Applied Thermal Engineering 125 (2017) 1518–1529

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Applied Thermal Engineering

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

Research Paper

Exergy aided pinch analysis to enhance energy integration towards

environmental sustainability in a chlorine-caustic soda production
process
Ali Ghannadzadeh a,⇑, Majid Sadeqzadeh b
a
Department of Chemical Engineering, Hamedan University of Technology, Hamedan, Iran
b
Ahwaz Faculty of Petroleum Alumni, Petroleum University of Technology, Ahwaz, Iran

h i g h l i g h t s

 Set energy targets through a bilateral thermal-exergy-based pinch approach.

 Considered all the possible thermal solutions supported by exergy analysis.
 Reduced cold utility targets from 13.00 MW to 0.40 MW through streams screening.

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

Article history: This paper presents a case study on the improvement of energy integration in a chlorine-caustic soda pro-
Received 9 January 2017 cess based on the main sources of thermal exergy losses. Exergy analysis has been performed to pinpoint
Revised 22 May 2017 the causes of thermal exergetic inefficiency. Thermal solutions have been then developed, leading to a
Accepted 7 July 2017
comprehensive list of cold and hot process streams. Finally, pinch analysis has been brought into action
Available online 8 July 2017
to estimate the minimum energy requirement, to select utilities and to design heat exchanger network.
As a result, the combined methodology followed here takes advantages of both exergy and pinch analy-
Keywords:
ses. This bilateral thermal-exergy-based pinch approach helps to set energy targets in a way that all the
Environmental sustainability
Energy efficiency
possible thermal solutions supported by exergy analysis are considered, including all hot and cold pro-
Exergy cess streams that have a high potential for heat integration during pinch analysis. To demonstrate this,
Pinch analysis energy targeting through conventional pinch analysis leads to 7.74 MW and 13.00 MW of hot and cold
Chlorine utility energy demand, respectively. These figures change to 8.17 MW and 0.40 MW of hot and cold utility
Caustic soda energy demand, respectively through streams screening by the combined methodology.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Chlorine is mainly produced along with caustic soda in chloral-
kali process and is among the mostly produced chemicals in the
world. The global production capacity of chlorine and caustic soda
has been about 65 Mt/yr in 2008 [1]. Chlorine-caustic soda produc-
tion process is also one of the main five technologies with a high
total exergy loss based on a recent study published by JVP Interna-
tional Inc. and Psage Research [2]. Although JVP International Inc.
and and Psage Research suggested a retrofit flowsheet that can
reduce losses [3], the proposed revamped process still displayed
relatively high exergy losses [4]. As a result, the revamped
⇑ Corresponding author.
E-mail address: ghannadzadeh@hut.ac.ir (A. Ghannadzadeh).
flowsheet has been investigated further by this work. The aim is
to provide an example of how a ‘systematic’ pinch analysis based
on the results of exergy study can include the advantages of both
techniques and to pave the way for a more sustainable production
of chemicals in general, and chlorine-caustic soda as a case study in
this paper.
Improving the energy efficiency of industrial processes has been
investigated in the literature mainly by two (independent)
approaches: (i) pinch analysis, and (ii) exergy analysis. Different
processes and systems have been studied using either one
approach or a combination of two methods. The following exam-
ples provide a list of processes investigated by pinch and/or exergy
analyses so far: chlorine-caustic soda production process [4],
ammonia synthesis process [5], ethylene production from ethane
[6], a five-column methanol distillation scheme [7], heat

http://dx.doi.org/10.1016/j.applthermaleng.2017.07.052
1359-4311/Ó 2017 Elsevier Ltd. All rights reserved.
 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529
exchangers network at subambient conditions with compression
and expansion of process streams [8], power plants [9], cascade
refrigeration in liquefied natural gas cycles [10], a thermosolar
and heat pump in a fish tinning industrial process [11] a dairy pro-
cess [12] a liquefied energy chain [13], waste heat recovery in
industrial processes [14], a refrigeration cycle in Natural Gas Liq-
uids (NGL) recovery plants [15], production of lignocellulosic etha-
nol, biomethane, heat, and power from straw [16], as well utilities
[17].
Pinch analysis [18], is a well-known screening and scoping tool,
which sets ‘‘targets” on minimum energy requirement based on
the first law of thermodynamics. Pinch analysis also helps to iden-
tify the type of required utility prior to the detailed design of heat
exchangers network [19]. However, one limitation of pinch analy-
sis is that it does not take the efficiency of the process equipment
and utilization rate of utilities into account [20].
Exergy analysis [21–25] on the other hand can serve as an indi-
cator of inefficiencies of a process [20]. Exergy analysis overcomes
the main limitation of energy analysis by considering both the first
and second laws of thermodynamics. This means that exergy is a
measure of both the quality and the quantity of energy involved
in transformations within a system and its transfer across the sys-
tem boundaries. Exergy analysis as a result can identify exergy
destruction and exergetic efficiency, which are then employed
along with process bottlenecks to propose enhancement measures
that can reduce the exergy destroyed [20,23,24] in the process. In
other words, exergy is a suitable indicator of the quality of
resources that are removed from nature and are transformed into
other formed of usable energy [26–29] rather than being
destroyed.
There is a diverse view [20] on which analysis technique is bet-
ter to use to improve the efficiency of industrial processes. Linnhoff
and Alanis [30] argued that pinch analysis does not only have more
meaningful targets but also considers design data and therefore
has advantages over exergy analysis. Gaggioli et al. [31] however
suggested that pinch analysis can only be used to design heat
exchangers network (HEN) and other possible improvements are
not considered if only pinch analysis is carried out. Exergy analysis
on the contrary can be used both to optimize the targets set by
pinch analysis and to identify other types of improvements
possible.
There is however a consensus among researchers that although
pinch and exergy analyses are different, they can be complemen-
tary. Exergy analysis estimates utilities efficiency and pinpoints
unit operations with poor performances, whereas pinch analysis
identifies heat transfer inefficiencies or lack of heat integration
[20]. As a result, pinch and exergy analyses can be both part of a
combined methodology that can be used to improve energy effi-
ciency [20,32,33].
This combined methodology can be developed in two ways. The
first option is to use a graphical approach such as heat availability
diagram [34], energy utilization diagram [35], exergy composite
curve and exergy grand composite curve [36], extended composite
curves [32], temperature vs. power availability diagram [37],
energy level (O) enthalpy (H) diagram [33], exergy level compos-
ite curve [38], extended pinch analysis and design [39], or exer-
getic temperatures approach [40]. The second option is to
combine exergy and pinch analyses as parallel steps in a unified
methodology. This option has been already evaluated in analyzing
specific systems such as utilities [17,41], a five-column methanol
distillation scheme [7], heat exchangers network at subambient
conditions with compression and expansion of process streams
[8], as well as power plants [9].
There are also a limited number of approaches where exergy
and pinch analyses are done in sequence. Sorin and Paris were
the first to introduce such a methodology where pinch analysis
1519
with exergy targeting was used to treat heat exchangers network
as a single unit operation, thus simplifying the graphical represen-
tation of exergy analysis and necessary computation steps [42] sig-
nificantly. Mateos-Espejel then presented a unified methodology in
which energy efficiency of a process was characterized by three
techniques. These included energy and exergy content indicators,
comparison with current industrial practice, and establishing tar-
gets for minimum energy and water requirements determined by
the thermal pinch and water pinch methods [20]. Ghannadzadeh
et al. [19] presented an approach where major inefficiencies of
an existing process were identified by an exergy analysis diagno-
sis; the results of which were then used in a pinch analysis to give
concrete solutions to improve its energy efficiency. This approach
was then applied to several case studies such as an industrial pulp
and paper process [19,43], and a cogeneration system [44].
Recently, Gourmelon presented a methodology based on previous
works [45,46], where the required expertise for exergy analysis is
partly capitalized in a case-based reasoning system, following
which pinch analysis combined with numerical tools was used to
develop alternatives [47].
There are only a couple of examples in the literature where
exergy analysis is used on a stand alone basis to improve energy
efficiency of the chlorine-caustic soda production process. Rabbani
et al. evaluated the effect of operating parameters in an electrolysis
based chloralkali reactor [48]. The authors then analyzed photo-
electrochemical chloralkali process for hydrogen and sodium
hydroxide production [49].
Pinch analysis was not been also widely applied to the chloral-
kali process. One example is the application of pinch analysis to
water, reagent and effluent management in a chloralkali facility
[50,51].
However, to the best of authors’ knowledge, there is not a
single study in the literature where exergy and pinch analyses
have been combined together to improve energy efficiency of
an industrial chlorine-caustic soda production process. Therefore,
this paper presents the first view on how an exergetic pinch
analysis can be applied to such a process and the added-values
it can provide. The work is based on Ghannadzadeh et al. [19]
methodology and the objective is to pave the way towards a
‘systematic’ pinch analysis based on the results of exergy
analysis.
Coupling exergy and pinch analyses to investigate any process
offers several advantages. As an example, it provides a thermodyna
mically-possible-configuration of heat exchangers network based
on the results of exergy analysis. This is the main advantage of
the method, as the proposed heat exchangers network includes
all the streams with a potential towards achieving the maximum
heat integration. This cannot be achieved using conventional pinch
analysis due to the complexity involved in the ‘data extraction’
stage of pinch analysis. In other words, although the ‘data extrac-
tion’ rules identify streams related to for example non-
isothermal mixing units (which overlap with the exergy-based
pinch analysis followed here), using pinch analysis alone does
not cover all the streams such as preheating and intercooling
streams. These streams can only be introduced through the exer-
getic analysis of the process as shown in this paper, or by expertise.
The paper starts with a summary of Ghannadzadeh et al.
methodology [19] which has been used as a starting point for the
current study. Exergy analysis of a revamped chlorine-caustic soda
production process is then presented. Next, the thermal exergetic
diagnosis of the entire process is explained, which helps to extract
hot and cold process streams in a systematic way to minimize total
energy demand. This reduction will in turn increase the overall
efficiency and enhances the sustainability of the process. The
results obtained using this combined methodology are then pro-
vided and discussed.
1520 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529

