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A New Efficiency Parameter for Exergy Analysis in Low Temperature Processes

Article  in  International Journal of Exergy · October 2014

DOI: 10.1504/IJEX.2015.069988

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Danahe Marmolejo-Correa Truls Gundersen

Universidad de Guanajuato Norwegian University of Science and Technology
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Int. J. Exergy, Vol. x, No. x, xxxx 1

A new efficiency parameter for exergy analysis in low

temperature processes

Danahe Marmolejo-Correa and

Truls Gundersen*
Department of Energy and Process Engineering,
Norwegian University of Science and Technology,
Kolbjoern Hejes vei 1.A,
NO-7491, Trondheim, Norway
E-mail: danahe.marmolejo@gmail.com
E-mail: truls.gundersen@ntnu.no
*Corresponding author

Abstract: Process design requires an effective parameter to evaluate each step

of the design procedure. Normally, processes are evaluated using total annual Author: Please
cost or payback period. However, it is sometimes preferable that this quality reduce abstract
parameter is independent of cost, which can be an uncertain and unreliable of no more than
measure. Thus, an ideal evaluator is exergy efficiency because it focuses on the
thermodynamic attributes of the process. However, due to lack of
150 words.
standardisation of exergy efficiency definitions, exergy classifications and
exergy decompositions, the use of exergy efficiency as a representative
measure of quality is not straightforward. In low temperature processes (LTPs),
the use of exergy efficiency as a process evaluator is even more obvious due to
the work requirement in refrigeration cycles (work is pure exergy).
Unfortunately, the calculation of exergy efficiency in LTPs using some of the
existing definitions, will not properly measure process quality. This is caused
by (i) the independent behaviour of the components of the exergy of matter,
and (ii) the discontinuity of the exergy of heat at ambient temperature (T0).
Moreover, the fact that normal operation of some units in LTPs starts below T0
and ends above T0 (or vice versa) adds complexity to exergy efficiency
calculations. This paper presents a systematic approach to address the problems
stated above. The approach is based on decomposing the exergy, studying
independently the changes of the components, and analysing the interactions
between them. An exergy transfer effectiveness (ETE) that works particularly
well for LTPs is defined. Another feature of the ETE is that it is also applicable
for processes operating across ambient temperature. The ETE utilises the Author: Please
simple concept of sources and sinks that is commonly used in process synthesis
and process integration; however, here applied in exergy analysis. In addition,
check intended
the proposed ETE is compared with four classical definitions of exergy meaning is
efficiency using an LTP as case study. The results show variations in the retained.
exergy efficiency figures for individual process units as well as for the overall
process. A deeper reflection on the reason for these differences is also made
towards the end of the paper.

Keywords: exergy efficiency; process design; low temperature process; LNG.

Reference to this paper should be made as follows: Marmolejo-Correa, D. and

Gundersen, T. (xxxx) ‘A new efficiency parameter for exergy analysis in low
temperature processes’, Int. J. Exergy, Vol. x, No. x, pp.xxx–xxx.

Copyright © 200x Inderscience Enterprises Ltd.

2 D. Marmolejo-Correa and T. Gundersen

Biographical notes: Danahe Marmolejo did her Bachelor’s degree in Chemical

Engineering at the University of Guanajuato and her Master’s degree in Process
Integration in the same Mexican institution. Her master thesis was focused on
reducing energy consumption of low temperature processes (LTPs). She
received a PhD degree in the Department of Energy and Process Engineering of
the Norwegian University of Science and Technology in November 2013.
Her research interest is the advanced exergy analysis of LTPs as well as
studding possibilities of minimising heat and power requirements utilising
exergy analysis during process design.

Truls Gundersen is a Professor of Energy and Process Engineering at the

Norwegian University of Science and Technology (NTNU) that he joined in
1996. He received a PhD in Chemical Engineering from the same university in
1982 and spent 12 years in industry with Norsk Hydro before joining academia
in 1993. His research interests include process integration and process synthesis
with special emphasis on the use of thermodynamics in the design phase. One
of his main expertise areas is synthesis and optimisation of heat exchanger
networks. He is also involved in CCS as the NTNU coordinator of BIGCCS, Author: If a previous
a 75 million USD program that runs for eight years until 2016. He was elected
member of the Norwegian Academy of Technological Sciences in 1991. As an version of your paper has
educator, he is teaching Engineering Thermodynamics and Process Integration, originally been presented
in both cases with some material on exergy. at a conference please
complete the statement to
This paper is a revised and expanded version of a paper entitled [title] this effect or delete if not
presented at [name, location and date of conference].
applicable.

1 Introduction

In conceptual process design, the evaluation of each decision during the design procedure
is fundamental for the quality and reliability of the final design. Due to the instability of
the international economic situation, it is suggested in this work that thermodynamic
attributes of the process should be the basis for a confident evaluation during the first
stages of the design procedure. Even though in most cases there is a trade-off between
investment cost and thermodynamic efficiency, a performance enhancement is favoured
in conceptual design. Rather than focusing on cost, thermodynamics may be used to
guide research towards more energy-efficient processes.
The obvious parameter on which to base a conceptual study is the exergy
performance of processes; however, several definitions are proposed in the literature to
measure this property (Bejan et al., 1996; Brodyansky et al., 1994; Grassmann, 1950;
Kotas, 1995; Moran, 1989; Szargut, 2005; Tsatsaronis, 1993). Cornelissen (1997)
compared three of the most commonly used exergy performance evaluators: the total or
overall efficiency (Lior and Zhang, 2007; Moran, 1989), the exergy efficiency (ηe)
(Brodyansky et al., 1994), and the rational efficiency (ψ) (Kotas, 1995). Brodyansky
et al. (1994) also evaluated these efficiencies using an air separation unit (ASU) as case
study, and they found three different values for the exergy performance. Lior and Zhang
(2007) classified and made distinctions between different definitions for energy, exergy,
and second law efficiencies. They also commented on the ambiguity of some efficiency
 A new efficiency parameter for exergy analysis in low temperature processes 3

expressions and common misinterpretations. Marmolejo-Correa and Gundersen (2012)

suggested that most of the exergy efficiency definitions in the literature could be
classified into two groups, input–output and consumed–produced. They also compared
the results of different efficiencies when applied to an LTP, e.g., the PRICO process
(Swenson, 1977) for liquefaction of natural gas.
A general overview of the literature shows that some exergy performance definitions
are open for individual interpretations. Consequently, this situation may lead to confusion
when two or more processes are compared under this metric, and designers are always
forced to explain their actual use of these definitions. The word ‘efficiency’ is sometimes
used indiscriminately, and almost any ratio between two quantities is referred to as
efficiency.
For the assessment of process performance, exergy analysis uses as its main
parameter the energy quality of material and energy streams. Therefore, it is expected
that exergy efficiency will adequately measure the perfection (or imperfection) of each
unit operation as well as the complete process. Sometimes, however, different values are
found when using different efficiencies. The concept of exergy, in particular the exergy
performance parameter, has been under development and studied for several decades
(Sciubba and Wall, 2007). Nevertheless, mistakes are still made in many studies when
evaluating the exergy efficiency of complex processes. One example, and the motivation
for this paper, is the exergy study and performance analysis of processes operating below
and across ambient temperature.

2 Exergy classification and decomposition

An accurate exergy classification and decomposition is needed in order to perform an

objective and correct exergy analysis of processes. Similar to energy, exergy can be
classified according to the nature of its origin (i.e., potential, kinetic, nuclear, or from
energy related to a material stream) and decomposed for a more detailed study. Several
authors (Bejan et al., 1996; Brodyansky et al., 1994; Dunbar et al., 1992; Kotas, 1995;
Lior and Zhang, 2007; Marmolejo-Correa and Gundersen, 2012; Moran and Shapiro,
2006; Petela, 2008; Rivero, 1993; Szargut, 2005; Szargut et al., 1988) have proposed
different classifications and decompositions for exergy. Some selected classifications
from the literature are shown in Table 1.
Szargut et al. (1988) claimed that all exergy forms have matter as carrier; thus he
proposed a rather simple decomposition. Kotas (1995) first differentiated between open
and closed systems in order to use the correct terms in the thermodynamic relations for
each exergy form. In Kotas’s classification, the physical exergy is divided into thermal
and pressure components. Rivero (1993) suggested that the sum of kinetic and potential
exergies should be referred to as inertial exergy. Brodyansky et al. (1994) recognised that
exergy may be carried by matter as well as by energy streams, and they differentiated
between exergy coming from ordered or disordered energy forms. This is equivalent to
saying that Exergy = Energy for ordered energy types and that Exergy < Energy for
disordered energy forms. They also indicated that exergy kinds could be formed by
exergy parts or decomposed into different exergy components. The main difference
between exergy kinds and exergy components is that the first can change independently,
while for the second, a change in one component affects the rest of the components.
4 D. Marmolejo-Correa and T. Gundersen

