO2
sources and CO2 sinks while reducing the difficulty of selection and design of the CO2 capture process.
A case study is developed and solved to demonstrate the application of this new method.
Ó 2019 Elsevier Ltd. All rights reserved.

⇑ Corresponding author.
E-mail address: El-Halwagi@tamu.edu (M.M. El-Halwagi).

https://doi.org/10.1016/j.ces.2019.03.066
0009-2509/Ó 2019 Elsevier Ltd. All rights reserved.
2 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11
Nomenclature
Sets
DISCHARGES allowable discharge species
EXTERNAL feedstock species available externally to the CHOSYN
i set of single objective optimization problems to consti-
tute the bi-objective optimization problem
j candidate intermediate reactions
p existing chemical plant
s any molecular species present in the CHOSYN
t capture technologies
Parameters
as number of carbon atoms in species s
bs number of hydrogen atoms in species s
cs number of oxygen atoms in species s
f a sufficiently large number to activate binary con-
straints
aj molar capacity of reaction j in overall stoichiometric
equation
ADemand
Xp total inlet flow rate of X atoms to plant p (X 2(carbon,
hydrogen, oxygen))
AInternal
Xp total effluent flow rate of X atoms from plant p (X 2(car-
bon, hydrogen, oxygen))
Anet
X net difference between internal supply and demand of X
atoms in the CHOSYN (X 2(carbon, hydrogen, oxygen))
AEcapture CO2 emissions associated with capturing one kmol of
p
CO2 from plant p
AEpurchase CO2 emissions associated with purchasing one kmol of s
s
C cature
p capture cost of CO2 from plant p ($/kmol)
C purchase
s purchase cost of species s ($/kmol)
1. Introduction
Over the past 650,000 years, CO2 levels varied between
180 ppm and 300 ppm with relatively stable levels between 260
and 280 ppm in the 10,000 years prior to the industrial revolution.
Since the industrial revolution of the mid-18th century, the cre-
ation of anthropogenic sources has outpaced the creation of
anthropogenic sinks resulting in significant increases in atmo-
spheric carbon dioxide concentration. In 2013, the atmospheric
concentration of CO2 exceeded 400 ppm for the first time in
recorded history and has continued to increase in recent years.
Gases such as carbon dioxide, water vapor, methane (collec-
tively referred to as greenhouse gasses or GHGs), are the primary
driving force behind the greenhouse effect which warms the
Earth’s climate to livable conditions. However, the aforementioned
increase in atmospheric carbon dioxide intensified the greenhouse
effect resulting in global climate change that, if left unmitigated,
may contribute to irreversible damage to eco-systems as well as
significant loss of social, economic and food security. Researchers
are actively exploring various strategies to bring CO2 sources and
sinks back into balance in order to mitigate climate change in
accordance with international objectives such as those outlined
at the 21st Conference of the Parties of the United Nations Frame-
work Convention of Climate Change (UNFCCC) (United Nations,
2015).
One of the enabling strategies to reduce the concentration of
CO2 in the atmosphere is carbon capture, utilization and sequestra-
tion (CCUS). A CCUS typically involves physically capturing the
streams containing CO2, separating the CO2 from other compo-
nents, compressing and transporting it to site(s) where it can be
utilized or sequestered. Utilization and sequestration strategies
Gs;p inlet molar flow rate of species s to plant p
Nsteps
j number of major process steps in the chemical process
to facilitate reaction j
mCHOSYN
s stoichiometrically proportional flow rate of species s in
overall stoichiometric equation
v s;j stoichiometric coefficient of species s in reaction j
W s;p effluent molar flow rate of species s from plant p
xin
CO2 p;t composition of CO2 that is fed to technology t from
plant p
Variables
i upper bound on the terminal CO2 flow rate for scenario i
of the multi objective optimization
bj binary variable denoting the existence of reaction j in
the CHOSYN
F CO
p;t
2
flow rate of CO2 from plant p to capture technology t
F CO 2 used
flow rate of CO2 used from plant p
p
F in flow rate of externally purchased feedstock species
s
s 2 EXTERNAL
F out flow rate of externally discharged waste species
s
s 2 DISCHARGES
Functions
Cj generalized cost function for non-feedstock operating
costs including (utilities, maintenance, labor, etc.)
Wt generalized cost function for capture technology t
Nj generalized annualized capital cost function for inter-
mediate process
rj candidate intermediate reaction
are wide ranging and include: sequestering CO2 in geological struc-
tures, chemicals, biological organisms, utilizing CO2 as a solvent,
and converting it to useful chemicals or fuels.
Many technologies exist to separate CO2 from other compo-
nents. These technologies include: absorption (primarily amines),
adsorption, membrane separation, looping, and cryogenic distilla-
tion. Depending on the source of the CO2 each technology has dis-
tinct advantages and disadvantage. Spigarelli et al. (2013) outlines
the various capture technologies and strategies used to separate
CO2 from material streams. The separated CO2 may be sequestered
via long-term storage. Alternatively, the captured CO2 may be uti-
lized to add value to industrial activities such as enhanced oil
recovery, use as a solvent, and conversion to fuels or chemicals.
Monetization of CO2 refers to the physical and chemical conversion
into value added chemicals and fuels. This is a particularly attrac-
tive strategy because there are large markets for some of the
potential products and a free market incentive to reduce emissions
is more sustainable than subsidized reduction strategies. A wide
variety of commercial and theoretical reaction pathways may be
considered in converting CO2 into chemicals and fuels (e.g.,
Aresta, 2010; Bhanage and Arai, 2014; Noureldin et al., 2015b;
Challiwala et al., 2017; Tilak and El-Halwagi, 2018).
In addition to considering emissions and utilization of CO2 asso-
ciated with individual industrial facilities, it is important to con-
sider macroscopic approaches that integrate multiple plants via
industrial symbiosis. One of the promising strategies for industrial
symbiosis is the creation of eco-industrial parks (EIPs) which
involve exchanging material streams (e.g., products, byproducts,
and wastes) and energy resources among adjacent industrial facil-
ities to create synergistic collaboration. CO2-laden waste streams
can be a valuable resource in an EIP (Al-Mohannadi and Linke,
 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11 3