2. Methods and process data reuse is maximized. This then helps to make a choice among sev-
eral solutions, through the targeting of the different configurations.
2.1. Exergetic pinch analysis methodology Finally, for the selected set of stream data, pinch analysis pre-
dicts the energy targets on hot and cold utilities, demonstrates
The methodology developed by Ghannadzadeh et al. [19] has how different utilities are allocated, and determines targets for
been used in this work. The developed methodology consists of cogeneration, even prior to the heat exchangers design.
three main steps, which are briefly described below.
Exergy analysis is first carried out which provides an initial 2.2. Process data
review of the existing process, main irreversibilities of each unit
operation, and technical ways to reduce internal exergy losses. As explained earlier, the alternative (i.e. revamped) chlorine-
Exergy analysis also leads to the calculation of external exergy caustic soda production process described in the report by Psage
losses associated with waste streams. Depending on the nature Research and JVP International, Inc and Psage Research [3] has
and amount of exergy losses, potential reuse of waste streams been investigated in this work, where the results from both
using different ways is then proposed. For example, thermal com- exergy balances and simulations are discussed and then
ponent of exergy can be valorized through waste heat recovery, recommendations are provided using the approach described in
which introduces additional hot or cold streams. Section 2.1.
The next step involves using cold and hot waste streams infor- The process flowsheet as well as heat and material balances and
mation obtained during exergy analysis step to carry out pinch exergy data are provided by JVP International, Inc and Psage
analysis. Building power sinks and sources using pinch analysis Research [3]. Exergy analysis data for each process unit is taken
then helps to propose improvement solutions to optimize both from our recent study [4], whereas the composite curves have been
the process and the utilities. This also helps to reduce the overall plotted using Hint software [52,53].
energy consumption. In other words, pinch analysis provides an Simplified process flow diagram of the chlorine-caustic soda
efficient tool to screen waste streams so that the internal heat load production process used in this work is given in Figs. 1–3.

Legend
Heat exchangers
Isothermal mixing
8 Preheang/Precooling
29
27A Intercooler
M-6
E-1 Dissolver Waste heat recovery
3
29-1
9 M-6-A DISSOLVE No. Cold stream
2 4 9 7
S-2 No Hot stream
1 5-1
MIX4 Seler
6
4A 5-3
31
M-2-4 8
37
Salt Washers
5-2 9-2 8-1
T-9
PH Adjusng Tank
S-1 77
9 2 9-OUT
Reactor-Seler 38

Fig. 1. Simplified process flow diagram of the feed pretreatment block in the revamped chlorine-caustic soda production process - raw data from JVP International Inc. and
Psage Research [3].

22
Q Q 15(OUT)
24 13
10
H1 39 24-2 12 MIX-24
H2
E-STEAM 15A
24-3 28 11 MIX-22
13D-2 15 V-201 S-V202

14A 13E 23 25 K-201

13D 14 16 17-OLD 17(OUT)
13F
NACL-H2O
E-203 Electrolysis Cells C-PROD 27-2 42 21-1 Legend
Electrolysis Cells SEP-N
P
Cells Membrane
n Separator 17G2 Heat exchangers
13C 17N 17G11 40
Isothermal mixing

E-202 E-S301 33
Preheang/Precooling
S-301
13B MIX-17 20A 1 20 32 2nd Effect Evaporator Intercooler
Waste heat recovery
E-201 E-S302
S-302 No. Cold stream
20-2 4 20-3
2 20-1 1st Effect Evaporator
No Hot stream
9 E-302
P-20
9 (IN) 3 21 41

Fig. 2. Simplified process flow diagram of the electrolysis block in the revamped chlorine-caustic soda production process - raw data from JVP International Inc. and Psage
Research [3].
 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529 1521

E-23-1
Legend 23 34 23-1A 6

Heat exchangers 48
K-1
24 26
Isothermal mixing 27A

Preheang/Precooling 27 VAPORB
C-5
Drying Column 28A 29
Intercooler
26-2 30 C-7
Waste heat recovery 23-1 E-9 Absorpon Column
Cold stream 22R 25 31
No. 5 26B V-4
26-5
No Hot stream 21 24 C-4 26A
Drying Column 36 18
TOSEP
K-2 47
18A 20 RFX S-1
35
32-1 44 C-2 22A 28
Cooling Column 30
46 26
16 17(IN) 17 19 21 C-6
18 VPR Washing Column

C-1 K-3
Cooling Column 23-2
17 LIQUID
VAPOR
15

15(IN) WASTE 43
C-3
23 Chlorine Water
Stripping Column
19 22

WASTE22 45

Fig. 3. Simplified process flow diagram of the gas treatment block in the revamped chlorine-caustic soda production process - raw data from JVP International Inc. and Psage
Research [3].