For instance, a change in the mechanical component affects the thermal component. For
exergy parts, specifically in the case of chemical exergy, the parts (reactional exergy that
is related to chemical reaction and concentrational exergy related to change of the system
composition without chemical reactions, i.e. mixing and separation) are connected by one
intensive property, which is the chemical potential. Bejan et al. (1996) and Tsatsaronis
(2007) proposed a classification similar to the one provided by Kotas. Moran and Shapiro
(2006) did not explicitly show a classification; however, they commented about different
types of exergy. Lior and Zhang (2007) made an interesting classification. Instead of
differentiating the relation between energy (ordered or disordered) and exergy, they were
focused on the direct interaction of the system with power production. They claimed that
any work interactions (including electrical energy) are straightforward, because they are
pure exergy and thus the exergy values of such interactions are equal to their energy
values. The exergy of non–work energy interactions (heat, for example) depends on the
type of energy interaction and the definition of the control volume under consideration.
The latter also depends on the objective of the analysis. Finally, Petela (2008) extended
the classification proposed by Szargut et al. (1988) and suggested that potential exergy
should be replaced by gravitational exergy, which is defined as the sum of the buoyant
(lift) and altitudinal exergies. He also indicated that the sum of physical and gravitational
exergies is the same as mechanical exergy.

Table 1 Different classifications of exergy (see online version for colours)

Author Classification

Szargut et al. (1988)

Kotas (1995)

Rivero (1993)
 A new efficiency parameter for exergy analysis in low temperature processes 5

Table 1 Different classifications of exergy (see online version for colours) (continued)

Author Classification

Brodyansky et al. (1994)

Bejan et al. (1996)

Moran and Shapiro (2006)

Tsatsaronis (2007)

Lior and Zhang (2007)

Petela (2008)
6 D. Marmolejo-Correa and T. Gundersen

One can notice that although there are differences between these classifications, there are
also considerable similarities. Marmolejo-Correa and Gundersen (2012) identified some
of these similarities and proposed a new classification (Figure 1) using the existing
classifications as basis. In principle, the classification and decomposition for open and
closed systems (flow vs. non-flow exergy) should be the same; however, the
thermodynamic elements involved in the components are different. The first level of
classification is based on the type of carrier:
• energy streams, or
• material streams.
The second level of classification refers to the so-called exergy ratio of energy (Rant,
1961) similar to the level of energy (Ishida and Kawamura, 1982) defined as
Exergy/Energy. Here, one distinguishes between systems or phenomena where the exergy
is equal to the energy content and those cases where the exergy is less than the energy
content.

Figure 1 Proposed classification and decomposition of exergy according to its energetic origin
(see online version for colours)

2.1 Thermo-mechanical exergy decomposition

If kinetic, potential, electrical, and nuclear energies are neglected, the stream
exergy is calculated only by its composition, temperature, and pressure. The chemical
composition generates the chemical exergy of the stream, whilst temperature and pressure
are responsible for the thermo-mechanical exergy (Aspelund et al., 2007; Brodyansky
et al., 1994). The latter is also referred to as physical exergy (Bejan et al., 1996;
 A new efficiency parameter for exergy analysis in low temperature processes 7

Szargut et al., 1988), and the sum of chemical and thermo-mechanical (physical) exergies
is also known as thermal exergy (Szargut et al., 1988).
The thermo-mechanical exergy of a process stream is calculated by equation (1), and
it can be decomposed into two parts as shown in equation (2): the temperature part
(equation (3)), and the pressure part (equation (4)). The decomposed parts are also known
as thermal and pressure components (Kotas, 1995), thermal and mechanical exergies
(Morosuk and Tsatsaronis, 2005; Rivero, 1993), and temperature-based and pressure-
based exergies (Aspelund et al., 2007; Marmolejo-Correa and Gundersen, 2012).
(1)
E TM = H (T , p ) − H (T0 , p0 ) − T0  S (T , p ) − S (T0 , p0 ) 

E TM = E T + E p (2)

E T = H (T , p ) − H (T0 , p ) − T0  S (T , p ) − S (T0 , p )  (3)

E p = H (T0 , p ) − H (T0 , p0 ) − T0  S (T0 , p ) − S (T0 , p0 )  . (4)

Figure 2(a) shows the graphical representation of the thermo-mechanical exergy and its
components in an Exergy–Enthalpy ( E − H ) diagram. It is worth noticing that the split
into E T and E p presented here is not unique and thus has no fundamental meaning (due
to the lack of a reference process). However, this representation illustrates the exergy
contributions by the temperature and pressure levels of the process streams when the
main exergy transformation occurs between E T , E p and shaft work, in particular for
operating conditions below ambient temperature.

Figure 2 (a) Temperature-based and pressure-based exergy and (b) Exergy content of heat vs.
temperature

2.2 Special behaviour of the exergy of heat and material streams below ambient
temperature
The exergy content of a process stream or heat reservoir depends on the temperature
level. The behaviour of the temperature-based exergy for a material stream, E T , is given
by the isobars in Figure 2(a). These isobars clearly show that the exergy requirement
below ambient temperature is larger than above ambient for the same change in
temperature (increment above T0 and decrement below T0). The exergy accompanying
8 D. Marmolejo-Correa and T. Gundersen

heat also depends on temperature. In Figure 2(b), one can observe that the exergy of heat
(energy stream) above T0 is horizontally asymptotic to Q ; i.e., the maximum work
produced even by an ideal (reversible) heat engine will always be less than the energy
supplied by the heat reservoir (Q ). Below T0, the exergy of heat is vertically asymptotic
to infinite when the temperature approaches 0 K; i.e., the minimum work required to take
Q from T0 to a lower temperature can be larger than Q (at T = 0 K, an infinite amount of
work is required). It is worth noticing that above ambient temperature, heat is always less
worth (lower exergy) than work, while for temperatures below half of T0, the ratio
between E Q and Q is larger than one (see Figure 2(b)); i.e., heat (cold thermal energy)
is more valuable than work. This special behaviour is expressed by equations (5) and (6).
 T 
E Q = Q ⋅ 1 − 0  for T ≥ T0 (5)
 T 

T 
E Q = Q ⋅  0 − 1 for T ≤ T0 . (6)
T 

3 Energy and exergy sources and sinks for processes operating above and
below ambient temperature

Every unit operation has energy and/or mass sources and sinks making it able to carry
out the task it is expected to perform. In fact, this has been the basis for heat and
mass integration techniques (El-Halwagi and Manousiouthakis, 1989; Linnhoff
and Hindmarsh, 1983). However, the sources and the sinks are not always the same for
energy and exergy flows. This section presents a deeper analysis of the exergy sources
and exergy sinks for some selected unit operations. The unit operations studied here are
the ones that are typically used in the production of liquefied natural gas (LNG).

3.1 Heat exchange

The diagrams in Figure 3 represent two heat exchangers where pressure drop is
neglected. One heat exchanger operates above ambient temperature and the other below.
Stream data for this example is provided in Table 2. It is obvious from the Temperature–
Enthalpy (T − H ) diagram (Figure 3(a)), that the energy (heat) source and sink are the
hot and the cold stream respectively, whether heat exchange occurs above or below
ambient temperature. For exergy, however, and due to the special behaviour of
temperature-based exergy, E T , the direction of exergy flow above T0 is the opposite of
the exergy flow below T0.

Table 2 Stream data for heat and exergy exchange

Type Ts (°C) Tt (°C)  p (kW/°C)

mc ∆H (kW) ∆E T (kW)
Hot 167 67 1.70 –170 –39.3
Cold 52 112 2.83 170 26.9
Hot 2 –98 1.70 –170 59.1
Cold –113 –53 2.83 170 –99.0
 A new efficiency parameter for exergy analysis in low temperature processes 9

Figure 3 Sources and sinks in heat exchange: (a) for energy and (b) for exergy (see online
version for colours)

This means that for a heat exchanger operating below ambient temperature, the exergy
source is the cold stream and the exergy sink is the hot stream. This can be observed
from the exergy source–sink representation in a Temperature–Exergy (T − E ) diagram
(Figure 3(b)). A careful interpretation of this exergy flow is needed to avoid confusion.
The exchange occurring between the hot and cold streams is about heat transfer (i.e., the
objective is heating and cooling), independent of the operating conditions (i.e., above or
below ambient temperature). This heat exchange results in an increment or decrement in
the capacity of the streams to produce work through a reversible heat engine (i.e.,
exergy). Consequently, this increase or decrease in exergy can be regarded as a sort of
exergy transfer between exergy sources and exergy sinks. However, one should have in
mind that exergy cannot be transferred alone; it should accompany either a material flow
(i.e. mixing or separation) or energy flow (i.e., heating or cooling). It is worth noticing
that the overlapping region between streams in Figure 3(b) is the actual exergy
transferred, and the exergy surplus is equal to the exergy destruction due to finite
temperature driving forces between streams (i.e., thermodynamic irreversibilities).
Generally, one could conclude that for heat exchange, a negative change (decrement) in
the exergy of a stream represents an exergy source while a positive change (increment) in
exergy represents an exergy sink.