2016). Recently, Noureldin and El-Halwagi (2015a) introduced the
problem of synthesizing Carbon, Hydrogen Oxygen SYmbiosis Net-
works (CHOSYNs) and developed multi-scale targeting approaches
to guide the design. Some of the unique features of the developed
CHOSYN design approaches is the ability to incorporate chemical
conversion pathways and to use atomic-level information to set
benchmarks for identifying the reaction pathways, integrating
streams and species among multiple plants, and creating an inte-
grated network with synergistic benefits to all participants. El-
Halwagi (2017b) developed a shortcut multi-scale targeting
approach to design CHOSYNs. Extended this approach to address
the grassroots design problem of an eco-industrial park when ini-
tial participants (anchors) have been identified and invited plants
(tenants) are to be selected to create symbiotic integration.
Juárez-García et al. (2018) developed a disjunctive programming
approach to design CHOSYNs. Mukherjee and El-Halwagi (2018)
addressed the problem of designing CHOSYNs under uncertainty.
Al-Fadhli et al. (2018) introduced a multi-period approach to the
design of CHOSYNs to address seasonal variabilities in plant oper-
ation. It is also worth noting that in addition to integrating mass,
energy can be integrated among multiple plants. Examples include
multi-plant heat integration and common islands for combined
heat and power (Song et al., 2017a; Song et al., 2017b).
The objective of this work is to address the problem of designing
a CHOSYN with the conversion of CO2 into value-added chemicals
while maintaining carbon-footprint constraints for the whole sys-
tem. This work, therefore, aims to address multiple strategic objec-
tives such as CO2 monetization, reduction of carbon footprint,
industrial symbiosis among multiple plants, and sustainable devel-
opment of industrial cities. A systematic approach is proposed for
the targeting and design of the network. The approach involves
the screening and selection of various participating plants and
streams, CO2 capture processes, and CO2 utilization processes. A
bi-objective optimization approach is adopted based on maximiz-
ing profitability and minimizing CO2 emissions. The integration is
subject to constraints such as available source stream composition
and flow rate, end use specifications, and waste heat availability.
N allowabledischarges þ N internalspecies g available in the complex. Each plant
(an internal sink) in the complex requires a specific flow rate,
Gs;p , of material feedstocks with certain specifications and/or pro-
duces a number of waste materials, by-product streams and CO2
emissions (internal sources), W s;p , which may be reused or recy-
cled. A subset of chemical species (EXTERNAL)
{sjs ¼ 1; 2;    ; N external } may also be purchased externally. The flow-
rate of each fresh feed, F in
s2EXTERNAL , is unknown but is limited to
availability constraints. Several streams of unused materials (DIS-
CHARGES) {sjs ¼ N external þ 1; N external þ 2; ; N external þ N allowabledischarges }
may be discharged from the CHOSYN to the environment,
waste processing, or disposal facilities. The flowrate of each dis-
charged stream, F out s2DISCHARGES , is unknown. The discharged species
are carefully considered, and CO2 discharge specifically is
constrained.
Both internal and external sources may be directly used by
plants in the complex or fed to a network of CO2 capture processes
{tjt ¼ 1; 2;    ; N separators } and chemical conversion processes
{jjj ¼ 1; 2;    ; N CO2 þ N intermediate } prior to final down-stream use by
the sinks. The CO2 separation processes, intermediate chemical
conversion processes and existing plants together constitute the
CHOSYN.
Table 1 summarizes the known data for the existing plants, the
external resources, and the candidate reaction and separation net-
works (see Tables 2a and 2b).
The objective is to create a CHOSYN that integrates the existing
plants with CO2-utilization pathways in a cost-effective manner
while satisfying the technical, economic, and environmental
requirements. Specifically, the design approach should determine
the following:

Raw material usage (F in
s2EXTERNAL )

Waste discharges (F out
s2DISCHARGES )

Intermediate reactions and costs (aj ; TAC)

CO2 capture network (F CO
p;t )
2

This paper is structured in the following manner. First, the problem
is stated in explicit terms identifying the specific design needs. Next,
the methodology for addressing the problem is presented. Finally, a
case study is solved to demonstrate the application of this method.
2. Problem statement
The problem of synthesizing a CHOSYN with CO2 footprint
reduction can be stated as follows:
Consider a region with a set of industrial plants {pjp ¼ 1; 2;    ;
N Plants } with a set of chemical species fsjs ¼ 1; 2;    N external þ

Network configuration
Fig. 1 is a conceptual representation of the CHOSYN. Internal
sources leaving the existing plants and external streams (fresh
resources) are fed to a separation and reaction network which
adjusts the flows and compositions of the various streams to meet
the requirements for the process sinks in the existing plants. The
products and discharges from the existing plants and the newly
added separation and reaction network exit the system while sat-
isfying product demands and maximum allowable levels of
discharges.

Table 1
Summary of the known data for the existing plants, the external resources, and the candidate reaction options.

Existing plants External resources and discharges Candidate CO2 utilization reactions

Internal source flow rate and composition
Raw material availability
CO2 utilization reactions (jjj ¼ 1; 2;    ; N CO2 )
(W s;p )
Allowable discharge for each
Other intermediate reactions

Sinks demands (Gs;p ) species (jjj ¼ N CO2 þ 1; N CO2 þ 2;    ; N CO2 þ N intermediate )

Table 2a
Internal source flow rates (kmol/h) (taken from El-Halwagi, 2017).

GTL Ethylene PDH MTP VAM Total

CO 930 930
CO2 2910 180 900 18 4008
H2 7830 135 2000 9965
CH4 39 39
4 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11

Table 2b In order to determine the capture costs, a small optimization

Internal sink demand (kmol/h). program is employed to select the economically optimum technol-
MTP VAM ogy for each given process stream. Eq. (1) represents the mass bal-
CH3OH 6500 ance for the CO2 containing streams allocated to various separation
CH3COOH 140 technologies.
X
W s¼CO2 ;p ¼ F CO
p;t
2
ð1Þ
t
3. Methodology
where F CO
p;t is the flow rate of CO2 leaving plant p that is separated
2

This section describes a systematic procedure that may be used using technology t.
to solve the problem described in the previous section. Eq. (2) represents the total annualized cost functions which are
First, a pre-synthesis analysis of the cost and efficiency of CO2 applied based on the selected technology, flow rate, and stream
capture is conducted for each CO2 containing stream to pre- composition. This cost function is minimized subject to Eq. (1)
screen the candidate separation technologies and to determine for each CO2 containing stream in order to determine the CO2 cap-
optimal policies of CO2 separation for each CO2-containing stream. ture cost target.
Next, a two types of targeting approaches are used to establish X
benchmarks ahead of detailed design:
minimize : cost ¼ Wt ðF CO
p;t ; xCO2 p;t Þ
2 in
ð2Þ
t

A stoichiometric-economic (stoichio-nomic) targeting is carried where Wt is the cost function for a given capture technology.
out for raw material usage and CO2 emissions subject to CO2 Capturing CO2 also results in substantial CO2 emissions due to
capture costs, raw material costs and life cycle analysis (LCA) the energy required to operate the equipment. It is important to

Economic targeting of the CO2-utilization plants while account- account for these emissions in the life cycle analysis as this reduces
ing for the capital and operating costs the net amount of CO2 which can be captured and utilized. These
additional emissions can be estimated using methods such as
Finally, a bi-objective optimization approach is adopted to emissions factors, process simulation or real plant data.
establish tradeoffs between minimizing CO2 emissions and mini-
mizing the cost of the CHOSYN. 3.2. Stoichio-nomic targeting
The process steps are illustrated in Fig. 2.
The following is a description of the multi-scale steps: In order to determine the minimum cost of raw materials for
the CHOSYN, the atomic targeting method described in El-
Halwagi (2017b) has been extended to account for the CO2 foot-
3.1. Pre-synthesis CO2 capture analysis print constraints in this work.
The first step is to determine the atomic demand of carbon,
Before the CHOSYN is synthesized, the cost and feasibility of hydrogen and oxygen required by the existing chemical plants
capturing and separating CO2 from available process streams must (sinks). These demands are calculated in Eqs. (3a)–(3c) as follows:
be analyzed. Many separation technologies exist, each with unique X
characteristics influencing the suitability to capture CO2 from a ADemand
Cp ¼ as Gs;p ; 8p ð3aÞ
s
given source. The analysis for screening CO2 removal technologies
is carried out for a broad range of flowrates and compositions. As X
such, the analysis is not restricted to a specific stream or a mixture ADemand
Hp ¼ bs Gs;p ; 8p ð3bÞ
s
of streams. The objective of this step is to develop a correlation for
the cost and CO2 emissions associated with recovering CO2 from X
each CO2 containing process stream. Two particularly important ADemand
Op ¼ cs Gs;p ; 8p ð3cÞ
s
variables to consider are the flow rate and the composition of the
CO2 containing stream. These variables can be used to estimate where Gs;p is the molar demand of species s for plant p, and
the capital and operating costs of various technologies to separate as ; bs ; and cs and the number of carbon, hydrogen and oxygen
CO2 from the available process streams. atoms in species s, respectively.