3. Results and discussions The exchangers in the electrolysis block also possess significant
exergy losses. In E-S301, 16.3 te/h of water and sodium hydroxide
3.1. Process diagnosis by exergy analysis at 90.0 °C and 1.0 bar is warmed up to 107.0 °C and vaporizes par-
tially (vapor fraction at the outlet = 0.25). Both of these phenomena
3.1.1. Heat exchangers lead to exergy losses.
Exergy analysis is used to analyze inlet and outlet streams of As another example in the gas treatment block, the temperature
each heat exchanger. Temperature differences between tube and difference between hot and cold streams is as high as 102.0 °C in E-
shell sides are then monitored (as they are the main sources of 23-1, where 5.2 te/h of high purity chlorine solution at 153.0 °C
exergy losses in exchangers) and if the differences are high enough and 2.7 bar is cooled down to 34.0 °C without phase change.
in a specific exchanger, the unit is considered for potential heat Similarly, in the E-9 refrigerator condenser, 5.4 te/h of chlorine
integration. with traces of water, is cooled from 25.0 °C down to 9.0 °C at
This method of heat integration is complementary to pinch 2.7 bar.
analysis where all heat exchangers in the process flowsheet are Lowering the driving forces in all the exchangers (E-201, E-
considered for heat integration and energy saving. S301, E-S302, E-302, ESTEAM, E-23-1, and E-9) therefore helps to
The heat exchangers that can be improved in the revamped reduce the total exergy losses. The driving force can be lowered
chlorine-caustic soda production process are shown with green cir- by cooling down hot inlet streams or heating up cold inlet streams
cles on their inlet streams in Figs. 1–3. These have been also dis- as shown in Table 1.
cussed further below. The governing principle both to reduce
exergy losses and to integrate heat exchangers is to reduce the 3.1.2. Isothermal mixing
temperature difference to a minimum value (e.g. 10.0 °C) which Besides identifying non-optimal heat exchangers, exergy analy-
ensures adequate heat transfer while keeping the exergy losses sis is used to characterize mixers with non-identical operating con-
down in the process of heating or cooling. ditions of inlet streams. Due to high temperature, pressure, and/or
Starting with exchangers in the feed pretreatment block, the E- composition driving force(s), exergy degradation could be signifi-
1 water heater is a unit that can be improved. E-1 is used to heat cant in these units [54] and thus these sould be considered for
12.7 te/h of water from 18.0 °C up to 26.0 °C which is although potential improvement. Although in theory the improvements
not leading to significant exergy losses, can still be improved by could be focused on ensuring mixing streams have similar temper-
reducing the temperature difference even further. atures, pressures, and compositions, only thermal solutions to

Table 1
List of hot and cold streams in heat exchangers that can be potentially improved.

Stream Description Stream type Tin (°C) Tout (°C) H (MW)

Process block Heat exchanger Stream
1 Electrolysis E-S301 20A Cold 90.0 108.0 4.22
2 E-201 9 Cold 19.0 80.0 4.63
3 E-302 E-302 Hot 51.0 49.0 0.16
4 E-S302 20-2 Cold 49.0 51.0 0.23
5 Gas Treatment E-9 26A Hot 26.0 9.0 0.44
6 E-23-1 23-1A Hot 154.0 34.0 0.93
1522 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529
ensure isothermal mixing have been considered in this work. This
is partly because isothermal mixing of inlet streams is thought to
be the easiest improvement that can be applied to decrease exergy
losses in mixers.
Ensuring that isothermal mixing takes place in non-optimized
mixers is carried out by either heating or cooling inlet streams to
mixers. As a result, these inlet streams are identified during this
stage of exergy analysis and are added to the global streams list
of the process that are analyzed during pinch analysis for heat
exchange and heat integration. A caveat to this approach is that
some of these inlet streams to mixers might lead to higher energy
demand for hot/cold utilities, if they are heated up or cooled down.
Clearly this is not desirable, but without detailed analysis it is not
possible to select the only streams that reduce energy demand at
this stage. As a result, the sensible decision is to include all the
additional hot/cold streams at this stage to have a full picture of
non-isothermal mixers, and then to analyze these streams individ-
ually during the screening stage of pinch analysis. The additional
streams that are shown to reduce energy demand during screening
stage are then kept, whilst those that increase energy demand are
taken out as they do not lead to an increased efficiency of the over-
all process.
This is better explained by discussing individual mixers of the
chlorine-caustic soda production process. There are three mixers
in the process that can be improved as shown in Figs. 1–3 by pur-
ple circles on their inlet streams.
In the feed pretreatment block, MIX4 mixes three streams with
different temperatures (two streams at 19 °C, one at 80.0 °C) and
compositions, which results in significant exergy losses. More
specifically 12.7 te/h of pure water is mixed with 42.0 te/h of aque-
ous solution of Na+, Na2SO4, NaCl, Cl , SO24 , and CO23 ; and 8.5 te/h
of aqueous solution of Na2SO4, MgSO4, CaSO4, NaCl, and Cl . To
reduce exergy losses, it is therefore suggested that the hot stream
27A is cooled down from 80.0 °C to 64.0 °C, and the two cold
streams 29 and 4 are heated up from 19.0 °C to 64.0 °C prior to
entering MIX4.
As another non-optimized mixer, inlet streams to MIX-22 in the
electrolysis block are at the same pressure and composition but
different temperatures (104.0 and 90.0 °C), thus contributing to
the overall exergy losses. As a result, it is recommended to reduce
the temperature of the hot stream 28 as well as increasing the tem-
perature of the cold stream 22 before they can enter MIX-22.
The other mixer that can be improved in the electrolysis block is
M-24. Although both streams entering M-24 are at the same tem-
perature (90.0 °C), they have different compositions and as a result
different heat capacities. This means that in the current configura-
tion, there is some heat exchange occurring inside M-24. This obvi-
ously results in exergy losses, and can only be eliminated if both
inlet streams are cooled down from 90.0 °C to 77.0 °C before enter-
ing the mixer.
Table 2 provides a summary of the inlet streams to mixers that
need to be heated up or cooled down in order to reduce exergy
losses.
Table 2
List of hot and cold streams for isothermal mixing.
Stream Description
Process block Mixer
7 Feed pretreatment MIX4
8 MIX4
9 MIX4
10 Electrolysis MIX-22
11 MIX-22
12 MIX-24
13 MIX-24
3.1.3. Preheating/precooling
In addition to heat exchangers and mixers, exergy analysis is
used to identify other unit operations with high exergy losses.
Once identified, these unit operations have been considered for
improvement. Although several improvements have been sug-
gested to reduce exergy losses in these units (see [4] for a detailed
analysis), thermal solutions are discussed in detail in this work.
One of the most important thermal solutions is to add a pre-
heater/precooler at the entrance of unit operations with a feed
temperature lower/higher than the prevailing temperature within
the equipment, respectively. The additional of this preheating/pre-
cooling step means that the cold/hot feed stream(s) are added to
the overall streams list, respectively which are analyzed later
through pinch analysis.
The unit operations that can be improved in the revamped
chlorine-caustic soda production process with the addition of a
preheater/precooler are shown with turquoise circles on their inlet
streams in Figs. 1–3.
There is no equipment that can be improved in the feed pre-
treatment block by the addition of a preheater. However, the C-
PROD electrolysis cells (see Fig. 2) in the electrolysis block are
one of the items that contain the largest exergy losses and can
be improved by a preheater. 72.4 te/h of aqueous solution of
Mg+, Na+, Na2SO4, NaCl, Cl , SO24 , CoO23 , H+, OH , and CaCO3 at
90.0 °C and 1.0 bar enters C-PROD that produces sodium hydrox-
ide, hydrogen, and chlorine at about 100.0 °C. Removing the tem-
perature difference between the feed and the reaction medium is
therefore suggested to eliminate the major source of irreversibility.
This can be achieved by addition of a feed preheater which heats
up the feed from 90.0 °C to 100.0 °C. Likewise, two preheaters are
suggested to be added before the NACL-H2O electrolysis cells, to
increase the temperature of the two feed streams from 80.0 °C to
90.0 °C and thus to reduce exergy losses.
Another equipment in the electrolysis block that can be
improved by precooling is S-301. About 16.3 te/h of a partially
vaporized (vapor fraction = 0.25) aqueous solution of sodium
hydroxide at 108.0 °C and 1.0 bar is mixed with 0.9 te/h of steam
at 51.0 °C and 0.1 bar the in S-301 separator to deliver a water-
rich stream as well as a concreted solution of sodium hydroxide.
Both of these effluent streams leave S-301 at 48.0 °C. Currently
the temperature difference between the feed streams and the col-
umn is the main source of irreversibility. As a result, it is suggested
to eliminate this temperature difference to reduce exergy losses. As
the separator is operating under an isothermal regime, this means
bringing the feeds’ temperature down to the effluents’ levels. This
can be achieved using two precoolers that would reduce the tem-
peratures of the feed streams 20 and 17G2 from 108.0 °C and
50.0 °C, respectively to 48.0 °C.
There are also six unit operations in the gas treatment block
that can be improved by adding a preheater (see Fig. 3). These
are explained in detail below.
The C-1 cooling column separates water from 0.5 te/h of vapor
hydrogen stream containing traces of water at 95.0 °C and 1.0 bar
Stream type Tin (°C) Tout (°C) H (MW)
Stream
29-1 Cold 19.0 64.0 0.77
27A Hot 80.0 64.0 0.97
4 Cold 19.0 64.0 0.25
22 Cold 90.0 95.0 1.48
28 Hot 104.0 95.0 1.60
24-2 Hot 90.0 77.0 0.70
24 Hot 90.0 77.0 1.68
 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529 1523