3.2 Pressure drop effects in heat exchange

The change in pressure-based exergy, E p , is always negative (decrease) in heat
exchangers; thus it could be categorised as an exergy source. However, one should have
in mind that pressure drop is the result of resistance from the wall of the heat exchanger
against the movement of the fluid. This resistance triggers a reduction in the theoretical
capacity for work production of the fluid, however, with the important difference that this
reduction is irreversibly lost (exergy destruction).
Figure 4 illustrates two heat exchangers: one operating above ambient temperature
(Figure 4(a)) and the other operating below ambient temperature (Figure 4(b)). In both
cases (heat exchange above and below ambient temperature), state 1 refers to the inlet
conditions of the hot stream, while state 2’ (without pressure drop) and state 2 (with
pressure drop) refer to the outlet conditions of the hot stream. Similarly, state 3 (inlet),
10 D. Marmolejo-Correa and T. Gundersen

state 4’ (outlet without pressure drop), and state 4 (outlet with pressure drop) are the
conditions of the cold stream. One can observe that for exergy sources (i.e., hot streams
above T0 and cold streams below T0), there is an increment in their negative change in
exergy (larger decrement) when pressure drop is assumed. This could be seen as a
positive effect on the exergy sources because the available exergy is increased; however,
as already noticed this reduction in exergy is related to irreversibilities and cannot be
utilised. This topic will be subject to further discussion later in the paper.

Figure 4 Pressure drop effects on the exergy sources and sinks in a heat exchanger operating (a)
above T0 and (b) below T0 (see online version for colours)

For the exergy sinks (cold streams above T0 and hot streams below T0), however, the
positive change in exergy is decreased (smaller increment) in comparison with the
situation without pressure drop. This is definitely a negative effect of the pressure drop
for the exergy sinks because it decreases the capacity of the exergy sink to ‘collect’
exergy from the sources. Thus at the end, pressure drop definitely has a two-sided
contribution to the exergy destruction by increasing the available exergy in the sources
and reducing the capacity of the exergy sinks.
In some more distinct cases, such as two-phase flow, high viscosity fluids or high-
pressure streams, the pressure drop can be considerable and for an exergy sink, the
negative effect of pressure change can cancel and even overcome the positive effect of
temperature change. This could be seen as a change of identity from sink to source.
This illustrates the dilemma of including the effect of pressure drop (which is related
to mechanical energy) in the analysis of heat exchange (which is related to thermal
energy).
It has already been pointed out that the apparent increase in the exergy source is
related to irreversible losses that cannot be utilised. However, since quite a few of the
proposed exergy efficiencies in the literature include these pressure drop effects one way
or another, for a fair comparison and to highlight the importance of a proper definition of
exergy sources and sinks, it was decided to include pressure-based exergy in the analysis
of heat transfer equipment.
An alternative way to deal with pressure drop in heat exchangers was illustrated by
Kotas (1995). He added compressors (could have been pumps for liquid streams) to bring
the pressures of the streams back to their initial values, see Figure 5.
 A new efficiency parameter for exergy analysis in low temperature processes 11

Figure 5 Control volume of a heat exchanger with compressors (see online version for colours)

Figures 6(a) and (b) show the distribution of exergy sinks, sources, and destructions for
two heat exchangers. The first (a) is operating above ambient temperature and the second
(b) is operating below ambient temperature. In both cases, methane is the hot stream and
nitrogen is the cold stream, pressure drop is considered, and the total heating load is 100
MW. Figures 6(c) and (d) illustrate the change in exergy of the two thermo-mechanical
exergy components (i.e., T-based and p-based) in both streams. The heat exchangers were
segmented into 10 elements with an equal heating load (i.e., 10 MW). The corresponding
temperatures of the segments are shown in the top and bottom arrows.
As discussed in Section 2.2, at temperatures above ambient, the T-based exergy of a
stream increases towards higher temperatures, while for streams below ambient
temperature, the T-based exergy increases towards lower temperatures. Ambient
conditions are assumed to be 25°C and 1 bar.
The heat exchanger operating above ambient temperature (Figures 6(a) and (c)) has a
minimum temperature difference of 5 K and a pressure drop of 8% in both streams. The
inlet pressures are 60 bar (methane) and 120 bar (nitrogen). Supply and target
temperatures are 130°C and 40°C for methane and 25°C and 125°C for nitrogen.
Below ambient temperature Figures 6(b) and (d)), one should notice that the change
in E TM of methane (hot stream) represents an exergy sink while the exergy source is the
change in E TM for nitrogen (cold stream). In addition, it should be mentioned that the
specific heat capacity of methane below ambient temperature is changing with
temperature in such a way that the smallest temperature difference is at some
intermediate temperature of the exchanger rather than in one of the ends.
For the overall picture, the heat exchanger above T0 is transferring 12.2 MW from
methane to nitrogen, while the exergy destruction is 7.8 MW. It should be noticed that
since the heat exchanger is balanced with respect to enthalpy, the exergy source must
always be larger than the exergy sink. The relations are shown in equations (7) and (8).
Thus, the exergy source for this case is equal to 20.0 MW.
12 D. Marmolejo-Correa and T. Gundersen

Figure 6 Representation of exergy sources and sinks for a heat exchanger operating (a) above T0
and (b) below T0 and the changes in exergy components for a heat exchanger operating
(c) above T0 and (d) below T0 (see online version for colours)

ESource = ESink + E Destruction (7)

E Transfer = ESink . (8)

Similarly, the exchanger below T0 is transferring 22.7 MW from nitrogen to methane,

while the exergy destruction is 52.9 MW. The exergy source is 75.6 MW.
Figure 6 is the result of rigorous calculations performed with the commercial
simulator Aspen HYSYS v7.1. The exergy calculations were performed using the option
User Variables in HYSYS that enables the user to calculate exergies from enthalpy and
entropy data with some modest programming efforts.

3.3 Compression and expansion operations

In the case of compression and expansion, the graphical representation of sources and
sinks is more complicated than for heat exchange, since the process streams can be both
source and sink. In addition, the special behaviour of E T below T0 should be taken into
account. Figures 7 and 8 represent compression and expansion of nitrogen (a) above T0
 A new efficiency parameter for exergy analysis in low temperature processes 13

and (b) below T0. In these figures, it is possible to visualise the change of the different
exergy types and components for such operations (i.e., work, E T and E p ).

Figure 7 Representation of exergy sources and sinks for compression of nitrogen (a) above T0
and (b) below T0 (see online version for colours)

In Figure 7(a), nitrogen is compressed from 1 bar and 25°C to different pressures with an
isentropic efficiency of 80%. Notice that for compression above T0, the only exergy
source is the supplied work (−W ), and the exergy content in this work is transformed to
both E T and E p .
On the other hand, when nitrogen is compressed below T0 (Figure 7(b)) from 1 bar
and –193°C with an isentropic efficiency of 80%, the exergy source is the sum of the
work supplied and the change in E T . This combined source transfers the exergy to E p
only. A flow rate of 1 kg/s was assumed. The calculation of exergy sources and sinks was
performed using rigorous simulation.
Figure 8(a) shows the expansion of nitrogen from 10 bar and 225°C to different
pressures with an isentropic efficiency of 80%. One can observe that for adiabatic
expansion above T0, the source is the sum of changes in E T and E p , and the sink is the
produced work. For expansion with work production below T0 shown in Figure 8b (from
10 bar and –100°C to different pressures with an isentropic efficiency of 80%), the
exergy source is the change in E p and the sink is the sum of the change in E T and
produced work (−W ).

3.4 Operations across ambient temperature

For processes operating across T0, the identification of exergy sources and sinks is in
some cases difficult, since the streams may change their identity from source to sink.

3.4.1 Heat exchange

If pressure drop is neglected, there are two possibilities for defining exergy sources and
sinks in terms of changes in temperature-based exergy. The first is to use the total change
in E T of the streams, paying no attention to the crossing of T0. If both streams are
14 D. Marmolejo-Correa and T. Gundersen

operating across T0, only three scenarios can actually take place with reference to
Figure 9:
• One stream is acting as exergy source, the other as exergy sink (Figures 9(a)
and (b)).
For example: Source: −∆E1− 2 and Sink: ∆E 3− 4
or Source: −∆E 3′′− 4 and Sink: ∆E1− 2′′

• Both streams are exergy sources (Figure 9(c)).