Fig. 1. Overall representation of CHOSYN.

 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11 5

Fig. 2. Targeting and design algorithm.

X X
The atomic demands can be satisfied by materials from a com- Anet
C þ as F ins  as F out
s ¼0 ð6aÞ
bination of two types of sources: waste streams from existing s2EXTERNAL s2DISCHARGES
plants (internal sources) or raw materials purchased from the mar- X X
ket (external sources). Any number of internal or external sources Anet
H þ bs F in
s  bs F out
s ¼0 ð6bÞ
may be used. The next step is to determine internal source streams s2EXTERNAL s2DISCHARGES
atomic flow rates of carbon, hydrogen and oxygen available for X X
reaction and integration in the CHOSYN. These atomic flow rates Anet
O þ cs F ins  cs F out
s ¼0 ð6cÞ
are calculated in Eqs. (4a)–(4c) as follows: s2EXTERNAL s2DISCHARGES
X
AInternal
Cp ¼ as W s;p ; 8p ð4aÞ where F ins is the molar flow rate of fresh feedstock, s 2 EXTERNAL,
s
and F out
s is the molar flow rate of discharge species, s 2 DISCHARGES.
X Although the reaction pathways have not yet been determined,
AInternal
Hp ¼ bs W s;p ; 8p ð4bÞ it is necessary to track the utilization of CO2 within the CHOSYN as
s
there is no need to pay to capture CO2 that will eventually be dis-
X charged. Eq. (7) is the mass balance for CO2 within the CHOSYN.
AInternal
Op ¼ cs W s;p ; 8p ð4cÞ X X
s F CO
p
2 used
¼ W s¼CO2 ;p  F out
s¼CO2 ð7Þ
p p
where W s;p is the molar flow rate of species s in plant p.
Finally, the difference between the internal supply and the
where F pCO2 used is the molar flow rate of CO2 utilized in the CHOSYN.
atomic demand represents the net supply of atoms to the CHOSYN
Each CO2 capture technology are also limited in the percentage
as calculated in Eqs. (5a)–(5c).
X X of CO2 it can separate from the CO2 containing stream. Eq. (8) is the
Anet
C ¼ Ainternal
Cp  Ademand
Cp ð5aÞ upper bound on CO2 usage.
p p
F pCO2 used  W s¼CO2 ;p  FR ð8Þ
X X
Anet
H ¼ Ainternal
Hp  Ademand
Hp ð5bÞ where FR is the fractional recovery of the CO2 separation technology
p p
used to capture CO2 from plant p.
X X If the number of raw materials available for purchase plus the
Anet
O ¼ Ainternal
Op  Ademand
Op ð5cÞ number of species available for discharge is equal to three, then
p p
there is one unique target for the CHOSYN. If this number is greater
The deficits and surpluses identified in the previous step must be than three, there are many possible solutions to the system of
satisfied by supplementing the internal sources with external equations. In this case an optimization program is applied to deter-
sources and allowing for external discharge of waste species. These mine the best solution for the system based on one or more objec-
overall atomic balances are calculated in Eqs. (6a)–(6c) as tives. Several individual objective functions may be chosen to
follows: determine various targets including: minimization of total costs
6 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11
(raw material purchase + waste treatment), minimization of raw
material costs, minimization of a particular discharge species,
etc. The two objective functions described in Eq. (9) are minimized
subject to Eqs. (3)–(8) in order to obtain different targets for the
system.
( P purchase P
rawmaterialcost ¼ s2EXTERNAL F in s  Cs þ p F CO
minimize P P
out CO2 used capture
CO2 out ¼ F s¼CO2 þ p F p  AEp þ s2EXTERNAL F s  AEpurchase
where C capture
p is the cost to capture one kmol of CO2 from plant p as
determined in pre-synthesis analysis, AEcapture
p is the CO2 emissions
associated with capturing one kmol of CO2 as determined in the
pre-synthesis analysis, and AEpurchase
s is the CO2 emissions associated
with procuring one kmol of species s.
3.3. Economic analysis
The next step is determining the annual costs for the intermedi-
ate plants. There are two steps in this process which can either be
conducted in series or in parallel: first, determine a feasible combi-
nation of reactions to satisfy the targets, and second, estimate the
costs for the processes.
One approach to determining a feasible combination of reac-
tions to satisfy the targets for a given CHOSYN is to select reactions
from a predetermined set of known reactions which contain all of
the relevant chemical species by using an overall stoichiometric
reaction. Other methods may also be used to determine a feasible
set of reactions and their capacities. Reaction pathway synthesis
approaches may be used to generate various implementations of
