Chapter 23
Exergy and Industrial Ecology
Chapter Outline
23.1 Introduction 475
23.2 Industrial Ecology 475
23.3 Linkage between Exergy and Industrial Ecology 476
23.3.1 Depletion Number 476
23.3.2 Integrated Systems 476
23.4 Illustrative Example 476
ABSTRACT
In this chapter, the integration of exergy analysis with industrial
ecology, and the application of such a combined method, is
described. Industrial ecology is an approach to designing industrial
systems that promotes environmental improvement by seeking
a reasonable balance between industrial profit and environmental
stewardship and thereby can contribute to sustainable develop-
ment. As exergy analysis pinpoints significant process and device
exergy losses, or nonrecoverable losses of fuel exergy, it can help
makes industrial technologies more ecologically benign and
efficient when integrated with industrial ecology. Illustrations are
discussed for combined cycle power plants, hydrogen production,
and crude oil distillation.
KEYWORDS
Exergy; Industrial ecology; Depletion number; Power plant; Gas
turbine; Combined cycle; Hydrogen production.
23.1 INTRODUCTION
Industrial ecology is an approach to designing industrial
systems that promotes systems that are less damaging to the
environment. This approach seeks a reasonable balance
between industrial profit and environmental stewardship;
thereby it can contribute to sustainable development.
Industrial ecology methods can beneficially incorporate
exergy to provide more powerful tools. Exergy analysis
pinpoints significant process and device exergy losses, or
nonrecoverable losses of fuel exergy. It is generally
accepted that an increase in efficiency of fossil-fuel
utilization makes industrial technologies more ecologically
benign and safe. Therefore, exergy methods can help in
rational modification of contemporary technologies.
Exergy. http://dx.doi.org/10.1016/B978-0-08-097089-9.00023-1
2013 Ibrahim Dincer and Marc A. Rosen. Published by Elsevier Ltd. All rights reserved
23.4.1 Gas-Turbine Combined Cycle with Hydrogen
Generation 477
23.4.2 Exergy Analysis of the Gas-Turbine Combined
Cycle with Hydrogen Generation 478
23.4.3 Results 478
23.5 Closing Remarks 480
Problems 481
Szargut (2005a,b) cites the following example. In
a combined power plant equipped with a coal boiler and gas
turbine, the heat transfer exergy losses in the heat recovery
boiler of the gas turbine can be reduced by shifting the steam
superheater from the coal boiler to the heat recovery boiler of
the gas turbine. In another example from the chemical
industry, energy and exergy analyses of a traditional one-
stage crude oil distillation unit and a newly proposed two-
stage unit are conducted to investigate the efficiencies and
exergy losses (Husain et al., 2003). The results are compared
for both one- and two-stage distillation units. The proposed
two-stage distillation unit exhibits a 43.8% decrease in
overall exergy losses and 125% increase in the overall exergy
efficiency, leading to the recommendation to perform distil-
lation in two stages, rather than one, to reduce the heat duty of
the heating furnace and thus reduce irreversible losses.
23.2 INDUSTRIAL ECOLOGY
Industrial ecology is concerned with shifting industrial
processes from linear (open loop) systems in which resource
and capital investments move through the system to become
wastes, to closed loop systems where wastes become inputs
for new processes (Graedel and Allenby, 1995). Industrial
ecology was popularized by Frosh and Gallopoulos (1989),
who asked why industrial systems do not behave like an
ecosystem, where wastes of one species are a resource to
another species. Why shouldnt the outputs of one industry be
the inputs of another, thereby reducing the use of raw mate-
rials and pollution and saving on waste treatment? Lowe and
Evans (1995) noted that industrial ecology suggests using the
design of ecosystems to guide the redesign of industrial
systems to achieve a better balance between industrial
475
476 Exergy