For example: Source: −∆E 3′′− 4 and Source: −∆E1− 2

• A stream with zero exergy change is neither a source, nor a sink (Figure 9d).
For example: ∆E1− 2′ or ∆E 3′− 4

A fourth scenario that is missing above would have been the case when both streams are
exergy sinks. While this intuitively sounds wrong, it would also be against the second law
of thermodynamics, since no process can have a net increase in the total exergy. Consider
Figures 9(a) and (b), where both ∆E 3− 4 and ∆E1− 2 '' are exergy sinks. If these streams
were to exchange heat in the same heat exchanger it would either mean that T4 > T1 or
T2 '' < T3 . This is most easily understood by moving points 3” or 4 along the isobar p3 in
Figure 9(b) until E 3" < E 4 . In both cases (T4 > T1 or T2 '' < T3 ), there would be a
temperature cross in the heat exchanger and thus infeasible heat transfer.
The reason why both the hot and the cold streams can be exergy sources (scenario
(ii)) is related to the fact that the two streams have supply temperatures on opposite sides
of T0. The hot stream starts above T0 while the cold starts below T0. Still, it does not seem
‘right’ that two streams exchanging heat can be exergy sources. It also seems ‘wrong’
that the two streams are neither a sink nor a source (scenario (iii)). These two
controversial scenarios clearly indicate that using the total change in E T based on supply
and target conditions is not an adequate procedure to define exergy sources and sinks.

Figure 8 Representation of exergy sources and sinks for expansion of nitrogen (a) above T0 and
(b) below T0 (see online version for colours)
 A new efficiency parameter for exergy analysis in low temperature processes 15

Figure 9 Heat exchange with operating conditions across T0 for both streams when the exergy
source is (a) the hot stream, (b) the cold stream, (c) both streams, and (d) when none of
the streams are exergy source or sink (see online version for colours)

The second possible definition is then to use T0 as an intermediate state between the
supply and target temperatures for both streams. The exergy source is the sum of the
exergy change for both streams from supply temperature to T0, and the exergy sink is the
sum of exergy change for both streams from T0 to target temperature.
Taking into account that E T is zero at T0, the sink becomes the sum of E T for both
stream’s target conditions, while the source is the sum of E T for both streams’ supply
conditions. This is similar to what Brodyansky et al. (1994) found while defining
exergy efficiency for processes operating across T0. However, it should be kept in
mind that the pressure drop has an effect on the magnitude of sinks and sources,
as discussed in Section 3.2. By comparing both approaches, the one proposed by
Brodyansky et al. (1994) and the one suggested in this paper, one should notice that
the first approach uses all changes in E p due to pressure drop as exergy sources, while
ETE considers these changes to decrease the exergy sinks and increase the exergy
sources (see Table 3).
16 D. Marmolejo-Correa and T. Gundersen

Table 3 Sources and sinks for selected unit operations above, across and below ambient
temperature

Unit Above T0 Below T0

Heat
exchange
Source
( ET
H,in − E T
H,out ) + ( E p
H,in − E p
H,out ) ( E T
C,in − ET
C,out ) + ( Ep
C,in − E C,out
p
)
Sink
( E T
C,out − E C,in
T
) − ( E p
C,in − E C,out
p
) ( E T
H,out − E H,in
T
) − ( Ep
H,in − E H,out
p
)
Compression Source W E inT − E out
T
+ W
(pumps and
compressors) Sink E out
TM
− E inTM E out
p
− E inp
Expansion Source E inTM − E out
TM
E inp − E out
p
(expander)
Sink W E out
T
− E inT + W
Expansion Source E inTM − E out
TM
E inp − E out
p
(valve)
Sink Dissipative losses E out
T
− E inT
Across T0
Heat Source
( E T
+ E HT ,in ) + ( E Hp ,in − E Hp ,T0 + E Cp,in − E Cp,T0 )
exchange C ,in

Sink
( ET
C ,out + E HT ,out ) − ( E Cp,T0 − E Cp,out + E H,p T0 − E H,out
p
)
Compression Source W + E inT
(pumps and
compressors) Sink E out
p
− E inp + E out
T

Expansion Source E inp − E out

p
+ E inT
(expander)
Sink W + E out
T

Expansion Source E inp − E out

p
+ E inT
(valve)
Sink E out
T

In the case where only one of the streams is operating across T0, the definition of source
and sink is a combination of the exergy sources and sinks from the systems operating
only above or below ambient temperature with those operating across T0.
For example, if only the hot stream operates across T0 and the cold stream is
operating entirely below T0 (while both streams have pressure drops), then the resulting
expressions are shown in equations (9) and (10).
Source : ( E HT ,in ) + ( E Hp ,in − E Hp ,T0 ) + ( E CT ,in − E CT ,out ) + ( E Cp,in − E Cp,out ) (9)

Sink : ( E HT ,out ) − ( E Hp ,T0 − E Hp ,out ) . (10)

As a result of the discussion about streams crossing ambient conditions, it is necessary to

add a complementary sentence to the source–sink definition provided in Section 3: If the
operating conditions of the stream (i.e., from state a to state b) are across T0, an
intermediate state i (T0, pi) is introduced, resulting in the existence of one source (from
state a to i) and one sink (from state i to b) for the change in E p .
 A new efficiency parameter for exergy analysis in low temperature processes 17

Figure 10 illustrates a heat exchange between methane and nitrogen where ambient
temperature is between the supply and target conditions for both streams. The heat
exchanger is segmented into 12 equal parts (approximately 8.3 MW) of the total heat load
(100 MW).

Figure 10 Representations of (a) exergy sources and sinks and (b) changes in exergy components
for a heat exchanger operating across ambient temperature (see online version for
colours)

The figure illustrates the shift of identity for the streams from exergy source to exergy
sink when passing ambient temperature, T0. In fact, there are three important elements
that contribute to a correct description of the exergy transfer that takes place in heat
exchangers:
1 Decomposition of thermo-mechanical exergy E TM into temperature-based exergy
E T and pressure-based exergy E p .
2 Proper identification of exergy sources and sinks by handling ambient temperature T0
as an intermediate state where streams change identity from exergy source to exergy
sink.
3 Discretisation of the heat exchanger to obtain accurate temperature profiles and
exergy values as well as to locate where streams cross T0.
The importance of considering the elements above can be illustrated by the following
simple numerical examples based on Figure 10:
a When the total change in E TM is used to determine the identity of the streams,
nitrogen with ∆E TM = −37.8 MW is the exergy source, while methane with
∆E TM = 3.2 MW is the exergy sink. Thus, the exergy transfer ratio is very low:
8.5%.
b When the ambient temperature T0 is used to properly define exergy sources and
sinks, the results from an exergy analysis of the heat exchanger are quite different.
The total exergy source is 58.9 MW (46.6 MW from nitrogen below T0 and 12.3
MW from methane above T0), while the total exergy sink is 24.3 MW (15.5 MW to
methane below T0 and 8.8 MW to nitrogen above T0). The corresponding ratio of
exergy transfer is 41.3%.
18 D. Marmolejo-Correa and T. Gundersen

The example shows the importance of properly defining the exergy sources and sinks
before performing an exergy analysis. Notice that in both cases, the exergy destruction is
34.6 MW.

Figure 11 Compression across T0: (a) several compressions with different outlet pressures;
(b) discretised compression from 1 to 10 bar (see online version for colours)

3.4.2 Compression and expansion

In compression and expansion, the total change in E T can result in three different
scenarios for the process streams, similar to heat exchange:
• The change in E T is positive; therefore it is a sink.
• The change in E T is negative; therefore it is a source.
• The change in E T is zero; therefore, it is neither a sink nor a source.
Figure 11(a) shows the compression of nitrogen from 1 bar and –50°C to several
pressures with an isentropic efficiency of 80%. Notice that the apparent shift in E T from
source to sink does not coincide with the crossing of T0. This mismatch is caused by the
fact that the compressed stream starts as an exergy source and changes to an exergy sink
at T0, while Figure 11(a) shows the total (or net) situation, which means that a
compression to slightly above T0 will be represented as a source. The effect will have a
stronger impact (larger delay in the shift from source to sink) with lower initial
temperature. Then, for a second time, one should notice that by using total changes in
exergy, the manner in which the exergy is transferred is not correctly represented. By
discretising the compression process (Figure 11(b)), it is possible to identify the actual
location where the change in E T switches from being a source to become a sink, when
compression is operating across T0. Thus, the exergy source is the sum of the total work
and the change in E T from supply temperature to T0, while the exergy sink is the sum of
the total change in E p and the change in E T from T0 to the target temperature.’
For expansion, a similar analysis can be performed. Figure 12(a) shows the expansion
of nitrogen from 10 bar and 75°C to several pressures with an isentropic efficiency of
80%. As with compression, the total change in E T hides the real exergy sources and
sinks. If the expansion is discretised, then the visualisation of the exergy components is
significantly improved (Figure 12(b)). Finally, the sink is the sum of the work produced
 A new efficiency parameter for exergy analysis in low temperature processes 19

and the change in E T from T0 to the target temperature, while the source is the sum of
the change in E p and the change in E T from supply temperature to T0.