the overall stoichiometric reaction (e.g., Pham et al., 2012; Bao
et al., 2011; Buxton et al., 1997). The methods presented by
Noureldin and El-Halwagi (2015a), and Topolski et al. (2018) can
be adapted to determine a feasible combination of reactions. In
order to employ the overall stoichiometric equation method, the
following equations are solved.
First, an overall stoichiometric equation can be written for the
CHOSYN. The stoichiometrically proportional flow rate (analogous
to a stoichiometric coefficient in a single chemical reaction) for
each species is the net supply or demand of each species s and
can be calculated as follows:
X X
mCHOSYN ¼ F in
s2EXTERNAL þ W s;p  F out
s2DISCHARGES 
s
p p
The overall stoichiometric equation can then be expressed as
follows:
X nario, i, i takes on a value between i¼1 ¼ CO2 out min , and
ov erallreaction : 0 ¼ mCHOSYN
s ð11Þ
s
where mCHOSYN
s denotes the overall flow rate of species s in the
CHOSYN.
The overall stoichiometric equation can also be expressed as a
sum of a given set, j, of reactions:
X
rj ¼ v s;j
s Consider the industrial complex described by El-Halwagi
where rj denotes a single reaction in the CHOSYN and v s;j denotes
the stoichiometric coefficient of species s in reaction j.
The overall stoichiometric equation can then be expressed as a
sum of the product of the chosen intermediate reactions and their
respective capacities:
X
ov erallreaction : 0 ¼ aj  r j
j lowed by the Fischer-Tropsch reaction (Eq. (20)) (Bao et al. 2010;
where aj is the molar capacity of each intermediate reaction, r j , in
the overall reaction.
Conceptually, a feasible combination of reactions is determined
by equating the two alternative forms of the stoichiometric coeffi-
cients in the overall reaction and solving for aj . Mathematically,
this is achieved by combining Eqs. (11) and (13) and substituting
the values determined by Eqs. (10) and (12). The result of this com-
bination is Eq. (14). The set of equations represented by Eq. (14) are
p
2 used
 C cature
p
solved simultaneously to determine values for aj .
in
s X
ð9Þ mCHOSYN
s ¼ aj  ms;j ð14Þ
j
In order to guarantee a solution, the number of candidate reactions
must be greater than or equal to the number of species present in
the CHOSYN. There are many combinations of reactions that would
satisfy the overall stoichiometric equation and it is therefore neces-
sary to conduct further analysis to select a final set. An optimization
program may be employed to determine a set of reaction pathways
that meets a particular objective such as the minimum total annual
costs or the minimum number of new processes. The total cost of
the intermediate processes is calculated using capital and operating
cost functions.
X
AFC ¼ Nj ðDj ; Oj Þ ð15aÞ
j
X
OPEX ¼ Cj ðDj ; Oj Þ ð15bÞ
j
TAC ¼ AFC þ OPEX ð15cÞ
where AFC is the annualized fixed cost, OPEX is the annualized oper-
ating cost, TAC is the total annualized cost, Dj and Oj are sets of
design and operating variables for reaction j, and Nj and Cj are gen-
eralized fixed and operating cost functions.
Fig. 3 shows the CHOSYN at this level of targeting.
3.4. CHOSYN design and CO2 constraint adjustment
Multiple objective functions may be combined in order to eval-
uate the tradeoffs between various metrics. In this work, the -
Constraint Method (e.g., Miettinen, 2012) is applied to observe
the tradeoffs between raw material cost minimization and CO2 dis-
charge minimization. In order to solve for both objective functions,
the following constraint is considered.
Gs;p ð10Þ
CO2 out  i
ð16Þ
The model defined in Sections 3.1–3.3 is solved repeatedly for var-
ious values of  with the objective of minimizing the cost. Each sce-
i¼Ncuts ¼ CO2 outmax . The collection of alternatives represents a set
of Pareto optimal CHOSYN configurations.
4. Case study
4.1. Existing plants
ð12Þ
(2017b) with five plants: gas-to-liquid (GTL), ethane cracking, pro-
pane dehydrogenation, methanol-to-propylene (MTP) and vinyl
acetate monomer (VAM). Each plant would like to participate in
creating an EIP. The following section describes each of the plants.
The GTL plant converts methane into liquids suitable for easier
transportation or use as a fuel. The primary reactions that drive the
ð13Þ plant are the methane reforming reactions (Eqs. (17)–(19)) fol-
Gabriel et al. 2014).
CH4 þ H2 O ! CO þ 3H2 O ð17Þ
 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11 7

Fig. 3. CHOSYN with reaction network.