by using 68.0 te/h of liquid pure water entering the column at
32.0 °C and 1.0 bar. The temperature difference between the inlet
streams and the tower cause therefore significant exergy losses
in C-1. This can be reduced by entering the feeds at prevailing col-
umn temperatures which requires the addition of two preheaters:
one to heat up the hydrogen-containing stream 15 from 95.0 °C to
105.0 °C; and another one to warm up the water stream 16 from
32.0 °C to 42.0 °C.
In the C-2 cooling column, stream 18A containing 68.5 te/h of
water at 35.0 °C and 2.7 bar enters from the top to absorb chlorine
from other inlet streams entering from the bottom; namely stream
17 with 13.5 te/h of partially vaporized (vapor fraction = 0.71) mix-
ture of water (70%) and chlorine (30%) at 95.0 °C and 1.0 bar, and
the recycling stream VPR containing 0.2 te/h of water (50%) and
chlorine (50%) at 146.0 °C, atmospheric pressure, and fully vapor
condition. The cooling separation results in a rich-chlorine vapor
stream (90% choline, 10% water) leaving the vessel from the top
at 35.0 °C and 1.0 bar, as well as 76.8 te/h of liquid water contain-
ing traces of chlorine at 82.0 °C and 1.0 bar exiting from the bot-
tom. The exergy losses in C-2 are again due to the temperature
differences, and can be reduced by heating up the feed streams.
This can be carried out by the addition of three preheating steps,
to increase the temperature of the feed stream 18A from 35.0 °C
to 45.0 °C, the feed stream 17 from 95.0 °C to 105.0 °C, and the feed
stream VPR from 146.0 °C to 156.0 °C.
The C3 chlorine water stripping column can be also improved
by eliminating the differences between the inlet streams’ temper-
atures and the corresponding column temperatures. Stream
LIQUID leaving C-2 containing 0.5 te/h of water and chlorine at
104.0 °C and 1.0 bar enters C-3 where it is washed with the water
stream 19 entering the column with a flow rate of 76.8 te/h and a
temperature and pressure of 82.0 °C and 1 bar, respectively. This
results in a liquid effluent stream called WASTE22 from the bottom
of C-3 at 85.0 °C and 0.5 bar, as well as the vapor stream VAPOR
which is rich in chlorine recycling back into C-2 at 81.0 °C and
0.5 bar. Preheating both feed streams (stream 19 from 104.0 °C to
114.0 °C and stream LIQUID from 82.0 °C to 92.0 °C) ensures the
feeds are introduced at prevailing column temperatures and thus
corresponding exergy losses are eliminated.
The C-4 and C-5 drying columns have similar configurations as
C-2 and C-3. This means the columns can be improved by adding
preheating steps. These steps help to increase the temperatures
of C-4 feed streams from 35.0 °C and 46.0 °C to 45.0 °C and
56.0 °C, respectively; as well as to increase C-5 feed temperatures
from 10.0 °C and 43.0 °C to 20.0 °C and 53.0 °C, respectively.
Thermal performance of the C-6 washing column can be
enhanced as well by introducing the feed at a proper temperature
level. This can be achieved by preheating the feed stream 23-1
from 32.0 °C to 42.0 °C before it enters C-6.
Finally, there are also possible improvements to be considered
for C-7. The C-7 absorption column is used to produce chlorine
solution with the required concentration. 0.1 te/h of air at 32.0 °C
and 2.7 bar enters the tower to remove traces of impurities, whilst
68.0 te/h of pure water at 35.0 °C and 2.7 bar as well as 0.5 te/h of
pure chlorine at 9.0 °C and 2.7 bar are fed to produce the required
chlorine concentration. The purge stream contains 0.1 te/hr of oxy-
gen, nitrogen, and traces of water at 35.0 °C and 2.7 bar, whilst the
product stream leaves from the bottom with 68.6 te/h of a 10%
aqueous chlorine solution at similar temperature and pressure.
As the C-7 feed streams do not enter the column at their ideal tem-
peratures, the major source of irreversibility can be overcome by
feed preheating. This means heating up the water stream 28A from
35 °C to 45 °C; the chlorine stream 26-2 from 9.0 °C to 1.0 °C; and
the air stream 26-5 from 32.0 °C to 42.0 °C.
The list of all additional streams for ideal preheating/precooling
is provided in Table 3.
3.1.4. Intercooling
Exergy analysis also pointed out that there are significant
exergy losses in certain compressors as explained further in this
section. In theory these losses can be lowered by either of two
approaches: (i) reducing inlet temperature; and/or (ii) addition of
intercoolers between different stages of compression. The first
option has the risk of condensation within the compressors and
thus is disregarded in this work; whilst the second technique helps
to reduce exergy losses without any significant risk. As a result, this
is the preferred solution explored in this work. The intermediate
hot streams that are cooled down are added to the global streams
list that is analyzed in the screening stage of pinch analysis.
The compressors that can be improved in the revamped
chlorine-caustic soda production process with the addition of an
intercooler are shown with oranges circles in Figs. 1–3. As it can

Table 3
List of cold/hot streams to reduce exergy losses through preheating/precooling.

Stream Description Stream type Tin (°C) Tout (°C) H (MW)

Process block Unit Stream
14 Electrolysis NACL-H2O 14A Cold 80.0 90.0 0.07
15 NACL-H2O 13D-2 Cold 80.0 90.0 1.50
16 C-PROD 13E Cold 90.0 100.0 3.34
17 Gas Treatment C-1 15 Cold 90.0 100.0 0.08
18 C-1 16 Cold 32.0 42.0 0.91
19 C-2 17 Cold 95.0 105.0 3.45
20 C-2 18A Cold 35.0 45.0 0.91
21 C-2 VPR Cold 146.0 156.0 5.2  10 4
22 C-3 19 Cold 104.0 114.0 0.36
23 C-3 LIQUID Cold 82.0 92.0 1.05
24 C-4 21 Cold 35.0 45.0 0.01
25 C-4 22R Cold 46.0 56.0 2.05  10 3
26 C-5 24 Cold 10.0 20.0 1.42  10 3
27 C-5 VAPORB Cold 43.0 53.0 7.37  10 3
28 C-6 23-1 Cold 32.0 42.0 8.81  10 3
29 C-7 28A Cold 35.0 45.0 0.91
30 C-7 26-2 Cold 9.0 1.0 0.04
31 C-7 26-5 Cold 32.0 42.0 3.0  10 3
32 Electrolysis S-301 20 Hot 108.0 48.0 4.89
33 S-301 17G2 Hot 51.0 48.0 1.06
1524 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529