Figure 12 Expansion across T0: (a) several expansions with different outlet pressures; (b)
discretised expansion from 10 to 1 bar (see online version for colours)

4 Coefficients of exergy performance

The calculation of “exergy efficiency” or coefficient of exergy performance (CEP) can be

a rather difficult task due to the lack of standardisation and ambiguity of some terms
found in the literature. There are several definitions available for exergy efficiency.
Different authors (Baehr, 1968; Bejan et al., 1996; Brodyansky et al., 1994; Grassmann,
1950; Kotas, 1980, 1995; Lazzaretto and Tsatsaronis, 2006; Szargut et al., 1988) have
proposed exergy efficiency equations for various processes. It is common to use terms
like useful product, exergy expenditure, exergy output, or exergy input to describe the
exergy efficiency of a process. The problem is that these phrases can lead to different
interpretations. Brodyansky et al. (1994) illustrated through examples how these terms
can lead to different formulations and results for exergy efficiency. Sciubba and Wall
(2007) showed in their commented historical paper, three general definitions as a
summary of the several exergy efficiencies published until 1960. However, Sciubba and
Wall (2007) keep using these ambiguous terms in their assessment. Moreover, by looking
at the exergy efficiency applications in the literature, it seems that different well-justified
directions of exergy efficiency formulations have been developed instead of finding a
unified approach. Therefore, in order to clarify their definitions, it is typical that authors
propose and list specific mathematical expressions for some unit operations
(compression, expansion, heat exchange, mixing, splitting, and separation) and typical
cyclic processes (heat engines, heat pumps, and refrigerators). When comparing the
mathematical expressions for the calculation of exergy efficiency for some unit
operations, it is possible to find similarities among some authors. Still, some definitions
differ or are undefined for some specific process conditions (i.e., in LTPs). Brodyansky
et al. (1994) give some expressions for below and across ambient temperature (T0), while
Kotas (1995) only presents expressions for expansion devices (expanders and valves)
below T0.
20 D. Marmolejo-Correa and T. Gundersen

It should be remarked that it is not our purpose to claim that any of the proposed
exergy efficiencies in the literature are wrong; they are all well grounded and valid in
many situations. They can, however, be wrongly used and misinterpreted.
The main contribution of this work is to show that any exergy efficiency has to be
based on a proper representation of exergy sources and sinks to give an objective measure
of the quality of a process.

4.1 Previous coefficients of exergy performance

Some recent CEPs are: the exergy efficiency (ηe) proposed by Brodyansky et al. (1994);
the rational efficiency (ψ) defined by Kotas (1995); the original exergetic efficiency (ε)
used by Tsatsaronis (1993) and Bejan et al. (1996); and a revised exergetic efficiency (ε’)
proposed by Lazzaretto and Tsatsaronis (2006).

4.1.1 Input–Output efficiency ηIn–Out

Equation (11) shows an intuitive and bookkeeping type efficiency that is commonly used
in the literature for process analysis.
Exergy out
η In − Out = . (11)
Exergy in

4.1.2 Exergetic efficiency (ε)

Equation (12) is first used as exergetic efficiency by Tsatsaronis (1993) and then later by
Bejan et al. (1996). The definitions of exergy products and exergy fuels for typical units
in thermal systems are listed in both references. For a compressor operating above
ambient temperature, for example, the exergy product is the increment in the thermo-
mechanical exergy and the exergy fuel is the compressor work.
Exergy of Products
ε = . (12)
Exergy of Fuel

4.1.3 Exergy efficiency ηe

Brodyansky et al. (1994) defined ηe as shown by Equation (13). The exergy in and exergy
out are the actual (or total) exergy streams entering and exiting the process boundaries
while the transit exergy is the non-transformed exergy passing through the process or unit
operation. A detailed calculation method for the transit exergy is provided in the
referenced book (Brodyansky et al., 1994). In the compression example discussed earlier,
the transit exergy is the total exergy of the compressor inlet.
Exergy out - Transit Exergy
ηe = . (13)
Exergy in - Transit Exergy

4.1.4 Rational efficiency (ψ)

Kotas (1995) used Equation (14) to define a generic type of exergy efficiency. He defined
specific desired outputs and necessary inputs for common unit operations and cyclic
 A new efficiency parameter for exergy analysis in low temperature processes 21

processes. For an above ambient temperature compression, the desired output is defined
as the increment of the thermo-mechanical exergy of the process stream while the
necessary input is the compressor work.
Desired Output
ψ = . (14)
Necessary Input

4.1.5 Revised exergetic efficiency ε′

Lazzaretto and Tsatsaronis (2006) presented a systematic and general methodology for
calculating efficiencies and costs for thermal systems. Their methodology is based on a
so-called specific exergy costing (SPECO) approach, in which the exergy fuel and exergy
product of a unit operation are defined by taking a systematic record of all exergy
additions to and removals from all exergy streams of the system (Lazzaretto and
Tsatsaronis, 2006). This revised definition was extended and complemented by
Tsatsaronis and Morosuk (2010). They stated: When the ambient temperature is crossed
by a stream during the operation of an element (unit operation), then it is not meaningful
to use the exergy difference between inlet and outlet for this stream. In this case the
exergy at the inlet of the stream crossing the ambient temperature belongs to the ‘fuel’
while the exergy at the outlet belongs to the ‘product’ of the component. By using the
SPECO approach, the definitions of exergy products and exergy fuels for processes
below ambient temperature are different from the original exergetic efficiency
(Tsatsaronis, 1993). In their assessment, neither Lazzaretto and Tsatsaronis (2006) nor
Tsatsaronis and Morosuk (2010) introduced an intermediate state when the operating
conditions are across ambient temperature.

4.1.6 Other efficiencies

a Reversible process efficiency (η rev )

This efficiency is not a CEP (Lior and Zhang, 2007) because it does not measure the
exergy transfer within the process or unit operation. However, it is commonly used for
evaluating energy systems. The reversible process efficiency for compressors and
turbines (expanders) is known as isentropic efficiency (see equation (15). Other
reversible process efficiencies are the Carnot factor η and the maximum coefficient of
C

performance (COPmax).
  min (W actual , W rev )  
η rev =    , Carnot factor or COPmax . (15)
  max (W
 actual , W rev ) 
 

b Second Law efficiency (η II )

This efficiency is the ratio between the energy (first law) efficiency (ηI) and the reversible
process efficiency (ηrev) (Lior and Zhang, 2007). This efficiency is not commonly used;
however it is also of interest.
ηI
η II = . (16)
η rev
22 D. Marmolejo-Correa and T. Gundersen

4.2 Exergy Transfer Effectiveness (ETE)

Recently, Marmolejo-Correa and Gundersen (2011) proposed an ETE where a proper
identification of the actual exergy sources and exergy sinks is utilised. As the name
indicates, the ETE is focused on measuring the exergy transfer and conversion within a
process from a thermodynamic point of view, and it is given by equation (17).
Exergy Sinks
ETE = . (17)
Exergy Sources

While the exergy contributions (i.e., sources and sinks) of process streams are easily
identified, energy streams (i.e., heat and power) must be handled with care. For a good
description of exergy transfer and a correct measure of exergy efficiency, both production
and consumption of power must be included as exergy sources and exergy sinks
respectively. When using net power production or consumption, a considerable part of
the exergy transfer is hidden from the analysis. Similarly, all additions and removals of
heat must be included rather than using net values for heat addition or removal.
The main contribution of the ETE and difference from other previously defined CEPs
is in the analysis of processes and unit operations operating below or across ambient
temperature. The key element is a proper identification of exergy sources and sinks.