CH4 þ 1:5O2 ! CO þ 2H2 O ð18Þ tract type, etc., these prices are for illustration purposes with most
updated for January 2019.
CO þ H2 O ! CO2 þ H2 ð19Þ
4.2. CO2 capture processes
nCO þ ð2n þ 1ÞH2 ! HðCH2 Þn H þ nH2 O ð20Þ
The ethylene plant produces ethylene from ethane primarily Various cost functions may be available for each capture tech-
through the ethane cracking reaction. The following additional side nology of interest. Data may come from a variety of sources includ-
reactions take place (Kamrava et al., 2015). ing: heuristic correlations, process simulation and industrial
implementations. In this case study, literature data of simulated
C 2 H 6 ! C 2 H4 þ H 2 ð21Þ
processes were collected and analyzed to estimate total annual
C 2 H6 þ C 2 H4 ! C 3 H6 þ CH4 ð22Þ cost functions for CO2 separation technologies. The selected input
variables are the total flow rate (in tons/hr) and inlet CO2 concen-
2C 2 H6 ! C 3 H8 þ CH4 ð23Þ tration (in mole fraction). In this case study, a consistent constraint
of 99 wt% of CO2 purity was used for all the sinks and reactions uti-
C 3 H 8 ! C 3 H6 þ H 2 ð24Þ lizing CO2. Also, a minimum CO2 fractional recovery of 0.9 was
used for all separation technologies.
Propane dehydrogenation (PDH) plant uses the high temperature In order to determine the cost curves, a sum of squares error
catalytic reaction to produce polymer grade propylene according minimization problem was solved for each data set. The objective
to the following reaction (Agarwal et al., 2018). function in Eq. (29) is minimized subject to Eq. (30):
C 3 H 8 ! C 3 H6 þ H 2 ð25Þ X X 2
minimize : SS ¼ TAC actual
f ;x  TAC model
f ;x ð29Þ
Methanol-to-propylene (MTP) converts methanol to dimethyl ether f x
(DME) that is subsequently reacted to produce propylene according
to the following overall reaction (Jasper and El-Halwagi, 2015). where f is the set of measured flow rates, x is the set of measured
3CH3 OH ! C 3 H6 þ H2 O ð26Þ inlet concentrations, SS is the total error, TAC actual
f ;x is the literature
value for the total annualized cost, and TAC model
f ;x is the value pre-
Vinyl acetate monomer (VAM) is produced by reacting acetic acid
with ethylene and oxygen according to the following reactions. dicted by the model. TAC model
f ;x is predicted according to the following
constraint:
CH3 COOH þ C 2 H4 þ 0:5O2 ! CH3 COOCHCH2 þ H2 O ð27Þ
 
TAC model ¼ a þ F nf bxCO2 x þ c ð30Þ
C 2 H4 þ 3O2 ! 2CO2 þ 2H2 O ð28Þ f ;x

The data for the internal sources and sinks are reported by El- where a; b and c are all fitting parameters, F is the process capacity
Halwagi (2017b) and summarized in 2a and 2b, respectively. in tons/hr and xCO2 is the mole fraction of CO2 in the inlet stream.
Available feedstocks and associated costs are summarized in The non-linear optimization problem is solved to determine the
Table 3. While actual prices vary significantly by date, region, con- parameters. Two candidate technologies are considered: a mono-

Table 3
Available feedstocks.

Price Unit $/kmol Upper bound (kmol/h)

CH4 3 $/MMBtu 2.50 10,000
O2 100 $/ton 3.50 5000
H2O 5 $/ton 0.10 5000
H2 1200 $/ton 2.50 3000
CH3OH 400 $/ton 14.00 6500
CH3COOH 900 $/ton 60.00 140
8 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11

ethanolamine (MEA) based absorption process and a polymeric In order to solve the optimization problem the following objec-
membrane separation process. tive function is minimized subject to Eqs. (10)–(15) and (40):
Eq. (31) describes the resultant cost function for MEA absorp- X
tion/stripping process. minimize : totalprocesssteps ¼ bj  Nsteps
j ð41Þ
0:6
  j
costMEA ¼ 3:912 þ F 3:086  xCO2 þ 0:394 ð31Þ
where N steps
j is the number of major process steps in the chemical
Eq. (32) describes the resultant cost function for MEA absorption/
process in which reaction j is the primary reaction.
stripping process.
 