performance and ecological constraints and, consequently, to

_ D
Ex
determine a path to sustainable development. Dp (23.2)
According to this conception, modern industrial tech- _ in
Ex
nologies should be designed like ecosystems where: (1) input which represents the relation between the exergy destruc-
mass and energy flows are minimized and (2) energy supply _ D and total exergy consumption rate Ex
tion rate Ex _ in (in
is provided by renewable energy sources. Minimization of this chapter, only direct exergies are considered).
the fossil-fuel energy consumption in industrial processes In line with the definition of exergy efficiency, if there
implies eliminating output waste energy flows or the emis- are no waste exergy emissions the exergy efficiency j is
sion of wastes that are in equilibrium with the conditions expressible as follows:
(pressure, temperature, composition) of the environment.
Applying these principles to industrial processes, like j 1  Dp (23.3)
power generation and transportation, leads to several The exergy efficiency is always a measure of how
interesting observations. The technical ability to transform nearly a process approaches the ideal.
renewable energy to electricity for industrial and other
needs is developed, but the relevant technologies involve
significant consumptions of resources such as construction 23.3.2 Integrated Systems
materials per unit of output generated and are often less
The efficiency of integrated or combined technologies (e.g.,
attractive economically and sometimes less attractive
cogeneration) can be evaluated and compared by exam-
environmentally than traditional fossil-fuel plants.
ining the depletion numbers Dp for the separate and
23.3 LINKAGE BETWEEN EXERGY AND combined technologies (see Figure 23.1).
The consumption of nonrenewable energy resources
INDUSTRIAL ECOLOGY corresponds to lower depletion numbers (see Eq. 23.2).
Graedel (1996) wrote, The term industrial ecology was Consequently, the depletion number for an advanced
conceived to suggest that industrial activity can be thought comb
combined technology Dp should be lower than the
of and approached in much the same way as a biological sep
weighted sum of the depletion numbers Dp for the
ecosystem and that in its ideal form it would strive toward
sep
integration of activities and cyclization of resources, as do separate technologies. For the system in Figure 23.1, Dp
natural ecosystems. He goes on to note that little has been is expressible as follows:
done to explore the usefulness of the analogy.
_ comb
Ex
The use of exergy in conjunction with industrial ecology p1
Dsep
p D1
can provide a useful tool that permits practical applications _ comb E_ x comb p
Ex p1 p2
(Connelly and Koshland, 2001a,b; Dewulf and Van Langen-
hove, 2002; Kay, 2002). Waste exergy emissions and exergy _ comb
Ex p2
D2 (23.4)
destructions, unlike energy losses, can account for the envi- _
Ex comb _ comb p
Ex
p1 p2
ronmental impacts of energy utilization (Dincer and Rosen,
2005). Szargut et al. (2002) suggested that the cumulative 1 2
where Dp and Dp are depletion numbers for two separate
consumption of nonrenewable exergy provided a measure of technologies and Ex _ comb are the rates of output
_ comb and Ex
p1 p2
the depletion of nonrenewable natural resources. exergy flows for products 1 and 2, respectively.
Reducing entropy generation leads to a decline in
exergy destruction (losses) Ex _ D due to reducing the irre-
versibility of the processes constituting an industrial 23.4 ILLUSTRATIVE EXAMPLE
system. According to the Gouy-Stodola formula, The principles discussed in this chapter are demonstrated for
_ D T0 S_gen
Ex (23.1) a combined gas-turbine cycle with a hydrogen generation unit
(Granovskii et al., 2006b). This design includes two impor-
where T0 is the reference environment temperature (often tant technologies: (1) a solid oxide fuel cell (SOFC) with
fixed at 298 K or the local temperature), and S_gen is the internal natural gas reforming and (2) a membrane reactor
entropy generation rate in a process or device. (MR), and their combination with a hydrogen generation unit.