4.3 Comparison between ETE and other CEPs

There are some agreements and disagreements between the ETE and previous CEPs;
however, the differences become more evident when the operating conditions are across
ambient temperature. Figures 13(a)–(c) show the comparisons made between CEP values
for heat exchange, compression, and expansion units operating across ambient
temperature. The calculations of the CEPs are performed with equations (18)–(20).
Heat exchange:
E TM − E TM 
ε = ψ = ETE =  TM
C ,out

C ,in

EH ,in − EH ,out
TM

 TC ,in , TC ,out , TH ,in , TH ,out > T0
ηe = ε ′ =
( ECT ,out − ECT ,in ) 
( E TM
H ,in − E TM ) + ( E p − E p
H ,out C ,in C ,out ) 


ETE =
E T
H ,out (
− E p
H ,T0 −E p
H ,out )+ E T
(
C ,out ) 
− ECp,T0 − ECp,out
EHT ,in + (E p
H ,in − EHp ,T0 )+ E T
+ ( E − E ) 
C ,in
p
C ,in
p
C ,T0
T , TH ,out < T0 < TC ,out , TH in
( E )
C ,in
T
H ,out + E T
C , out  (18)
ηe = ε ′ = 
( E HT ,in + ECT ,in ) + ( E p
H ,in

−E p
)+( E − E ) 
H ,out
  p
C ,in
p
C ,out

E TM − E TM 
ε = ψ = ETE = HTM,out  TM
H ,in

EC ,in − EC ,out 
 TC ,in , TC ,out , TH ,in , TH ,out < T0
ηe = ε ′ =
( H ,out H ,in )
E T
− E T

( E TM
C ,in − EC ,out ) + ( EH ,in − EH ,out ) 
 TM  p  p
 A new efficiency parameter for exergy analysis in low temperature processes 23

Compression :
E out
TM
− E inTM ε ,ψ : 0 < T < ∞
ε = ψ = ηe = ε ′ = ETE = 
W ηe , ε ′, ETE : T0 < Tin
E p − E p + E T (19)
ηe = ε ′ = ETE = out  T in  out Tin < T0 < Tout
E +W in

E p − E p
ηe = ε ′ = ETE =  T out  T in  Tout < T0
E − E +W
in out

Expansion :
W T >T
ε = ψ = ηe = ε ′ = ETE =  TM  TM  out 0

Ein − Eout ε : 0 < T < ∞

W + E T (20)
ηe = ε ′ = ETE =  p  p out  T Tin > T0 > Tout
Ein − Eout + Ein
W + E out
T
− E inT
ψ = ηe = ε ′ = ETE = T0 > Tin
E inp − E out
p

Figure 13 Comparison between different CEPs for operating conditions across T0: (a) heat
exchange, (b) compression and (c) expansion (see online version for colours)
24 D. Marmolejo-Correa and T. Gundersen

4.4 Heat exchange

The comparison between CEPs in Figure 13(a) corresponds to the evaluation of the heat
exchanger in Figure 10. There is an accumulative effect of exergy exchange in the
plotting of the CEPs. This means that the first point of all CEPs corresponds to the exergy
transfer in segment number 1 while the second point is the accumulated exergy transfer
in segments 1 and 2. The third point corresponds to the evaluation in segments 1, 2, and
3, and so on.
One can notice that ε and ψ decrease when the process streams are crossing
ambient temperature from below. This is because the source–sink identity of the streams
is not switched for ε and ψ, giving as a result a continuous reduction of both exergy
source and exergy sink. In order to demonstrate the latter more clearly, let us assume
that nitrogen is the exergy source and methane is the exergy sink during all heat
exchange, by using total changes of exergy from left to right in Figure 13(a). Notice that
for this example, the supply temperature of the cold stream and the target temperature of
the hot stream are known while the two other temperatures depend on the number of
intervals used for the evaluation of the heat exchanger. Thus, after adding the segments of
exergy to the exergy source and exergy sink from left to right, one should expect that the
efficiency is increasing due to a reduction in exergy destruction before reaching ambient
temperature. In the segments close to ambient, ε and ψ should remain almost constant,
due to the very small exergy transfer in these segments. Then, after ambient temperature
is crossed, nitrogen and methane have negative values as exergy source and exergy sink
respectively. Thus, ε and ψ start decreasing with the addition of those segments. This is
the reason for the shape of the curves corresponding to ε and ψ in Figure 13(a).
In contrast, ETE continues to increase after ambient temperature is crossed, because it
uses the correct exergy source and exergy sink in each accumulated segment. The main
reason for the difference in values between (ηe, ε′) and ETE is the manner in which the
change in E p due to pressure drop is handled. For ηe and ε′, the change in E p is
considered a ‘source’ or ‘fuel’ of exergy, while for ETE it is considered that the change in
E p can be both a source and a sink. In conclusion, the CEP values for the total heat
exchange (from segment 1 to 12) are 41% for ETE, 47% for ηe and ε′, and 8% for ψ
and ε.
Considering the formulation for ψ, ε and ETE in Equation (18), it is clear that for heat
exchange totally above or below ambient temperature, these three CEPs give identical
results. It is when heat exchange takes place across ambient temperature that the
difference between (ψ, ε) and ETE becomes visible. This is caused by (i) the special
characteristics of E T when crossing T0 and (ii) the proper identification of exergy
sources and sinks that forms the basis for the definition of the ETE.

4.5 Compression
The comparison shown in Figure 13(b) takes as basis the compression shown in Figure
11. Since ε and ψ neglect the special behaviour of E T across T0, they use total changes of
exergy for determining each value (see equation (19)). For the calculation of ETE, the
following considerations were made:
• ETE is calculated as compression below T0 until the moment when the outlet
temperature reaches T0
 A new efficiency parameter for exergy analysis in low temperature processes 25

• when the compression ratio is large enough to cause the outlet temperature to cross
T0, ETE is calculated as a compression operating across T0.
One should notice that ETE coincides with ηe and ε′, while ψ and ε have lower values,
since they neglect the shift in the change of E T from exergy source to exergy sink.

4.6 Expansion
In the case of expansion above T0, all CEPs coincide as demonstrated in equation (20)
and Figure 13(c). For expansions to temperatures below T0, ψ and ε have lower values
than ETE, ε′ and ηe due to an improper treatment of temperature-based exergy.

4.7 Summary
Table 4 shows a matrix with the coincidences and disagreements between the ETE and
previous CEPs, in line with what has been discussed in the previous sections. Notice that
in this matrix, the input–output efficiency is also included, and it is different from all the
other CEPs for all unit operations.

Table 4 Coincidence matrix for ETE with previous CEPs

Revised
Input – output Exergetic Exergy Rational exergetic
Operating efficiency (ηIn– efficiency efficiency efficiency efficiency
condition Unit operation Out) (ε) (ηe) (ψ) (ε′)
Heat exchange No Yes No Yes No
Above T0 Compression No Yes Yes Yes Yes
Expansion No Yes Yes Yes Yes
Heat exchange No No* No No* No
Across T0 Compression No No* Yes No* Yes
Expansion No No* Yes No* Yes
Heat exchange No Yes No Yes No
Below T0 Compression No No* Yes No* Yes
Expansion No No* Yes Yes Yes
*The authors do not present expressions for these unit operations.

The comparison of the CEPs cannot be complete without a numerical example. In the
next section, two LNG processes are evaluated using all CEPs presented and discussed in
previous sections.

5 Case studies: exergy analysis of LNG processes

5.1 The PRICO process

Figure 14 shows a simplified version of the PRICO process (Swenson, 1977). PRICO is
the simplest LNG process using a single mixed refrigerant (SMR). PRICO utilises a
single refrigeration cycle with a mixture of light hydrocarbons (e.g., methane,
26 D. Marmolejo-Correa and T. Gundersen

ethylene/ethane, propane, n-butane) and nitrogen as working fluid to liquefy the natural
gas. For exergy calculations, it is assumed that the ambient conditions are 15°C and 1
bar. The commercial simulator ASPEN HYSYS v.7.1 was applied for mass and energy
balances, and the SRK equation of state was used for thermodynamic property
calculations. The compositions of natural gas and the working fluid are the same as the
ones used by Marmolejo-Correa and Gundersen (2012) and are shown in Table 5. The
process stream data and exergy content are given in Table 6.

Figure 14 Flow diagram of the PRICO process (see online version for colours)

Table 5 Stream compositions (mole %)

Component NG feed Refrigerant LNG Purge

Nitrogen 4.0 11.6 1.57 37.9
Methane 87.5 28.4 89.32 62.1
Ethane 5.5 30.7 5.89 0.0
Propane 2.1 14.0 2.25 0.0
n–Butane 0.5 5.7 0.54 0.0
iso–Butane 0.3 0.0 0.32 0.0
iso–Pentane 0.1 9.5 0.11 0.0

Table 6 Process stream data and exergy content for the PRICO process
E T * (kW) E p * (kW)
T (°C) p (bar) m (kg/s)
1 33.9 4.0 9.0 9.4 881.7
2a 86.2 10.0 9.0 153.4 1420.6
2b 36.9 9.5 9.0 31.5 1390.1
2 93.6 24.4 9.0 259.9 1848.2
3 36.9 23.1 9.0 33.3 1824.3
4 –162.0 22.0 9.0 2265.5 1799.9
5 –164.8 4.2 9.0 3070.2 915.2
6 40.0 70.0 1.1 3.0 595.1
7 –156.4 66.5 1.1 406.6 588.1
8 –163.1 1.2 1.1 924.3 26.5
 A new efficiency parameter for exergy analysis in low temperature processes 27

Table 6 Process stream data and exergy content for the PRICO process (continued)
E T * (kW) E p * (kW)
T (°C) p (bar) m (kg/s)
CW1 15.0 1.5 19.2 0.0 1.2
CW2 25.0 1.4 19.2 14.4 1.1
CW3 15.0 1.5 37.6 0.0 2.5
CW4 25.0 1.4 37.6 28.3 2.1
*Normalised by 1kg/s of LNG produced.