costmembrane ¼ 3:068 þ F 4:031  xCO2 þ 0:961 ð32Þ
5. Results
Key metrics to calculate energy related emissions for these tech-
nologies are summarized in Table 4. 5.1. Carbon capture analysis

4.3. Intermediate reactions The results of the CO2 capture cost analyses are shown in
Table 5.
In addition to the existing plants, the following overall reactions
govern intermediate chemical processes which may be added to 5.2. Stoichio-nomic target
the CHOSYN in order to facilitate the material exchange.
Acetic Acid may be produced through the process of methanol Before analyzing targets for a CHOSYN, the base case for the un-
carbonylation according to the following reaction. integrated plants is established. Annual feedstock costs are shown
CH3 OH þ CO ! CH3 COOH ð33Þ in Table 6.
CO2 emissions associated with procuring various feedstocks of
Methanol may be synthesized from syngas or by reacting CO2 and interest are summarized in Table 7. The CO2 emissions in the un-
hydrogen according to the following reactions. integrated industrial complex are summarized in Table 8.
2H2 þ CO ! CH3 OH ð34Þ
Table 5
CO2 þ 3H2 ! CH3 OH þ H2 O ð35Þ CO2 capture costs by source.

The following reforming reactions may be added. CO2 flow rate CO2 purity Capture cost
(kmol/hr) (mol frac) ($/kmol CO2)
CH4 þ H2 O ! CO þ 3H2 ð36Þ GTL 2910 0.15 $2.31
PDH 180 0.2 $3.95
CH4 þ 2H2 O ! CO2 þ 4H2 ð37Þ MTP 900 0.15 $3.32
VAM 18 0.6 $4.85

CH4 þ CO2 ! 2CO þ 2H2 ð38Þ

Additional hydrogen may be produced through the water gas shift
Table 6
reaction.
Base case feedstock costs.
CO þ H2 O ! CO2 þ H2 ð39Þ Cost (MM$/year)

In this work, a simple optimization program is applied to the CH3OH 725

methodology described in Section 3.3 to select the combination of CH3COOH 67
Total 792
equations that minimizes the total number of intermediate process-
ing steps (the sum of the number of processing steps in each inter-
mediate reaction), heuristically minimizing the cost of the
interception network. Two binary variables and constraint equa- Table 7
LCA data for feedstocks.
tions are needed to implement the optimization program.
Feedstock Source CO2 emissions (mol Reference
aj  bj  f ð40aÞ CO2/mol feedstock)
Acetic Methanol 0.4 N/Aa
aj  bj  f ð40bÞ Acid carbonylation
Hydrogen Steam 0.48 Koroneos et al.
where bj is a binary variable indicating whether reaction j is Reforming (2004)
included in the CHOSYN, and f is a large number. Methane Natural Gas 0.53 Forman and
Unnasch (2015)
Methanol Syngas 0.22 Wang and Lee
Table 4 (2017)
Carbon capture technology energy demand. a
This value was estimated for the case study.
Technology Emission factor Associated Reference
emissions
(mol CO2
Table 8
emitted/mol
Base case CO2 emissions.
CO2 captured)
MEA 316 kWh/t CO2 0.06 Li et al. (2016) CO2 emissions (kmol/h)
Membrane 198 kWh/t CO2 0.04 Zhao et al. (2010) Raw material LCA 1486
Electricity 181.1 g CO2/kWh – Energy Information Process emissions 4008
Administration (2016) Total 5494
 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11 9

Table 9 Table 11
Material flow rates based on stoichio-nomic targeting. Cost and emissions improvement based on stoichio-nomic targeting.

Base case Integrated Base case Integrated

Raw materials Raw material cost ($MM/yr) 792 65.3
CH4 – 3192 CO2 capture cost ($MM/yr) – 48.4
H2O – 612 Annual cost ($MM/yr) 792 113.7
CH3OH 6500 –
Cost savings (%) – 86%
CH3COOH 140 –
Unused CO2 (kmol/h) 4008 1389
Discharges CO2 emissions from raw material LCA (kmol/h) 1486 1692
CO2 4008 1389 CO2 emissions from capture (kmol/h) – 157
H2 9965 3759 Net CO2 emissions (kmol/h) 5494 3238
CO 930
Emissions reduction (%) – 41%
CH4 39

The first step in the targeting procedure is to establish bench- Table 12

Capital costs of intermediate conversion processes.
marks based on stoichio-nomic targets. The raw material usage
and waste discharge targets are shown in Table 9. The CO2 utiliza- F (MTPA) CAPEX ($MM/yr)
tion is shown in Table 10. Overall metrics for the base case inte- Methanol from CO2 1,699,840 95.3
grated scenario are compared in Table 11. Steam reforming to CO2 206,784 19.4
Water gas shift 290,720 12.1
Acetic acid 67,200 14.0
5.3. Economic analysis
Total 140.8

The next step is to determine the intermediate processes and

estimate the annual costs associated with the reaction network.
Eq. (42), proposed by Zhang and El-Halwagi (2017), is used to esti- Table 13
mate the fixed capital investment (FCI) of each intermediate plant. Cost impacts of intermediate process CAPEX.