A common feature of SOFCs and MRs is their utilization
of high-temperature oxygen ion-conductive membranes.
23.3.1 Depletion Number
Such membranes are conductive to negatively charged ions
Connelly and Koshland (2001a.b) suggest that the effi- of oxygen and permit the separation of oxygen from air. This
ciency of fossil-fuel consumption be characterized by property accounts for their application as an electrolyte in
a depletion number Dp: SOFCs, where the chemical exergy of methane, through an
Chapter | 23 Exergy and Industrial Ecology
intermediate stage involving its conversion to hydrogen and
carbon monoxide and electrochemical oxidation with
oxygen, is transformed into electrical work. In a membrane
reactor, the membrane conducts both oxygen ions and
electrons in opposite directions; such membranes are
consequently often called mixed conducting membranes. In
the present case, electrical work is not generated, but oxygen
is separated from air and fuel combustion proceeds in an
atmosphere of oxygen.
Oxygen ion-conductive membranes are made of
ceramic materials (usually zirconia oxides) and have good
performance characteristics at temperatures higher than
700 C. An SOFC stack is often introduced into traditional
power generation cycles, where it operates at temperatures
of 800 Ce1100 C (e.g., Chan et al., 2002; Kuchontchara
et al., 2003a,b). An MR is being developed for operation up
to 1250 C, as a substitute for combustion chambers in
advanced zero-emission power plants (e.g., Sundkvist
et al., 2001). New materials for the anodes of SOFCs
contain a catalyst for the methane-reforming process,
allowing methane conversion into a mixture of hydrogen
and carbon monoxide directly on the surface of the anode
(Eguchi et al., 2002; Weber et al., 2002). SOFCs thereby
become more flexible, compact, and effective, avoiding the
need for preliminary reforming of methane.
23.4.1 Gas-Turbine Combined Cycle with
Hydrogen Generation
A combined gas-turbine cycle with a hydrogen generation
unit is presented in Figure 23.2. The initial stream of
natural gas, after heating in device 14 (in order to achieve
477
FIGURE 23.1 Input and output exergy rates
for separate and combined technologies to
produce two products.
after compression the temperature of combustion products)
and compression in device 15, is divided into two flows.
The first is mixed with combustion products (carbon
dioxide and steam) and directed to the anodes of the SOFC
stack (device 4), where two processes occur simulta-
neously: (1) conversion of methane into a mixture of carbon
monoxide and (2) hydrogen on the surface of the anodes
and electrochemical oxidation of the resultant mixture with
oxygen. The oxygen reduction is accompanied by elec-
tricity generation in the SOFCs. The gaseous mixture from
the anodes (conversion and combustion products) is cooled
in a heat exchanger (device 10), compressed in device 11,
and directed to the MR (device 1), where the remainder of
the conversion products combust in oxygen, and then
expand in a turbine (device 2).
The combustion products are then divided into two flows.
The first is mixed with the initial flow of methane and directed
to the SOFC stack, while the other is mixed with the second
flow of methane and enters the catalytic methane converter
(device 5). After methane conversion to hydrogen and carbon
monoxide in device 5, the gaseous mixture is expanded in
a turbine (device 8), cooled in a heat exchanger (device 9),
and directed to the shift reactor, where the remainder of the
carbon monoxide and steam is converted to hydrogen.
Air is heated in device 12, compressed in device 13, and
directed to the MR (device 1), where some quantity of
oxygen is transferred through the oxygen ion-conductive
membrane and combusted with fuel. The air heating in
device 12 is required in order to achieve after compression
the temperature of the fuel flow that is directed, like air, to
the MR.
The temperature of air reaches its maximum at the MR
(device 1) outlet, at which point it is expanded in the turbine
478 Exergy