be seen, there are only two compressors with high exergy losses,
namely K-1 and K-2 in the gas treatment block, that can be
improved by intercooling and these are explained further below.
K-1 compresses the gas from 1.0 bar (the inlet stream 23) to
2.7 bar (the outlet stream 23-1A). This compression is currently
accompanied with a temperature rise which is a source of internal
exergy losses. Addition of an intercooler can reduce temperature
rise and as a result reduce losses. Such an intercooler is suggested
to be added at the second compression stage to reduce the temper-
ature of hot intermediate stream from 227.0 °C to 154.0 °C. It
should be noted that there is no need for intercooler at the first
stage.
Similarly, K-2 is an air compressor which pressurizes 0.1 te/h of
air from 1.0 bar to 2.7 bar along with a temperature rise. To reduce
internal exergy losses as a result of this heating, intercoolers are
the preferred option again. Note that it is recommended to add
intercoolers both at the first and second stages of compressions
here. At the first stage, an intercooler is used to cool the gas down
from 80.0 °C to 32.0 °C; whilst a second-stage intercooler reduces
the temperature from 97.0 °C to 32.0 °C.
In addition to K-1 and K-2, there are other compressors in the
revamped chlorine-caustic soda production process, however
these do not generate excessive exergy losses and as a result have
not been considered for improvement in this work. One observa-
tion for K-201 compressor though is the presence of condensate
in the feed stream (vapor fraction = 0.64). This could be detrimen-
tal for compressor performance, and although raising the inlet
temperature increases exergy losses, the authors recommend that
for this exceptional case this should be implemented, so that the
feed entering the compressor is condensate-free. This is however
not considered in this work in detail.
Table 4 describes the details of the hot streams introduced as a
result of intercooler additions at intermediate stages of
compression.
3.1.5. Waste heat recovery
Besides internal exergy losses, external ones have an important
contribution in total exergy losses. These losses can be avoided if
the effluents are reused efficiently. For example, heat recovery of
hot streams can reduce external exergy losses. The following para-
graphs show how this could be done in the revamped chlorine-
caustic soda production process. Streams with potential for waste
heat recovery are shown with yellow circles in Figs. 1–3.
Stream 17G1 from the second effect evaporator (S-301) is
responsible for more than 54% of total exergy losses generated in
the electrolysis block due to waste heat release, and therefore is
the primary stream to be considered for imprvoement. These
exergy losses are mainly due to the significantly high flow rate of
stream 17G1 leading to 4.07 MW of thermal energy losses. Waste
heat recovery for this stream reduces the exhaust temperature of
17G1 from the current value of 48.0 °C to 25.1 °C and thus avoids
some of the losses.
There are other streams in the electrolysis block that can be
used for waste heat recovery. Stream 21 from E-302 for example,
has the second largest exergy losses by losing 2.84 MW of thermal
energy. To reduce this external exergy loss, a waste-heat exchanger
at the outlet of E-302 is required to recover its thermal energy fur-
ther. Other streams in this block to be considered for heat recovery
include streams 15A and 27-2.
There are also streams in other process blocks that can be used
for waste heat recovery. Table 5 summarizes all these streams that
cause external exergy losses and how these losses can be lowered
by addition of extra heat recovery streams.
3.2. Process diagnosis by pinch analysis
Once the exergy analysis is carried out generating a list of hot
and cold streams, these have been used in the pinch analysis to
investigate possible improvements from a different angle. This sec-
tion provides the results of pinch analysis which has been carried
out using three steps as explained in sections 3.2.1–3.2.3.
3.2.1. Data extraction
The first step of any pinch study is to identify all parts of the
process that require heating or cooling. These parts of the process
are then investigated in more detail with their data being extracted

Table 4
List of hot streams from compressors to reduce losses through intercooling.

Stream Description Stream type Tin (°C) Tout (°C) H (MW)

Process block Compressor Stage
34 Gas treatment K-1 Stage 2 Hot 227.0 154.0 0.05
3
35 K-2 Stage 1 Hot 80.0 32.0 1.41  10
3
36 K-2 Stage 2 Hot 97.0 32.0 1.91  10

Table 5
List of low-grade hot and cold streams to avoid physical external exergy losses.

Stream Description Type Tin (°C) Tout (°C) H (MW)

Process Block Unit Stream
4
37 Feed pretreatment M-6-A 31 Cold 18.5 25.1 6.4  10
4
38 S-2 7 Cold 18.5 25.1 1.9  10
39 Electrolysis SEP-N 15A Hot 90.0 25.1 0.32
40 S-301 17G1 Hot 48.0 25.1 4.07
41 E-302 21 Hot 49.0 25.1 2.84
42 S-V202 27-2 Hot 51.0 25.1 0.24
43 Gas treatment C-1 WASTE Hot 36.0 25.1 0.97
44 C-1 32-1 Hot 32.0 25.1 0.02
45 C-3 WASTE22 Hot 86.0 25.1 6.26
46 C-4 22A Hot 45.0 25.1 4.58  10 3
47 C-7 18 Hot 35.0 25.1 0.09
48 C-7 27A Hot 35.0 25.1 5.4  10 4
 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529 1525

for pinch analysis. The required data is primarily temperature
levels of process streams, amounts of heat required to bring about
desired temperature changes, specific heat capacities, and mass
flow rates.
Data extraction has been carried out in this work with the
widely accepted rules developed as guidelines [55,56]. An example
of these guidelines is that a heat exchange needs to be considered
when streams with different temperatures are mixed and this cor-
responds to a degradation of the higher temperature level. We
have also extended the data extraction to both the process and
the utilities, in accordance with the guidelines. Once the data
extraction is carried out, we have used energy targets and screen-
ing to simultaneously heat and cool multiple streams to reduce the
number of required heat exchangers. This is further explained in
the next section. Finally, heat losses in heat exchangers are
neglected in this work.
3.2.2. Energy targets and screening
The next step of pinch analysis is to predict energy targets.
Energy targets are the minimum amount of utilities needed to sat-
isfy process stream requirements [57]. Pinch analysis has been
used to predict energy targets, even before the design of a heat
exchangers network (HEN). This was carried out by plotting hot
(red) and cold (blue) composite curves of the process as demon-
strated in Fig. 4. Hot and cold composite curves provide an indica-
tion of the heat availability and heat demand in the process,
respectively. Streams considered during exergy analysis are also
displayed in Fig. 4. Part of the hot composite curve is currently
located directly above the cold composite curve. What this means
is that for this zone, the energy demand can be simply met by the
energy available in the process and thus no external heat is
required. The hot composite curve is however extended to the left
with no cold composite curve below it. This overshoot is an indica-
tion of the external cooling duty required to cool certain streams
down. Similarly, the cold composite curve is extended to the right,
meaning some additional heating duty is required for the process.
Based on the results of pinch analysis for the base composite
curves, this translates into a heating duty of 9.27 MW, and a cool-
ing duty of 9.57 MW for the existing configuration of the revamped
chlorine-caustic soda process. Fig. 4 also suggests temperature at
which the cold utility has to be. Moreover, Fig. 4 shows the pinch
temperature (85.0 °C on the hot side), which is the closest
temperature between the hot and cold composite curves assuming
a minimum temperature difference between streams (a value of
10.0 °C has been chosen as the DTmin).
Low-grade hot streams to avoid physical external exergy losses:
Fig. 4 shows that the Low-grade Hot streams to avoid physical
External Exergy Losses (LHEEL) [19] are all located below the pinch
temperature. This means that these streams are not good nominees
to achieve the Minimum Energy Requirement (MER) of the process
since they lead to increase in the minimum cold utility require-
ment. Accordingly, a new set of data should be built where LHEEL
are excluded.
Preheating/precooling of cold/hot streams to reduce exergy losses:
Fig. 4 also helps to identify if the preheating/precooling of cold/
hot streams can reduce exergy losses. Streams 19, 21, 22, 23, 31,
37, 38, 39, 40, 32 and 33 which have been defined in Section 3.1.3
to preheat/precool feeds, are all located above the pinch tempera-
ture in Fig. 4. This again shows that these streams lead to increase
in the minimum hot utility requirement and therefore cannot help
to achieve the MER of the process. Again, a new dataset should be
built where these streams are excluded.
Intercooling of hot streams from compressor to reduce exergy
losses: Hot streams coming from intermediate stages of the com-
pression to reduce exergy losses can be seen in Fig. 4. As streams
35 and 36 are both located below the hot pinch temperature, these
streams can increase in the minimum cold utility requirement, and
T (°C)
226
176
126
76
26
-24
0. 2000. 4000. 6000. 8000. 10000. 12000 14000
H (kW)
Fig. 5. Modified composite curves of revamped chlorine-caustic soda production
process.