Base case Integrated

FCIj ¼ 17000  Nsteps
j  F 0:65
j ð42Þ
Raw material cost ($MM/yr) 792 65.3
CO2 capture cost ($MM/yr) – 48.4
where N steps
j is the number of major process steps in reaction j and F j Intermediate process AFC ($MM/yr) – 140.8
is the plant capacity in metric tons per annum. Annual cost ($MM/yr) 792 254.5
The FCI may be depreciated over a 10 year period following a Cost savings (%) – 68%
straight line depreciation schedule with negligible salvage value.
The annualized fixed cost is given in Eq. (43).

FCIj Guillen-Cuevas et. al., 2018). This approach provides a consistent

Nj ¼ AFC j ¼
10
Tables 12 and 13 describe the cost implications of the various
intermediate conversion processes.
5.4. CHOSYN design
The model was optimized to tradeoff the two objective func-
tions described in Eq. (9). Seven scenarios were evaluated and
the results of the tradeoffs between total annual costs and CO2
emissions are shown in Fig. 4. The net emissions figures reported
in Fig. 4 include the emissions resulting from unused CO2, raw
material LCA and CO2 capture unit operations. These values are
shown in Table 11 for the cost minimization scenario. The Annual-
ized costs include the raw material cost, CO2 capture cost and the
annualized fixed costs of the intermediate processes. These values
are shown in Table 13 for the cost minimization scenario. In addi-
tion to the tradeoff analysis shown in Fig. 4, multi-criteria decision
making approaches may also be used to evaluate the tradeoffs
between cost and CO2 emissions. One such approach is the use of
sustainability weighted return on investment (El-Halwagi, 2017a;
ð43Þ basis for addressing economic and sustainability issues (e.g. carbon
footprint) through a profitability framework.
In the seven scenarios analyzed, all of the captured CO2 is uti-
lized via the reaction of CO2 and hydrogen to manufacture metha-
nol. This is consistent with expectations of real-world observations
as methanol manufacturing is one of the few commercially avail-
able CO2 conversion technologies. The primary tradeoff among
the various scenarios is the capacity of the steam reforming pro-
cess and the quantity of CO2 captured and utilized from the MTP,
PDH and VAM plants. In the CO2 minimization scenario, the max-
imum amount of captured CO2 + waste hydrogen is used as feed
to the methanol process; however, in the cost minimization sce-
nario, a portion of the CO2 + hydrogen needed for methanol manu-
facturing is supplied via steam reforming of methane. This occurs
is because it is cheaper to generate the CO2 and hydrogen via steam
reforming than it is to capture the CO2 from MTP, PHD and VAM
plants; however, utilizing waste H2 + CO2 captured from GTL plant
is cheaper than steam reforming due to economy of scale. Imple-
mentations for the two extreme scenarios (cost minimization and
CO2 emissions minimization) are shown by Figs. 5 and 6. It should
be noted that Figs. 5 and 6 show the CO2 flow rates made available

Table 10
CO2 usage/discharge based on stoichio-nomic targeting.

Base case Integrated case

Emissions Utilization Discharge Emissions Utilization Discharge
GTL 2910 – 2910 2910 2619 291
Others 1098 – 1098 1098 – 1098
Total 4008 – 4008 4008 2619 1389
10 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11

Fig. 4. Cost/emissions tradeoffs.

Fig. 5. Conceptual representation of cost minimization scenario.

Fig. 6. Conceptual representation of CO2 minimization scenario.

 M. Panu et al. / Chemical Engineering Science 203 (2019) 1–11
for mass integration, and do not include emissions associated with
operating CO2 capture units or raw material LCA.
6. Conclusions
A multi-scale synthesis and optimization approach has been
proposed for the design of CHOSYNs while addressing economic
and carbon-footprint objectives. First, atomic-based information
and economic data are employed in a targeting approach to deter-
mine benchmarks for utilizing CO2-laden process (internal)
sources, purchasing external sources, and discharging CO2. Candi-
date reactions are considered for substituting fresh resources and
converting CO2 into value-added chemicals. A pre-synthesis step
has been introduced to determine optimal policies for the selec-
tion, design, and cost of applicable CO2 capture. A bi-objective opti-
mization approach has been used to establish tradeoffs between
cost and CO2-footprint objectives. A case study has been solved
to illustrate the usefulness of the proposed methodology. The
results showed that significant reduction in CO2 emissions may
be achieved via integration in the CHOSYN while reducing overall
costs compared to the unintegrated scenarios. Future research
should investigate the development of a combined mass and
energy integration approach to further reduce CO2 emissions and
operating costs. Additionally, factors such as process controls and
reliability should also be explored.
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