FIGURE 23.2 An application of a SOFC and MR in 1

a combined gas-turbine cycle with a hydrogen generation 3
unit. Numbers indicate devices according to the following
legend: 1: MR; 2,3,6,8: turbines; 11,13,15: compressors; 4: a
SOFC stack; 5: methane converter; 7,9,10,12,14: heat
exchangers; a: oxygen ion-conductive membranes; b, c: 13 11
anode and cathode of SOFC stack.

E5 2

12 Electricity

Air (P0 =1atm,

T0=298K)
- +
4
15
b c
10
a 14
5
E4
E1 6
7 d

Natural gas (methane)

Exhaust gases 9 (P0=1atm, T0=298K)
(P0=1atm, T0=298K) E2
Syngas to shift reactor for
8
hydrogen production
(P0=1atm, T=673K)
E3

(device 3) and directed to the cathodes of the SOFCs (device
4). In the SOFCs, the oxygen concentration in the air
decreases, and the air is heated and enters the space between
pipes in the catalytic converter (device 5). In device 5, heat
is transferred from the air to the reaction mixture in the
pipes. The mixture is then expanded in the turbine (device 6)
and cooled in the heat exchanger (device 7).
The power generation design combines a traditional
gas-turbine cycledwhich consists of compressors (devices
11 and 13), a combustion chamber (which is represented by
the MR, device 1), and turbines (devices 2 and 3)dwith the
SOFC stack (device 4) and the methane converter (device
5). Heat exchangers are conditionally divided into the heat-
releasing (devices 7, 9, and 10) and heat-receiving (devices
12 and 14) types. Mechanical work is produced in the
turbines and consumed in the compressors. The work is
transformed into electrical energy, which is also directly
generated in the SOFC stack. The endothermic process of
methane conversion to hydrogen (via a synthesis gas) in
device 5 is implemented into the power generation cycle.
23.4.2 Exergy Analysis of the Gas-Turbine
Combined Cycle with Hydrogen Generation
The general assumptions applied in the exergy analysis of
the proposed design include: (1) gases are modeled as ideal,
(2) energy losses due to mechanical friction are negligible,
(3) thermodynamic and chemical equilibria are achieved at
the outlet of the SOFC stack and methane converter, and (4)
all combustible components are combusted completely in
the MR. The general parameters used in the combined
power generation cycle are listed in Table 23.1. Values for
the parameters ht, hcmp, Pmax, Pmin, and Tmax are often cited
(e.g., Kirillin et al., 1979).
An exergy balance of a system permits evaluation of the
efficiency with which input energy flows are utilized. For
the power generation scheme presented in Figure 23.2, the
exergy balance can be expressed as:
X
_ Ex
DEx _ in  Ex_ out SW_ i DEx
_ T _ Di
Ex
(23.5)
where DEx _ is the rate of exergy change in the system; Ex
_ in
is the sum of the exergy rates of the input flows of methane
_ out is the sum of the exergy rates of the output
and air; Ex
flows of conversion products (synthesis gas) directed to
a shift converter and exhaust gases; SW_ i is the sum of
powers generated in the turbines and in SOFCs and
consumed in the compressors (with a negative sign); DEx _ T
is the sum of thermal exergy rates released in heat
exchangers 7, 9, and P 10 and consumed in 4 and 12 (with
a negative sign); and _ Di is the sum of the exergy loss
Ex
rates in the devices of the system.
23.4.3 Results
The analysis results are presented in Tables 23.2e23.4.
Table 23.3 presents the mechanical and electrical work
generated in the turbines and SOFC stack, the mechanical
Chapter | 23 Exergy and Industrial Ecology 479

TABLE 23.1 General Parameter Values for the Combined Power Generation Cycle in Figure 23.2

Parameter Value
Isentropic efficiency of turbines ht 0.93
Isentropic efficiency of compressors hcmp 0.85

Operational circuit voltage of the SOFC stack V 0.85

Maximum pressure in the gas-turbine cycle pmax, atm 10
Minimum pressure in the gas-turbine cycle pmin, atm 1
Maximum temperature in the cycle (at the MR outlet) Tmax , K 1573
Temperature of fuel at the inlet of the SOFC stack Ts, K 1273
Temperature of fuel and air at the outlet of the SOFC stack Ts, K 1273

Ratio of methane combusted in the power generation cycle to the methane converted 1.0:0.7
Molar ratio of combustion products after the MR to methane combusted in the power generation cycle 6
Ratio of amounts of combustion products directed to SOFC and methane converter 1:1
Standard temperature T0, K 298
Standard pressure p0, atm 1
Air composition, volume percentage 21% O2, 79% N2

work consumed in the compressors (with a negative sign),
and the exergy losses accompanying these processes. Table
23.4 presents the exergy losses in the MR and methane
converter. Table 23.4 also lists the exergy losses ExDtr
accompanying the heat transfer from hot to cool flows and
the excess of thermal exergy DExT , which can be converted
to mechanical work in a bottoming steam-water (Rankine)
cycle (not shown in Figure 23.2) with an exergy efficiency
jR of about 60% (Cengel and Turner, 2005), so that
WR hR DExT and ExDR DExT  WR (23.6)
After substituting WR and ExDR into Equation 23.5 instead
of DET , the exergy change DEx 684:8 kJ=mol in the
system is distributed only between work W 516.8 kJ/mol
and the exergy losses (destruction) ExD 168.0 kJ/mol.
Since data are calculated per mole of methane com-
busted to generate electricity and 0.7 mol of methane
converted to hydrogen, and the value of standard exergy of

TABLE 23.2 Generated Work and Exergy Losses for the Processes in the Combined Gas-Turbine Cycle in Figure 23.2*

Device number in Figure 23.2 W, kJ/mol ExD , kJ/mol

2 89.7 1.6

3 207.1 4.1
4 497.4 29.4
6 85.0 2.3
8 35.6 0.2
11 89.8 4.2
13 324.4 22.3

15 18.8 0.7
Total 481.8 64.8

*Data are given per mole of methane combusted in the power generation cycle.
480 Exergy