T (°C)
Pre-Heating
226
32, 33 Waste Heat
176
35, 36 34 Inter-Cooling
8 12, 13 10
126 MIX-4
16, 17, 18, 42, 43, 44, 46, 45, 47, 48
MIX-22
76
19, 21, 22, 23, 31, 37, 38, 39, 40 MIX-24
26 14, 15 11 To be included

20, 24, 25, 26, 27, 28, 29, 30, 41

-24
To be excluded
7, 9
-74 No. Cold Stream
0. 5000. 10000. 15000 20000 25000 30000 35000
No. Hot Stream
H (kW)

Fig. 4. Base composite curves of revamped chlorine-caustic soda production process.

1526 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529

T (°C) T (°C)
426 1026
(a) (b)

926
326

726

226

526

126

326

26
126

-74 -74
0. 1000. 2000. 3000. 4000. 5000. 6000. 7000. 8000. 0. 1000. 2000. 3000. 4000. 5000. 6000. 7000. 8000. 9000.
H (kW) H (kW)

Fig. 6. (a) Grand composite curve with LP steam; (b) Grand composite curve with fired heater.

therefore not useful to achieve the MER. This means that in the hot utility, respectively. They also demonstrate how different
new dataset, these streams will be also excluded. utilities listed in Table 6 are allocated using the GCC-based
Hot and cold streams for isothermal mixing: Finally, hot and cold method.
streams for isothermal mixing to reduce exergy losses are also
included in Fig. 4. Inlet streams are located either below the pinch
temperature or above it, meaning that total energy requirements T (°C)
do not change substantially by either including or excluding these 227
streams. However, including them can lead to reduced driving
force to achieve the decrease in exergy losses. Therefore, it was
decided to include these streams in the new dataset to be built.
Note also that Fig. 4 reports another story for MIX-3 as both inlet
streams are hot streams. 177

Having considered the above observations, a new set of data has

been built where LHEEL and other streams are excluded. This leads
to a modified composite curve as shown in Fig. 5 where the mini-
mum hot and cold utility requirement, are estimated as 8.17 MW
127
and 0.40 MW, respectively whereas the cold pinch temperature is
at 21.0 °C with the minimum temperature difference of 10.0 °C.

3.2.3. Utility load allocation, cogeneration targeting

Fig. 6a and b shows targets in the Grand Composite Curve (GCC) 77
for all utilities for Low Pressure (LP) steam and fired heater as the

Table 6
List of hot and cold utilities.
27
Type Description Tin (°C) Tout (°C)
Cooling Refrigerant 1 25.0 24.0
Air 30.0 35.0
Cooling water 20.0 25.0
Heating High pressure (HP) steam 250.0 249.0 -23
Medium pressure (MP) steam 175.0 174.0
0. 1000. 2000. 3000. 4000. 5000. 6000. 7000. 8000. 9000.
Low pressure (LP) steam 125.0 124.0
Hot oil 280.0 250.0 H (kW)
Fired heater 1000.0 400.0
Fig. 7. A pocket in the grand composite curve.
 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529 1527

Note that it is assumed that pockets are self-sufficient in energy.
Therefore, all pockets in the GCC are isolated. If a large pocket
exists in the GCC and is situated between the inlet and outlet util-
ity temperatures, a line is drawn from the outlet pinch tempera-
ture to the inlet temperature such that it touches the GCC only at
one point. The load can be then determined as graphically shown
in Fig. 7. Targets for cogeneration can be also determined using
Iterative Bottom-to-Top Model (IBTM) methodology [58]. IBTM is
based on a simple steam turbine expansion model with a constant
isentropic efficiency to calculate the shaft power of the steam tur-
bines presented in the Site Utility Grand Composite Curve (SUGCC).
Table 7 reports the necessary input data and results for cogen-
eration targeting of the site utility system interacting with
revamped chlorine-caustic soda production process units. The
steam system comprises of five steam levels with the Cooling
Water (CW) utility. The Very High Pressure (VHP) steam is gener-

Table 7
Input data and results of IBTM.

Input data
Steam mains operating pressure VHP 128.0 bar
HP 47.0 bar
MP2 25.0 bar
MP1 10.0 bar
LP 2.4 bar
Turbine specification Degree of superheat at exhaust of last turbine (°C) 25.0 °C
Constant isentropic efficiency 0.60
Site configuration data Boiler Feed Water (BFW) temperature (°C) 105.0 °C
Condensate return temperature (°C) 105.0 °C
Process steam load LP 8.17 MW
Results
Turbine Shaft power (MW) Flow rate (t/h) Steam Mains Temperature (°C)
VHP 500.0
VHP-HP 0.61 12.64
HP 385.9
HP-MP2 0.35 12.64
MP2 324.3
MP2-MP1 0.45 12.64
MP1 247.7
MP1-LP 0.60 12.64
LP 151.0
Total 2.01 –

T (°C) T (°C)

426 1126
(a) (b)

926
326

726

226

526

126

326

26
126

-74 -74
0. 1000. 2000. 3000. 4000. 5000. 6000. 7000. 8000. 0. 1000. 2000. 3000. 4000. 5000. 6000. 7000. 8000. 9000.
H (kW) H (kW)