The theoretical minimum work required for the liquefaction of the natural gas stream is
352.7 kJ/kg LNG. This theoretical minimum is calculated assuming reversible unit
operations by equation (21). Notice that the phase separator is not included in the
calculation. This is to avoid having to deal with chemical exergy effects of separation,
since the main focus is on the liquefaction process.
Wmin
theo
= E8TM − E 6TM . (21)

The work consumed by K–101 and K–102 is 815.3 kJ/kg LNG and 816.2 kJ/kg LNG
respectively. The heat released by the natural gas is 889.1 kJ/kg LNG; thus the PRICO
process has a COP of 0.55 (equation (22)). The maximum COPmax is 2.1, calculated by
equation (23).
Q NG
ηI = (22)
WTotal

(T7 − T6 )
T 
ln  7 
TC , LM  T6 
η rev = COPmax = = . (23)
TH , LM − TC , LM (TCWout − TCWin ) − (T7 − T6 )
T  T 
ln  CWout  ln  7 
 TCWin   T6 
Thus, the PRICO process has a second law efficiency of 26.2%. In INTERC–101 and
COND–101, the working fluid (refrigerant) rejects heat to sea water (environment);
therefore the sink for these units is the environment. This means that from a process point
of view, these two units have zero contribution to the CEP of the process; however, from
an equipment point of view, they have an exergy transfer rate.
In order to analyse the process with the intention to reduce the irreversibilities for
improving its performance, the effectiveness in which exergy is transferred should be
calculated even when exergy is lost to the environment. CW1 and CW3 are cooling water
streams entering INTERC−101 and COND−102, while CW2 and CW4 are the exiting
streams. Pressure drop in all heat exchangers is equal to 5.5% of the inlet pressure
(Swenson, 1977).
A summarised list of expressions for the calculation of exergy efficiencies is given in
Table 7. In Table 8, the ETE is compared with the bookkeeping efficiency (input–output)
and four previously proposed CEPs (ε, ηe, ψ and ε′). The efficiencies are calculated for
individual unit operations as well as for the total process.
28 D. Marmolejo-Correa and T. Gundersen

Table 7 Expressions for exergy efficiency calculations for the PRICO process
 A new efficiency parameter for exergy analysis in low temperature processes 29

Table 8 Results of the CEP calculations for the PRICO process

Revised Exergy
Input–output Exergetic Exergy Rational exergetic transfer
efficiency efficiency efficiency efficiency efficiency effectiveness
(ηIn–Out) (%) (ε) (%) (ηe) (%) (ψ) (%) (ε’) (%) (ETE) (%)
K–101 92.2 83.8 83.8 83.8 83.8 83.8
INTERC–101 91.2 9.3 9.5 9.3 9.5 9.3
K–102 94.2 84.1 84.1 84.1 84.1 84.1
COND–101 89.5 11.2 11.3 11.2 11.3 11.2
HX–101 92.4 84.2 84.6 84.2 84.6 84.4
VLV–101 98.0 0.0 90.9 90.9 90.9 90.9
VLV–201 95.6 0.0 92.2 92.2 92.2 92.2
Overall process 42.6 21.6 42.0 21.6 42.0 42.0

The simultaneous use of Tables 7 and 8 is highly recommended for better understanding
of the differences between the CEP results. The input–output efficiency is
straightforward, as indicated by equation (11).
Two initial comments should be made before discussing the results in Table 8:
• The assumed pressure drop in the process units is too small to give significant
contributions to the exergy calculations.
• The calculations for ε and ψ are not performed for processes operating across
ambient conditions due to lack of expressions for this case. Instead, the equations for
above T0 are used.
For the unit operations one can observe that:
• The compressors (K–101 and K–102) are operating above T0, thus the ETE coincides
with all the other CEPs.
• Heat exchangers INTERC–101, COND–101 are also operating above ambient
temperature and the difference between ε, ψ and ETE on one hand and ηe and ε’ on
the other is about 0.2% points.
• The expression for ε does not work for valves below ambient temperature (VLV–101
and VLV–201).
• The expressions for ψ and ε do not consider the exergy transfer across T0 in HX–101.
• For the calculation of ETE for HX–101, the intermediate state ETp0 was calculated for
natural gas, the nitrogen hot pass and the nitrogen cold pass. These values are
594.5 kJ/kg LNG (@ 69.7 bar), 1820.7 kJ/kg LNG (@ 22.8 bar) and 883.19 kJ/kg
LNG (@ 4.01 bar). The pressure drop is assumed to be linear with the change in
enthalpy.

5.2 The PRICO process with liquid expanders

Now, instead of using throttling valves for expanding natural gas and the working fluid,
liquid expanders are used as shown in Figure 15. The overall CEPs for the process
30 D. Marmolejo-Correa and T. Gundersen

increase about 4% points (Table 9). Some temperatures have changed after the inclusion
of liquid expanders. The temperatures of streams 5, 7, and 8 are now –165.9°C, –
163.2°C, and –166.7°C respectively. The mass flows of the natural gas and the refrigerant
are now 1.05 kg/kg LNG and 8.52 kg/kg LNG respectively. This change is due to the
reduction of purge gas in the separator that is caused by the new temperature of stream 8.

Figure 15 Flow diagram of the PRICO process with liquid expanders (see online version for
colours)

Table 9 Results of the CEPs for the PRICO process using liquid expanders

Revised Exergy
Input – output Exergetic Exergy Rational exergetic transfer
efficiency efficiency efficiency efficiency efficiency effectiveness
(ηIn–Out) (%) (ε) (%) (ηe) (%) (ψ) (%) (ε’) (%) (ETE) (%)
K–101 92.2% 83.8% 83.8% 83.8% 83.8% 83.8%
INTERC–101 91.2% 9.3% 9.5% 9.3% 9.5% 9.3%
K–102 94.2% 84.1% 84.1% 84.1% 84.1% 84.1%
COND–101 89.5% 11.2% 11.3% 11.2% 11.3% 11.2%
HX–101 92.4% 84.3% 84.7% 84.3% 84.7% 84.5%
LIQ–EXP–101 99.6% 59.8% 98.2% 98.2% 98.2% 98.2%
LIQ–EXP–201 99.2% 59.6% 98.5% 98.5% 98.5% 98.5%
Overall Process 47.0% 25.9% 45.4% 25.9% 45.4% 46.3%

The theoretical minimum work for this modified PRICO process is 389.2 kJ/kg LNG
(equation (21)). The reason why the theoretical work in this case is larger is that some
flows and temperatures have changed compared to the case with throttling valves.
The liquid expanders work with an isentropic efficiency of 80%. The power output of
LIQ–EXP–101 and LIQ–EXP–201 are 22.5 kJ/kg LNG and 11.7 kJ/kg LNG. The
compression work is 768.8 kJ/kg LNG and 769.6 kJ/kg LNG for K–101 and K–102.
The compressors work with an isentropic efficiency of 80%. Thus, the total actual work
is 1504.2 kJ/kg LNG. The heat rejected by the natural gas in HX–101 is 861.2 kJ/kg
LNG. Then, the COP and COPmax are 0.57 and 1.9 respectively. The latter is calculated
by equation (23).
The second law efficiency is now 30.0%, which means an increase of 3.8% points
from the previous case where the expansions are carried out with throttling valves.
 A new efficiency parameter for exergy analysis in low temperature processes 31

Table 7 shows the expressions used for the calculation of CEP values in Table 9.
Comparing the ETE on one hand with ηe and ε’ on the other, notice there is a discrepancy
of 0.9% points. This small difference is a result of how compression and expansion work
are evaluated in the different efficiencies. As previously discussed, it is important for a
correct analysis of the exergy transfer that production and consumption of work are
treated as separate sources and sinks rather than using total (net) values.
Also notice that there is not much difference among the CEPs for HX–101, except for
the input–output efficiency that is very high. These results reflect that for this unit, the
pressure drop and stream pressures are relatively low. Another reason is the limited
amount of heat transfer across T0.