TABLE 23.3 Exergy Losses in the MR and Methane Converter*

Device number in Figure 23.2 ExD , kJ/mol

1 27.6
5 15.9

Methane mixing 10.0

Total 53.5

*Data are given per mole of methane combusted in the power generation cycle, which corresponds to 0.7 mole of methane converted in methane converter 5.

methane Ex0CH4 831.7 kJ/mol (Szargut et al., 1988), the 1

The limiting value of Dp for the separate electricity
comb comb
depletion number of the combined system Dp becomes generation process can be obtained by equalizing Dp
P sep 2
comb ExDi 168:0 Dp with the given value of Dp . In this case, the limiting
Dp 0
0:12 (23.7) 1
1:7ExCH4 1414:0 value is found to be Dp 0.068, which corresponds to an
The combined system yields two products: (1) electricity exergy efficiency of electricity generation j1 0.93 (Eq.
and (2) synthesis gas (a mixture of carbon monoxide and 23.3). This value is unrealistic, as it exceeds even the
hydrogen). The exergy of electrical work is equal to its energy highest SOFC efficiency obtained in laboratory experi-
and standard exergies of carbon monoxide and hydrogen are ments (e.g., Larminie and Dicks, 2003). Thus, this
Ex0H2 236.1 kJ/mol and Ex0CO 275.1 kJ/mol (Szargut magnitude of efficiency can be attained only through an
et al., 1988). Then the exergy of the synthesis gas directed to integrated process like cogeneration.
the shift reactor to produce hydrogen (see Figure 23.1) is The conducted analysis confirms that integrated
Ex0SG 656.1 kJ/mol (for one mole of methane combusted energy systems, developed via an appropriate combina-
and 0.7 mol of methane converted). The exergy efficiency of tion of technologies, represent an important opportunity
a combined gas-turbine steam power cycle where only elec- for increasing the utilization efficiency of natural
trical work is generated is j1 0.54 (e.g., Cleveland, 2004) resources, thereby achieving the aims of industrial
and the exergy efficiency of methane conversion to synthesis ecology.
gas is j2 0.84 (e.g., Rosen and Scott, 1998). With
1
Equation 23.3, the depletion numbers are calculated Dp 23.5 CLOSING REMARKS
2
0.46 and Dp 0.16. Substitution of these values into the Industrial ecology is an approach that suggests designing
sep
expression for Dp (Eq. 23.4) yields the following: industrial systems like ecosystems, where the wastes of one
W Ex0SG species are often the resource of another. Important ways of
Dsep
p D1
p D2 0:29 implementing industrial ecology include the appropriate
W ExSG
0 W Ex0SG p
combination of separate technologies in order to match the
(23.8) waste outputs of one with the inputs of the other, and the
The depletion number for the separate technologies introduction of processes that reduce nonrenewable energy
sep consumption. Exergy analysis can help in designing
Dp is seen to be more than two times greater than that for industrial systems that follow the principles of industrial
comb
the combined system Dp . The implication is that the ecology, and in the evaluation of the efficiencies and losses
combined technology is more environmentally benign (and for such activities. One such evaluation measure is the
behaves more like an ecosystem) than the separate devices, depletion number, which relates the exergy destruction and
and requires combustion of less natural gas. exergy input for a system.

TABLE 23.4 Released Thermal Exergy DE xT and Its Utilization in the Rankine Bottoming Cycle*

DE xT , kJ/mol E xDtr , kJ/mol WR , kJ/mol E xDR , kJ/mol

58.4 26.3 35.0 23.4

*Data are given per mole of methane combusted in the power generation cycle.
Chapter | 23 Exergy and Industrial Ecology
In this chapter, an example was used to illustrate how to
compare depletion numbers for separate and combined
technologies to assess the effectiveness of their integration.
The analysis suggests that an exergy-based approach to
industrial ecology can be advantageous in the creation and
modification of industrial systems, through integrating
separate technologies and other measures.
PROBLEMS
23.1 What is industrial ecology? How is it related to exergy?
23.2 What is the difference between exergetic life cycle
assessment and industrial ecology?
481
23.3 What is the relationship between industrial ecology
and the environmental impact of energy systems?
23.4 What is the depletion number? How is it related to
industrial ecology?
23.5 What is the relationship between depletion number
and exergy efficiency?
23.6 What is the effect of depletion number on resource
sustainability?
23.7 Are the depletion numbers for renewable energy
systems zero? Explain.
23.8 Obtain a published article on industrial ecology. Using
the data provided in the article, try to duplicate the results.
Compare your results to those in the original article.