Fig. 8. HP (red) and LP (pink) steam levels at the grand composite curve (a); and at the grand composite curve with the fired heater (b).
1528 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529
ated in the boiler house at 128.0 bar. The HP, MP2, MP1 and LP
levels correspond to pressures of 47.0, 25.0, 10.0 and 3.0 bar,
respectively determined based on Fig. 8.
4. Conclusions
The current work suggests how the energy efficiency of an
industrial chlorine-caustic soda process can be improved through
a combined exergy and pinch analyses approach. It has been
shown that exergy analysis which pinpoints main sources of inef-
ficiency in a given system, can serve as a preliminary step for defin-
ing the set of hot and cold streams. Pinch analysis then screens
these streams for maximum heat recovery.
This combined approach helps to identify and to propose solu-
tions that can save energy and natural resources used to produce
chemicals in general and choline-caustic soda in particular, as
demonstrated in the current study. As an example, the total cold
energy demand of the revamped chlorine-caustic soda production
process can be reduced dramatically from 13.00 MW to 0.40 MW
by identifying certain hot waste streams and interstage hot
streams in compressors, as well as isothermal mixing in mixers.
Proper heat recovery from these hot streams helps to reduce the
external energy demand required. Similarly, the proposed principle
is also applicable to cold streams, although it is accompanied with
a slight rise in hot utility requirements (from 7.74 MW to
8.17 MW). To sum up, the proposed improvements in the future
revamping of the process can lead to a more sustainable
chlorine-caustic soda production flowsheet and a lower exergy
loss.
In terms of future works, the authors recommend that steps not
considered in this work such as transportation of feedstock and
products to and from the site should be included to provide a life
cycle assessment. In addition to energy and efficiency evaluations,
life cycle assessment helps to identify the environmental footprint
of the process and provide guidelines on how the environmental
sustainability can be improved in the system. An example of such
a comprehensive analysis is provided in our recent work [59].
Although the current work is focused on the chlorine-caustic
soda production, the way it has been presented helps similar
approaches to be developed for other processes of interest. This
then helps the process developers to continuously analyze either
the existing or new processes, and to apply lessons learned in
one area to another. The current case study also illustrates that
even though a technology may be well-developed; there can be
still room for thermodynamically justifiable energy (and exergy)
efficiency improvements.
References
[1] M.L.M. Broeren, D. Saygin, M.K. Patel, Forecasting global developments in the
basic chemical industry for environmental policy analysis, Energy Pol. 64
(2014) 273–287, http://dx.doi.org/10.1016/j.enpol.2013.09.025.
[2] JVP International, Inc., Psage Research, Industrial Technologies Program -
Chemical Bandwidth Study Exergy Analysis: A Powerful Tool for Identifying
Process Inefficiencies in the US Chemical Industry, 2006. http://www.eere.
energy.gov/industry/chemicals (accessed 12.12.09).
[3] JVP International, Inc., Psage Research, Final Report: Evaluation of Alternative
Technologies for Ethylene, Caustic-Chlorine, Ethylene Oxide, Ammonia, and
Terephthalic Acid, 2007. http://www1.eere.energy.gov/manufacturing/
resources/chemicals/pdfs/alt_tech_pub.pdf (accessed 13.07.2017).
[4] A. Ghannadzadeh, M. Sadeqzadeh, Evaluation of an alternative chlorine
production process for energy saving toward sustainability, Environ Prog
Sustain Energy 35 (2016) 1512–1520, http://dx.doi.org/10.1002/ep.12374.
[5] A. Ghannadzadeh, M. Sadeqzadeh, Diagnosis of an alternative ammonia
process technology to reduce exergy losses, Energy Convers. Manage. 109
(2016) 63–70, http://dx.doi.org/10.1016/j.enconman.2015.11.040.
[6] A. Ghannadzadeh, A and M. Sadeqzadeh, Exergy analysis as a scoping tool for
cleaner production of chemicals: a case study of an ethylene production
process, J Clean Prod 129 (2016) 508–520, http://dx.doi.org/10.1016/j.
jclepro.2016.04.018.
[7] J. Sun, F. Wang, T. Ma, H. Gao, P. Wu, L. Liu, Energy and exergy analysis of a five-
column methanol distillation scheme, Energy 45 (2012) 696–703, http://dx.
doi.org/10.1016/j.energy.2012.07.022.
[8] A. Wechsung, A. Aspelund, T. Gundersen, P.I. Barton, Synthesis of heat
exchanger networks at subambient conditions with compression and
expansion of process streams, AIChE J. 57 (2011) 2090–2108, http://dx.doi.
org/10.1002/aic.12412.
[9] A. Arriola-Medellín, E. Manzanares-Papayanopoulos, C. Romo-Millares,
Diagnosis and redesign of power plants using combined Pinch and Exergy
Analysis, Energy 72 (2014) 643–651, http://dx.doi.org/10.1016/j.
energy.2014.05.090.
[10] M. Kamalinejad, M. Amidpour, S.M. Mousavi Naeenian, Optimal synthesis of
cascade refrigeration in liquefied natural gas cycles by pinch-exergy, J. Oil Gas
Petrochem. Technol. 1 (2014) 29–44.
[11] J.A. Quijera, A. García, M.G. Alriols, J. Labidi, Heat integration options based on
pinch and exergy analyses of a thermosolar and heat pump in a fish tinning
industrial process, Energy 55 (2013) 23–37, http://dx.doi.org/10.1016/j.
energy.2013.02.025.
[12] J.A. Quijera, J. Labidi, Pinch and exergy based thermosolar integration in a dairy
process, Appl. Therm. Eng. 50 (2013) 464–474, http://dx.doi.org/10.1016/j.
applthermaleng.2012.06.044.
[13] A. Aspelund, The Process Synthesis Pyramid: Conceptual design of a Liquefied
Energy Chain using Pinch Analysis, Exergy Analysis, Deterministic
Optimization and Metaheuristic Searches, 2012. http://brage.bibsys.no/
xmlui/handle/11250/234604 (accessed 02.02.16).
[14] M. Bendig, F. Maréchal, D. Favrat, Defining the potential of usable waste heat in
industrial processes with the help of pinch and exergy analysis, Chem. Eng.
Trans. 29 (2012) 103–108, http://dx.doi.org/10.3303/CET1229018.
[15] B. Ghorbani, G.R. Salehi, H. Ghaemmaleki, M. Amidpour, M.H. Hamedi,
Simulation and optimization of refrigeration cycle in NGL recovery plants
with exergy-pinch analysis, J. Nat. Gas Sci. Eng. 7 (2012) 35–43, http://dx.doi.
org/10.1016/j.jngse.2012.03.003.
[16] A. Modarresi, P. Kravanja, A. Friedl, Pinch and exergy analysis of lignocellulosic
ethanol, biomethane, heat and power production from straw, Appl. Therm.
Eng. 43 (2012) 20–28, http://dx.doi.org/10.1016/j.applthermaleng.2012.01.
026.
[17] F. Thibault, A. Zoughaib, S. Pelloux-Prayer, A MILP algorithm for utilities
pre-design based on the Pinch Analysis and an exergy criterion, Comput.
Chem. Eng. 75 (2015) 65–73, http://dx.doi.org/10.1016/j.compchemeng.
2014.12.010.
[18] B. Linnhoff, A user guide on process integration for the efficient use of energy,
Institution of Chemical Engineers, Rugby, 1994.
[19] A. Ghannadzadeh, R. Thery-Hetreux, N. Raimondi, P. Floquet, O. Baudouin, B.A.
Khalil, P. Baudet, X. Joulia, Toward an approach combining exergy analysis
and pinch analysis for improving the energy efficiency of industrial
sites: application to a pulp and paper process, in: SFGP 2011 Lille, 2011.
http://scholar.google.com/scholar?cluster=5568744128145655765&hl=en&oi=
scholarr (accessed 31.01.16).
[20] E. Mateos-Espejel, Development of a Strategy for Energy Efficiency
Improvement in a Kraft Process Based on Systems Interactions Analysis, PhD
Thesis, École Polytechnique de Montréal, 2009. https://publications.polymtl.
ca/162/ (accessed 31.01.16).
[21] A. Bejan, Entropy Generation Through Heat and Fluid Flow, Wiley, New York,
1982.
[22] T.J. Kotas, The Exergy Method of Thermal Plant Analysis, Krieger Pub. Co,
Malabar, 1995.