5.3 The reverse Brayton process

The second case study used to evaluate and compare the different CEPs is also related to
the liquefaction of natural gas. The Reverse Brayton process (Figure 16) has been
proposed for offshore installations and for liquefaction plants on LNG ships. Nitrogen is
used as working fluid. Normally, the energy efficiency of this liquefaction process is
quite low. This is due to the large mass flow of nitrogen in the refrigeration cycle and
multiple re-compressions steps. In this example, the compression is performed in six
steps with intercooling and with an isentropic efficiency of 80%. The compression stages
have equal pressure ratios and cooling water is used as coolant. Cooling water enters at
15°C and 1.5 bar, and it has an increment of 10°C in temperature and a pressure drop of
3%. After compression, nitrogen is cooled in AC–100 for conditioning. AC–100 also
uses cooling water as cooling agent. The working fluid is further cooled in the main heat
exchanger (HX–100); at the same time natural gas is liquefied. The cold stream used to
liquefy the natural gas and to chill the nitrogen hot pass is the turbine (TUR–100) outlet
stream (nitrogen cold pass). The turbine operates with an isentropic efficiency of 80%.
Finally, nitrogen from the cold pass enters the compression stages to complete the cycle.
After HX–100, the LNG is expanded to 1.2 bar in a liquid expander (LIQ–EXP–100).
The liquid expander has an isentropic efficiency of 80%. The separation of purge gas and
LNG is not shown in Figure 16. Notice that in the Reverse Brayton process, the working
fluid is not condensed at any time during the process.
Table 10 shows the stream data and exergy content of the most important streams in
the Reverse Brayton process. Pressure drop in the main heat exchanger is 5% of the inlet
pressure.
The theoretical minimum work for the liquefaction of the natural gas is 358.2 kJ/kg
LNG. The total compression and expansion work are 3384.4 kJ/kg LNG and 763.79
kJ/kg LNG respectively. The heat released by the natural gas in the main heat exchanger
is 814.2 kJ/kg LNG. Therefore, the COP and COPmax for the Reverse Brayton process are
0.31 and 2.0 respectively. The latter is obtained from equation (23). Thus, the second law
efficiency is only 15.5%. These results reflect the fact that expansion cycles are less
efficient energy-wise than mixed refrigerant processes, such as PRICO.
Notice that all compressors and intercoolers operate above ambient, the liquid
expander and turbine operate below, and the main heat exchanger operates across
ambient temperature. Actually, all three streams in HX–100 operate across ambient
temperature. The formulas for all unit operations are similar to the ones shown in
Table 7.
32 D. Marmolejo-Correa and T. Gundersen

The results for the different CEPs are shown in Table 11. For calculating the ETE of
HX–100 it was necessary to obtain the pressure and resulting E p at ambient temperature
for all three streams. These are 535.7 kJ/kg LNG (natural gas @ 69.7 bar), 3753.2 kJ/kg
LNG (nitrogen hot pass @ 114.9 bar), and 1507.4 kJ/kg LNG (nitrogen cold pass @ 6.7
bar). The pressure drop in HX–100 is assumed to be linear with the change in enthalpy.

Figure 16 Flow diagram of the reverse Brayton process (see online version for colours)

Table 10 Process stream data with exergy content for the Reverse Brayton process

Stream T (°C) p (bar) m * (kg/s) E T * (kW) E p * (kW)

1 30.0 6.7 9.3 3.7 1504.2
2 83.1 120.0 9.3 77.3 3788.1
3 40.0 116.4 9.3 11.6 3763.6
4 –52.0 110.6 9.3 117.5 3722.4
5 –163.6 7.1 9.3 1011.3 1544.8
6 40.0 70.0 1.0 2.7 536.1
7 –160.6 66.5 1.0 385.8 530.4
8 –165.6 1.2 1.0 873.2 23.8
*
Normalised by 1kg/s of LNG produced.
 A new efficiency parameter for exergy analysis in low temperature processes 33

Table 11 Results of the exergy efficiency calculations for the Reverse Brayton process

Revised Exergy
Input – output Exergetic Exergy Rational exergetic transfer
efficiency efficiency efficiency efficiency efficiency effectiveness
(ηIn–Out) (%) (ε) (%) (ηe) (%) (ψ) (%) (ε’) (%) (ETE) (%)
COM–100–105 96.8 83.6 83.7 83.7 83.7 83.7
E–100–4 97.0 10.3 10.4 10.3 10.4 10.3
AC–100 97.9 8.8 8.9 8.8 8.9 8.8
HX–100 91.2 42.2 45.5 42.2 45.5 47.9
TUR–100 86.2 58.6 75.6 75.6 75.6 75.6
LIQ–EXP–100 99.2 59.8 98.5 98.5 98.5 98.5
Overall process 42.3 13.7 27.8 27.8 27.8 42.0

One can notice that there are larger differences between the CEP results for HX–100 and
the overall process than in the previous PRICO examples. These differences are mainly
caused by two special situations.
• For HX–100, the pressure level of nitrogen (cold pass) has a significant impact on
the change of E p , which then highlights the different handling of pressure change
among the CEPs
• The results for the overall process show that the variations between the ETE and the
rest of the CEPs are quite large (between 14.2% points and 28.3% points). The use of
compression work and expansion work as separate quantities and not using the total
(or net) work either as an exergy source or as a sink is the main reason for these
discrepancies. Notice that all the other CEPs use the net work required as an exergy
source for this case, since total compression work is larger than total expansion
work.

6 Conclusions

In this paper, the special behaviour of temperature-based exergy of material streams in

LTPs is reviewed and discussed, and an ETE is proposed. A general rule for the use of
the ETE is suggested in order to generalise the definition and to avoid confusion in the
calculations. The concept of exergy sources and sinks is applied in establishing the ETE
to evaluate the performance of a process or a unit operation. For selected unit operations,
exergy sources and sinks are illustrated at different operating conditions (above, across,
and below ambient temperature, T0). After the identification of sources and sinks, a
generic rule was suggested for these units. It was proposed that for process streams
completely above or below T0, any negative change in the exergy components is an
exergy source while a positive change is an exergy sink. If the operating conditions are
across T0, then an intermediate state i (T0, pi) is introduced. An analysis of previous
expressions for CEP and their applicability to LTPs is presented, as well as a comparison
between these selected CEPs and ETE. The comparison was made for two processes for
the liquefaction of natural gas: the PRICO process and the Reverse Brayton process. Two
variations of the PRICO process were analysed. The first variation is the original PRICO
34 D. Marmolejo-Correa and T. Gundersen

process in which throttling valves are used for expansion, and the second variation when
the valves are replaced by liquid expanders. The variations of the PRICO process
illustrate the effect that compression and expansion work have on the CEPs, i.e., whether
total production and total consumption are included separately or only net values
(production or consumption) are used. It was demonstrated with the evaluation of the
Reverse Brayton process, that the change in pressure-based exergy ( E p ) can have a
significant effect on the CEPs when the pressure drop is considerable. It is important to
mention that the objective of this paper is to show that some coefficients of exergy
performance are not applicable for processes and unit operations operating below and
across ambient temperature. For instance, the exergetic efficiency, ε (Tsatsaronis, 1993)
should not be used for these kind of processes. Instead, one could use the rational
efficiency, ψ (Kotas, 1995) for processes operating below ambient temperature except for
compressors and units operating across ambient. Another alternative is to use either the
exergy efficiency, ηe (Brodyansky et al., 1994), or the improved exergetic efficiency, ε’
(Lazzaretto and Tsatsaronis, 2006), for systems operating above, below, and across
ambient temperature, however, with the restrictions of small pressure drop in heat
exchangers and small temperature cross with respect to ambient temperature.
The authors highly recommend the use of the ETE (Marmolejo-Correa and
Gundersen, 2011) instead of the other CEPs because it can be used for all temperature
conditions and it ensures the correct use of exergy sources and exergy sinks for the
evaluation of exergy transfer in processes. The ETE still needs to be extended to other
unit operations where the stream composition changes; however, the authors expect that
by following the above-mentioned rule for exergy sources and sinks, such an extension to
other units should be fairly straightforward.

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 36 D. Marmolejo-Correa and T. Gundersen

Nomenclature
cp Specific heat capacity (kJ/kg°C)
COP Coefficient of performance
E Exergy flow (kW)
ETE Exergy transfer effectiveness
H Enthalpy flow (kW)
m Mass flow (kg/s)
P Pressure (bar)
Q Heat flow (kW)
S Entropy flow (kW/K)
T Temperature (°C or K)
W Power (kW)
Greek symbols
∆ Difference
Ε Exergetic efficiency
ψ Rational efficiency
η Exergy efficiency
ηe Exergy efficiency
Subscripts and superscripts
‘ Exergetic efficiency using the SPECO approach
0 Environmental conditions
C Cold stream
H Hot stream
I First law efficiency
II Second law efficiency
I Intermediate state
In Inlet stream
LM Logarithmic mean
Out Outlet stream
P Pressure-based exergy
Q Exergy of heat
rev Reversible
T Temperature-based exergy
TM Thermo-mechanical exergy
CW Cooling water
Abbreviations
CEP Coefficient of exergy performance
LNG Liquefied natural gas
LTP Low temperature process
NG Natural gas
SPECO Specific exergy costing approach

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