[23] T.J. Kotas, exergy Method of Thermal Plant Analysis, Butterworths, London,
1985.
[24] D.R. Szargut, F.R. Morris, Steward, Exergy analysis of thermal, chemical, and
metallurgical processes, Hemisphere Publishing Corporation, New York, 1988.
_ Dinçer, M.A. Rosen, Exergy: Energy, Environment, and Sustainable
[25] I.
Development, Elsevier, Oxford, 2007.
[26] M.E. Bösch, S. Hellweg, M.A. Huijbregts, R. Frischknecht, Applying cumulative
exergy demand (CExD) indicators to the ecoinvent database, Int. J. Life Cycle
Assess. 12 (2007) 181, http://dx.doi.org/10.1065/lca2006.11.282.
[27] I. Dincer, Exergy as a potential tool for sustainable drying systems, Sustain.
Cities Soc. 1 (2011) 91–96, http://dx.doi.org/10.1016/j.scs.2011.04.001.
[28] M. Aghbashlo, H. Mobli, S. Rafiee, A. Madadlou, A review on exergy analysis of
drying processes and systems, Renew. Sustain. Energy Rev. 22 (2013) 1–22,
http://dx.doi.org/10.1016/j.rser.2013.01.015.
[29] M.J. Jokandan, M. Aghbashlo, S.S. Mohtasebi, Comprehensive exergy analysis of
an industrial-scale yogurt production plant, Energy 93 (2015) 1832–1851,
http://dx.doi.org/10.1016/j.energy.2015.10.003.
[30] B. Linnhoff, F.J. Alanis, Integration of a new process into an existing site: a case
study in the application of pinch technology, J. Eng. Gas Turbines Power. 113
(1991) 159–168, http://dx.doi.org/10.1115/1.2906537.
[31] R.A. Gaggioli, D.A. Sama, S. Qian, Y.M. El-Sayed, Integration of a new process
into an existing site: a case study in the application of exergy analysis, J. Eng.
Gas Turbines Power. 113 (1991) 170–180, http://dx.doi.org/10.1115/
1.2906540.
[32] F. Staine, D. Favrat, Energy integration of industrial processes based on the
pinch analysis method extended to include exergy factors, Appl. Therm. Eng.
16 (1996) 497–507, http://dx.doi.org/10.1016/1359-4311(95)00036-4.
[33] X. Feng, X.X. Zhu, Combining pinch and exergy analysis for process
modifications, Appl. Therm. Eng. 17 (1997) 249–261, http://dx.doi.org/
10.1016/S1359-4311(96)00035-X.
 A. Ghannadzadeh, M. Sadeqzadeh / Applied Thermal Engineering 125 (2017) 1518–1529
[34] T. Umeda, T. Harada, K. Shiroko, A thermodynamic approach to the synthesis of
heat integration systems in chemical processes, Comput. Chem. Eng. 3 (1979)
273–282, http://dx.doi.org/10.1016/0098-1354(79)80046-0.
[35] M. Ishida, K. Kawamura, Energy and exergy analysis of a chemical process
system with distributed parameters based on the enthalpy-direction factor
diagram, Ind. Eng. Chem. Process Des. Dev. 21 (1982) 690–695, http://dx.doi.
org/10.1021/i200019a025.
[36] B. Linnhoff, V.R. Dhole, Shaftwork targets for low-temperature process design,
Chem. Eng. Sci. 47 (1992) 2081–2091, http://dx.doi.org/10.1016/0009-2509
(92)80324-6.
[37] M. Homšak, P. Glavič, Pressure exchangers in pinch technology, Comput.
Chem. Eng. 20 (1996) 711–715, http://dx.doi.org/10.1016/0098-1354(95)
00204-9.
[38] R. Anantharaman, O.S. Abbas, T. Gundersen, Energy Level Composite Curves—a
new graphical methodology for the integration of energy intensive processes,
Appl. Therm. Eng. 26 (2006) 1378–1384, http://dx.doi.org/10.1016/j.
applthermaleng.2005.05.029.
[39] A. Aspelund, D.O. Berstad, T. Gundersen, An Extended Pinch Analysis and
Design procedure utilizing pressure based exergy for subambient cooling,
Appl. Therm. Eng. 27 (2007) 2633–2649, http://dx.doi.org/10.1016/j.
applthermaleng.2007.04.017.
[40] D. Marmolejo-Correa, T. Gundersen, A new procedure for the design of LNG
processes by combining Exergy and Pinch Analyses, in: 25th Int. Conf. Effic.
Cost Optim. Simul. Energy Convers. Syst. Process., 2012: p. 24. http://
www.torrossa.it/gs/resourceProxy?an=2520327&publisher=FF3888#page=51
(accessed 31.01.16).
[41] F. Maréchal, B. Kalitventzeff, Identification of the optimal pressure levels in
steam networks using integrated combined heat and power method, Chem.
Eng. Sci. 52 (1997) 2977–2989, http://dx.doi.org/10.1016/S0009-2509(97)
00102-4.
[42] M. Sorin, J. Paris, Combined exergy and pinch approach to process analysis,
Comput. Chem. Eng. 21 (Supplement) (1997) S23–S28, http://dx.doi.org/
10.1016/S0098-1354(97)87473-X.
[43] R. Thery-Hetreux, P. Floquet, A. Ghannadzadeh, N. Raimondi, O. Baudouin, X.
Joulia, Toward an approach combining exergy analysis and pinch analysis for
improving the energy efficiency of industrial sites, in: CAPE Forum 2012, 2012.
http://scholar.google.com/scholar?cluster=5568744128145655765&hl=en&
oi=scholarr (accessed 31.01.16).
[44] S. Gourmelon, R. Hetreux, P. Floquet, P. Baudet, O. Baudouin, Premises for a
combined Exergy and Pinch Optimization within ProSimPlusÒ simulator,
Comput. Aided Chem. Eng. 33 (2014) 1507–1512, http://dx.doi.org/10.1016/
B978-0-444-63455-9.50086-6.
[45] A. Ghannadzadeh, R. Thery-Hetreux, O. Baudouin, P. Baudet, P. Floquet, X.
Joulia, General methodology for exergy balance in ProSimPlusÒ process
simulator, Energy 44 (2012) 38–59, http://dx.doi.org/10.1016/j.
energy.2012.02.017.
1529
[46] A. Ghannadzadeh, Exergetic balances and analysis in a Process Simulator: A
way to enhance Process Energy Integration, PhD Thesis, Institut National
Polytechnique, 2013. http://ethesis.inp-toulouse.fr/archive/00002116/
(accessed 04.10.13).
[47] S. Gourmelon, Méthodologie d’analyse et de rétro-conception pour
l’amélioration énergétique des procédés industriels, PhD Thesis, 2015. http://
oatao.univ-toulouse.fr/14492/ (accessed 31.01.16).
[48] M. Rabbani, I. Dincer, G.F. Naterer, Experimental investigation of processing
parameters and effects on chloralkali products in an electrolysis based
chloralkali reactor, Chem. Eng. Process. Process Intensif. 82 (2014) 9–18,
http://dx.doi.org/10.1016/j.cep.2014.04.007.
[49] M. Rabbani, I. Dincer, G.F. Naterer, Efficiency assessment of a photo
electrochemical chloralkali process for hydrogen and sodium hydroxide
production, Int. J. Hydrog. Energy 39 (2014) 1941–1956, http://dx.doi.org/
10.1016/j.ijhydene.2013.11.127.
[50] P. Gianadda, C. Brouckaert, R. Sayer, C. Buckley, The application of pinch
analysis to water, reagent and effluent management in a chlor-alkali facility,
Water Sci. Technol. 46 (2002) 21–28.
[51] P. Gianadda, C.J. Brouckaert, C.A. Buckley, The Application of Pinch Analysis to
Water Effluent Management in a Chlor-Alkali Facility, in: WISA Bienn. Conf.
Sun City South Afr., 2000. http://www.ewisa.co.za/literature/files/
172gianadda.pdf (accessed 31.01.16).
[52] Á. Martín, F.A. Mato, Hint: An educational software for heat exchanger
network design with the pinch method, Educ. Chem. Eng. 3 (2008) e6–e14,
http://dx.doi.org/10.1016/j.ece.2007.08.001.
[53] E. Gholami, Pinch Analysis of a Chlorine Production, Process, Conceptual
Process Design Course Project, Hamedan University of Technology, 2016.
[54] L.E. Savulescu, A. Alva-Argaez, Direct heat transfer considerations for
improving energy efficiency in pulp and paper Kraft mills, Energy 33 (2008)
1562–1571, http://dx.doi.org/10.1016/j.energy.2008.07.015.
[55] R. Smith, Chemical process design and integration, John Wiley, West Sussex,
2005.
[56] J.J. Klemeš, P.S. Varbanov, Implementation and pitfalls of process integration,
Chem. Eng. Trans. 21 (2010) 1369–1374, http://dx.doi.org/10.3303/
CET1021229.
[57] S.A. Papoulias, I.E. Grossmann, A structural optimization approach in process
synthesis-I: Utility systems, Comput. Chem. Eng. 7 (1983) 695–706, http://dx.
doi.org/10.1016/0098-1354(83)85022-4.
[58] A. Ghannadzadeh, S. Perry, R. Smith, Cogeneration targeting for site utility
systems, Appl. Therm. Eng. 43 (2012) 60–66, http://dx.doi.org/10.1016/j.
applthermaleng.2011.10.006.
[59] A. Ghannadzadeh, Assessment of power generation from natural gas and
biomass to enhance environmental sustainability of a polyol ether process for
production of rigid foam polyurethane, Renew. Eng. (2017), http://dx.doi.org/
10.1016/j.renene.2017.07.059.